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Versatile and controlled synthesis of resorbable star-shaped polymers using a spirocyclic tin initiator: Reaction optimization and kinetics
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.ORCID iD: 0000-0002-5850-8873
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.ORCID iD: 0000-0002-1922-128X
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
2006 (English)In: Journal of Polymer Science Part A: Polymer Chemistry, ISSN 0887-624X, E-ISSN 1099-0518, Vol. 44, no 1, 596-605 p.Article in journal (Refereed) Published
Abstract [en]

A spirocyclic tin initiator was synthesized from pentaerythritol ethoxylate and dibutyltin oxide and used to polymerize L-lactide with dichloromethane, chloroform, toluene, and chlorobenzene as solvents. The reactions were performed at different temperatures and it is concluded that neither the temperature nor the solvent affects the molecular weight or the molecular weight distribution of the star-shaped polymers. The reaction rate was significantly increased by raising the reaction temperature or choosing a solvent with a low dielectric constant. All polymers showed a molecular-weight distribution below 1.19 and a molecular-weight determined by the initial monomer to initiator concentration ([M](0)/[1]). No induction period was seen for the polymerizations. They were all first order in initiator and the degree of aggregation in toluene at 110 degrees C was found to be 4/5. The glass transition temperature and the melting temperature of the star-shaped polymers increase with increasing arm length.

Place, publisher, year, edition, pages
2006. Vol. 44, no 1, 596-605 p.
Keyword [en]
narrow molecular-weight distribution, poly(L-lactide), polymerization kinetics, spirocyclic tin initiator, star-shaped architecture
National Category
Polymer Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-8048DOI: 10.1002/pola.21192ISI: 000234091800058Scopus ID: 2-s2.0-30344470475OAI: oai:DiVA.org:kth-8048DiVA: diva2:13267
Note
QC 20100901Available from: 2008-03-03 Created: 2008-03-03 Last updated: 2010-09-01Bibliographically approved
In thesis
1. Macromolecular design and architecture of aliphatic polyesters
Open this publication in new window or tab >>Macromolecular design and architecture of aliphatic polyesters
2008 (English)Doctoral thesis, comprehensive summary (Other scientific)
Abstract [en]

Public health care has reached a level where tissue or organ reconstruction by means of biodegradable short-term implants via e.g. tissue engineering will be practicable in the near future. The vital issue now is to be able to reproducibly fabricate and design new materials with the appropriate properties and three-dimensional shape, and to facilitate their sterilization. In this thesis, macromolecular design and polymer architecture techniques are used to synthesize well-defined polymers with narrow molecular weight distributions (MWD), and to control the reactions upon sterilization, and the degradation rate and profile.

A model system for the ring-opening polymerization of L-lactide (LLA) initiated by a spirocyclic tin initiator was developed to synthesize star-shaped polymers. It was shown that an increase in temperature and a decrease in the dielectrical constant of the solvents increased the reaction rate. The versatility of the spirocyclic tin initiator system was subsequently established, by homopolymerization of ε-caprolactone (CL) and 1,5-dioxepan-2-one (DXO) and this system was compared with a conventional system using stannous octoate (Sn(Oct)2) and pentaerythritol ethoxylate. Two different strategies were assessed for the two initiator systems for the synthesis of copolymers that are random or blocky in their nature. Random copolymers with distinct sequence lengths were synthesized using both initiator systems, together with block poly(DXO-co-LLA) and poly(CL-co-LLA) with narrow MWD.

Three different types of copolymers of LLA, CL and DXO were synthesized using Sn(Oct)2 and ethylene glycol. A solvent casting and particulate leaching technique was developed and applied to construct porous scaffolds of the copolymers. The porous scaffolds were subsequently sterilized using electron beam or γ-irradiation and it was shown that the reactions induced by radiation can be used to tailor the end-properties of the materials.

Homo- and copolymers of CL and DXO with different macromolecular designs (triblock and multiblock) and different polymer architectures (linear and cross-linked) were synthesized and degraded in a phosphate buffer solution for up to 364 days. By altering the network composition, the release pattern of acidic degradation products was controlled, where an increase in DXO content led to an increase in the release of both monomeric hydroxy-acids. Varying the distribution of the more hydrolysis-susceptible DXO-sequences in the linear copolymers also enabled the amount of monomeric hydroxy acids released to be controlled, where the triblock copolymer showed the highest release.

Place, publisher, year, edition, pages
Stockholm: KTH, 2008. 62 p.
Series
Trita-CHE-Report, ISSN 1654-1081 ; 2008:11
Keyword
Ring-opening polymerization, L-lactide, 1, 5-dioxepane-2-one, ε-caprolactone, Polymerization kinetics, Star-shaped architecture, Spirocyclic tin initiator
National Category
Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-4657 (URN)978-91-7178-883-2 (ISBN)
Public defence
2008-03-20, F3, KTH, Lindstedtsvägen 26, Stockholm, 09:00
Opponent
Supervisors
Note
QC 20100901Available from: 2008-03-03 Created: 2008-03-03 Last updated: 2010-09-01Bibliographically approved
2. Design of polyester and porous scaffolds
Open this publication in new window or tab >>Design of polyester and porous scaffolds
2005 (English)Licentiate thesis, comprehensive summary (Other scientific)
Abstract [en]

The use of synthetic materials for tissue and organ reconstruction, i. e. tissue engineering, has become a promising alternative to current surgical therapies and may overcome the shortcomings of the methods in use today. The challenge is in the design and reproducible fabrication of biocompatible and bioresorbable polymers, with suitable surface chemistry, desirable mechanical properties, and the wanted degradation profile. These material properties can be achieved in various manners, including the synthesis of homo- and copolymers along with linear and star-shaped architectures. In many applications the materials’ three-dimensional structure is almost as important as its composition and porous scaffolds with high porosity and interconnected pores that facilitate the in-growth of cells and transportation of nutrients and metabolic waste is desired.

In this work linear and star-shaped polymers have been synthesized by ring-opening polymerization using a stannous-based catalyst and a spirocyclic tin initiator. A series of linear copolymers with various combinations of 1,5-dioxepane-2-one (DXO), Llactide (LLA) and ε-caprolactone (CL) have been polymerized using stannous octoate as catalyst. It is shown that the composition of the polymers can be chosen in such a manner that the materials’ mechanical and thermal properties can be predetermined. A solvent-casting and particulate leaching scaffold preparation technique has been developed and used to create three-dimensional structures with interconnected pores. The achieved physical properties of these materials’ should facilitate their use in both soft and hard tissue regeneration.

Well defined star-shaped polyesters have been synthesized using a spirocyclic tin initiator where L-lactide was chosen as a model system for the investigation of the polymerization kinetics. Neither the temperature nor the solvent affects the molecular weight or the molecular weight distribution of the star-shaped polymers, which all show a molecular weight distribution below 1.19 and a molecular weight determined by the initial monomer-to-initiator concentration.

Place, publisher, year, edition, pages
Stockholm: KTH, 2005. 47 p.
Series
Trita-FPT-Report, ISSN 1652-2443 ; 2005:36
Keyword
ring-opening polymerization, porous scaffold, L-lactide, 5-dioxepane-2-one, ε-caprolactone, spirocyclic initiator, star-shaped polyester
National Category
Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-493 (URN)91-7178-182-X (ISBN)
Presentation
2005-11-25, Salongen, KTHB, Osquara backe 31, Stockholm, 11:00
Opponent
Supervisors
Note
QC 20101217Available from: 2005-11-17 Created: 2005-11-17 Last updated: 2010-12-17Bibliographically approved

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Odelius, KarinFinne, Anna

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