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用反相气相色谱法测定聚(甲基丙烯酸环己酯)的热力学性质

Determination of thermodynamic properties of poly (cyclohexyl methacrylate) by inverse gas chromatography.

作者信息

Kaya Ismet, Pala Cigdem Yigit

出版信息

Se Pu. 2014 Jul;32(7):746-52. doi: 10.3724/sp.j.1123.2014.04028.

Abstract

In this work, some thermodynamic properties of poly (cyclohexyl methacrylate) were studied by inverse gas chromatography (IGC). For this purpose, the polymeric substance was coated on Chromosorb W and which was filled into a glass column. The retention times (t(r)) of the probes were determined from the interactions of poly (cyclohexyl methacrylate) with n-pentane, n-hexane, n-heptane, n-octane, n-decane, methanol, ethanol, 2-propanol, butanol, acetone, ethyl methyl ketone, benzene, toluene and o-xylene by IGC technique. Then, the specific volume (Vg(0)) was determined for each probe molecule. By using (1/T; lnVg(0)) graphics, the glass transition temperature of poly (cyclohexyl methacrylate) was found to be 373 K. The adsorption heat under the glass transition temperature (deltaH(a)), and partial molar heat of sorption above the glass transition (deltaH1(S)), partial molar free energy of sorption (deltaG1(S)) and partial molar entropy of sorption (deltaS1(S)) belonging to sorption for every probe were calculated. The partial molar heat of mixing at infinite dilution (deltaH1(infinity)), partial molar free energy of mixing at infinite dilution (deltaG1(infinity)), Flory-Huggins interaction parameter (chi12(infinity)) and weight fraction activity coefficient (a1/w1)(infinity) values of polymer-solute systems were calculated at different column temperatures. The solubility parameters (delta2) of the polymer were obtained by IGC technique.

摘要

在本研究中,采用反相气相色谱法(IGC)对聚(甲基丙烯酸环己酯)的一些热力学性质进行了研究。为此,将该聚合物涂覆在Chromosorb W上,并填充到玻璃柱中。通过IGC技术,根据聚(甲基丙烯酸环己酯)与正戊烷、正己烷、正庚烷、正辛烷、正癸烷、甲醇、乙醇、2-丙醇、丁醇、丙酮、甲乙酮、苯、甲苯和邻二甲苯的相互作用,测定了探针的保留时间(t(r))。然后,测定了每个探针分子的比容(Vg(0))。通过使用(1/T;lnVg(0))图,发现聚(甲基丙烯酸环己酯)的玻璃化转变温度为373 K。计算了玻璃化转变温度下的吸附热(deltaH(a)),以及玻璃化转变温度以上的吸附偏摩尔热(deltaH1(S))、吸附偏摩尔自由能(deltaG1(S))和吸附偏摩尔熵(deltaS1(S))。在不同柱温下,计算了聚合物-溶质体系在无限稀释时的混合偏摩尔热(deltaH1(infinity))、混合偏摩尔自由能(deltaG1(infinity))、Flory-Huggins相互作用参数(chi12(infinity))和重量分数活度系数(a1/w1)(infinity)值。通过IGC技术获得了聚合物的溶解度参数(delta2)。

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