物理化学学报 >> 1999, Vol. 15 >> Issue (01): 28-34.doi: 10.3866/PKU.WHXB19990106

研究论文 上一篇    下一篇

丙烯酸酯共聚物无皂水溶胶与金属离子的络合交联

杨立群, 谢志明, 李卓美   

  1. 中山大学高分子研究所,广州 510275
  • 收稿日期:1998-03-03 修回日期:1998-06-16 发布日期:1999-01-15
  • 通讯作者: 李卓美

Coordination-crosslinking of Acrylate Copolymer Soap-free Hydrosol with Metal lon

Yang Li-Qun, Xie Zhi-Ming, Li Zhuo-Mei   

  1. Institute of Polymer Science,Zhongshan University,Guangzhou 510275
  • Received:1998-03-03 Revised:1998-06-16 Published:1999-01-15
  • Contact: Li Zhuo-Mei

摘要:

用交联剂M(NH3)42+(M2+为Zn2+、Cu2+、Ni2+和Co2+)络合交联丙烯酸酯无皂水溶胶形成涂膜,用差示量热法和重量分析法考察了涂膜的交联程度,得出一致的结论,均表明交联剂Zn(NH3)42+的交联效果最佳,适宜的交联固化条件是80℃加热30min;用透射电镜观察到Zn(NH3)42+与丙烯酸酯水溶胶形成交联网状结构的过程;还用差示扫描量热法初步分析了交联反应的动力学,求出反应级数为3.3,活化能为34.0kJ•mol-1.

关键词: 水溶胶, 金属离子, 络合交联

Abstract:

A copolymer containing hydrophobic monomers(styrene, methyl methacrylate and butyl acrylate)and hydrophilic momomer (acrylacrylic acid)was synthesized by solution polymerization, and then neutralized by N,N-diethylamino ethanol to form soap-free hydrosol. The hydrosol coating could be prepared by mixing this hydrosol with the crosslinking agent M(NH3)42+ (M2+ could be either Zn2+,Cu2+. Ni2+ or Co2+). It was supposed that in the soap-free acrylate hydrosol/M(NH3)42+ mixed system, before heating,M2+ in the form of M(NH3)42+could not react with the hydrosol(P-COO-)completely leaving some _COO-free to stabilize the hydrosol, and after heating(or curing),M2+ could be set free from NH3 ligand to join the coordination-crosslinking reaction with(P-COO-) forming network structure (P-COO-)n M2+.IR spectrographic analysis, fluorescence analysis and the linear sweep voltammetry plarogrphic analysis identified the existence of (P-COO-)nM2+ in the coating film. The crosslinking extent of the coating film was investigated by DSC and gravimetric analysis. All results indicated that the appropriate crosslinking agent was Zn(NH3)-2+ and the optimum curing condition was heating at 80℃ for 30 min. The crosslinking process of the hydrosol with Zu(NH3)42+ was examined by TEM. The kinetics of the crosslinking reaction has been studied preliminarily by DSC showing that the reaction activation energy was 34.0kJ•mol-1 and the order of reaction was 3.3, indicating that the crosslinking reaction may be a rather complex reaction. 

Key words: Hydrosol, Metal ion, Coordination-crosslinking