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L-lactide macromonomer synthesis initiated by new cyclic tin alkoxides functionalized for brushlike structures
KTH, Superseded Departments, Polymer Technology.ORCID iD: 0000-0002-1922-128X
KTH, Superseded Departments, Polymer Technology.
2001 (English)In: Macromolecules, ISSN 0024-9297, E-ISSN 1520-5835, Vol. 34, no 21, 7281-7287 p.Article in journal (Refereed) Published
Abstract [en]

L-Lactide macromonomers with an incorporated double bond were successfully synthesized by controlled ring-opening polymerization initiated by two new cyclic tin alkoxides (1,1-di-n-butyl-stanna-2,7-dioxacyclo-4-heptene and 9,9,20,20-tetrabutyl-8,10,19,21-tetraoxa-9,20-distanna-dispiro[5.5.5.5]d ocosa-2,14-diene). Initiators and crude reaction mixtures were characterized by NMR. H-1 NMR analysis showed that the initiators were completely reacted in the polymerization and that both tin-oxygen bonds were reactive and participated in propagation. The polymerizations were performed in chloroform at 60 degreesC, and the molecular weight was effectively controlled by adjusting the monomer-to-initiator ratio. The molecular weight distribution was narrow (<1.1) for both high and low molecular weights (3000-72 000 g/mol). A plot of M-n vs conversion was linear up to a conversion of 98%, showing a system propagating in a controlled manner. The kinetic investigation showed that all of the polymerizations were first order in monomer and that no termination reactions occurred during polymerization.

Place, publisher, year, edition, pages
2001. Vol. 34, no 21, 7281-7287 p.
Keyword [en]
ring-opening polymerization, poly(l-lactide) macromonomers, macrocyclic polymerization, multiblock copolymers, aluminum alkoxides, graft-copolymers, polylactones, polyesters, pentaerythritol, caprolactone
National Category
Polymer Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-13186DOI: 10.1021/ma0106898ISI: 000171386300011OAI: oai:DiVA.org:kth-13186DiVA: diva2:321693
Note
QC 20100602Available from: 2010-06-02 Created: 2010-06-02 Last updated: 2017-12-12Bibliographically approved
In thesis
1. Novel Possibilities for Advanced Molecular Structure Design for Polymers and Networks
Open this publication in new window or tab >>Novel Possibilities for Advanced Molecular Structure Design for Polymers and Networks
2003 (English)Doctoral thesis, comprehensive summary (Other scientific)
Abstract [en]

Synthetic and degradable polymers are an attractive choicein many areas, since it is possible to control the way in whichthey are manufactured; more specifically, pathways tomanipulate the architecture, the mechanical properties and thedegradation times have been identified. In this work,L-lactide, 1,5-dioxepan-2-one and ε-caprolactone were usedas monomers to synthesize polymers with different architecturesby ring-opening polymerization. By using novel initiators,triblock copolymers, functionalized linear macromonomers andstar-shaped aliphatic polyesters with well-defined structureshave been synthesized. To synthesize triblock copolymers,cyclic germanium initiators were studied. The polymerizationproceeded in a controlled manner although the reaction rateswere low. To introduce functionality into the polymer backbone,functionalized cyclic tin alkoxides were prepared and used asinitiators. During the insertion-coordination polymerization,the initiator fragment consisting mainly of a double bond wasincorporated into the polymer backbone. The double bond wasalso successfully epoxidized and this gave unique possibilitiesof synthesizing graft polymers with precise spacing. Themacromonomer technique is a very effective method for producingwell-defined graft polymers. Spirocyclic tin initiators weresynthesized and used to construct star-shaped polymers. Thestar-shaped polymers were subsequently crosslinked in apolycondensation reaction. These crosslinked structures swelledin water, and swelling tests showed that by changing thestructure of the hydrogel network, the degree of swelling canbe altered. A first evaluation of the surface characteristicsof the linear triblock copolymers was also performed. AFManalysis of the heat-treated surfaces revealed nanometer-scalefibers and tests showed that keratinocytes were able to growand proliferate on these surfaces.

Place, publisher, year, edition, pages
Stockholm: KTH, 2003. 78 p.
Keyword
ring-opening polymerization, coordination-insertion, germanium, cyclic tin alkoxides, spirocyclic initiators, poly(L-lactide), poly(1, 5-dioxepan-2-one), triblock, star-shaped, network, functionalization, morphology, AFM
National Category
Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-3623 (URN)91-7283-577-X (ISBN)
Public defence
2003-10-31, 00:00 (English)
Note
QC 20100602Available from: 2003-10-28 Created: 2003-10-28 Last updated: 2010-06-02Bibliographically approved

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