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Macromolecular Design via an Organocatalytic, Monomer-Specific and Temperature-Dependent "On/Off Switch": High Precision Synthesis of Polyester/Polycarbonate Multiblock Copolymers
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: 0000-0002-5850-8873
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
2015 (English)In: Macromolecules, ISSN 0024-9297, E-ISSN 1520-5835, Vol. 48, no 6, 1703-1710 p.Article in journal (Refereed) Published
Abstract [en]

The employment of a monomer-specific on/off switch was used to synthesize a nine-block copolymer with a predetermined molecular weight and narrow distribution (D = 1.26) in only 2.5 h. The monomers consisted of a six-membered cyclic carbonate (i.e., 2-allyloxymethyl-2-ethyl-trimethylene carbonate (AOMEC)) and epsilon-caprolactone (epsilon CL), which were catalyzed by 1,5,7-triazabicyclo[4.4.0]-dec-5-ene (TBD). The dependence of polymerization rate with temperature was different for the two monomers. Under similar reaction conditions, the ratio of the apparent rate constant of AOMEC and epsilon CL [k(p)(app)(AOMEC)/k(p)(app)(epsilon CL)] changes from 400 at T = -40 degrees C to 50 at T = 30 degrees C and 10 at T = 100 degrees C. Therefore, by decreasing the copolymerization temperature from 30 degrees C to -40 degrees C, the conversion of epsilon CL can be switched off, and by increasing the temperature to 30 degrees C, the conversion of epsilon CL can be switched on again. The addition of AOMEC at T = -40 degrees C results in the formation of a pure carbonate block. The cyclic addition of AOMEC to a solution of epsilon CL along with a simultaneous temperature change leads to the formation of multiblock copolymers. This result provides a new straightforward synthetic route to degradable multiblock copolymers, yielding new interesting materials with endless structural possibilities.

Place, publisher, year, edition, pages
2015. Vol. 48, no 6, 1703-1710 p.
National Category
Polymer Technologies
Identifiers
URN: urn:nbn:se:kth:diva-165214DOI: 10.1021/acs.macromol.5b00254ISI: 000351792200011Scopus ID: 2-s2.0-84925424349OAI: oai:DiVA.org:kth-165214DiVA: diva2:810192
Note

QC 20150506

Available from: 2015-05-06 Created: 2015-04-24 Last updated: 2017-12-04Bibliographically 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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Odelius, Karin

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