Influence of Chemical Structure and Polymerizaion Conditions on Chiroptical Properties of Bulky Vinyl Polymers

Cao, Hongqing; Liu, An-Hua; Yu, Zhenning; Zhang, Jie; Wan, Xinhua; Chen, Xiaofang; Zhou, Qifeng

doi:10.3724/sp.j.1105.2007.00999

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“…Radical copolymerizations of MBPS and BHPSt were carried out in anisole at 90 °C with benzoyl peroxide (BPO) as the initiator (Scheme ). The high reaction temperature was chosen, as it has been shown to yield PMBPS with a large optical rotation 15c,d. The polymerization results are summarized in Table 1.…”

Section: Resultsmentioning

confidence: 99%

Unusual Chiral Transfer in Radical Copolymerization of Vinyl Monomers Bearing Side‐on p‐Terphenyl Pendants

Cui

Liu

Cao

et al. 2010

Chemistry An Asian Journal

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Radical copolymerization of a chiral monomer, (+)-2,5-bis[4'-((S)-2-methylbutoxy)phenyl]styrene and an achiral monomer, 2,5-bis(4'-hexyloxyphenyl)styrene, is carried out in anisole at 90 degrees C with benzoyl peroxide as the initiator. The resultant optically active helical copolymers show an unusual linear relationship between optical activity and composition, in sharp contrast with Green's "sergeants-and-soldiers" and "majority" rules. Analysis of the polarimetry, circular dichroism, and chain extension results suggest that the weak steric interaction between the propagation helical radical and the incoming monomer drove the copolymer chain to grow in a specific direction. Moreover, the helical macroinitiator is successfully used to induce the helix-sense-selective atom transfer radical polymerization of an achiral analogous monomer to yield optically-active block copolymers, which indicate a convenient way to prepare helical polymers with an excess screw sense from an achiral monomer by means of radical polymerization.

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Section: Resultsmentioning

confidence: 99%