In-depth study on aminolysis of poly(ε-caprolactone): Back to the fundamentals  

作　　者：ZHU Yang MAO ZhengWei SHI HuaYu GAO ChangYou 

机构地区：[1]MOE Key Laboratory of Macromolecular Synthesis and Functionalization,Department of Polymer Science and Engineering,Zhejiang University,Hangzhou 310027,China

出　　处：《Science China Chemistry》2012年第11期2419-2427,共9页中国科学（化学英文版）

基　　金：financially supported by the National Natural Science Foundation of China (20934003);the National Basic Research Program of China (2011CB606203)

摘　　要：The aminolysis can effectively introduce primary amine （- quent surface fiiofunctionalization reactions. However, less NH2） groups onto polyester materials, enabling a variety of subse- attention has been paid to the basic knowledge of aminolysis reac- tion in terms of reaction kinetics and its influences on materials properties. In this study, taking the widely used poly（e-caprolactone） （PCL） as a typical example, the influences of diamines and solvent property on the surface -NH2 density are firstly assessed by using X-ray photoelectron spectroscopy （XPS） and colorimetric analysis. Results show that smaller dia- mine molecules and nonpolar alcohols could accelerate the reaction. The reaction kinetics with 1,6-hexanediamine is further investigated as a function of temperature, reaction time, and diamine concentration. During the initial stage, the reaction shows a 1^st order kinetics with the diamine concentration and has an activation energy of 54.5 kJ/mol. Ionization state of the -NH2 groups on the PCL surface is determined, revealing that the pKa of -NH3^＋ （〈5） is much lower than that of the corresponding diamine molecules in solution. After aminolysis, surface hydrophilicity of PCL membrane is significantly enhanced, while surface elastic modulus and average molecular weight are decreased to some extent, and others such as weight, surface mor- phology and bulk mechanical strength are not apparently changed. The introduced -NH2 groups are found to be largely lost at 37 ℃, but can be mostly maintained at low temperature.The aminolysis can effectively introduce primary amine (NH2) groups onto polyester materials, enabling a variety of subsequent surface biofunctionalization reactions. However, less attention has been paid to the basic knowledge of aminolysis reaction in terms of reaction kinetics and its influences on materials properties. In this study, taking the widely used poly(ε-caprolactone) (PCL) as a typical example, the influences of diamines and solvent property on the surface -NH 2 density are firstly assessed by using X-ray photoelectron spectroscopy (XPS) and colorimetric analysis. Results show that smaller diamine molecules and nonpolar alcohols could accelerate the reaction. The reaction kinetics with 1,6-hexanediamine is further investigated as a function of temperature, reaction time, and diamine concentration. During the initial stage, the reaction shows a 1 st order kinetics with the diamine concentration and has an activation energy of 54.5 kJ/mol. Ionization state of the NH 2 groups on the PCL surface is determined, revealing that the pK a of NH 3 + (<5) is much lower than that of the corresponding diamine molecules in solution. After aminolysis, surface hydrophilicity of PCL membrane is significantly enhanced, while surface elastic modulus and average molecular weight are decreased to some extent, and others such as weight, surface morphology and bulk mechanical strength are not apparently changed. The introduced NH 2 groups are found to be largely lost at 37 o C, but can be mostly maintained at low temperature.

关 键 词：poly（ε-caprolactone） AMINOLYSIS surface modification BIOMATERIALS 

分 类 号：O631.3[理学—高分子化学]