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Photoinduced synthesis of α,ω-telechelic sequence-controlled multiblock copolymers
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Anastasaki, Athina, Nikolaou, Vasiliki, McCaul, Nicholas William, Simula, Alexandre, Godfrey, Jamie, Waldron, Christopher, Wilson, Paul, Kempe, Kristian and Haddleton, David M. (2015) Photoinduced synthesis of α,ω-telechelic sequence-controlled multiblock copolymers. Macromolecules, 48 (5). pp. 1404-1411. doi:10.1021/acs.macromol.5b00058 ISSN 0024-9297 .
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Official URL: http://dx.doi.org/10.1021/acs.macromol.5b00058
Abstract
Photoinduced living radical polymerization has been employed to synthesize α,ω-telechelic multiblock copolymers of a range of acrylic monomers including methyl acrylate (MA), ethyl acrylate (EA), ethylene glycol methyl ether acrylate (EGA), and solketal acrylate (SA). Under carefully optimized conditions, a well-defined tricosablock (23 blocks) copolymer was obtained (Đ = 1.18) with high conversion (>98%) achieved throughout all the iterative monomer additions. Crucially, a reduced temperature (15 °C) was found to result in an observed decrease in the dispersities (1.14 vs 1.45) as opposed to when higher temperatures (50 °C) were employed. A number of bifunctional initiators were employed, including ethylene bis(2-bromoisobutyrate) (EbBiB), a PEG initiator (average Mw = 1000 g mol–1), and bis[2-(2′-bromoisobutyryloxy)ethyl] disulfide ((BiBOE)2S2), resulting in narrow dispersed multiblock copolymers in various molecular weights (DPn ∼ 2/13/50/100 per block). Impressively, a high molecular weight undecablock (11 blocks) copolymer of Mn = 150 000 g mol–1 and Đ = 1.22 was also synthesized. In order to demonstrate the symmetry of the resulting telechelic materials, a well-defined tridecablock (13 blocks, Đ = 1.18, Mn = 25 000 g mol–1) was synthesized utilizing a bifunctional disulfide initiator which was cleaved postpolymerization, yielding a narrow disperse polymer at half the molecular weight of the parent polymer (Đ = 1.10, Mn = 12 400 g mol–1).
| Item Type: | Journal Article | ||||||
|---|---|---|---|---|---|---|---|
| Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry | ||||||
| Journal or Publication Title: | Macromolecules | ||||||
| Publisher: | American Chemical Society | ||||||
| ISSN: | 0024-9297 | ||||||
| Official Date: | 27 February 2015 | ||||||
| Dates: |
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| Volume: | 48 | ||||||
| Number: | 5 | ||||||
| Page Range: | pp. 1404-1411 | ||||||
| DOI: | 10.1021/acs.macromol.5b00058 | ||||||
| Status: | Peer Reviewed | ||||||
| Publication Status: | Published | ||||||
| Access rights to Published version: | Restricted or Subscription Access | ||||||
| Adapted As: |
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