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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.

Poly(N-isopropylacrylamide)s (PNIPAM) with low polydispersity and different isotacticity have been synthesized successfully in different compositions of environment-friendly and less toxic methanol-water mixtures by RAFT polymerization in the presence of 0.1 M Yttrium trifluoromethanesulfonate [Y(OTf) 3]. The reactions were successful with high yield in the solvent compositions having mole-fraction of methanol (x m) at or above 0.31. Molecular weights were found to be in between 2.78 × 10 4 – 5.7 × 10 4 and polydispersity index (M w/ M n= 1.11 – 1.37) was close to unity. Isotacticity [meso diad (m), %] of the polymers increased from 55 to 86% with the increase in the x m value from 0.31 to 1.0. The lower critical solution temperature (LCST) of the formed PNIPAMs in water decreased with the increase in their isotacticity.