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Block Copolymers of Macrolactones/Small Lactones by a "Catalyst-Switch" Organocatalytic Strategy. Thermal Properties and Phase Behavior

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. http://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.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/acs.macromol.8b00153DOIArticle
https://pubs.acs.org/doi/10.1021/acs.macromol.8b00153PublisherArticle
https://pubs.acs.org/doi/suppl/10.1021/acs.macromol.8b00153PublisherSupporting Information
ORCID:
AuthorORCID
Bilalis, Panayiotis0000-0002-5809-9643
Gnanou, Yves0000-0001-6253-7856
Hadjichristidis, Nikos0000-0003-1442-1714
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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Funding AgencyGrant Number
King Abdullah University of Science and Technology (KAUST)UNSPECIFIED
Record Number:CaltechAUTHORS:20180316-160011662
Persistent URL:http://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:25 Apr 2018 16:35

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