高熔体强度聚丙烯中长支链结构的分析与表征方法新进展

doi:10.16085/j.issn.1000-6613.2021-2538

摘要/Abstract

摘要：

高熔体强度聚丙烯（high melt strength polypropylene，HMSPP）是具有较高熔体强度和弹性、在熔融拉伸时存在应变硬化现象的一种新型聚丙烯材料。近年来，对长支链（LCB）型HMSPP（LCB-HMSPP）的研发引起了学术界和工业界的广泛关注。在利用各种方法和工艺制备LCB-HMSPP之后，所得聚合物是否具有长支链结构，长支链的化学组成、密度及链长度等拓扑结构信息，都需要通过各种仪器分析与表征方法对其进行定性或定量验证。本文着重对傅里叶变换红外光谱（FTIR）法、核磁共振碳谱（¹³C NMR）法、凝胶渗透色谱（GPC）及其联用方法、流变学表征法和结晶行为表征法在LCB-HMSPP中LCB链结构分析与表征中的研究新进展进行总结和评述，介绍了这些方法各自的优缺点和适用性并对这些方法进行了对比，最后对用于LCB-HMSPP中LCB链结构的分析与表征方法研究的未来发展及应用前景进行了展望。

关键词: 高熔体强度聚丙烯, 长支链, 傅里叶变换红外光谱, 核磁共振, 凝胶渗透色谱, 流变学, 结晶

Abstract:

High melt strength polypropylene (HMSPP) is a new kind of polypropylene material with high melt strength, elasticity and strain hardening during melt stretching. In recent years, the research and development of long chain branched (LCB) HMSPP (LCB-HMSPP) has attracted extensive attention in both academia and industry. After preparing LCB-HMSPP via various methods and processes, whether the obtained polymer has long chain branched structure, and the topological structure information such as chemical composition, density and chain length of long chain branch need to be qualitatively or quantitatively verified by various instrumental analysis and characterization methods. The new progress in the analysis and characterization of LCB structures in HMSPP by Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (¹³C NMR), gel permeation chromatography (GPC) and its combined methods, rheology and crystallization behavior characterization, were summarized and reviewed. The advantages, shortcomings and applicability of these methods were introduced and compared. Finally, the future development and application of the analysis and characterization methods of LCB chain structure in LCB-HMSPP were prospected.

Key words: high melt strength polypropylene, long chain branch, Fourier transform infrared spectroscopy, magnetic resonance spectroscopy (NMR), gel permeation chromatography, rheology, crystallization

中图分类号:

O631.6

崔崑, 黄晋, 赵巧玲, 马志. 高熔体强度聚丙烯中长支链结构的分析与表征方法新进展[J]. 化工进展, 2022, 41(10): 5425-5440.

CUI Kun, HUANG Jin, ZHAO Qiaoling, MA Zhi. New progress in analysis and characterization of long chain branched structure in high melt strength polypropylene[J]. Chemical Industry and Engineering Progress, 2022, 41(10): 5425-5440.

图/表 13

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对比内容	FTIR	¹³C NMR	GPC（SEC）及联用方法	流变学表征法	结晶行为表征法
支化链结构的形成	定性判定	定性判定	定性判定	定性判定	定性判定
支化链数目及分布	定量分析（支化点附近或支链链端要具有特征官能团）	定量分析（不适用于低含量 LCB样品）	定量分析（不适用于低含量LCB样品）	定量分析（适用于低含量LCB样品）	定性判定
支化链长度	无法判定	可以判定（限于碳数≤16的支化链）不适用于后反应器法或交联法制备的样品	可以判定（大分子单体/反应物作为支化链）	无法判定	无法判定
支化链长度	无法判定	可以判定（限于碳数≤16的支化链）不适用于后反应器法或交联法制备的样品	无法判定（后反应器法体系/交联法体系）	无法判定	无法判定
样品用量^①	约10mg（KBr压片法） 50~100mg（薄膜法）	20~50mg（液体）约200mg（固体/熔体）	10~20mg	20~50mg	5~15mg
测试条件^①	常温、干燥	110~120℃（液体）； 150~180℃（固体/熔体）	150℃	210~230℃	室温~200℃ （多个升降温程序）
测试周期^①	约5min	约16h（液体）；约8h（固体/熔体）	约2h	约2h	0.5h（结晶温度） 5h（结晶动力学）

对比内容	FTIR	¹³C NMR	GPC（SEC）及联用方法	流变学表征法	结晶行为表征法
支化链结构的形成	定性判定	定性判定	定性判定	定性判定	定性判定
支化链数目及分布	定量分析（支化点附近或支链链端要具有特征官能团）	定量分析（不适用于低含量 LCB样品）	定量分析（不适用于低含量LCB样品）	定量分析（适用于低含量LCB样品）	定性判定
支化链长度	无法判定	可以判定（限于碳数≤16的支化链）不适用于后反应器法或交联法制备的样品	可以判定（大分子单体/反应物作为支化链）	无法判定	无法判定
支化链长度	无法判定	可以判定（限于碳数≤16的支化链）不适用于后反应器法或交联法制备的样品	无法判定（后反应器法体系/交联法体系）	无法判定	无法判定
样品用量^①	约10mg（KBr压片法） 50~100mg（薄膜法）	20~50mg（液体）约200mg（固体/熔体）	10~20mg	20~50mg	5~15mg
测试条件^①	常温、干燥	110~120℃（液体）； 150~180℃（固体/熔体）	150℃	210~230℃	室温~200℃ （多个升降温程序）
测试周期^①	约5min	约16h（液体）；约8h（固体/熔体）	约2h	约2h	0.5h（结晶温度） 5h（结晶动力学）

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