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Chemoselective Polymerization of Polar Divinyl Monomers with Rare-Earth/Phosphine Lewis Pairs
Pengfei Xu1, Lei Wu2, Liqiu Dong3,4
1Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, China. 20164009015@stu.suda.edu.cn.
Abstract:
This work reports the chemoselective polymerization of polar divinyl monomers, including allyl methacrylate (AMA), vinyl methacrylate (VMA), and 4-vinylbenzyl methacrylate (VBMA), by using simple Lewis pairs comprised of homoleptic rare-earth (RE) aryloxide complexes RE(OAr)₃ (RE = Sc (1), Y (2), Sm (3), La (4), Ar = 2,6-tBu₂C₆H₃) and phosphines PR₃ (R = Ph, Cy, Et, Me). Catalytic activities of polymerizations relied heavily upon the cooperation of Lewis acid and Lewis base components. The produced polymers were soluble in common organic solvents and often had a narrow molecular weight distribution. A highly syndiotactic poly(allyl methacrylate) (PAMA) with rr ~88% could be obtained by the scandium complex 1/PEt₃ pair at -30 °C. In the case of poly(4-vinylbenzyl methacrylate) (PVBMA), it could be post-functionalized with PhCH₂SH. Mechanistic study, including the isolation of the zwitterionic active species and the end-group analysis, revealed that the frustrated Lewis pair (FLP)-type addition was the initiating step in the polymerization.
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