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This work investigated the cyclization possibility and melt spinnability of carbon fiber precursors, poly(acrylonitrile-co-methyl acrylate) (AN/MA) and poly(acrylonitrile-co-dimethyl itaconate) (AN/DMI). The onset temperature of cyclization of the AN/DMI copolymer is lower than that of the AN/MA copolymer and also the polyacrylonitrile (PAN) homopolymer. The enthalpy (ΔH) of the AN/DMI copolymer is about 3–4 times that of the PAN homopolymer and about 1.8 times that of the AN/MA copolymer, indicating that the degree of cyclization of the AN/DMI copolymer is relatively higher. The melt dwell time of the AN/DMI copolymer is increased to about 3–5 times that of the AN/MA copolymer, especially when synthesized with a feed molar ratio of AN/DMI = 85/15. The AN/DMI copolymer (AN/DMI = 85/15) has the longest melt dwell time, 24.8 min, at the lowest melting temperature, 190oC, among all the PAN-related copolymers synthesized herein. Furthermore, the AN/DMI copolymer (AN/DMI = 85/15) can be rapidly cyclized at the cyclization temperature of 260℃, which is 25℃ lower than that of the AN/MA copolymer (AN/MA = 85/15). In short, this work demonstrates that the carbon fiber precursor made by the AN/DMI copolymer (AN/DMI = 85/15) will be superior to that of the AN/MA copolymer (AN/MA = 85/15) with respect to the melt spinnability and cyclization at low temperature. [ABSTRACT FROM AUTHOR]

In this study, we prepared a series of thermosensitive polymers with low polydispersity index (PDI) values by nitroxidemediated controlled radical polymerization (NMRP) with 2,2,6,6-tetramethyl-1-piperdinyloxy nitroxide (TEMPO) as a stable nitroxide-free radical. Poly(N-isopropyl acrylamide) (PNIPAAm)-block-poly(N-tert-butyl acrylamide) (PNTBA) was successfully synthesized, first, through polymerization with N-isopropyl acrylamide to obtain the reactive polymer PNIPAAm-TEMPO and, second, through polymerization by the addition of N-tert-butyl acrylamide (NTBA). The added molar fraction of NTBA during the second polymerization was adjusted accordingly to obtain the final polymerization product, a thermosensitive polymer (PNIPAAm-block- PNTBA), which had a targeted lower critical solution temperature (LCST). The result shows that the synthesis method used in this study effectively controlled the formation of the polymer to obtain a low PDI. The thermosensitive block copolymer, PNIPAAm-b- PNTBA (molar ratio = 9:1), with LCSTs in the range 27.7-39.8°C, was obtained through controlled living radical polymerization with PNIPAAm-TEMPO. Specifically, the 5 wt % aqueous solution of PNIPAAm-b-PNTBA (molar ratio = 9:1) had an LCST of 37.4°C; this was close to body temperature, 37°C. The 5 wt % aqueous solution of PNIPAAm-b-PNTBA (molar ratio59:1) showed potential for use in biomedical applications. [ABSTRACT FROM AUTHOR]

ABSTRACT Poly( N-isopropylacrylamide) (NIPAAm) is well known as a smart material with good thermal sensitivity and favorable biocompatibility. A series of new smart hydrogels, NIPAAm copolymerized with IAM (itaconamic acid; 4-amino-2-methylene-4-oxobutanoic acid), were synthesized through radical solution polymerization in this work. Poly(NIPAAm- co-IAM) can respond to the changes of temperature as well as pH value. Such a characteristic is due to the fact that IAM contains not only a hydrophilic acrylic acid moiety but also an acrylamide moiety to be thermal and pH sensitive. The experimental results show that the lower critical solution temperature (LCST) of the copolymer increases as the molar fraction of IAM increases. Moreover, based on the current experimental data, 3 wt % of Poly(NIPAAm- co-IAM) aqueous solution in this study exhibits a phase transition temperature (37.8°C) close to the human body temperature in the buffer solution of pH 7 possibly to be useful in drug delivery. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42367. [ABSTRACT FROM AUTHOR]

In this work, a smart copolymer, Poly(nipam-co-IAM) was synthesized by copolymerization of N -isopropylacrylamide (nipam) and itaconamic acid (IAM) through reversible addition-fragmentation chain-transfer (RAFT) polymerization. Poly(nipam-co-IAM) has been studied previously synthesized via radical polymerization without stereo-control, and this work used cumyl dithiobenzoate and Ytterbium(III) trifluoromethanesulfonate as RAFT and stereo-control agents, respectively. The stereo-control result in this work shows that tacticity affects the lower critical solution temperature (LCST) and/or the profile of phase separation of Poly(nipam-co-IAM). In the pH 7 and pH 10 buffer solutions, the P(nipam-co-IAM) copolymer solutions showed soluble⁻insoluble⁻soluble transitions, i.e., both LCST and upper critical solution temperature (UCST) transitions, which had not been found previously, and the insoluble to soluble transition (redissolved behavior) occurred at a relatively low temperature. The insoluble to soluble transition of P(nipam-co-IAM) in alkaline solution occurred at a temperature of less than 45 °C. However, the redissolved behavior of P(nipam-co-IAM) was found only in the pH 7 and pH 10 buffer solutions and this redissolved behavior was more prominent for the atactic copolymers than in the isotactic-rich ones. In addition, the LCST results under our experimental range of meso content did not show a significant difference between the isotactic-rich and the atactic P(nipam-co-IAM). Further study on the soluble-insoluble-soluble (S-I-S) transition and the application thereof for P(nipam-co-IAM) copolymers will be conducted.