Influence of Molecular Weight Distribution on the Thermoresponsive Transition of Poly(N‐isopropylacrylamide)

A series of poly(N‐isopropylacrylamide) (PNIPAm) homopolymers with narrow molecular weight distributions (MWDs) is prepared via photoinduced electron/energy transfer–reversible addition‐fragmentation chain transfer (PET–RAFT) polymerization. The thermal transition temperature of these polymer samples is analyzed via turbidity measurements in water/N,N'‐dimethylformamide mixtures, which show that the cloud point temperatures are inversely proportional to the weight average molecular weight (Mw). Binary mixtures of the narrowly distributed PNIPAm samples are also prepared and the statistical parameters for the MWDs of these blends are determined. Very interestingly, for binary blends of the PNIPAm samples, the thermoresponsive transition is not only dependent on the Mw, which has been shown previously, but also on higher order statistical parameters of the MWDs. Specifically, at very high values of skewness and kurtosis, the polymer blends deviate from a single sharp thermoresponsive transition toward a broader thermal response, and eventually to a regime of two more distinct transitions. This work highlights the importance of in‐depth characterization of polymer MWDs for thermoresponsive polymers. The thermoresponsive transition for mixtures of poly(N‐isopropylacrylamide) with varied molecular weight distributions is investigated. The thermoresponsive transition depends on the weight average molecular weight, skewness, and kurtosis of the mixture. Upon increasing skewness and kurtosis, polymer blends deviate from a single sharp thermoresponsive transition to a broader transition, and then to a regime of two distinct transitions.