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Ring-Closing Depolymerization: A Powerful Tool for Synthesizing the Allyloxy-Functionalized Six-Membered Aliphatic Carbonate Monomer 2-Allyloxymethyl-2-ethyltrimethylene Carbonate
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.ORCID iD: 0000-0002-5850-8873
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.
2014 (English)In: Macromolecules, ISSN 0024-9297, E-ISSN 1520-5835, Vol. 47, no 18, 6189-6195 p.Article in journal (Refereed) Published
Abstract [en]

Ring-dosing depolymerization is demonstrated to be a powerful synthetic methodology for the formation of six-membered functional aliphatic carbonate monomers, providing a rapid, straightforward, inexpensive, and green route for obtaining six-membered functional aliphatic carbonate monomers at a scale greater than 100g. The utility of this technique was observed via the synthesis of the allyloxy-functionalized six-membered cyclic carbonate monomer 2-allyloxymethyl-2-ethyltrimethylene carbonate (AOMEC). The synthesis was performed in a one-pot bulk reaction, starting from trimethylolpropane allyl ether, diethyl carbonate, and NaH, resulting in a final AOMEC yield of 63%. The synthetic methodology is based upon the reversible nature of this class of polymers. The anionic environment produced by NaH was observed to mediate the monomer equilibrium concentration; thus, an additional catalyst is not required to induce depolymerization. 1,5,7-Triazabicyclo[4.4.0]dec-5-ene (TBD) was demonstrated to be a very active catalyst for the ring-opening polymerization (ROP) of AOMEC, resulting in a rapid (k(p)(aPP) =28.2 s(-1)) and controlled polymerization with a low dispersity D = 1.2). The availability and activity of the functionality of poly(AOMEC)s were established through subsequent postpolymerization functionalization via the UV-initiated thiol-ene chemistry of poly(AOMEC) with 1-dodecanethiol and benzophenone as a radical initiator. The functionalization proceeded with high control and with a linear relation between the molecular weight and conversion of the unsaturation, revealing the high orthogonality of the reaction and the stability of the carbonate backbone. Hence, as a synthetic methodology, depolymerization provides a straightforward and simple approach for the synthesis of the highly versatile functional carbonate AOMEC. In addition, formation of the monomer does not require any solvents, reactive ring-dosing reagents, or transition-metal-based depolymerization catalysts, thereby providing a "greener" route for obtaining functional carbonate monomers and polymers.

Place, publisher, year, edition, pages
2014. Vol. 47, no 18, 6189-6195 p.
Keyword [en]
Opening Polymerization, Cyclic Carbonates, 2, 2-Dimethyltrimethylene Carbonate, Efficient Synthesis, Organic Carbonates, Copolymers, Esters, Polycarbonates, Mechanism, Polymers
National Category
Polymer Technologies
Identifiers
URN: urn:nbn:se:kth:diva-154373DOI: 10.1021/ma5012304ISI: 000342184700006Scopus ID: 2-s2.0-84918537979OAI: oai:DiVA.org:kth-154373DiVA: diva2:757108
Funder
EU, European Research Council, 246776
Note

QC 20141021

Available from: 2014-10-21 Created: 2014-10-20 Last updated: 2017-12-05Bibliographically approved
In thesis
1. Functional Degradable Polymers: from the monomeric point of view
Open this publication in new window or tab >>Functional Degradable Polymers: from the monomeric point of view
2015 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Degradable polymers is key, within the future vison, of creating a sustainable society were all aspects, cradle to grave, can be realized in a sustainable way. It is imperative to consider, how the monomer is formed, its polymerization, the material properties created and the final degradation behavior. In this thesis, the major focus will be placed on the three former aspects from the vantage point of the monomer. The immense variety of different monomers available within the realm of polymer chemistry necessitates a logical division among them. Herein, we make such a division according to their respective inherent thermodynamic properties and how these translate into the synthetic behavior of the corresponding polymers. These divisions are as follows: stable monomers (monomers that resist becoming polymers), meta-stable monomers (monomers for which temperature is of immense importance during polymer formation), and unstable monomers (monomers that desire to be in the polymeric state). From this viewpoint, three different investigations were conducted, thereby demonstrating the inherent advantages and disadvantages of each type together with the importance of using the “right” catalyst for the “right” monomer.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2015. 75 p.
Series
TRITA-CHE-Report, ISSN 1654-1081 ; 2015:26
National Category
Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-166872 (URN)978-91-7595-585-8 (ISBN)
Public defence
2015-06-12, D2, Lindstedtsvägen 5, KTH, Stockholm, 09:00 (English)
Opponent
Supervisors
Note

QS C 20150222

Available from: 2015-05-22 Created: 2015-05-20 Last updated: 2015-05-22Bibliographically approved

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