Ladelta, Viko and Kim, Joey D. and Bilalis, Panayiotis and Gnanou, Yves and Hadjichristidis, Nikos (2018) Block Copolymers of Macrolactones/Small Lactones by a "Catalyst-Switch" Organocatalytic Strategy. Thermal Properties and Phase Behavior. Macromolecules, 51 (7). pp. 2428-2436. ISSN 0024-9297. doi:10.1021/acs.macromol.8b00153. https://resolver.caltech.edu/CaltechAUTHORS:20180316-160011662
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Abstract
Poly(macrolactones) (PMLs) can be considered as biodegradable alternatives of polyethylene; however, controlling the ring-opening polymerization (ROP) of macrolactone (ML) monomers remains a challenge due to their low ring strain. To overcome this problem, phosphazene (t-BuP_4), a strong superbase, has to be used as catalyst. Unfortunately, the one-pot sequential block copolymerization of MLs with small lactones (SLs) is impossible since the high basicity of t-BuP_4 promotes both intra- and intermolecular transesterification reactions, thus leading to random copolymers. By using ROP and the “catalyst-switch” strategy [benzyl alcohol, t-BuP_4/neutralization with diphenyl phosphate/(t-BuP_2)], we were able to synthesize different well-defined PML-b-PSL block copolymers (MLs: dodecalactone, ω-pentadecalactone, and ω-hexadecalactone; SLs: δ-valerolactone and ε-caprolactone). The thermal properties and the phase behavior of these block copolymers were studied by differential scanning calorimetry and X-ray diffraction spectroscopy. This study shows that the thermal properties and phase behavior of PMLs-b-PSLs are largely influenced by the PMLs block if PMLs components constitute the majority of the block copolymers.
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Additional Information: | © 2018 American Chemical Society. Received: January 22, 2018; Revised: March 2, 2018; Publication Date (Web): March 16, 2018. Research was supported by King Abdullah University of Science and Technology (KAUST). The authors declare no competing financial interest. | ||||||||||||
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Issue or Number: | 7 | ||||||||||||
DOI: | 10.1021/acs.macromol.8b00153 | ||||||||||||
Record Number: | CaltechAUTHORS:20180316-160011662 | ||||||||||||
Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20180316-160011662 | ||||||||||||
Official Citation: | Block Copolymers of Macrolactones/Small Lactones by a “Catalyst-Switch” Organocatalytic Strategy. Thermal Properties and Phase Behavior. Viko Ladelta, Joey D. Kim, Panayiotis Bilalis, Yves Gnanou, and Nikos Hadjichristidis. Macromolecules 2018 51 (7), 2428-2436. DOI: 10.1021/acs.macromol.8b00153 | ||||||||||||
Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | ||||||||||||
ID Code: | 85351 | ||||||||||||
Collection: | CaltechAUTHORS | ||||||||||||
Deposited By: | Tony Diaz | ||||||||||||
Deposited On: | 26 Mar 2018 20:09 | ||||||||||||
Last Modified: | 15 Nov 2021 20:27 |
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