Controlled synthesis of biodegradable lactide polymers and copolymers using novel in situ generated or single-site stereoselective polymerisation initiators

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Abstract

Polylactides and their copolymers are key biodegradable polymers used widely in biomedical, pharmaceutical and ecological applications. The development of synthetic pathways and catalyst/initiator systems to produce pre-designed polylactides, as well as the fundamental understanding of the polymerization reactions, has continuously been an important topic. Here, we will address the recent advances in the ring-opening polymerization of lactides, with an emphasis on the highly versatile in situ generated initiator systems and single-site stereoselective initiators. The in situ generated initiators including in situ formed yttrium, calcium and zinc alkoxides all have been shown to bring about a rapid and living polymerization of lactides under mild conditions, which facilitated the preparation of a variety of advanced lactide-based biomaterials. For example, well-defined di- and tri-block copolymers consisting of hydrophilic poly(ethylene glycol) blocks and hydrophobic polyester blocks, which form novel biodegradable polymersomes or biodegradable thermosensitive hydrogels, have been prepared. In the past few years, significant progress has also been made in the area of stereoselective polymerization of lactides. This new generation of initiators has enabled the production of polylactide materials with novel microstructures and/or properties, such as heterotactic (–RRSSRRSSRRSS–) polylactide, crystalline syndiotactic (–RSRSRSRSRSRS–) polylactide and isotactic stereoblock (–RnSnRnSn–) polylactide, exhibiting a high melting temperature. The recently developed polymerizations using in situ generated initiators and stereoselective polymerizations have no doubt opened a brand-new avenue for the design and exploration of polylactides and their copolymers.
Original languageUndefined
Pages (from-to)929-946
JournalJournal of biomaterials science : polymer edition
Volume15
Issue number7
DOIs
Publication statusPublished - 2004

Keywords

  • in situ polymerization
  • living polymerization
  • stereoselective polymerization
  • IR-71383
  • Ring-opening polymerization
  • Polylactide
  • METIS-223575
  • Biodegradable polymers

Cite this

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title = "Controlled synthesis of biodegradable lactide polymers and copolymers using novel in situ generated or single-site stereoselective polymerisation initiators",
abstract = "Polylactides and their copolymers are key biodegradable polymers used widely in biomedical, pharmaceutical and ecological applications. The development of synthetic pathways and catalyst/initiator systems to produce pre-designed polylactides, as well as the fundamental understanding of the polymerization reactions, has continuously been an important topic. Here, we will address the recent advances in the ring-opening polymerization of lactides, with an emphasis on the highly versatile in situ generated initiator systems and single-site stereoselective initiators. The in situ generated initiators including in situ formed yttrium, calcium and zinc alkoxides all have been shown to bring about a rapid and living polymerization of lactides under mild conditions, which facilitated the preparation of a variety of advanced lactide-based biomaterials. For example, well-defined di- and tri-block copolymers consisting of hydrophilic poly(ethylene glycol) blocks and hydrophobic polyester blocks, which form novel biodegradable polymersomes or biodegradable thermosensitive hydrogels, have been prepared. In the past few years, significant progress has also been made in the area of stereoselective polymerization of lactides. This new generation of initiators has enabled the production of polylactide materials with novel microstructures and/or properties, such as heterotactic (–RRSSRRSSRRSS–) polylactide, crystalline syndiotactic (–RSRSRSRSRSRS–) polylactide and isotactic stereoblock (–RnSnRnSn–) polylactide, exhibiting a high melting temperature. The recently developed polymerizations using in situ generated initiators and stereoselective polymerizations have no doubt opened a brand-new avenue for the design and exploration of polylactides and their copolymers.",
keywords = "in situ polymerization, living polymerization, stereoselective polymerization, IR-71383, Ring-opening polymerization, Polylactide, METIS-223575, Biodegradable polymers",
author = "Zhiyuan Zhong and Dijkstra, {Pieter J.} and Jan Feijen",
note = "Festschrift on the occasion of the 70th birthday of Allan S. Hoffman: Gels, Genes, Grafts and Giants. Part 3",
year = "2004",
doi = "10.1163/1568562041271066",
language = "Undefined",
volume = "15",
pages = "929--946",
journal = "Journal of biomaterials science : polymer edition",
issn = "0920-5063",
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TY - JOUR

T1 - Controlled synthesis of biodegradable lactide polymers and copolymers using novel in situ generated or single-site stereoselective polymerisation initiators

AU - Zhong, Zhiyuan

AU - Dijkstra, Pieter J.

AU - Feijen, Jan

N1 - Festschrift on the occasion of the 70th birthday of Allan S. Hoffman: Gels, Genes, Grafts and Giants. Part 3

PY - 2004

Y1 - 2004

N2 - Polylactides and their copolymers are key biodegradable polymers used widely in biomedical, pharmaceutical and ecological applications. The development of synthetic pathways and catalyst/initiator systems to produce pre-designed polylactides, as well as the fundamental understanding of the polymerization reactions, has continuously been an important topic. Here, we will address the recent advances in the ring-opening polymerization of lactides, with an emphasis on the highly versatile in situ generated initiator systems and single-site stereoselective initiators. The in situ generated initiators including in situ formed yttrium, calcium and zinc alkoxides all have been shown to bring about a rapid and living polymerization of lactides under mild conditions, which facilitated the preparation of a variety of advanced lactide-based biomaterials. For example, well-defined di- and tri-block copolymers consisting of hydrophilic poly(ethylene glycol) blocks and hydrophobic polyester blocks, which form novel biodegradable polymersomes or biodegradable thermosensitive hydrogels, have been prepared. In the past few years, significant progress has also been made in the area of stereoselective polymerization of lactides. This new generation of initiators has enabled the production of polylactide materials with novel microstructures and/or properties, such as heterotactic (–RRSSRRSSRRSS–) polylactide, crystalline syndiotactic (–RSRSRSRSRSRS–) polylactide and isotactic stereoblock (–RnSnRnSn–) polylactide, exhibiting a high melting temperature. The recently developed polymerizations using in situ generated initiators and stereoselective polymerizations have no doubt opened a brand-new avenue for the design and exploration of polylactides and their copolymers.

AB - Polylactides and their copolymers are key biodegradable polymers used widely in biomedical, pharmaceutical and ecological applications. The development of synthetic pathways and catalyst/initiator systems to produce pre-designed polylactides, as well as the fundamental understanding of the polymerization reactions, has continuously been an important topic. Here, we will address the recent advances in the ring-opening polymerization of lactides, with an emphasis on the highly versatile in situ generated initiator systems and single-site stereoselective initiators. The in situ generated initiators including in situ formed yttrium, calcium and zinc alkoxides all have been shown to bring about a rapid and living polymerization of lactides under mild conditions, which facilitated the preparation of a variety of advanced lactide-based biomaterials. For example, well-defined di- and tri-block copolymers consisting of hydrophilic poly(ethylene glycol) blocks and hydrophobic polyester blocks, which form novel biodegradable polymersomes or biodegradable thermosensitive hydrogels, have been prepared. In the past few years, significant progress has also been made in the area of stereoselective polymerization of lactides. This new generation of initiators has enabled the production of polylactide materials with novel microstructures and/or properties, such as heterotactic (–RRSSRRSSRRSS–) polylactide, crystalline syndiotactic (–RSRSRSRSRSRS–) polylactide and isotactic stereoblock (–RnSnRnSn–) polylactide, exhibiting a high melting temperature. The recently developed polymerizations using in situ generated initiators and stereoselective polymerizations have no doubt opened a brand-new avenue for the design and exploration of polylactides and their copolymers.

KW - in situ polymerization

KW - living polymerization

KW - stereoselective polymerization

KW - IR-71383

KW - Ring-opening polymerization

KW - Polylactide

KW - METIS-223575

KW - Biodegradable polymers

U2 - 10.1163/1568562041271066

DO - 10.1163/1568562041271066

M3 - Article

VL - 15

SP - 929

EP - 946

JO - Journal of biomaterials science : polymer edition

JF - Journal of biomaterials science : polymer edition

SN - 0920-5063

IS - 7

ER -