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通过无限稀释反相气相色谱法表征固体基质物理化学性质的新方法。II. 不同立构规整度的聚甲基丙烯酸甲酯以及吸附在氧化铝和二氧化硅上的聚甲基丙烯酸甲酯的转变温度研究。

New approach to characterise physicochemical properties of solid substrates by inverse gas chromatography at infinite dilution. II. Study of the transition temperatures of poly(methyl methacrylate) at various tacticities and of poly(methyl methacrylate) adsorbed on alumina and silica.

作者信息

Hamieh Tayssir, Schultz Jacques

机构信息

Département de Chimie, Faculté des Sciences, Université Libanaise, Mont-Liban, Beyrouth, Lebanon.

出版信息

J Chromatogr A. 2002 Sep 6;969(1-2):27-36. doi: 10.1016/s0021-9673(02)00358-8.

DOI:10.1016/s0021-9673(02)00358-8
PMID:12385374
Abstract

The determination of the temperature transitions in polymers and more particularly when polymers are adsorbed on oxides is very important in many industrial processes. In this second part, we used inverse gas chromatography (IGC) at infinite dilution to determine the second order transition temperatures of poly(methyl methacrylate) (PMMA) adsorbed (or not) on alumina or on silica. Three types of PMMA were used: atactic (a), syndiotactic (syndio) and isotactic (iso). The IGC technique allowed to obtain the net retention volume Vn and the dispersive component of the surface energy gamma(s)d for various theoretical models of molecules, using the results of Part I. By plotting RT ln Vn as a function of (1/T) or gamma(s)d as a function of the temperature T, we proved the presence of three particular temperatures that correspond respectively to the transition temperature relative to beta-relaxation (Tbeta), the glass transition temperature (Tg), and the liquid-liquid transition temperature or order-disorder transition (T1.1). Results obtained in this part allowed us to show the effect of the tacticity of PMMA and the recovery fraction of polymer adsorbed on alumina or silica on the transition temperatures.

摘要

在许多工业过程中,确定聚合物的温度转变,尤其是聚合物吸附在氧化物上时的温度转变非常重要。在第二部分中,我们使用无限稀释反相气相色谱法(IGC)来测定吸附(或未吸附)在氧化铝或二氧化硅上的聚甲基丙烯酸甲酯(PMMA)的二级转变温度。使用了三种类型的PMMA:无规立构(a)、间规立构(syndio)和等规立构(iso)。利用第一部分的结果,IGC技术能够获得各种分子理论模型的净保留体积Vn和表面能γ(s)d的色散分量。通过绘制RT ln Vn作为(1/T)的函数或γ(s)d作为温度T的函数,我们证明了存在三个特定温度,它们分别对应于相对于β-弛豫的转变温度(Tβ)、玻璃化转变温度(Tg)以及液-液转变温度或有序-无序转变温度(T1.1)。这部分获得的结果使我们能够展示PMMA的立构规整性以及吸附在氧化铝或二氧化硅上的聚合物的回收分数对转变温度的影响。

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