Citation: Zhen Zhang, Zhong-Yi Cai, Yu-Peng Pan, Yan-Li Dou, Shi-Hui Li, Dong-Mei Cui. Substituent Effects of Pyridyl-methylene Cyclopentadienyl Rare-earth Metal Complexes on Styrene Polymerization[J]. Chinese Journal of Polymer Science, ;2019, 37(6): 570-577. doi: 10.1007/s10118-019-2209-0 shu

Substituent Effects of Pyridyl-methylene Cyclopentadienyl Rare-earth Metal Complexes on Styrene Polymerization

Zhen Zhang ¹ ,
Zhong-Yi Cai ¹ ,
Yu-Peng Pan ² ,
Yan-Li Dou ^1,, ,
Shi-Hui Li ^2,, ,
Dong-Mei Cui ^2,,

a.
Key Laboratory of Automobile Materials of Ministry of Education, Department of Materials Science and Engineering, Jilin University, Changchun 130022, China
b.
State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China

Corresponding author: Yan-Li Dou, douyl@jlu.edu.cn Shi-Hui Li, Shihui-li@ciac.ac.cn Dong-Mei Cui, dmcui@ciac.ac.cn
Received Date: 17 November 2018
Revised Date: 29 November 2018
Accepted Date: 9 December 2018
Available Online: 4 January 2019

Salt metathesis reactions between pyridyl-methylene-cyclopentadienyl lithium salt and LnCl₃ followed by the addition of two equivalents of LiCH₂SiMe₃ afforded a series of constrained-geometry-configuration rare-earth metal bis(alkyl) complexes (Cp′CH₂-Py)Ln(CH₂SiMe₃)₂(THF)_n (Py = C₅H₄N, Cp′ = C₅H₄ (Cp), Ln = Sc, n = 0 (1); Cp′ = C₉H₆ (Ind), Ln = Sc, n = 0 (2); Cp′ = 3-Me₃Si-C₉H₅ (3-Me₃Si-Ind), Ln = Sc, n = 0 (3a), Ln = Lu (3b), Y (3c), n = 1; Cp′ = 2,7-(^tBu)₂C₁₃H₈ (2,7-(^tBu)₂-Flu), Ln = Sc (4a), n = 0, Ln = Lu (4b), Y (4c), n = 1) in moderate to good yields, which were characterized by NMR spectroscopy and single-crystal X-ray diffraction (for complex 3a). In the presence of [Ph₃C][B(C₆F₅)₄] and AlⁱBu₃, these complexes displayed different performances towards styrene polymerization. Rare-earth metal bis(alkyl) precursors bearing Cp, Ind, and 3-Me₃Si-Ind segments exhibited very low catalytic activity to afford syndiotactic polystyrene. All electron-donating ^tBu substituted complexes 4a, 4b, and 4c showed very high activity and perfect syndiotactivity (rrrr > 99%), producing high molecular weight polystyrene (up to 54.1 × 10⁴) with relatively narrow molecular distribution (PDI = 1.28−2.49).
- Polystyrene,
- Syndiotactic,
- Rare-earth metal,
- Constrained-geometry configuration
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