Citation: Hong-ran Fu, Yun-yun Song, Xiao-rui Ren, Fang Guo. Copolymerization of Myrcene and Butadiene Catalyzed by Half-sandwich Scandium Complexes[J]. Acta Polymerica Sinica, ;2018, 0(11): 1416-1421. doi: 10.11777/j.issn1000-3304.2018.18088 shu

Copolymerization of Myrcene and Butadiene Catalyzed by Half-sandwich Scandium Complexes

State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian 116024

Corresponding author: Fang Guo, guofang@dlut.edu.cn
Received Date: 21 March 2018
Revised Date: 8 April 2018
Available Online: 19 July 2018

Polymerization of myrcene and its copolymerization with butadiene by half-sandwich scandium complexes, (C₅Me₄SiMe₃)Sc(CH₂SiMe₃)₂(THF) (1) and Cp′Sc(CH₂C₆H₄NMe₂-o)₂ (2: Cp′ = C₅Me₄SiMe₃; 3: Cp′ = C₅H₅), have been examined. The microstructures and thermal properties of the obtained polymers were characterized by ¹H-NMR, ¹³C-NMR, GPC and DSC. Significant ligand influence on the catalytic activity, selectivity, and polymer molecular weight has been observed in the homopolymerization of myrcene. The scandium complexes 1 and 2 bearing large C₅Me₄SiMe₃ ligand showed relatively low activity (10⁴ g polymer mol_Sc⁻¹ h⁻¹) and preferred 3,4-selectivity (74% for 1 and 61% for 2). The myrcene homopolymers prepared by complexes 1 and 2 have low molecular weight (M_n = 1.7 × 10⁴ − 5.6 × 10⁴) and relatively high glass transition temperature (−48 and −45 °C). The complex 3 bearing small C₅H₅ ligand showed high activity (10⁵ g polymer mol_Sc⁻¹ h⁻¹) and high cis-1,4-selectivity (95%). The myrcene homopolymers prepared by complex 3 have high molecular weight (M_n = 7.0 × 10⁴ − 2.31 × 10⁵) and low glass transition temperature (T_g = −70 °C). By use of complex 3, the copolymerization of myrcene with butadiene was also achieved for the first time to afford a novel family of rubber materials. The copolymerization reaction was completed within 5 min, irrespective of the monomer feed ratio, and the copolymerization activity was raised to as high as 10⁵ g polymer mol_Sc⁻¹ h⁻¹. The copolymer composition was in agreement with the co-monomer feed ratio, suggesting that both monomers were completely incorporated into their copolymers. The obtained myrcene-butadiene copolymers showed a random monomer sequence distribution, and the cis-1,4 contents of both monomers in the copolymers were more than 92%. All of these copolymers showed a single T_g varing with the myrcene/butadiene ratio. The T_gs of the copolymers with myrcene content of 19 mol% − 75 mol% fell in a range of −95 °C to −71 °C, which are between those of homopolymyrcene (−70 °C) and homopolybutadiene (−107 °C). The T_g of the copolymers decreased with increasing butadiene content. The molecular weight of the myrcene-butadiene copolymers can be controlled simply by changing the monomer/catalyst ratio.
- Scandium,
- Myrcene,
- Butadiene,
- Copolymerization
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沈阳化工大学材料科学与工程学院沈阳 110142

Copolymerization of Myrcene and Butadiene Catalyzed by Half-sandwich Scandium Complexes

南开大学师唯/华北电力大学（保定）刘景维：二维配位聚合物中有序的亲锂冠醚位点用于无枝晶锂沉积

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通讯作者: 陈斌, bchen63@163.com