Synthesis and Characterization of Poly(l-lactide)−Poly(ε-caprolactone) Multiblock Copolymers

Jeon, Oju; Lee, Soo-Hong; Kim, Soo Hyun; Lee, Young Moo; Kim, Young Ha

doi:10.1021/ma034006v

Cited by 168biodegradable polymer synthesis and propertiesBlock Copolymer Self-AssemblyPolymer crystallization and properties

Synthesis and Characterization of Poly(l-lactide)−Poly(ε-caprolactone) Multiblock Copolymers

Jeon, Oju, Lee, Soo-Hong, Kim, Soo Hyun, Lee, Young Moo, Kim, Young Ha·2003·Macromolecules

DOI 10.1021/ma034006v

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Abstract

New poly( l -lactide) (PLLA)−poly(ε-caprolactone) (PCL) multiblock copolymers were prepared by using the coupling reaction between the bischloroformates of carboxylated PLLA with PCL-diol in the presence of pyridine. All the copolymers were characterized by 1 H NMR and GPC and investigated further by using DSC, TGA, SAXD, WAXD, polarizing microscope, and Instron testing. The molecular weights of PLLA−PCL multiblock copolymers produced lay in the range 40 000−50 000. The multiblock copolymers produced exhibited only one melting peak, corresponding to the PLLA phase, even at a relatively high PCL content, whereas the PLLA−PCL−PLLA triblock copolymers had two melting peaks. The tensile moduli and strengths of the triblock copolymer were very high. On the other hand, the multiblock copolymers were flexible and elastic with relatively good mechanical properties. These copolymers behaved like thermoplastic elastomer due to the presence of physical cross-linking and strain recoveries of more than 95% at 100% strain. Degradation of the copolymers was investigated in PBS for up to 150 days. The random copolymer was found to be rapidly degraded, while the triblock and multiblock polymers were slowly degraded. The molecular weight of the multiblock copolymers decreased with time, but there were no significant changes in their chemical compositions. From 1 H NMR studies, chain scission occurred in the PLLA blocks.

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The decrease in PCL peak crystallization temperature with increasing PLLA content could be a result of topological constraints because PLLA crystallizes first and forms spherulites regardless of composition.
“This could be a result of topological constraints since PLLA crystallizes first when the samples are cooled from the melt and in a break-out fashion whereby spherulites are formed regardless of composition. [6,16,21]”
From Melt Structure and its Transformation by Sequential Crystallization of the Two Blocks within Poly( <scp>L</scp> ‐lactide)‐ block ‐Poly( ε ‐caprolactone) Double Crystalline Diblock Copolymers (2006) · cites this paper as [21]
Jeon et al. reported that multiblock and triblock PLLA-b-PCL copolymers were phase separated in the melt.
“They reported that the multiblock and triblock copolymers were phase separated in the melt since they found a single small angle X-ray scattering (SAXS) reflection that they interpreted as arising from the diffraction of poorly ordered spherical or hexagonally packed cylinders for multiblock copolymers and lamellar microdomains for triblock copolymers”
From Melt Structure and its Transformation by Sequential Crystallization of the Two Blocks within Poly( <scp>L</scp> ‐lactide)‐ block ‐Poly( ε ‐caprolactone) Double Crystalline Diblock Copolymers (2006) · cites this paper as [21]
A spherulitic morphology was found regardless of composition for all copolymers examined by Jeon et al.
“Aditionally, a spherulitic morphology was found regardless of composition for all copolymers examined.”
From Melt Structure and its Transformation by Sequential Crystallization of the Two Blocks within Poly( <scp>L</scp> ‐lactide)‐ block ‐Poly( ε ‐caprolactone) Double Crystalline Diblock Copolymers (2006) · cites this paper as [21]
Double-crystalline PLLA-b-PCL diblock copolymers have been reported as miscible or weakly segregated in the melt, depending on composition and molecular weight.
“The double-crystalline PLLAb -PCLdiblock copolymers have been reported as miscible or weakly segregated in the melt, depending on composition and molecular weight. 23 -29”
From Crystallization Kinetics and Morphology of Biodegradable Double Crystalline PLLA- b -PCL Diblock Copolymers (2010) · cites this paper as [26]

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Authors: Jeon, O., Lee, S.-H., Kim, S. H., Lee, Y. M., & Kim, Y. H.
Affiliations: Hanyang University (KR)
Corresponding author: Kim, Soo Hyun
ORCID: Jeon, Oju
Kim, Soo Hyun
Lee, Young Moo
Venue: Macromolecules
Publisher: American Chemical Society (ACS)
Published: 2003-06-25
Volume: 36
Issue: 15
Pages: 5585-5592
ISSN: 0024-9297 (ISSN-L)
1520-5835
DOI: 10.1021/ma034006v
OpenAlex: W1982644887
Cited by: 168
References: 19
Citations by year: 2026: 1 · 2025: 3 · 2024: 5 · 2023: 4 · 2022: 2 · 2021: 3 · 2020: 2 · 2019: 9 · 2018: 9 · 2017: 10 · 2016: 13 · 2015: 10 · 2014: 7 · 2013: 7 · 2012: 14
FWCI: 3.05
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: poly(L-lactic acid), polycaprolactone, multiblock copolymers, triblock copolymers, physical crosslinking, thermoplastic elastomers, strain recovery, biodegradation, chain scission, mechanical properties, melting behavior

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Synthesis and Characterization of Poly(l-lactide)−Poly(ε-caprolactone) Multiblock Copolymers

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