Macromolecular Weight Growth and Spectral Characterization of PA66 during Solid-state Polymerization

Ping Zhu; Chen-long Su; Xiao-hua Wang; Hui Li; Chao Qiu; Yu-ting Ren; Yong Zhou; Ying Zhao; Xia Dong; Du-jin Wang

doi:10.11777/j.issn1000-3304.2025.25021

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Macromolecular Weight Growth and Spectral Characterization of PA66 during Solid-state Polymerization

更新时间：2025-06-09

- Macromolecular Weight Growth and Spectral Characterization of PA66 during Solid-state Polymerization
- Acta Polymerica Sinica Pages: 1-12(2025)
- 作者机构：
  
  1.中国科学院化学研究所北京分子科学国家研究中心中国科学院工程塑料院重点实验室北京 100190
  2.中国科学院大学北京 100049
  3.华峰集团有限公司温州 325200
- 作者简介：
  
  Xia Dong, E-mail: xiadong@iccas.ac.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2025.25021
  CLC：
- CSTR：32057.14.GFZXB.2025.7383
- Received：28 February 2025，
  
  Accepted：13 May 2025，
  
  Published Online：09 June 2025，
- 稿件说明：
移动端阅览
朱平, 苏晨龙, 王晓华, 李慧, 仇超, 任宇婷, 周勇, 赵莹, 董侠, 王笃金. PA66固相增黏过程中分子量增长规律和谱学表征分析. 高分子学报, doi: 10.11777/j.issn1000-3304.2025.25021

Zhu, P.; Su, C. L.; Wang, X. H.; Li, H.; Qiu, C.; Ren, Y. T.; Zhou, Y.; Zhao, Y.; Dong, X.; Wang, D. J. Macromolecular weight growth and spectral characterization of PA66 during solid-state polymerization. Acta Polymerica Sinica, doi: 10.11777/j.issn1000-3304.2025.25021
朱平, 苏晨龙, 王晓华, 李慧, 仇超, 任宇婷, 周勇, 赵莹, 董侠, 王笃金. PA66固相增黏过程中分子量增长规律和谱学表征分析. 高分子学报, doi: 10.11777/j.issn1000-3304.2025.25021 DOI： CSTR： 32057.14.GFZXB.2025.7383.

Zhu, P.; Su, C. L.; Wang, X. H.; Li, H.; Qiu, C.; Ren, Y. T.; Zhou, Y.; Zhao, Y.; Dong, X.; Wang, D. J. Macromolecular weight growth and spectral characterization of PA66 during solid-state polymerization. Acta Polymerica Sinica, doi: 10.11777/j.issn1000-3304.2025.25021 DOI： CSTR： 32057.14.GFZXB.2025.7383.

摘要

聚酰胺66 (PA66)的固相增黏是调控树脂切片分子量和机械力学性能的重要手段. 本研究通过使用一维和二维核磁共振谱、基质辅助激光解吸电离飞行时间质谱分析推断固相增黏前后PA66切片样品中副产物的结构，并结合端基滴定、液质联用谱等方法，阐明了固相增黏过程中分子量增长规律、副产物种类等. 甲醇抽提试验说明固相增黏在显著提高PA66切片分子量的同时使得环状PA66含量降低，尤其是重复单元数为1~4的环状PA66含量显著下降. 鉴于PA66切片中各种副产物难以有效分离，本研究使用的谱学表征分析方法能够在复杂的核磁和质谱中辨识出它们的信号，有望为定量计算副产物含量奠定基础，继而为优化PA66的聚合和固相增黏工艺、提高PA66切片品质提供支持.

Abstract

The solid-state polymerization (SSP) of polyamide 66 (PA66) is a critical method for adjusting its macromolecular weight and mechanical properties. In this study

one-dimensional and two-dimensional nuclear magnetic resonance spectroscopy (NMR) and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) were used to analyze the chemical structures of the by-products in the PA66 pellets before and after SPP. By integrating techniques such as end-group titration and liquid chromatography-mass spectrometry (LC-MS)

this study elucidates the patterns of the macromolecular weight increase during the SSP process and identifies the types of by-products. Methanol extraction experiments indicated that SSP could also lead to a decrease in the cyclic PA66 content

particularly a notable reduction in cyclic PA66 with repeat unit numbers from 1 to 4. Considering the difficulty in effectively separating various by-products present in PA66 pellets

the spectroscopic characterization methods in this research could identify their signals within the complex NMR and MS spectra. This approach promises to establish a foundation for quantitatively calculating the by-product content

thereby supporting the optimization of the PA66 polymerization and SPP processes and enhancing the quality of PA66 pellets.

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Keywords

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