Crystallinity and Miscibility of Poly(vinyl isobutyl ether)/Poly(ε-L-lysine) Blends by Solid State 13C NMR Study

A. Asano, Y. Murata, Takuzo Kurotsu
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引用次数: 9

Abstract

The relation between crystallinity and miscibility of semicrystalline polymer blends of poly(vinyl isobutyl ether) (PVIBE) and poly(e-L-lysine) (e-PL) is investigated by 13C cross-polarization with magic-angle-spinning (CPMAS) NMR (nuclear magnetic resonance) and DSC measurements. Analysis of the 1H spin-lattice relaxation curves observed from both PVIBE and e-PL signals, which are indirectly obtained from well-resolved 13C CPMAS NMR spectra, suggested that the domains of e-PL in the blends are in the range of 50–100 nm scale. Two-spin or three-spin models were used to simulate the 1H relaxation curves taking into account the contribution of a 1H spin-diffusion rate between PVIBE and e-PL. Furthermore, it was found that blending e-PL largely influences the crystallinity of PVIBE but that of e-PL is little affected by blending PVIBE except for 10/1 composition. The observed melting point of e-PL shifted towards lower temperature accompanied by PVIBE content. This shift was explained by the Gibbs-Thomson effect that the decrease of thickness of crystalline phase causes the depression of the melting point.
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聚乙烯醇异丁基醚/聚ε- l -赖氨酸共混物的结晶度和混相研究
采用13C交叉极化、核磁共振和DSC测量方法研究了聚乙烯基异丁基醚(PVIBE)和聚e- l -赖氨酸(e-PL)半结晶共混物的结晶度和混相关系。从高分辨的13C CPMAS NMR间接获得的PVIBE和e-PL信号的1H自旋-晶格弛豫曲线分析表明,共混物中的e-PL畴在50-100 nm范围内。考虑PVIBE和e-PL之间1H自旋扩散速率的影响,采用双自旋或三自旋模型模拟1H弛豫曲线。此外,发现共混e-PL对PVIBE的结晶度影响很大,但除10/1组成外,共混PVIBE对e-PL的结晶度影响不大。随着PVIBE含量的增加,e-PL的熔点向低温方向移动。这种变化可以用吉布斯-汤姆逊效应来解释,即晶相厚度的减小导致熔点的降低。
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