Citation: Jing Tian, Yin-ran Wang, Hong-ran Fu, Fang Guo. Copolymerization of Ethylene and Conjugated Dienes Catalyzed by Half-sandwich Scandium Complexes[J]. Acta Polymerica Sinica, ;2019, 50(8): 826-833. doi: 10.11777/j.issn1000-3304.2019.19020 shu

Copolymerization of Ethylene and Conjugated Dienes 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: 25 January 2019
Revised Date: 22 February 2019
Available Online: 17 April 2019

The copolymerization of ethylene with conjugated dienes such as isoprene and butadiene catalyzed by the half-sandwich scandium complexes (C₅Me₄SiMe₃)Sc(CH₂C₆H₄NMe₂-o)₂ ( 1 ) and (C₅Me₄SiMe₃) Sc(CH₂SiMe₃)₂(THF) ( 2 ) has been detailedly studied. Microstructures and thermal properties of the copolymers obtained were characterized by NMR, GPC and DSC. Results showed that ethylene could be copolymerized with either isoprene or butadiene under 1.01 × 10⁵ Pa of ethylene, and the copolymerization activity both reached up to 10⁵ g polymer mol_Sc⁻¹ h⁻¹ at room temperature. The ethylene-isoprene and ethylene-butadiene copolymers with controllable compositions (ethylene content = 32 mol% − 79 mol%), high molecular weight (M_n = 8.0 × 10⁴ ~ 19.7 × 10⁴), and narrow molecular weight distribution (M_w/M_n = 1.11 − 1.32) were readily obtained by changing the feed ratio of isoprene or butadiene. The structures of catalysts and conjugated dienes could exert significant effects on the stereoselectivity and comonomer distribution sequences in the resulting copolymers. For the copolymerization of ethylene and isoprene, scandium complex 1 afforded multiblock ethylene-isoprene copolymers with different isoprene contents but a predominant 3,4-structure. These copolymers exhibited a glass transition temperature (T_g, about −16 °C) and a melting temperature (T_m, 127 °C), which originated from the attributes of polyisoprene blocks and polyethylene blocks, respectively. Scandium complex 2 could give alternating ethylene-isoprene copolymers or random ethylene-isoprene copolymers with polyethylene blocks and isolated isoprene units at high or low amount of isoprene monomer used, and the isoprene in these copolymers mainly existed in 3,4-structure and trans-1,4-structure. The ethylene-isoprene alternating copolymers only showed a T_g at −46 °C, but as the isoprene content was lower than 32 mol%, T_m that derived from polyethylene blocks appeared at 130 °C while T_g of −46 °C still existed due to the ethylene-isoprene alternating structures. As for the copolymerization of ethylene and butadiene, both scandium complexes 1 and 2 afforded multiblock ethylene-butadiene copolymers with different butadiene contents and predominant cis-1,4-structure, whereas the random degree of sequence distributions in copolymers prepared by 2 was higher than that in copolymers prepared by 1 . Moreover, these ethylene-butadiene copolymers displayed T_gs (−98 °C) and T_ms (71 − 125 °C) simultaneously, which were ascribed to polybutadiene blocks and polyethylene blocks, respectively.
- Scandium,
- Ethylene,
- Isoprene,
- 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 Ethylene and Conjugated Dienes 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