Amphiphilic block copolymers of high‐molecular‐weight poly(ethylene oxide) and either ε‐caprolactone or γ‐methyl‐ε‐caprolactone: Synthesis and characterization
Abstract
Abstract Ethylene oxide (EO) has been block‐polymerized with both ε‐caprolactone (ε‐CL) and γ‐methyl‐ε‐caprolactone (MCL) through the combination of the anionic polymerization of EO and the ring‐opening polymerization (ROP) of ε‐CL and MCL. ω‐Hydroxyl poly(ethylene oxide) has been reacted with triethylaluminum (OH/Al = 1) and converted into a macroinitiator for ROP of ε‐CL and MCL. In toluene at room temperature, this polymerization leads to a bimodal molecular weight distribution as a result of monomer insertion in only some of the aluminum alkoxide bonds. However, in a more polar solvent (methylene chloride) added with 1 equiv of a Lewis base (pyridine), the expected diblock is formed selectively, and this indicates that aggregation of the active species in toluene is responsible for a macroinitiator efficiency of less than 1. A series of amphiphilic diblock copolymers with poly(ε‐caprolactone) (semicrystalline) and poly(γ‐methyl‐ε‐caprolactone) (amorphous) as the hydrophobic blocks have been prepared and characterized with size exclusion chromatography,1H NMR, IR, and wide‐angle X‐ray scattering. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1132–1142, 2004
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Macroinitiators prepared by reaction of mono- or dihydroxy PEO with triethylaluminum or using tin octoate allow the synthesis of AB diblock and BAB triblock copolymers where PEO is hydrophilic and the hydrophobic block is biodegradable polyester (PCL, PLA, PLGA, PGA, etc.) with complete control of copolymer composition and size.
“Macroinitiators prepared by reaction of mono-or dihydroxy PEO with triethylaluminum or using tin octoate allow the synthesis of AB diblock and BAB triblock copolymers (Scheme 2 a, c) where (a) is the hydrophilic PEO and (b) the hydrophobic block of biodegradable polyesters (PCL, PLA, PLGA, PGA,...) with a complete control of the copolymer composition and size [159].”
From Recent advances in the synthesis of aliphatic polyesters by ring-opening polymerization☆ (2008) · cites this paper as [159]
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References 36 · Cited by 38
- Authors
- Vangeyte, P., & Jérôme, R.
- Affiliations
- University of Liège (BE)
- Corresponding author
- Jérôme, R.
- Venue
- Journal of Polymer Science Part A: Polymer Chemistry
- Publisher
- Wiley
- Published
- 2004-01-20
- Volume
- 42
- Issue
- 5
- Pages
- 1132-1142
- ISSN
- 0887-624X (ISSN-L)
- 1099-0518
- OpenAlex
- W2066496923
- Cited by
- 38
- References
- 36
- Citations by year
- 2024: 2 · 2018: 1 · 2017: 3 · 2016: 1 · 2014: 1 · 2013: 3 · 2012: 1
- FWCI
- 3.17
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Journal of Polymer Science Part A Polymer Chemistry (publishedVersion)
- ORBi (University of Liège) (submittedVersion)
- Topics
- Physical Sciences › Chemistry › Organic Chemistry › Advanced Polymer Synthesis and Characterization
- Physical Sciences › Materials Science › Biomaterials › biodegradable polymer synthesis and properties
- Physical Sciences › Materials Science › Materials Chemistry › Block Copolymer Self-Assembly
- Keywords
- amphiphilic block copolymers, poly(ethylene oxide), ε-caprolactone, ring-opening polymerization, anionic polymerization, macroinitiator, triethylaluminum, bimodal molecular weight distribution, hydrophobic block, semicrystalline polymers, amorphous polymers, solvent effects on polymerization
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