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Synthesis and polymerization of alkyl halide-functional cyclic carbonates
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Materials Chemistry, Polymer Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Materials Chemistry, Polymer Chemistry.
2011 (English)In: Polymer, ISSN 0032-3861, E-ISSN 1873-2291, Vol. 52, no 25, 5716-5722 p.Article in journal (Refereed) Published
Abstract [en]

To increase the diversity in functional aliphatic polycarbonates, a series of novel chloro- and bromo-functional six-membered cyclic carbonate monomers were synthesized. Despite asymmetry in the monomer functionalities, homopolymerization of the monomers afforded semicrystalline polycarbonates with a high tendency to crystallize from the melt and/or on precipitation from a THF solution. Melting points were found in the 90-105 degrees C or 120-155 degrees C range for polymers comprising methyl or ethyl moieties, respectively, in the backbone. The monomers were further copolymerized with trimethylene carbonate to form random copolymers. Even among some of these random copolymers elements of semicrystallinity were found as confirmed by melting endotherms in DSC. The results clearly show that the incorporation of alkyl halide functionalities in aliphatic polycarbonates may lead to materials with a high ability to form crystallites, even in random copolymers, likely driven by polar interactions due to the presence of the halide functionalities.

Place, publisher, year, edition, pages
2011. Vol. 52, no 25, 5716-5722 p.
Keyword [en]
Cyclic carbonate monomers, Polycarbonates, Semicrystalline polymers
National Category
Chemical Sciences Polymer Chemistry
Research subject
Chemistry with specialization in Polymer Chemistry
URN: urn:nbn:se:uu:diva-165694DOI: 10.1016/j.polymer.2011.10.027ISI: 000297539000004OAI: oai:DiVA.org:uu-165694DiVA: diva2:474834
Available from: 2012-01-10 Created: 2012-01-09 Last updated: 2012-04-19Bibliographically approved
In thesis
1. Functional Cyclic Carbonate Monomers and Polycarbonates: Synthesis and Biomaterials Applications
Open this publication in new window or tab >>Functional Cyclic Carbonate Monomers and Polycarbonates: Synthesis and Biomaterials Applications
2012 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The present work describes a selection of strategies for the synthesis of functional aliphatic polycarbonates. Using an end-group functionalization strategy, a series of DNA-binding cationic poly(trimethylene carbonate)s was synthesized for application as vectors for non-viral gene delivery. As the end-group functionality was identical in all polymers, the differences observed in DNA binding and in vitro transfection studies were directly related to the length of the hydrophobic poly(trimethylene carbonate) backbone and the number of functional end-groups. This enabled the use of this polymer system to explore the effects of structural elements on the gene delivery ability of cationic polymers, revealing striking differences between different materials, related to functionality and cationic charge density.

In an effort to achieve more flexibility in the synthesis of functional polymers, polycarbonates were synthesized in which the functionalities were distributed along the polymer backbone. Through polymerization of a series of alkyl halide-functional six-membered cyclic carbonates, semicrystalline chloro- and bromo-functional homopolycarbonates were obtained. The tendency of the materials to form crystallites was related to the presence of alkyl as well as halide functionalities and ranged from polymers that crystallized from the melt to materials that only crystallized on precipitation from a solution. Semicrystallinity was also observed for random 1:1 copolymers of some of the monomers with trimethylene carbonate, suggesting a remarkable ability of repeating units originating from these monomers to form crystallites.

For the further synthesis of functional monomers and polymers, azide-functional cyclic carbonates were synthesized from the bromo-functional monomers. These were used as starting materials for the click synthesis of triazole-functional cyclic carbonate monomers through Cu(I)-catalyzed azide–alkyne cycloaddition. The click chemistry strategy proved to be a viable route to obtain structurally diverse monomers starting from a few azide-functional precursors. This paves the way for facile synthesis of a wide range of novel functional cyclic carbonate monomers and polycarbonates, limited only by the availability of suitable functional alkynes.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2012. 73 p.
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 911
DNA condensation, gene delivery, ionomers, polyplexes, self-assembly, amphiphiles, biodegradable, biological applications of polymers, transfection, cyclic carbonate monomers, polycarbonates, semicrystalline polymers, click chemistry, triazoles, cycloaddition
National Category
Organic Chemistry Polymer Chemistry Biochemistry and Molecular Biology
Research subject
Chemistry with specialization in Polymer Chemistry
urn:nbn:se:uu:diva-169677 (URN)978-91-554-8310-4 (ISBN)
Public defence
2012-05-04, Häggsalen, Ångströmlaboratoriet, Uppsala, 09:00 (English)
Available from: 2012-04-13 Created: 2012-03-05 Last updated: 2012-04-19Bibliographically approved

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