Citation: Wei Liu, Yun-yun Song, Kai-ying Diao, Fang Guo. Copolymerization of Myrcene with Styrene Catalyzed by Half-sandwich Scandium Complexes[J]. Acta Polymerica Sinica, ;2019, 50(9): 957-963. doi: 10.11777/j.issn1000-3304.2019.19056 shu

Copolymerization of Myrcene with Styrene Catalyzed by Half-sandwich Scandium Complexes

State Key Laboratory of Fine Chemicals, Department of Polymer Science and Engineering, School of Chemical Engineering, Dalian University of Technology, Dalian 116024

Corresponding author: Fang Guo, guofang@dlut.edu.cn
Received Date: 20 March 2019
Available Online: 10 May 2019

The copolymerization of myrcene with styrene by the half-sandwich scandium complexes (C₅H₅)Sc(CH₂SiMe₃)₂(THF) ( 1 ) and (C₅Me₄SiMe₃)Sc(CH₂SiMe₃)₂(THF) ( 2 ) was studied. The structures and thermal properties of the obtained copolymers were characterized by NMR, GPC and DSC. The copolymerization of myrcene with styrene at room temperature had been achieved and the copolymerization activity reached up to 10⁴ g polymer mol_Sc^–1 h^–1. The myrcene-styrene copolymers with controllable compositions (myrcene content = 22 mol% – 83 mol%), high molecular weight (M_n = 4.8 × 10⁴ – 11.3 × 10⁴) and narrow molecular weight distribution (M_w/M_n = 1.49 – 1.99) were conveniently obtained by changing the feed ratio of myrcene and styrene. Significant influence of catalyst structure on the stereoselectivity and comonomer distribution sequences in the resulting copolymers was observed. In the copolymerization of myrcene and styrene catalyzed by scandium complex 1 , styrene started to incorporate into chains after myrene was almost completely consumed, and diblock copolymers containing cis-1,4-polymyrcene (selectivity 95%) block and atactic polystyrene block were obtained. The obtained copolymers with different myrcene contents possessed two glass transition temperatures (T_g, – 63 and 96 °C), close to those of cis-1,4-polymyrcene and atactic polystyrene. In contrast, in the copolymerization of myrcene and styrene catalyzed by scandium complex 2 , myrene content showed a gradient decline accompanied by styrene content increasing gradually, producing gradient copolymers containing 3,4-polymyrcene (3,4-selectivity 75%, cis-1,4-selectivity 25%) and syndiotactic polystyrene. The obtained copolymers with different myrcene contents possessed a T_g at –35 °C and a melting temperature (T_m) at 254 °C, originating from polymyrcene block and syndiotactic polystyrene block, respectively. There is a great difference in the reactivity ratios between myrcene and styrene in the copolymerization catalyzed by scandium 1 (r_My >> r_St). However, the gap between the reactivity ratios of myrcene and styrene in the copolymerization catalyzed by scandium complex 2 was much smaller (r_My = 8.47, r_St = 0.76) and gradient copolymers were generated.
- Scandium,
- Myrcene,
- Styrene,
- Copolymerization
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沈阳化工大学材料科学与工程学院沈阳 110142