Synthesis of organosilicon‐containing macromonomers through an anionic polyaddition reaction

Abstract

Lithium diisopropylamide (LDA) induces metalation reaction of 4-(trimethylsilylmethy1)-styrene (SMS) to form lithiated SMS (SMSLi). SMSLi initiates the anionic polymerization of SMS to form oligomers with a polymerizable vinyl end-group. Mechanistic studies revealed that the propagation proceeds mainly by the addition reactions of SMSLi to the double bond of preformed oligomers in the early stage of the polymerization. In the later stage of the polymerization, propagations between preformed oligomers take place concurrently. The extent of polyaddition enchainments in the oligomers was found to increase when the reaction was carried out keeping the monomer concentration as low as possible. Reactivities of the organosilicon-containing macromonomers were also estimated by UV, MO calculations, and radical homopolymerization.

Design and Non‐Covalent DNA Binding of Platinum(II) Metallacalix[4]arenes

“…Gel‐permeation chromatography (GPC) measurement of the resultant poly( p ‐DVB) showed a weight‐average molecular weight ( M w ) and number‐average molecular weight ( M n ) of 20 300 and 2000, respectively, with respect to a polystyrene standard 9. Spectroscopic characterization of the resultant poly( p ‐DVB) (see the http://www.wiley-vch.de/contents/jc_2001/2007/z700242_s.pdf) indicated a unique polymer structure that suggests a selective linear polymerization of p ‐DVB in the nanochannel 5a. For example, the IR spectrum of poly( p ‐DVB) contains absorption bands similar to those of p ‐DVB and polystyrene, and an absorption at 1629 cm −1 suggests the existence of residual vinyl moieties in poly( p ‐DVB).…”

Topotactic Linear Radical Polymerization of Divinylbenzenes in Porous Coordination Polymers

“…The precipitate was collected and washed several times with MeOH and subsequently dried under reduced pressure at room temperature to give the poly(DVB). The structures of the poly(DVB)s obtained are similar to those produced by controlled anionic polymerization 5a…”

“…Hence, in contrast to the case of p ‐DVB polymerization, m ‐DVB is polymerized in the channels of both 1 a and 1 b to give soluble polymeric products (polymerization in 1 a : 47 % conversion, M w =48 300, M n =9500; polymerization in 1 b : 48 % conversion, M w =10 900, M n =5800). Full spectroscopic characterization of the resultant poly( m ‐DVB) clearly indicated that only one vinyl moiety of m ‐DVB participates in the polymerization, analogous to the polymerization of p ‐DVB in 1 a 5a…”

“…Gel‐permeation chromatography (GPC) measurement of the resultant poly( p ‐DVB) showed a weight‐average molecular weight ( M w ) and number‐average molecular weight ( M n ) of 20 300 and 2000, respectively, with respect to a polystyrene standard 9. Spectroscopic characterization of the resultant poly( p ‐DVB) (see the http://www.wiley-vch.de/contents/jc_2002/2007/z700242_s.pdf) indicated a unique polymer structure that suggests a selective linear polymerization of p ‐DVB in the nanochannel 5a. For example, the IR spectrum of poly( p ‐DVB) contains absorption bands similar to those of p ‐DVB and polystyrene, and an absorption at 1629 cm −1 suggests the existence of residual vinyl moieties in poly( p ‐DVB).…”