Polylactide–Poly(6-methyl-ε-caprolactone)–Polylactide Thermoplastic Elastomers
Abstract
Amorphous ABA type block aliphatic polyesters can be useful as degradable and biorenewable thermoplastic elastomers. These materials can be prepared by sequential ring-opening transesterification polymerization (ROTEP) reactions and can exhibit a range of physical properties and morphologies. In this work a set of amorphous polylactide–poly(6-methyl-ε-caprolactone)–polylactide aliphatic polyester ABA triblock copolymers were prepared by consecutive controlled ring-opening polymerizations. Ring-opening polymerization of neat 6-methyl-ε-caprolactone in the presence of 1,4-benzenedimethanol and tin(II) octoate afforded α,ω-hydroxyl-terminated poly(6-methyl-ε-caprolactone). High conversions of 6-methyl-ε-caprolactone (>96%) afforded polymers with molar masses ranging from 12 to 98 kg mol –1, depending on monomer-to-initiator ratios, polymers with narrow, monomodal molecular weight distributions. An array of polylactide–poly(6-methyl-ε-caprolactone)–polylactide triblock copolymers with controlled molecular weights and narrow molecular weight distributions were synthesized using the telechelic poly(6-methyl-ε-caprolactone) samples as macroinitiators for the ring-opening polymerization of d, l -lactide. The morphological, thermal, and mechanical behaviors of these materials were explored. Several triblocks adopted well-ordered microphase-separated morphologies, and both hexagonally packed cylindrical and lamellar structures were observed. The Flory–Huggins interaction parameter was…
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Since the hard block is poly(lactide), at a fixed molar mass, decreasing the polarity of the midblock segment effectively increases the segregation strength of the two blocks.
“Since in this work the hard block is poly(lactide), at a fi xed molar mass, decreasing the polarity of the midblock segment e ff ectively increases the segregation strength of the two blocks. 11,13,64,85 -89”
From Aliphatic Polyester Block Polymer Design (2016) · cites this paper as [11]
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- Authors
- Martello, M. T., & Hillmyer, M. A.
- Affiliations
- University of Minnesota (US)
- Corresponding author
- Hillmyer, Marc A.
- ORCID
- Hillmyer, Marc A.
- Venue
- Macromolecules
- Publisher
- American Chemical Society (ACS)
- Published
- 2011-10-14
- Volume
- 44
- Issue
- 21
- Pages
- 8537-8545
- ISSN
- 0024-9297 (ISSN-L)
- 1520-5835
- OpenAlex
- W2081214922
- Cited by
- 137
- References
- 5
- Citations by year
- 2026: 7 · 2025: 7 · 2024: 13 · 2023: 7 · 2022: 10 · 2021: 12 · 2020: 8 · 2019: 7 · 2018: 7 · 2017: 10 · 2016: 12 · 2015: 10 · 2014: 13 · 2013: 6 · 2012: 7
- FWCI
- 3.54
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Macromolecules (publishedVersion)
- Topics
- Physical Sciences › Materials Science › Biomaterials › biodegradable polymer synthesis and properties
- Physical Sciences › Materials Science › Materials Chemistry › Block Copolymer Self-Assembly
- Physical Sciences › Materials Science › Polymers and Plastics › Polymer crystallization and properties
- Keywords
- polylactic acid, ABA triblock copolymers, ring-opening polymerization, macroinitiator, telechelic polymers, microphase separation, lamellar morphology, Flory-Huggins interaction parameter, order-disorder transition, elastic recovery, biodegradable polymers
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