Locci Emanuela, Roose Patrice, Bartik Kristin, Luhmer Michel
Dipartimento di Scienze Chimiche, Università di Cagliari, Cittadella Universitaria di Monserrato, S.S.554 Bivio per Sestu, 09042 Monserrato (CA), Italy.
J Colloid Interface Sci. 2009 Feb 15;330(2):344-51. doi: 10.1016/j.jcis.2008.10.061. Epub 2008 Oct 29.
Model aqueous dispersions of polystyrene, poly(methyl methacrylate), poly(n-butyl acrylate) and a statistical copolymer poly(n-butyl acrylate-co-methyl methacrylate) were studied using xenon NMR spectroscopy. The (129)Xe NMR spectra of these various latexes reveal qualitative and quantitative differences in the number of peaks and in their line widths and chemical shifts. Above the glass transition temperature, exchange between xenon sorbed in the particle core and free xenon outside the particles is fast on the (129)Xe spectral time-scale and a single (129)Xe signal is observed. At temperatures below the glass transition temperature, the exchange between sorbed and free xenon is slow on the (129)Xe spectral time-scale and two (129)Xe NMR signals can be observed. If the signal of sorbed (129)Xe is observed, its chemical shift, line width and integral relative to the integral of free (129)Xe can be used for the characterization of the particle core. The line width of free (129)Xe provides the residence time of xenon outside the particles and can be used to determine the rate constant characterizing the kinetics of penetration of xenon in the particles. This rate constant emerges as promising parameter for the characterization of the polymer particle surface.
使用氙核磁共振光谱研究了聚苯乙烯、聚(甲基丙烯酸甲酯)、聚(丙烯酸正丁酯)以及统计共聚物聚(丙烯酸正丁酯 - 甲基丙烯酸甲酯)的模型水分散体。这些不同胶乳的(129)Xe核磁共振谱在峰的数量、线宽和化学位移方面显示出定性和定量的差异。在玻璃化转变温度以上,吸附在颗粒核心中的氙与颗粒外部的游离氙之间的交换在(129)Xe光谱时间尺度上很快,观察到单一的(129)Xe信号。在低于玻璃化转变温度的温度下,吸附的氙与游离氙之间的交换在(129)Xe光谱时间尺度上很慢,可以观察到两个(129)Xe核磁共振信号。如果观察到吸附的(129)Xe的信号,其化学位移、线宽以及相对于游离(129)Xe积分的积分可用于表征颗粒核心。游离(129)Xe的线宽提供了氙在颗粒外部的停留时间,可用于确定表征氙在颗粒中渗透动力学的速率常数。该速率常数有望成为表征聚合物颗粒表面的参数。