Influence of ionic association on the nonisothermal crystallization kinetics of sodium sulfonate poly(butylene succinate) ionomers
Influence of ionic association on the nonisothermal crystallization kinetics of sodium sulfonate poly(butylene succinate) ionomers
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DOI：
10.1002/polb.21427
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发表时间：
2008-05
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影响因子：
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通讯作者：
J. Lim;Youngil Lee;S. Im
中科院分区：
文献类型：
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作者：
J. Lim;Youngil Lee;S. Im
研究了磺酸钠引入磺化富马酸二甲酯（SDMF）合成的聚丁二酸丁二醇酯（PBS）离聚物中离子取代基与非等温结晶行为的关系。此外，我们研究了钠离子对PBS骨架的分子结构的影响，通过固态23 Na NMR分析。钠离子聚集体（多重态）主要是创建与离子基团的浓度，熔体流变学和动态熔体分析结果表明，多重态的形成不仅诱导显着的异质性，但也在PBS链的高度聚类。在较低的离子基团浓度下，分散良好的多重态在PBS离聚物的结晶过程中起到了有效的成核作用，加速了结晶速率。随着离子基团浓度的增加，结晶速率下降，由于阻碍链的流动性由许多多重态组成的集群。Ozawa方程和Avrami方程相结合能更好地描述PBS及其离聚体的非等温结晶动力学。观察到的成核活性表明，非等温结晶速率是不直接成正比的离子基团浓度。在含有1 mol % SDMF的PBS离聚物中观察到上级成核活性。© 2008 Wiley Periodicals，Inc.聚合物科学杂志B部分：聚合物物理46：925-937，2008
We evaluated the relationship between the ionic substituents and nonisothermal crystallization behavior in poly(butylene succinate) (PBS) ionomers, synthesized by the introduction of sulfonated dimethyl fumarate (SDMF) with sodium sulfonate. In addition, we investigated the effect of sodium ions on the molecular structure of the PBS backbone by solid-state 23Na NMR analysis. Sodium ion aggregates (multiplets) was predominately created with the ionic group concentration, and melt rheology and dynamic melt analysis results showed that multiplet formation induced not only remarkable heterogeneity, but also a high degree of clustering in the PBS chains. At low ionic group concentration, well dispersed multiplets behaved as effective nuclei during the crystallization of the PBS ionomer and accelerated the rate of crystallization. As ionic group concentration grew higher, crystallization rates decreased due to hindered chain mobility by clusters consisting of numerous multiplets. A combined Ozawa and Avrami equation proved to be more effective than the Ozawa equation in describing the nonisothermal crystallization kinetics of PBS and its ionomers. The observed nucleation activity indicates that the nonisothermal crystallization rate is not directly proportional to the ionic group concentration. Superior nucleation activity was observed in PBS ionomer containing 1 mol % SDMF. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 925–937, 2008