Addition-Isomerization Polymerization of Chiral Phosphaalkenes: Observation of Styrene–Phosphaalkene Linkages in a Random Copolymer
| Autor: | Spencer C. Serin, Derek P. Gates, Gregory R. Dake |
|---|---|
| Rok vydání: | 2016 |
| Předmět: |
Polymers and Plastics
010405 organic chemistry Organic Chemistry Radical polymerization Nuclear magnetic resonance spectroscopy 010402 general chemistry 01 natural sciences 0104 chemical sciences Styrene Inorganic Chemistry chemistry.chemical_compound Monomer Polymerization chemistry Polymer chemistry Materials Chemistry Copolymer Phosphaalkene Isomerization |
| Zdroj: | Macromolecules. 49:4067-4075 |
| ISSN: | 1520-5835 0024-9297 |
| DOI: | 10.1021/acs.macromol.6b00667 |
| Popis: | These studies provide the first evidence for styrene–phosphaalkene connectivities in a phosphaalkene copolymer. The synthesis and structural characterization of new phosphaalkene–oxazolines, ArP═C(Ph)(3-C6H4Ox) [1a,b, Ar = Mes (1a), Mes* (1b), Ox = CNOCH(iPr)CH2], are reported. The radical-initiated homo- and copolymerization of 1a with styrene affords P-functional poly(methylenephosphine) (4a: Mn = 5300 g mol–1, PDI = 1.2) and poly(methylenephosphine-co-styrene) (5a: Mn = 4000 g mol–1, PDI = 1.1). Multinuclear NMR spectroscopic analyses of 4a and 5a provided evidence for the predominance of an addition-isomerization mechanism for the radical polymerization of 1a. In addition, signals could be assigned to CHPh–P(CHPhAr) (i.e., S–1a) and ArCH2–CH2 (i.e., 1a–S) linkages in copolymer 5a. With a monomer feed ratio of 1a:S (1:2, 33 mol % 1a) the inverse gated 13C{1H} NMR spectrum suggested an incorporation of 19 mol % 1a in copolymer 5a. Polymers 4a and 5a were further functionalized to Au(I)-containing macrom... |
| Databáze: | OpenAIRE |
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