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Polymers 2015, 7(3), 418-452; doi:10.3390/polym7030418

Facile Synthesis of Well-Defined MDMO-PPV Containing (Tri)Block—Copolymers via Controlled Radical Polymerization and CuAAC Conjugation

1
Polymer Reaction Design (PRD) Group, Instituut voor Materiaalonderzoek (IMO), Hasselt University, Agoralaan Building D, Diepenbeek B-3590, Belgium
2
Institute for Polymer Chemistry and Chemical Technology, Preparative Macromolecular Chemistry, Karlsruhe Institute of Technology, Engesser str. 18, Karlsruhe 76128, Germany
3
IMEC associated laboratory IMOMEC, Wetenschapspark 1, Diepenbeek B-3590, Belgium
*
Author to whom correspondence should be addressed.
Academic Editor: Alexander Böker
Received: 18 January 2015 / Revised: 6 February 2015 / Accepted: 12 February 2015 / Published: 24 February 2015
(This article belongs to the Special Issue Precision Polymer Synthesis)

Abstract

A systematic investigation into the chain transfer polymerization of the so-called radical precursor polymerization of poly(p-phenylene vinylene) (PPV) materials is presented. Polymerizations are characterized by systematic variation of chain transfer agent (CTA) concentration and reaction temperature. For the chain transfer constant, a negative activation energy of −12.8 kJ·mol−1 was deduced. Good control over molecular weight is achieved for both the sulfinyl and the dithiocarbamate route (DTC). PPVs with molecular weights ranging from thousands to ten thousands g·mol−1 were obtained. To allow for a meaningful analysis of the CTA influence, Mark–Houwink–Kuhn–Sakurada (MHKS) parameters were determined for conjugated MDMO-PPV ([2-methoxy-5-(3',7'-dimethyloctyloxy)]-1,4-phenylenevinylene) to α = 0.809 and k = 0.00002 mL·g−1. Further, high-endgroup fidelity of the CBr4-derived PPVs was proven via chain extension experiments. MDMO-PPV-Br was successfully used as macroinitiator in atom transfer radical polymerization (ATRP) with acrylates and styrene. A more polar PPV counterpart was chain extended by an acrylate in single-electron transfer living radical polymerization (SET-LRP). In a last step, copper-catalyzed azide alkyne cycloaddition (CuAAC) was used to synthesize block copolymer structures. Direct azidation followed by macromolecular conjugation showed only partial success, while the successive chain extension via ATRP followed by CuAAC afforded triblock copolymers of the poly(p-phenylene vinylene)-block-poly(tert-butyl acrylate)-block-poly(ethylene glycol) (PPV-b-PtBuA-b-PEG). View Full-Text
Keywords: poly(p-phenylene vinylene); MDMO-PPV; radical polymerization; chain transfer polymerization; (tri)block copolymers; ATRP; CuAAC poly(p-phenylene vinylene); MDMO-PPV; radical polymerization; chain transfer polymerization; (tri)block copolymers; ATRP; CuAAC
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

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MDPI and ACS Style

Zaquen, N.; Vandenbergh, J.; Schneider-Baumann, M.; Lutsen, L.; Vanderzande, D.; Junkers, T. Facile Synthesis of Well-Defined MDMO-PPV Containing (Tri)Block—Copolymers via Controlled Radical Polymerization and CuAAC Conjugation. Polymers 2015, 7, 418-452.

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