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化学进展 2022, Vol. 34 Issue (7): 1576-1589 DOI: 10.7536/PC220327 前一篇   后一篇

• 综述 •

浅析高分子树脂无溶剂生产技术中的高分子凝聚态相关化学问题

陈峥, 姜振华*()   

  1. 吉林大学高性能聚合物合成技术国家地方联合工程实验室 特种工程塑料教育部工程研究中心 化学学院 长春 130012
  • 收稿日期:2022-02-27 修回日期:2022-03-25 出版日期:2022-07-24 发布日期:2022-06-20
  • 通讯作者: 姜振华
  • 基金资助:
    吉林省科技发展计划项目(20200404177YY)
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Discussion on Some Chemical Problems of Polymer Condensed Statein Solvent-Free Polymer Production Technology

Zheng Chen, Zhenhua Jiang()   

  1. National & Local Joint Engineering Laboratory for Synthesis Technology of High-Performance Polymers, Engineering Research Center of High-Performance Plastics, Ministry of Education, College of Chemistry, Jilin University,Changchun 130012, China
  • Received:2022-02-27 Revised:2022-03-25 Online:2022-07-24 Published:2022-06-20
  • Contact: Zhenhua Jiang
  • Supported by:
    Jilin Province Science and Technology Department Science Fund(20200404177YY)

在没有溶剂介质参与的高分子聚合反应中,高分子凝聚态的变化与化学反应之间的作用关系变得更加直接。以熔融聚合、反应挤出、固相聚合为代表的高分子树脂无溶剂生产技术是集高分子树脂合成、材料加工制备及工程一体化的新兴科学与技术,是当代材料科学领域发展的前沿领域,代表着高分子树脂生产技术发展的必然趋势。本文将上述这三种典型的树脂工业合成技术及相应机理进行了简要的介绍,并分别以聚对苯二甲酸乙二醇酯(PET)和聚乳酸(PLA)的实际生产研究情况为例,展示三种生产技术之间的相互联系,揭示这三种无溶剂型高分子制备技术过程中出现的高分子凝聚态变化与化学反应之间的基本问题,为广大科研工作提供一些有价值的参考。

关键词： 无溶剂聚合反应, 熔融缩聚, 固相缩聚, 反应挤出

The interaction between the changes of polymer condensed states and chemical reactions becomes more directly in the solvent-free polymer polymerizations. Melt polymerization (MP), reactive extrusion (REX) and solid phase polymerization (SPP) are classical solvent-free polymerization production technologies. The solvent-free polymerization production technology is a new science and technologies integrating polymer resin synthesis, material processing and preparation and engineering. It is the frontier field of contemporary material science, and represents the inevitable trend of the development of the resin production technology. In this paper, the three typical resin industrial synthesis technologies and their corresponding mechanisms are briefly introduced, and the actual productions of polyethylene terephthalate (PET) and polylactic acid (PLA) were shown, and the relationship between the three production technologies were also exhibited. In here, the basic problems of polymer condensed state changes and related chemical reactions were revealed by these three solvent-free polymerization technologies, and some valuable references for scientific researcher were provided.

Contents

1 Introduction

2 Three typical polymer resin production technologies without solvent participation

2.1 Melt condensation polymerization

2.2 Solid state polycondensation

2.3 Reactive extrusion

3 Typical applications of solvent-free resin production technology

3.1 Solvent-free production of PET resins

3.2 Solvent-free production of PLA resin

4 Conclusion and perspective

Key words: solvent-free polymerizations, melt polycondensation (MP), solid state polycondensation (SSP), reaction extrusion (REX)
()
图1 PET的生产技术路线
Fig. 1 The technical route of PET production
表1 不同特性黏度指数PET的作用
Table 1 The applications of PETs with various intrinsic viscosity
[η]/dL/g 数均分子量 用途
0.55~0.64 19000~22000 纺织涤纶纤维
0.64~0.68 22000~24000 薄膜
0.68~0.74 24000~26000 工业丝
0.74~0.90 26000~34000 瓶、工程塑料、易拉罐、拉链
0.84~1.10 31000~39000 超强工业丝线
1.04 37000 结晶聚酯
图2 PET固相缩聚反应机理
Fig. 2 Reaction mechanism of solid-state polycondensation of PET
表2 固相缩聚工艺中连续法和间歇法之间的特点比较[47]
Table 2 Comparison of characteristics between continuous and batch processes in solid state polycondensation[47]
连续法固相缩聚 间歇法固相缩聚
产物特性黏度较为均匀 不同批次产物的特性
更换原料特性黏度时不够灵活 更换原料特性黏度较为灵活
原料要有较为稳定的来源 原料可以有多种来源
采用氮气除去小分子产物 采用抽真空法除去小分子产物
利用实现自动化,生产效率较高 方便把控产品质量,较小的产品CV值
产能较大,可实现批量生产 操作便捷,生产能力小
图3 碳酸二苯酯与PET的反应
Fig. 3 Reaction of PET resins and the chain extender DPC
图4 丙交酯开环(两步法)制备聚乳酸
Fig. 4 Lactide ring-opening (two-step) preparation of polylactic acids
图5 直接缩聚(一步法)制备PLA
Fig. 5 Preparation of PLA by direct polycondensation (one-step method)
图6 直接缩聚制备PLA的逐步缩合机理
Fig. 6 Progressive condensation mechanism of PLA prepared by the direct polycondensation
图7 直接缩聚法制备聚乳酸的过程中存在的副反应
Fig. 7 Side reactions of the PLA direct polycondensation method
图8 聚乳酸的制备方法总汇
Fig. 8 Summary of preparation methods of PLA
图9 聚乳酸的固相缩聚机理示意图
Fig. 9 Solid state polycondensation mechanism of PLA
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