Polymers 2017, 9(4), 139; https://doi.org/10.3390/polym9040139
Stereoregular Brush Polymers and Graft Copolymers by Chiral Zirconocene-Mediated Coordination Polymerization of P3HT Macromers
1
Department of Chemistry, Colorado State University, Fort Collins, CO 80523-1872, USA
2
School of Fundamental Sciences, China Medical University, Shenyang 110122, China
3
Department of Chemical and Biological Engineering, Colorado State University, Fort Collins, CO 80523-1370, USA
4
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China
*
Authors to whom correspondence should be addressed.
Academic Editor: Marinos Pitsikalis
Received: 22 March 2017 / Revised: 8 April 2017 / Accepted: 10 April 2017 / Published: 13 April 2017
(This article belongs to the Special Issue Metal Complexes-Mediated Catalysis in Polymerization)
Abstract
Two poly(3-hexylthiophene) (P3HT) macromers containing a donor polymer with a polymerizable methacrylate (MA) end group, P3HT-CH2-MA and P3HT-(CH2)2-MA, have been synthesized, and P3HT-(CH2)2-MA has been successfully homopolymerized and copolymerized with methyl methacrylate (MMA) into stereoregular brush polymers and graft copolymers, respectively, using chiral ansa-zirconocene catalysts. Macromer P3HT-CH2-MA is too sterically hindered to polymerize by the current Zr catalysts, but macromer P3HT-(CH2)2-MA is readily polymerizable via either homopolymerization or copolymerization with MMA in a stereospecific fashion with both C2-ligated zirconocenium catalyst 1 and Cs-ligated zirconocenium catalyst 2. Thus, highly isotactic (with mm% ≥ 92%) and syndiotactic (with rr% ≥ 93%) brush polymers, it-PMA-g-P3HT and st-PMA-g-P3HT, as well as well-defined stereoregular graft copolymers with different grafted P3HT densities, it-P(M)MA-g-P3HT and st-P(M)MA-g-P3HT, have been synthesized using this controlled coordination-addition polymerization system under ambient conditions. These stereoregular brush polymers and graft copolymers exhibit both thermal (glass and melting) transitions with Tg and Tm values corresponding to transitions within the stereoregular P(M)MA and crystalline P3HT domains. Acceptor molecules such as C60 can be effectively encapsulated inside the helical cavity of st-P(M)MA-g-P3HT to form a unique supramolecular helical crystalline complex, thus offering a novel strategy to control the donor/acceptor solar cell domain morphology. View Full-Text
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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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Wang, Y.; Bailey, T.S.; Hong, M.; Chen, E.Y.-X. Stereoregular Brush Polymers and Graft Copolymers by Chiral Zirconocene-Mediated Coordination Polymerization of P3HT Macromers. Polymers 2017, 9, 139.
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