Efficient Switching of RAFT to Hydroxy Capped Polymers as Versatile Scaffolds for Block Copolymer Synthesis
Final Report Abstract
As a summary of the project, it can be stated that the thiocarbonyl thio to OH switch of RAFT based polymers functions well for most polymer and RAFT agent classes. The resulting sulfur-free narrow dispersity block copolymers can be efficiently employed in ROP chain extension reactions to prepare linear and star block copolymers as well as polyaddition polymers based on RAFT segments, which can be readily imaged with two dimensional chromatographic techniques. The introduction of cyclopentadienyl functionality into polymers is best conducted via a –Br to Cp switch based on nickelocene, rather than by transforming OH terminal polymers via a tosylation and subsequent nucleophilic substitution by Cp-. The block copolymer formation based on Cp terminal units with activated dithioester capped macromolecules proceeds fast and efficient, while the preparation of star polymers via such a route is beset with end group fidelity limitations.
Publications
- "Facile Conversion of RAFT Polymers into Hydroxyl Functional Polymers: A Detailed Investigation of Variable Monomer and RAFT Agent Combinations". Polym. Chem. 2010, 1, 634-644
Dietrich, M.; Glassner, M.; Gruendling, T.; Schmid, C.; Falkenhagen, J.; Barner- Kowollik, C.
(See online at https://doi.org/10.1039/B9PY00273A) - "An Efficient Avenue to Poly(styrene)-block-(-Caprolactone) Polymers via Switching from RAFT to Hydroxyl Functionality: Synthesis and Characterization" J. Polym. Sci. – Polym. Chem. 2011, 49, 1-10
Schmid, C.; Falkenhagen, J.; Barner-Kowollik, C.
(See online at https://doi.org/10.1002/pola.24299) - "Visualizing the Efficiency of Rapid Modular Block Copolymer Construction". Polym. Chem. 2011, 2, 126-136
Inglis, A. J.; Barner-Kowollik, C.
(See online at https://doi.org/10.1039/C0PY00189A) - "Efficient Switching of RAFT to Hydroxyl Capped Polymers as a Versatile Scaffold for Block Copolymer Synthesis". Dissertation, 2012
Christina Schmid
- "In-Depth LCCC-(GELC)-SEC Characterization of ABA Block Copolymers Generated by a Mechanistic Switch from RAFT to ROP". Macromolecules 2012, 45, 87-99
Schmid, C.; Weidner, S.; Falkenhagen, J.; Barner-Kowollik, C.
(See online at https://doi.org/10.1021/ma2022452) - "Multi-Block Polyurethanes via RAFT End-group Switching and their Characterization by Advanced Hyphenated Techniques". Macromolecules 2012, 45, 6353−6362
Schmid, C.; Falkenhagen, J.; Beskers, T. F.; Nguyen, L.-T. T.; Wilhelm, M.; Du Prez, F. E.; Barner-Kowollik, C.
(See online at https://doi.org/10.1021/ma301117k)
