Structure-kinetics-properties relationships in polymerization reactions have slowly been gathered over the past century. Thanks to ever-improving optoelectronic devices, kinetic analysis has dramatically improved in precision, sensitivity and performance, while becoming increasingly accessible. Hence, real-time infrared spectroscopy for polymerization monitoring (RTIR), introduced in 19881, is now commonly preferred over discrete FT-IR, NMR and photoacoustic spectroscopy techniques; as well as over time-response-limited tools, such as calorimetry, dilatometry and IR-radiometry. Moreover, RTIR allows correlation of kinetics to mechanical properties during and after polymerization2. However, RTIR-integration into a versatile, robust, one-sample technique has not been fully exploited3.  We designed a robust high-throughput set-up incorporating real-time UV-Vis and fluorescence spectroscopy to RTIR with millisecond resolution, which permits post-polymerization analysis. Experiments run parallel to RTIR/rheometry and prior to GPC, DMA or TGA characterization; thus, kinetics can be directly correlated to polymer structure. Thermal, redox or photo-initiation schemes can be studied, time-resolved reactions performed and a variety of conditions and synthetic approaches tested. We have quantified photopolymerization quantum-inefficacies due to mobility restrictions in bulk polymerization of (meth)acrylate networks, linked fluorescence of molecular rotors to polymer micro-environment and elucidated complex photocatalysis-based initiation schemes. We aim at targeting partially resolved mechanisms, e.g. photo-CuAAC �click�4 or light-activated living radical (ATRP) polymerizations5. Our ultimate goal is to refine fundamental understanding of the intricate connections between monomer structure, polymer growth and final properties to aid rational design of smarter and greener materials.         (1)     Decker, C.; Moussa, K. Die Makromolekulare Chemie 1988 , 189, 2381�2394.(2)     Pfeifer, C. S.; Wilson, N. D.; Shelton, Z. R.; Stansbury, J. W. Polymer 2011 , 52, 3295�3303.(3)     Decker, C. J. Polym. Sci. A Polym. Chem. 1992 , 30, 913�928.(4)     Wang, J.-S.; Matyjaszewski, K. J. Am. Chem. Soc. 1995 , 117, 5614�5615.(5)     Fors, B. P.; Hawker, C. J. Angew. Chem. Int. Ed. 2012 , 51, 8850�8853.

Comprehensive high-throughout analysis of polymer formation and final properties: Towards refined understanding of structure-kinetics-properties relationships

248th National Meeting (2014)

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