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Reactive imidazole intermediates: simplified synthetic approach to functional aliphatic cyclic carbonates
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology.
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.ORCID iD: 0000-0001-7543-5322
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.ORCID iD: 0000-0001-6112-0450
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2014 (English)In: Polymer Chemistry, ISSN 1759-9954, E-ISSN 1759-9962, Vol. 5, no 23, p. 6651-6655Article in journal (Refereed) Published
Abstract [en]

Reactive imidazole intermediates based on AB(2) and A(3) monomers, i.e. bis(methylol) propionic acid (bis-MPA) and trimethylolpropane (TMP) have successfully been synthesized and isolated on a 100 gram scale via a facile synthetic protocol using 1,1' -carbonyldiimidazole (CDI) as a key reagent. The robustness of the imidazole intermediates as bench stable precursors enabled the synthesis of a library of functional cyclic carbonates bearing relevant functionalities including hydrophilic PEGs, bioactive cholesterol and clickable groups. A number of functional polycarbonates were obtained by ring-opening polymerization, and their relevance in biomedical applications was highlighted by their low cytotoxicity on human dermal fibroblasts (hDF).

Place, publisher, year, edition, pages
Royal Society of Chemistry, 2014. Vol. 5, no 23, p. 6651-6655
Keywords [en]
Cyclic carbonates, Synthetic approach
National Category
Polymer Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-157251DOI: 10.1039/c4py00911hISI: 000344374500003Scopus ID: 2-s2.0-84908471876OAI: oai:DiVA.org:kth-157251DiVA, id: diva2:769538
Funder
Knut and Alice Wallenberg Foundation, 2012-0196Swedish Research Council, 2010-453
Note

QC 20141208

Available from: 2014-12-08 Created: 2014-12-08 Last updated: 2018-03-22Bibliographically approved
In thesis
1. Versatile Synthetic Strategies to Highly Functional Polyesters and Polycarbonates
Open this publication in new window or tab >>Versatile Synthetic Strategies to Highly Functional Polyesters and Polycarbonates
2018 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Polymers have become ubiquitous in today’s society and are found in everything from household items to airplanes and automobiles. Synthetic polymeric materials are as diverse as their applications and their final properties are highly reliant on the building blocks and methods used to assemble them. In the field of biomedical materials, polyesters and polycarbonates have been hailed as excellent materials in large part due to their inherent hydrolytic degradability. With this in mind, careful choice of monomers can ensure that materials not only conform to the desired physical properties, but also elicit a favorable biological response. The utilization of post-polymerization modification of these promising materials has the capability of opening up further avenues to target even more advanced applications. Unfortunately, rigorous and difficult reaction conditions, including multi-step synthesis have to a certain extent held back the adoption of these complex functional materials in applied research. In a pragmatic approach, a sustainable framework was developed in this thesis to seek out more practical methods, limiting the amount of reaction steps and overtly hazardous chemicals.

In a first study, we set out to simplify and scale-up the synthesis of cyclic carbonates with pendant functional groups, capable of undergoing controlled ring-opening polymerization. By avoiding the use of protective-group chemistry we were able two devise a two-step method to create a library of functional monomers. Results in this study show that reactive intermediates could be isolated on 100 g scales, which in a second step was functionalized with a desired alcohol.

With this framework in mind, key practical decisions were made to drastically re-think the work up procedures for greater scalability of bis-MPA dendrimers. In this work, a more efficient, scalable and sustainable approach was devised. Elimination of traditional arduous purification steps led to the synthesis of monodisperse dendrimers up to the sixth generation, with 192 functional groups on 50 g scales. Further work included the omission of protective group-chemistry, using orthogonal functional groups to cut the number of synthetic steps by half.

The know-how developed in the first two projects led us to pursue greater scalability of functional polycarbonates through a simpler polymerization technique. The method allowed the step-growth polymerization of functional materials from more easily accessible monomers isolated on 100 g scales. Subsequent polymerization afforded materials with glass transition temperatures in the range of -45 °C to 169 °C. The method served as a complement to cyclic carbonates, offering a wider range of functional monomers. Furthermore, by careful choice of assembly method, both alternating and scrambled compositions could be achieved.

In a final study, we set out to take advantage of the scrambling mechanism. Control of the final composition of highly rigid degradable polycarbonates was pursued, using renewable building-blocks derived from sugar. In a proof of concept study, thermal and hydrolytic stability of these materials is shown to be dependent on both amount and configuration of each monomer in the final material.

Place, publisher, year, edition, pages
KTH Royal Institute of Technology, 2018. p. 60
Series
TRITA-CBH-FOU ; 2018:6
National Category
Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-224754 (URN)978-91-7729-711-6 (ISBN)
Public defence
2018-04-13, Kollegiesalen, Brinellvägen 8, Stockholm, 10:00 (English)
Opponent
Supervisors
Note

QC 20180322

Available from: 2018-03-22 Created: 2018-03-22 Last updated: 2018-03-22Bibliographically approved

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Hult, DanielGarcia-Gallego, SandraMalkoch, Michael

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