Aqueous cationic homo- and co-polymerizations of β-myrcene and styrene: a green route toward terpene-based rubbery polymers

• Published in: Polymer chemistry 2018-12, Vol.9 (48), p.5690-5700
• Main Authors: Hulnik, Maksim I., Vasilenko, Irina V., Radchenko, Alexei V., Peruch, Frédéric, Ganachaud, Francois, Kostjuk, Sergei V.
• Format: Article
• Language: English
• Subjects: Catalysis; Catalysts; Cationic polymerization; Chemical Sciences; Chemical synthesis; Copolymerization; Emulsion polymerization; Glass transition temperature; Lewis acid; Molecular weight; NMR; Nuclear magnetic resonance; Polymer chemistry; Polymerization; Polymers; Sodium dodecylbenzenesulfonate; Styrenes; Surfactants; Temperature; Ytterbium
• ISSN: 1759-9954; 1759-9962
• DOI: 10.1039/C8PY01378K

Aqueous cationic polymerization of β-myrcene, a naturally occurring monomer, was performed for the first time using a water-dispersible Lewis acid surfactant combined catalyst (LASC) prepared from ytterbium chloride and a branched sodium dodecylbenzenesulfonate surfactant. At 40 °C, poly(β-myrcene)s of high molecular weight ( M n up to 150 kg mol −1 ) and low glass transition temperature ( T g < −63 °C) were obtained. They possess predominantly 1,4-units (∼43% cis and ∼50% trans ) and few 3,4-units (∼7%) together with both regular head-to-tail (62–72%) and inverse (5–10% head-to-head and 23–28% tail-to-tail) sequences. The LASC showed also high efficiency in catalyzing the emulsion cationic copolymerization of β-myrcene and styrene, affording the synthesis of random copolymers with high molecular weights ( M n from 60 to 120 kg mol −1 ) and single glass transition temperatures ( T g 's from −43 to 15 °C). Finally, a simple procedure was developed to recover the catalyst from the reaction mixture, which showed high activity in the β-myrcene emulsion cationic polymerization even after five successive cycles of extraction.