Heat capacity and index of refraction of polyzwitterions. (21st September 2022)

• Record Type: Journal Article
• Authors: Clark, Andrew; Rosenbaum, Michael; Biswas, Yajnaseni; Asatekin, Ayşe; Cebe, Peggy
• Is Part Of: Polymer. Volume 256(2022)
• Publication Date: 2022-09-21
• Subjects: Polymers -- Periodicals; Polymerization -- Periodicals; Polymères -- Périodiques; Polymérisation -- Périodiques; 547.7
• DOI: 10.1016/j.polymer.2022.125176
• Languages: English
• ISSNs: 0032-3861

Abstract

Abstract: Specific heat capacities and indices of refraction were measured for a series of six sulfobetaine zwitterionic polymers and compared to topological and group contribution models. Poly(sulfobetaine methacrylate) (PSBMA), poly(sulfobetaine acrylate) (PSBA), poly(ethyl sulfobetaine methacrylate) (PESBMA), poly(sulfobetaine methacrylamide) (PSBMAm), poly(sulfobetaine 2-vinylpyridine) (PSB2VP) and poly(sulfobetaine 4-vinylpyridine) (PSB4VP) were specially synthesized with changes of chemical structure in order to study effects of either the polymer backbone or the side group on their properties. Temperature modulated differential scanning calorimetry (TMDSC) as well as quasi-isothermal TMDSC were used to determine the temperature dependent specific heat capacity, cp (T) from 30 to 200 °C. The solid state specific heat capacities were measured for all the polyzwitterions, while liquid state heat capacity measurements were limited to PSBA and PESBMA. Ellipsometry at wavelengths from 300 nm to 3000 nm was used to measure the index of refraction for polyzwitterion thin films at room temperature. Theoretical room temperature values of cp and n were calculated for the polyzwitterions using topological and group contribution methods and compared to the measured values. The measured index of refraction values agree well with predictions for the polyzwitterions. However, for the solid state heat capacity, the model produces accurate prediction only for PSB2VP and PSB4VP. The discrepancy between the measured and predicted cp values is most likely due to the reduction of vibrational degrees of motion in the solid state for some of the polyzwitterions due to physical crosslinking. Graphical abstract: Image 1 Highlights: We studied sulfobetaine zwitterionic polymers (PZIs) with different chemistries. At slow heating rates, degradation onset temperatures were below 240 °C. Solid state heat capacities (cp ) and refractive indices were measured. Results were compared to predictions from both topological and group models. Physical crosslinking in PZIs impacts the predictive power of the models.