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Influence of grafting density and distribution on material properties using well-defined alkyl functional poly(styrene-co-maleic anhydride) architectures synthesized by RAFT
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Moriceau, Guillaume, Tanaka, Joji, Lester, Daniel, Pappas, George S., Cook, Alexander B., O’Hora, Paul, Winn, Joby, Smith, Timothy and Perrier, Sébastien (2019) Influence of grafting density and distribution on material properties using well-defined alkyl functional poly(styrene-co-maleic anhydride) architectures synthesized by RAFT. Macromolecules, 52 (4). pp. 1469-1478. doi:10.1021/acs.macromol.8b02231 ISSN 0024-9297 .
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WRAP-influence-grafting-density-distribution-material-properties-well-defined-alkyl-functional-poly(styrene-co-maleic anhydride)-architectures-synthesized-RAFT-Perrier-2019.pdf - Accepted Version - Requires a PDF viewer. Download (1953Kb) | Preview |
Official URL: http://dx.doi.org/10.1021/acs.macromol.8b02231
Abstract
Poly(styrene-co-maleic anhydride) copolymers (PSMA) with controlled number and distribution of maleic anhydride (MAnh) units were synthesized by reversible addition–fragmentation chain transfer polymerization using chain-transfer agents (CTA) suitable for industrial scale processes. Linear- and star-shaped alternating PSMA polymers were prepared in a single-step synthesis, while a one-pot sequential chain-extension strategy was utilized to prepare diblock, multiblock, and multisite copolymer architectures. A library of grafted PSMAs with controlled density and distribution of side chains was achieved by the subsequent grafting of long aliphatic alcohol chains (C22) to the MAnh units. The influence of structure, composition, and long alkyl chain addition on PSMAs behavior in solution was studied with triple-detection size exclusion chromatography, while their thermal properties were examined by thermogravimetric analysis and differential scanning calorimetry. Overall, the side chain density and distribution did not impact the polymer conformations in solution (random coil); however, an effect on the molecular size (Rh) and structure density (intrinsic viscosity) were observed. The materials density was shown to be dependent on polymer architectures as lower intrinsic viscosity was observed for the star copolymer. All the materials had similar degradation points (400 °C), while the rate of degradation showed a dependence on the MAnh content and polymeric architecture. Ultimately, the grafting of long aliphatic side chains (crystalline) onto the PSMA backbone, even at low density, was shown to drastically change the microphase ordering, as all the grafted copolymers became semicrystalline. The difference of the crystallization temperature between low density multisite materials (Tc ≈ 8 °C) and the high density alternating material (Tc ≈ 40 °C) highlights the major importance of controlling copolymer composition and structure to tune material properties.
Item Type: | Journal Article | ||||||||
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Subjects: | Q Science > QD Chemistry T Technology > TP Chemical technology |
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Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry Faculty of Science, Engineering and Medicine > Engineering > WMG (Formerly the Warwick Manufacturing Group) |
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Library of Congress Subject Headings (LCSH): | Polystyrene, Addition polymerization, Fragmentation reactions | ||||||||
Journal or Publication Title: | Macromolecules | ||||||||
Publisher: | American Chemical Society | ||||||||
ISSN: | 0024-9297 | ||||||||
Official Date: | 2019 | ||||||||
Dates: |
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Volume: | 52 | ||||||||
Number: | 4 | ||||||||
Page Range: | pp. 1469-1478 | ||||||||
DOI: | 10.1021/acs.macromol.8b02231 | ||||||||
Status: | Peer Reviewed | ||||||||
Publication Status: | Published | ||||||||
Reuse Statement (publisher, data, author rights): | This document is the Accepted Manuscript version of a Published Work that appeared in final form in Macromolecules, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.macromol.8b02231 | ||||||||
Access rights to Published version: | Restricted or Subscription Access | ||||||||
Date of first compliant deposit: | 9 April 2019 | ||||||||
Date of first compliant Open Access: | 4 February 2020 | ||||||||
RIOXX Funder/Project Grant: |
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