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- W4313528985 abstract "Motivated by the need for sustainable, bio-based materials, the living anionic polymerization of the under-explored terpene monomer β-ocimene (Oc) was investigated for the first time. Homopolymers with Mn up to 50 kg mol–1 of the Oc isomeric mixture (E:Z = trans:cis = 70:30) were synthesized in cyclohexane and analyzed with respect to molecular weight control, dispersity, microstructure, and glass transition temperature, Tg. Employing styrene as a comonomer, diblock copolymers, and a series of statistical copolymers with Mn up to 20 kg mol–1 with varying comonomer compositions offered the opportunity to tailor the glass transition of the copolymers. Real-time 1H nuclear magnetic resonance (NMR) kinetics indicated a remarkably divergent reactivity of the trans and cis isomers. This unveiled the unique observation that the homopolymerization of Oc is in fact a copolymerization of the cis and trans isomers, which one might name as “stereo-copolymerization” (rtrans = 3.16; rcis = 0.32). Kinetic studies of the statistical copolymerization of the Oc isomeric mixture with styrene revealed an astonishingly contradictory reactivity of the two isomers (rtrans < rcis). The reactivity differences of the cis and trans isomers in the polymerization were utilized to isolate the individual isomers for the first time. Subsequently, they were independently homo- and copolymerized with styrene. The complex mechanism of these polymerizations and the rather high polymer dispersities (Đ ≈ 1.6–2) are discussed using various kinetic models supported by density functional theory modeling. The surprisingly different behavior of the two isomers with styrene was validated experimentally via a 1H NMR-monitored chemical titration." @default.
- W4313528985 created "2023-01-06" @default.
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- W4313528985 date "2023-01-03" @default.
- W4313528985 modified "2023-10-03" @default.
- W4313528985 title "Anionic Polymerization of the Terpene-Based Diene β-Ocimene: Complex Mechanism Due to Stereoisomer Reactivities" @default.
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- W4313528985 doi "https://doi.org/10.1021/acs.macromol.2c02241" @default.
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