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Thermal degradation kinetics of thermoresponsive poly(N-isopropylacrylamide-co-N,N-dimethylacrylamide) copolymers prepared via RAFT polymerization

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Abstract

Reversible addition-fragmentation chain transfer polymerization at 70 °C in N,N-dimethylformamide was used to prepare poly(N-isopropylacrylamide-co-N,N-dimethylacrylamide) copolymers in various compositions to afford well-defined polymers with pre-determined molecular weight, narrow molecular weight distribution, and precise chain end structure. The copolymer compositions were determined by 1H NMR spectroscopy. The reactivity ratios of N-isopropylacrylamide (NIPAM) and N,N-dimethylacrylamide (DMA) were calculated as r NIPAM = 0.838 and r DMA = 1.105, respectively, by the extended Kelen–Tüdös method at high conversions. The lower critical solution temperature of PNIPAM can be altered by changing the DMA content in the copolymer chain. Differential scanning calorimetry and thermogravimetric analysis at different heating rates were carried out on these copolymers to understand the nature of thermal degradation and to determine its kinetics. Different kinetic models were applied to estimate various parameters like the activation energy, the order, and the frequency factor. These studies are important to understand the solid state polymer degradation of N-alkyl substituted polymers, which show great potential in the preparation of miscible polymer blends due to their ability to interact through hydrogen bonding.

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Acknowledgements

The authors acknowledge the Indian Institute of Science Education and Research-Kolkata and the Department of Science and Technology (DST), New Delhi [SR/S1/OC-51/2010] for partial financial support of this research. Kamal Bauri acknowledges Council of Scientific and Industrial Research (CSIR), Government of India for his fellowships.

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Authors and Affiliations

  1. Department of Chemical Sciences, Polymer Research Centre, Indian Institute of Science Education and Research-Kolkata, Mohanpur, Nadia, West Bengal, 741252, India

    Kamal Bauri, Saswati Ghosh Roy, Simran Arora, Rajib Kumar Dey & Priyadarsi De

  2. Department of Chemical Engineering, Indian Institute of Science, Bangalore, 560012, India

    Ankur Goswami & Giridhar Madras

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  1. Kamal Bauri
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  2. Saswati Ghosh Roy
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Correspondence to Priyadarsi De.

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Bauri, K., Roy, S.G., Arora, S. et al. Thermal degradation kinetics of thermoresponsive poly(N-isopropylacrylamide-co-N,N-dimethylacrylamide) copolymers prepared via RAFT polymerization. J Therm Anal Calorim 111, 753–761 (2013). https://doi.org/10.1007/s10973-012-2344-0

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