化学学报 ›› 2008, Vol. 66 ›› Issue (16): 1909-1914. 上一篇    下一篇

研究论文

多孔酚醛树脂热解碳材料的制备与结构

王存国*,a 林 琳a 路乃群a 赵 强a,b
孙 琳a 赵树高a 王荣顺c

  

  1. (a青岛科技大学橡塑材料与工程教育部重点实验室 青岛 266042)
    (b复旦大学先进材料研究院 上海 200433)
    (c东北师范大学化学学院 功能材料化学研究所 长春 130024)

  • 投稿日期:2007-09-04 修回日期:2008-03-17 发布日期:2008-08-28
  • 通讯作者: 王存国

Preparation and Structure of Porous Carbons by Pyrolysis of Phenol Formaldehyde Resin

WANG, Cun-Guo *,a LIN, Lin a LU, Nai-Qun a ZHAO, Qiang a,b SUN, Lin a
ZHAO, Shu-Gao a WANG, Rong-Shun c
  

  1. (a Key Laboratory of Rubber-plastics (QUST), Ministry of Education, Qingdao 266042)
    (b Institute of Advanced Materials, Fudan University, Shanghai 200433)
    (c Institute of Function Material Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun 130024)
  • Received:2007-09-04 Revised:2008-03-17 Published:2008-08-28
  • Contact: WANG, Cun-Guo

用苯酚和甲醛在氨水催化下合成了可溶性酚醛树脂, 经掺杂不同质量比发泡剂(氯化锌)后在惰性气氛下进行热裂解(500~900 ℃), 制备了多孔热解碳导电材料(PPAS); 用FTIR, XRD, TG, SEM, BET等方法对所制备材料进行了结构表征, 详细讨论了发泡剂的加入对热解碳导电材料结构和性能的影响. 研究发现: 酚醛树脂经掺杂一定量发泡剂后再进行热裂解, 一方面加快了酚醛树脂分子间的脱水速度, 降低了热裂解温度范围; 另一方面, 裂解产物内部结构的微晶尺寸和层间距发生了明显变化, 未掺杂发泡剂的裂解产物呈现尖锐棱角的无定形结构, 而掺杂发泡剂的裂解产物则为多孔的球形和椭球形结构; 表面吸附实验测试结果表明, 当酚醛树脂与发泡剂的质量比为1∶3, 升温速率为30 ℃/h, 热裂解温度为600 ℃时, 热裂解产物的比表面积可达2150 m2•g-1, 平均孔径在11 Å左右.

关键词: 酚醛树脂, 导电聚合物, 发泡剂, 氯化锌, 多孔碳材料

Soluble phenolic resin was synthesized by phenol and formaldehyde with NH4OH catalyst. Porous polyacenic semiconductor carbon (PPAS) materials were prepared by heat treatment of phenol formaldehyde (PF) resin doped with different contents of a foaming agent (ZnCl2) at lower temperatures (500~900 ℃) in inert gas atmosphere. The structure of the synthesized materials was characterized by means of FTIR, XRD, TG, SEM and other analysis methods. The effects of the foaming agent on the structure of PPAS were studied in detail. The experimental results showed that doping the foaming agent, on one hand, could increase the dehydration speed of pyrolysis processing of PF resin, and decrease the pyrolysis temperatures of it at the same time; on the other hand, the structures changed greatly in crystallite sizes and interlayer spaces for doped pyrolysis materials. Furthermore, when PF resin was doped with the foaming agent, the pyrolysis materials showed the ball or ellipsoid states, however, the un-doped pyrolysis materials showed the bulky and amorphous states with sharp edges and angles. The surface area measurements (BET method) showed that when resin-ZnCl2 ratio was 1∶3 (mass ratio), and the speed of heat treatment, 30 ℃/h, and the pyrolysis temperature, 600 ℃, the specific surface area could increase to 2150 m2•g-1, and the average diameter of the powders got to 11 Å.

Key words: phenol formaldehyde resin, conducting polymer, foaming agent, zinc chloride, porous carbonaceous material