Polymerization of 5-alkyl δ-lactones catalyzed by diphenyl phosphate and their sequential organocatalytic polymerization with monosubstituted epoxides

Handle URI:
http://hdl.handle.net/10754/563958
Title:
Polymerization of 5-alkyl δ-lactones catalyzed by diphenyl phosphate and their sequential organocatalytic polymerization with monosubstituted epoxides
Authors:
Zhao, Junpeng; Hadjichristidis, Nikolaos ( 0000-0003-1442-1714 )
Abstract:
Organocatalytic ring-opening polymerization (ROP) reactions of three renewable 5-alkyl δ-lactones, namely δ-hexalactone (HL), δ-nonalactone (NL) and δ-decalactone (DL), using diphenyl phosphate (DPP) were investigated. Room temperature, together with a relatively high monomer concentration (≥3 M), was demonstrated to be suitable for achieving a living ROP behavior, a high conversion of the lactone, a controlled molecular weight and a low dispersity of the polyester. HL, containing a 5-methyl substituent, showed a much higher reactivity (polymerization rate) and a slightly higher equilibrium conversion than the compounds with longer alkyl substituents (NL and DL). The effectiveness of DPP-catalyzed ROP of 5-alkyl δ-lactones facilitated the one-pot performance following the t-BuP4-promoted ROP of monosubstituted epoxides. It has been shown in an earlier study that substituted polyethers acted as "slow initiators" for non-substituted lactones. However, efficient initiations were observed in the present study as substituted lactones were polymerized from the substituted polyethers. Therefore, this reinforces the previously developed "catalyst switch" strategy, making it a more versatile tool for the synthesis of well-defined polyether-polyester block copolymers from a large variety of epoxide and lactone monomers. © The Royal Society of Chemistry 2015.
KAUST Department:
Physical Sciences and Engineering (PSE) Division; Polymer Synthesis Laboratory; Chemical Science Program; KAUST Catalysis Center (KCC)
Publisher:
Royal Society of Chemistry (RSC)
Journal:
Polym. Chem.
Issue Date:
4-Feb-2015
DOI:
10.1039/c5py00019j
Type:
Article
ISSN:
17599954
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorZhao, Junpengen
dc.contributor.authorHadjichristidis, Nikolaosen
dc.date.accessioned2015-08-03T12:20:51Zen
dc.date.available2015-08-03T12:20:51Zen
dc.date.issued2015-02-04en
dc.identifier.issn17599954en
dc.identifier.doi10.1039/c5py00019jen
dc.identifier.urihttp://hdl.handle.net/10754/563958en
dc.description.abstractOrganocatalytic ring-opening polymerization (ROP) reactions of three renewable 5-alkyl δ-lactones, namely δ-hexalactone (HL), δ-nonalactone (NL) and δ-decalactone (DL), using diphenyl phosphate (DPP) were investigated. Room temperature, together with a relatively high monomer concentration (≥3 M), was demonstrated to be suitable for achieving a living ROP behavior, a high conversion of the lactone, a controlled molecular weight and a low dispersity of the polyester. HL, containing a 5-methyl substituent, showed a much higher reactivity (polymerization rate) and a slightly higher equilibrium conversion than the compounds with longer alkyl substituents (NL and DL). The effectiveness of DPP-catalyzed ROP of 5-alkyl δ-lactones facilitated the one-pot performance following the t-BuP4-promoted ROP of monosubstituted epoxides. It has been shown in an earlier study that substituted polyethers acted as "slow initiators" for non-substituted lactones. However, efficient initiations were observed in the present study as substituted lactones were polymerized from the substituted polyethers. Therefore, this reinforces the previously developed "catalyst switch" strategy, making it a more versatile tool for the synthesis of well-defined polyether-polyester block copolymers from a large variety of epoxide and lactone monomers. © The Royal Society of Chemistry 2015.en
dc.publisherRoyal Society of Chemistry (RSC)en
dc.rightsThis article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence.en
dc.titlePolymerization of 5-alkyl δ-lactones catalyzed by diphenyl phosphate and their sequential organocatalytic polymerization with monosubstituted epoxidesen
dc.typeArticleen
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentPolymer Synthesis Laboratoryen
dc.contributor.departmentChemical Science Programen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.identifier.journalPolym. Chem.en
dc.eprint.versionPublisher's Version/PDFen
dc.contributor.institutionFaculty of Materials Science and Engineering, South China University of TechnologyGuangzhou, Chinaen
kaust.authorHadjichristidis, Nikolaosen
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