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Influence of Molecular Weight Distribution on the Thermoresponsive Transition of Poly( N ‐isopropylacrylamide)
Author(s) -
Xu Sihao,
Trujillo Francisco J.,
Xu Jiangtao,
Boyer Cyrille,
Corrigan Nathaniel
Publication year - 2021
Publication title -
macromolecular rapid communications
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.348
H-Index - 154
eISSN - 1521-3927
pISSN - 1022-1336
DOI - 10.1002/marc.202100212
Subject(s) - polymer , materials science , polymer chemistry , chain transfer , poly(n isopropylacrylamide) , thermoresponsive polymers in chromatography , cloud point , branching (polymer chemistry) , glass transition , thermodynamics , polymerization , molar mass distribution , kurtosis , chemical engineering , radical polymerization , chemistry , aqueous solution , copolymer , composite material , organic chemistry , physics , high performance liquid chromatography , statistics , mathematics , reversed phase chromatography , engineering
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 ( M w ). 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 M w , 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.