Synthesis and Characterization of Double Crystalline Cyclic Diblock Copolymers of Poly(ε-caprolactone) and Poly(l(d)-lactide) (c(PCL-b- PL(D)LA))

Romain Liénard; Nerea Zaldua; Thomas Josse; Julien De Winter; Manuela Zubitur; Agurtzane Mugica; Amaia Iturrospe; Arantxa Arbe; Olivier Coulembier; Alejandro J Müller

doi:10.1002/marc.201600309

Synthesis and Characterization of Double Crystalline Cyclic Diblock Copolymers of Poly(ε-caprolactone) and Poly(l(d)-lactide) (c(PCL-b- PL(D)LA))

Macromol Rapid Commun. 2016 Oct;37(20):1676-1681. doi: 10.1002/marc.201600309. Epub 2016 Aug 29.

Authors

Affiliations

¹ Laboratory of Polymeric and Composite Materials, University of Mons - UMONS, Place du Parc 23, 7000, Mons, Belgium.
² Organic Synthesis and Mass Spectrometry Laboratory, University of Mons - UMONS, Place du Parc 23, 7000, Mons, Belgium.
³ POLYMAT and Polymer Science and Technology Department, Faculty of Chemistry, University of the Basque Country UPV/EHU, Paseo Manuel de Lardizabal 3, 20018, Donostia-San, Sebastiań, Spain.
⁴ Chemical and Environmental Engineering Department, Polytechnic School, University of the Basque Country UPV/EHU, 2008, Donostia-San Sebastián, Spain.
⁵ Centro de Física de Materiales (CFM) (CSIC-UPV/EHU) - Materials Physics Center (MPC), Paseo Manuel de Lardizabal 5, 20018, San Sebastián, Spain.
⁶ Laboratory of Polymeric and Composite Materials, University of Mons - UMONS, Place du Parc 23, 7000, Mons, Belgium. [email protected].
⁷ POLYMAT and Polymer Science and Technology Department, Faculty of Chemistry, University of the Basque Country UPV/EHU, Paseo Manuel de Lardizabal 3, 20018, Donostia-San, Sebastiań, Spain. [email protected].
⁸ IKERBASQUE, Basque Foundation for Science, 48013, Bilbao, Spain. [email protected].

PMID: 27568984
DOI: 10.1002/marc.201600309

Abstract

The synthesis of symmetric cyclo poly(ε-caprolactone)-block-poly(l(d)-lactide) (c(PCL-b-PL(D)LA)) by combining ring-opening polymerization of ε-caprolactone and lactides and subsequent click chemistry reaction of the linear precursors containing antagonist functionalities is presented. The two blocks can sequentially crystallize and self-assemble into double crystalline spherulitic superstructures. The cyclic chain topology significantly affects both the nucleation and the crystallization of each constituent, as gathered from a comparison of the behavior of linear precursors and cyclic block copolymers. The stereochemistry of the PLA block does not have a significant effect on the nonisothermal crystallization of both linear and cyclo PCL-b-PDLA and PCL-b-PLLA copolymers.

Keywords: crystallization; cyclic block copolymers; poly(ε-caprolactone).

MeSH terms

Crystallization
Molecular Structure
Particle Size
Polyesters / chemical synthesis
Polyesters / chemistry*
Surface Properties

Substances

Polyesters
polycaprolactone
poly(lactide)