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化学进展 2021, Vol. 33 Issue (11): 1972-1982 DOI: 10.7536/PC200874 前一篇   后一篇

• 综述 •

热塑性淀粉制备的化学与物理机制及方法

周文1, 张鑫1, 马宏鹏1, 许杰2, 郭斌1,3,4,*(), 李盘欣3,4   

  1. 1 南京林业大学理学院 南京 210037
    2 武汉纺织大学材料科学与工程学院 武汉 430200
    3 河南省农林产品深加工院士工作站 漯河 462600
    4 河南省南街村集团博士后科研工作站 漯河 462600
  • 收稿日期:2020-08-27 修回日期:2020-10-12 出版日期:2020-12-28 发布日期:2020-12-28
  • 通讯作者: 郭斌
  • 基金资助:
    江苏省政府留学基金; 南京林业大学“青年拔尖人才”计划; 2019年度江苏省研究生科研与实践创新计划项目(SJKY19_0867); 2018年度南京林业大学大学生创新训练计划项目(201810298078Y); 江苏省自然科学基金青年基金项目(BK20140967)
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Chemical and Physical Mechanism and Method of Preparation of Thermoplastic Starch

Wen Zhou1, Xin Zhang1, Hongpeng Ma1, Jie Xu2, Bin Guo1,3,4(), Panxin Li3,4   

  1. 1 College of Science, Nanjing Forestry University,Nanjing 210037, China
    2 College of Materials Science and Engineering, Wuhan Textile University,Wuhan 430200, China
    3 Agricultural and Forest Products Processing Academician Workstation of Henan Province,Luohe 462600, China
    4 Post-Doctoral Research Center of Nanjiecun Group,Luohe 462600, China
  • Received:2020-08-27 Revised:2020-10-12 Online:2020-12-28 Published:2020-12-28
  • Contact: Bin Guo
  • Supported by:
    Jiangsu Government Scholarship for Overseas Studies; Nanjing Forestry University Yong Top Talent Program; PostGraduate Research & Practice Innovation Program of Jiangsu Province in 2019(SJKY19_0867); Higher school in Jiangsu Province College Students’ Practice Innovation Training Programs in 2018(201810298078Y); Natural Science Foundation of Jiangsu Province(BK20140967)

淀粉是一大类来源丰富、可再生、可完全生物降解及价格低廉的天然高分子,广泛应用于食品、降解塑料、包装和医药等领域。然而,淀粉内部的结晶和半晶结构使其熔融温度大于分解温度,因而不能热塑加工,这一问题严重制约了其在各领域的应用与发展。因此,研究制备热塑性淀粉过程中所涉及的化学与物理机制及具体方法是影响和拓宽其应用的关键科学问题之一。本文以此为出发点,系统总结了近年来国内外该领域的相关研究工作和进展,将制备热塑性淀粉过程中的化学与物理机制归纳为8种(氢键、化学键、压力、剪切力、导热、微波、热空气和γ射线),并以实践中的8种方法(熔融法、溶液法、模压法、球磨法、喷雾干燥、高静压、化学改性和高能辐射)为主线,以不同形成机制和方法之间的相互关系为重点,系统介绍了该领域的研究进展,以期为热塑性淀粉的深入应用与发展提供一定的理论基础。

关键词： 热塑性淀粉, 制备, 机制, 方法

Starch, as a natural polymer, its attractiveness stems from the annual renewability, low cost and biodegradability in the areas of food, degradable plastics and packaging materials etc. However, the natural starch cannot be directly used in plastics application due to the strong intra- and inter-molecular hydrogen bonds, resulted in the lower thermal decomposition temperature than its melting point. It must be plasticized with low molecular weight compounds such as polyols to form thermoplastic starch(TPS) for processing on conventional processing equipment. Therefore, studying the mechanisms and methods in the processing of TPS is the key point to expand its application. Herein, based on the recent works reported, and considering different physical and chemical nature in mechanism, we summarized as 8 factors(hydrogen bond, chemical bond, stress, shear force, thermal conductivity, microwave, hot-air, γ-ray) in TPS formation, and discussed 8 preparation methods(melting, solution, compression molding, ball milling, spray drying, high hydrostatic pressure, chemical modification, high-energy radiation) of TPS, emphasizing on their relationship. This review is expected to be helpful in studying and developing various TPS products in future.

Contents

1 Introduction

2 Preparation methods

2.1 Melting method

2.2 Solution method

2.3 Compression molding

2.4 Ball milling

2.5 Spray drying

2.6 High hydrostatic pressure

3 Chemical modification

3.1 Oxidation

3.2 Esterification

3.3 Etherification

3.4 Cross-linking

3.5 Dual modification

4 High-energy radiation

5 Conclusion and outlook

Key words: thermoplastic starch, preparation, mechanisms, methods
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表1 热塑性淀粉的制备机理及方法
Table 1 Preparation mechanism and method of thermoplastic starch
Preparation method Preparation mechanism
Chemistry Physics
Hydrogen bond Chemical bond Stress Shear force Thermal conductivity Microwave Hot-air γ-ray
Melting method √ √ √ √ √
Solution method √ √ √
Compression molding √ √ √
Ball milling √ √ √
Spray drying √ √
High hydrostatic pressure √ √
Chemical modification √ √
High-energy radiation √
图1 淀粉和马来酸酐的反应性挤出反应
Fig. 1 Reaction between starch and maleic anhydride by reactive extrusion
图2 壳聚糖(CTS)与聚乙烯(PE)接枝马来酸酐在熔融共混过程中发生的反应
Fig. 2 Proposed reaction between chitosan(CTS)and polyethylene(PE)-graft-maleic anhydride that occurred during melt-blending
图3 干法制备酯化淀粉
Fig. 3 The preparation of the esterified starches by dry method
图4 淀粉与氯乙酸钠(SMCA)反应的示意图
Fig. 4 A schematic representation of the reaction of starch with sodium monochloroacetate(SMCA)
图5 淀粉与几种常用交联剂的反应
Fig. 5 Reactions of starch with some commonly used cross-linking reagents
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