ABSTRACT
Eight-armed A4B4-type hetero-arm star-shaped PCL-PLA polymers ((PCL)4-POSS-(PLA)4, SPLA30) with POSS core were successfully prepared via combination of the "arm-first" approach utilizing ring-opening polymerization (ROP) and click chemistry techniques. Firstly, alkyne-functional PLA and PCL polymers having arms with 30 repeating units were synthesized via ROP with utilizing propargyl alcohol as initiator and stannous octoate (Sn(Oct)2) as catalyst. Then, the obtained hetero-armed star-shaped polymers were prepared by Cu(I)-catalyzed alkyne-azide cycloaddition (CuAAC) click reaction between alkyne functional polymers (1:1 PCL:PLA) and azido functional polyhedral oligomeric silsesquoxane (POSS-(N3)8) molecules. Finally, these obtained star-shaped SPLA30 was blended with neat PLA at different PLA/SPLA30 ratios (95/5 and 90/10 wt%) via melt blending by utilizing micro-compounder (a lab-scale) to enhance thermal, morphological, and mechanical properties of neat PLA. Also, different diisocyanates (1,4-phenylene diisocyanate (PDI), isophorone diisocyanate (IPDI), methylene diphenyl diisocyanate (MDI), and toluene 2,4-diisocyanate (TDI)) at constant ratio (1 wt%) were used as a chain extender bonding terminal group of polymers. It was found that addition of SPLA30 and SPLA30+ diisocyanates provided improvements in mechanical properties (especially in elongation at break and impact strength) of neat PLA. When the thermal properties were examined, it was seen that the decomposition temperatures of the blends decreased significantly compared to neat PLA and that there was a significant increment in the Tg and Tm values. In addition, it has been found that especially the diisocyanates added to provide good interfacial adhesion with polymer blends and show a homogeneous distribution on the surface.
Subject(s)
Polyesters , Polymers , TemperatureABSTRACT
A pyrene-functional polystyrene copolymer was prepared via 1,3-dipolar cycloaddition reaction (Sharpless-type click recation) between azide-functional styrene copolymer and 1-ethynylpyrene. Subsequently, nanofibers of pyrene-functional polystyrene copolymer were obtained by using electrospinning technique. The nanofibers thus obtained, found to preserve their parent fluorescence nature, confirmed the avoidance of aggregation during fiber formation. The trace detection of trinitrotoluene (TNT) in water with a detection limit of 5 nM was demonstrated, which is much lower than the maximum allowable limit set by the U.S. Environmental Protection Agency. Interestingly, the sensing performance was found to be selective toward TNT in water, even in the presence of higher concentrations of toxic metal pollutants such as Cd(2+), Co(2+), Cu(2+), and Hg(2+). The enhanced sensing performance was found to be due to the enlarged contact area and intrinsic nanoporous fiber morphology. Effortlessly, the visual colorimetric sensing performance can be seen by naked eye with a color change in a response time of few seconds. Furthermore, vapor-phase detection of TNT was studied, and the results are discussed herein. In terms of practical application, electrospun nanofibrous web of pyrene-functional polystyrene copolymer has various salient features including flexibility, reproducibility, and ease of use, and visual outputs increase their value and add to their advantage.
