自组装聚合法制备木质素磺酸/聚吡咯柔性导电纸

doi:10.7503/cjcu20180122

摘要/Abstract

摘要：

以造纸废液中的木质素为分散剂和掺杂剂, 采用自组装聚合法制备了具有高电导率、负载可控、高稳定性且抗张强度保持较好的木质素磺酸/聚吡咯柔性导电纸. 采用红外光谱、四探针、扫描电镜、抗张强度和电化学等手段对导电纸的性能进行了表征, 并研究了掺杂剂类型和组装层数对导电纸导电性能和力学性能的影响. 结果表明, 随着组装层数的增加, 聚吡咯导电纸的负载量、电导率及导电稳定性均有提高. 与原位聚合法相比, 自组装聚合法制备的导电纸的性能更优. 木质素磺酸在聚吡咯导电纸体系不仅可以起到掺杂和分散的作用, 其对导电纸综合性能的增强效果优于盐酸和聚苯乙烯磺酸. 由于木质素磺酸具有三维网络空间结构及其与纤维之间具有较强的氢键作用力, 显著提高了导电纸的抗张强度及弯曲状态下的导电稳定性, 其抗氧化和防水性还可以提高导电纸在空气和湿气中的导电稳定性.

关键词: 自组装聚合法, 木质素磺酸/聚吡咯柔性导电纸, 组装层数, 导电稳定性, 抗张强度

Abstract:

Flexible and load-controllable lignosulfonate-polypyrrole conductive paper with high-stability was prepared by self-assembly polymerization method using lignin derived from the pulping liquor as dispersant and dopant. The infrared spectroscopy(IR), scanning electron microscope(SEM), conductivity, tensile strength and electrochemical tests were used to characterize the properties of the conductive paper. The effects of dopants and assembled layers on electrical and mechanical properties of the conductive paper were also investigated. The results showed that the loading amount, conductivity and stability of lignosulfonate-polypyrrole paper were improved with the increase of layers, and the load was linearly correlated with the number of layers. Compared with in-situ polymerization, the conductive paper prepared by self-assembly polymerization had better properties. Lignosulfonate not only played a role as dispersant and dopant but also better improved the comprehensive performance of the conductive paper than hydrochloric and polystyrene sulfonic. More importantly, since lignosulfonate had a three-dimensional network structure and strong interaction with the fibres, the conductive stability under various bending states and the tensile strength of conductive paper were remarkably improved. The oxidation resistance and waterproof of lignosulfonate could also increase the conductive stability of conductive paper in air and moisture.

Key words: Self-assembly polymerization, Lignosulfonate-polypyrrole flexible conductive paper, Number of layer, Conductive stability, Tensile strength

中图分类号:

O636.2

TrendMD:

黄文靖, 丁子先, 邱学青, 杨东杰. 自组装聚合法制备木质素磺酸/聚吡咯柔性导电纸. 高等学校化学学报, 2018, 39(11): 2601.

HUANG Wenjing, DING Zixian, QIU Xueqing, YANG Dongjie. Preparation of Flexible and Conductive Lignosulfonate-polypyrrole Paper by Self-assembly Polymerization^†. Chem. J. Chinese Universities, 2018, 39(11): 2601.

图/表 12

Fig.1 Preparation of PPy/Paper by in-situ polymerization(Ⅰ) and self-assembly polymerization(Ⅱ)

Fig.2 Bending angles of PPy/Paper(A) 0°; (B) 30°; (C) 60°; (D) 90°.

Fig.3 Particle size distribution of PPy doped with different dopants

Table 1 Elemental analysis of PPy doped with different dopants

Sample	N(%)	C(%)	H(%)	S(%)	N/S	C/N
SAL	0.02	25.42	3.87	8.49	<0.01
PSS	0	37.61	5.16	13.34	0
HCl-PPy	12.16	63.04	4.45	0.03		5.18
SAL-PPy	9.60	59.20	5.02	5.89	1.63	6.17
PSS-PPy	9.48	59.01	5.63	6.36	1.55	6.22

Fig.4 IR spectra of polypyrrole papers with different dopants(A) In-situ polymerization method; (B) self-assembly polymerization method.

Fig.5 Conductivity(A) and loading amount(B) of PPy/Paper(layer=0, in-situ polymerization method; layer=1—6: self-assembly polymerization method)

Fig.6 Conductive stability of PPy/Paper in air(A), in water(B) and contact angle of water droplet(C) on the surface of PPy/Paper

Fig.7 Conductive stability of PPy/Paper under different angles(A—F) and different cycles(A'—F')(A, A') (HCl-PPy)0/Paper; (B, B') (PSS-PPy)0/Paper; (C, C') (SAL-PPy)0/Paper; (D, D') (HCl-PPy)6/Paper;(E, E') (PPS-PPy)6/Paper; (F, F') (SAL-PPy)6/Paper.

Fig.8 Retention rate of tensile strength of PPy/Paper

Fig.9 SEM images of blank Paper(A), (HCl-PPy)0/Paper(B), (PSS-PPy)0/Paper(C), (SAL-PPy)0/Paper(D), (SAL-PPy)1/Paper(E), (SAL-PPy)3/Paper(F) and (SAL-PPy)6/Paper(G)

Fig.10 Cross-section SEM images of (SAL-PPy)0/Paper(A), (HCl-PPy)6/Paper(B), (SAL-PPy)6/Paper(C) and (PSS-PPy)6/Paper(D)

Scheme 1 Proposed schematic of the fabrication of (SAL-PPy)n/Paper

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