Department of Chemical Engineering, Laboratory of Physical Chemistry, Aristotle University of Thessaloniki, 54124 Thessaloniki, Greece.
J Chromatogr A. 2012 Mar 16;1229:230-6. doi: 10.1016/j.chroma.2012.01.055. Epub 2012 Jan 25.
The thermodynamic characterization of a fluorinated methacrylic homopolymer was conducted by means of inverse gas chromatography (IGC) at infinite dilution. The polymer under study, poly(1,1,1,3,3,3-hexafluoroisopropyl methacrylate) (PHFIMA) was synthesized via a free radical polymerization reaction and was properly characterized prior to IGC measurements. The IGC characterization encompassed the calculation of the thermodynamic sorption parameters, the parameters of mixing at infinite dilution, the weight fraction activity coefficients and the Flory-Huggins interaction parameters of 15 probes. Moreover, the total and partial solubility parameters of the polymer were determined. The impact of the temperature and the chemical nature of the probes on the aforementioned thermodynamic parameters are discussed. Results demonstrate that PHFIMA is insoluble in almost every tested solvent, with the exception of chloroform, due to its proton donor character which is favorable for the formation of hydrogen bonds with the fluorine groups and the oxygen atoms of the carbonyl groups (proton acceptors) of the polymer. Furthermore, the total and dispersive solubility parameters descend in a linear manner with the increase of temperature, whereas the polar and hydrogen bonding solubility parameters increase when temperature rises, probably due to the conformational changes of the polymer on the solid support.
通过无限稀释反相气相色谱法 (IGC) 对含氟甲基丙烯酸酯均聚物进行了热力学特性研究。研究中使用的聚合物为聚（1,1,1,3,3,3-六氟异丙基甲基丙烯酸酯）（PHFIMA），通过自由基聚合反应合成，并在 IGC 测量前进行了适当的特性描述。IGC 特性研究包括热力学吸附参数、无限稀释下混合参数、15 种探针的重量分数活度系数和 Flory-Huggins 相互作用参数的计算。此外，还确定了聚合物的总和部分溶解度参数。讨论了温度和探针化学性质对上述热力学参数的影响。结果表明，由于质子供体特性，PHFIMA 几乎不溶于除氯仿以外的所有测试溶剂，与聚合物的氟原子和羰基（质子受体）的氧原子形成氢键有利于质子供体特性。此外，总溶解度参数和色散溶解度参数随温度升高呈线性下降，而极性和氢键溶解度参数随温度升高而增加，这可能是由于聚合物在固体载体上的构象变化。
