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Effect of Isotacticity of Linear Poly(N-isopropylacrylamide) on its Gelation in Benzyl Alcohol

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Abstract

Thermoreversible gelation of three different isotactic linear poly(N-isopropylacrylamide) (PNIPAM)s having meso dyad (m) values 62, 68 and 81% has been observed in benzyl alcohol. All the gels were transparent in nature. SEM image of the dried gels showed fibrillar network morphology. Melting temperature of the gels gradually increased with the increase in the concentration. XRD data of dry polymers and their corresponding dry gels showed shifting in the peak positions. Rheological study showed that stronger gels were formed with increasing isotacticity of PNIPAM while lower isotactic sample exhibited typical polymer melt rheology. The formation of a plunge in the storage modulus as well as in the viscosity plot at the same frequency range indicates the reversible nature of the structure breaking/reformation under frequency sweep. Moreover, the mechanical strength of the gel decreased with increase in temperature. UV-Vis kinetic study also indicated the change in the conformation and aggregation of PNIPAM chains during gelation. Molecular modelling calculation showed that the number of solvent molecules involved in forming gel (polymer-solvent compound) decreased with the increase in the isotacticity of the polymer. Gelation rate of these gels was studied as a function of temperature, concentration and isotacticity using test-tube tilting method. It increased with the increase in the concentration and isoacticity of the polymer, and with the decrease in the temperature. Critical gelation concentration of the gel gradually increased with the decrease in the isotacticity and with the increase in the temperature. All these experimental results indicated that gelation occurs presumably through polymer-solvent compound formation.

Thermoreversible gelation of different isotactic [meso diad (m) = 62, 68 and 81%] linear poly(N-isopropylacrylamide) (PNIPAM)s has been observed in benzyl alcohol. Gelation rate depends on temperature, concentration, and isotacticity of PNIPAM. SEM, XRD, rheology and UV-Vis studies, and molecular modelling support its formation presumably via polymer-solvent compound formation.

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Acknowledgements

BR gratefully acknowledges the financial support from the Council of Science and Industrial Research, Government of India, through Grant no. 02(0002)/11/EMR-II.

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  1. CHANDRA SEKHAR BISWAS

    Present address: Nanshan District Key Lab for Biopolymers and Safety Evaluation, College of Materials Science and Engineering and Optoelectronic Engineering Postdoctoral Centre, Shenzhen University, 518060, Shenzhen, China

Authors and Affiliations

  1. Department of Chemistry, Institute of Science, Banaras Hindu University, Varanasi, 221 005, India

    CHANDRA SEKHAR BISWAS, KHEYANATH MITRA, SHIKHA SINGH, BISWAJIT MAITI & BISWAJIT RAY

  2. School of Material Science and Technology, Indian Institute of Technology, Banaras Hindu University, Varanasi, 221 005, India

    DINESH K PATEL & PRALAY MAITI

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Supplementary Information (SI)

Results of X-ray analysis data of m-81 PNIPAM and its dry gels, DSC thermograms of m-62 and m-68 PNIPAM gels, plots of complex viscosity vs. frequency of gels, UV-Vis spectral changes during gelation, gelation kinetics, and plot of log \(t_{\text {gel}}^{\mathrm {-1}}\) vs. log [(C-C ∗)/C ∗] are shown in Supplementary Information which is available at www.ias.ac.in/chemsci.

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BISWAS, C.S., MITRA, K., SINGH, S. et al. Effect of Isotacticity of Linear Poly(N-isopropylacrylamide) on its Gelation in Benzyl Alcohol. J Chem Sci 128, 941–950 (2016). https://doi.org/10.1007/s12039-016-1086-0

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