Preparation and properties of strong polyaniline-polyacrylic acid/polyacrylamide conductive hydrogel
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摘要: 将导电聚合物引入到水凝胶网络中的导电高分子基导电水凝胶,因结合了水凝胶的三维网络结构、良好的生物相容性、优异的力学性能等和导电高分子良好电学性能等优点而被广泛研究,特别是以聚苯胺(PANI)为导电高分子的导电水凝胶。但PANI不溶于水,因此很难制备PANI基导电水凝胶。本文以制备高强度PANI基导电水凝胶为目的,尝试将PANI接枝在亲水性聚合物聚丙烯酸(PAA)上,获得能在水中均匀分散的PANI-PAA导电复合物,再使其与丙烯酰胺(AM)聚合得到高强度的PANI-PAA/PAM导电水凝胶。通过力学性能及电化学性能测试,发现该导电水凝胶具有良好的力学性能和电化学性能。当以十二烷基硫酸钠(SDS)为分散剂时,其电导率可达4.63 S·m−1,可承受压缩应力1.33 MPa (压缩耗散能为85.50 kJ·m−3),拉伸断裂伸长率达964%,相应的断裂强度为0.25 MPa;而以NaOH为分散剂时,凝胶的电导率可达4.19 S·m−1,可承受压缩应力1.13 MPa (压缩耗散能为73.45 kJ·m−3),拉伸断裂伸长率达896%;相应的断裂强度为 0.14 MPa。该研究为高强度聚苯胺基导电水凝胶的制备提供了思路。Abstract: The conductive polymer-based conductive hydrogels which introduced conductive polymers into the hydrogel network have been extensively studied because of the combination of three-dimensional network structure, good biocompatibility, excellent mechanical properties and electrical properties, especially the conductive hydrogels with polyaniline (PANI) as conductive polymer. However, PANI is insoluble in water, so it is difficult to prepare PANI-based conductive hydrogels. In order to prepare high-strength PANI based conductive hydrogels, this paper attempted to graft PANI onto the hydrophilic polymer polyacrylic acid (PAA) to obtain a PANI-PAA conductive composite that could be uniformly dispersed in water, and then it was polymerized with polyacrylamide (PAM) to obtain a strong PANI-PAA/PAM conductive hydrogel. Through mechanical and electrochemical tests, it is found that the conductive hydrogel has good mechanical and electrochemical properties. When SDS was used as dispersant, the conductivity could reach 4.63 S·m−1, meanwhile, it could withstand compression stress of 1.33 MPa (corresponding dissipation energy of compression is 85.50 kJ·m−3), the elongation at break is 964%, and the corresponding breaking strength is 0.25 MPa. Under the condition of NaOH as dispersant, the conductivity could reach 4.19 S·m−1, and it could bear the compression stress of 1.13 MPa (corresponding dissipation energy of compression is 73.45 kJ·m−3), the tensile elongation at break reaches 896%, and the corresponding fracture strength is 0.14 MPa. This study provides ideas for the preparation of high-strength polyaniline-based conductive hydrogels.
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Key words:
- conductive hydrogels /
- strong hydrogels /
- polyaniline /
- polyacrylic acid /
- conductive complex
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图 3 以SDS ((a)~(d)) 和NaOH ((e)~(g)) 为分散剂制备PANI-PAA/PAM导电水凝胶
Figure 3. Preparation of PANI-PAA/PAM conductive hydrogel with SDS ((a)-(d)) and NaOH ((e)-(g)) as dispersant, respectively ((a) PANI-PAA/SDS; (b) PANI-PAA/SDS; (c) PANI-PAA/SDS/AM; (e) PANI-PAA/NaOH solution; (f) PANI-PAA/NaOH dispersion; (g) PANI-PAA/NaOH/AM dispersion; ((d), (h)) PANI-PAA/PAM conducting hydrogel)
表 1 聚苯胺-聚丙烯酸/聚丙烯酰胺 (PANI-PAA/PAM) 导电水凝胶的配方
Table 1. Formula of polyaniline-polyacrylic acid/polyacrylamide (PANI-PAA/PAM) conductive hydrogels
PANI-PAA/g H2O/g SDS/g NaOH/g AM/g MBA(0.25wt%)/μL APS/g TEMED/μL 0 5 0.01 — 1.5 1 100 0.02 100 0.01 5 0.01 — 1.5 1 100 0.02 100 0.02 5 0.02 — 1.5 1 100 0.04 100 0.03 5 0.03 — 1.5 1 100 0.06 100 0 5 — 0.03 1.5 1 100 0.025 100 0.05 5 — 0.03 1.5 1 100 0.025 100 0.075 5 — 0.0475 1.5 1 100 0.0375 100 0.1 5 — 0.06 1.5 1 100 0.05 100 Notes: SDS—Sodium dodecyl sulfate; AM—Acrylamide; MBA—N, N'-methylene bisacrylamide; APS—Ammonium persulfate; TEMED—Tetramethylethylenediamine. 表 2 PANI-PAA/PAM导电水凝胶的压缩性能
Table 2. Compression properties of PANI-PAA/PAM conductive hydrogels
Dispersant PANI-PAA/g Compressive stress/MPa Elastic modulus/Pa Dissipated energy/(kJ·m−3) SDS 0 1.75 282.00 96.13 0.01 1.33 251.33 85.50 0.02 0.52 75.47 32.13 0.03 0.94 109.33 51.71 NaOH 0 1.25 220.79 71.86 0.05 0.98 214.10 66.79 0.075 1.13 183.48 73.45 0.1 0.68 111.09 39.96 表 3 PANI-PAA/PAM导电水凝胶的电导率
Table 3. Conductivity of PANI-PAA/PAM conducting hydrogel
Dispersant PANI-PAA/g Conductivity/(S·m−1) SDS 0 0.023 0.01 2.38 0.02 2.69 0.03 4.63 NaOH 0 0.015 0.05 3.53 0.075 3.07 0.1 4.19 -
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