Polymerization of alkyl diazoacetates initiated by the amidinate/Pd system: efficient synthesis of high molecular weight poly(alkoxycarbonylmethylene)s with moderate stereoregularity. Issue 27 (26th June 2017)

• Record Type: Journal Article
• Authors: Shimomoto, Hiroaki; Kawamata, Junya; Murakami, Hirokazu; Yamashita, Kazuki; Itoh, Tomomichi; Ihara, Eiji
• Is Part Of: Polymer chemistry. Volume 8:Issue 27(2017)
• Page Start: 4030
• Page End: 4037
• Publication Date: 2017-06-26
• Subjects: Polymers -- Periodicals; Macromolecules -- Periodicals; Polymerization -- Periodicals; 547.705
• DOI: 10.1039/c7py00816c
• Languages: English
• ISSNs: 1759-9954

Abstract

Abstract : The initiating ability of a new system, amidinate/Pd, for the polymerization of diazoacetates is described. Abstract : The initiating ability of a new system, amidinate/Pd, for the polymerization of diazoacetates is described. The system is effective in affording relatively high number-average molecular weight ( M n ) polymers from ethyl diazoacetate (EDA, e.g., M n = 45 100, 44% yield) and methyl diazoacetate (MDA, e.g., M n = 26 200, 56% yield) in moderate yield. The polymerization of n -hexyl diazoacetate (nHDA ) and benzyl diazoacetate (BDA ) by the amidinate/Pd system yields high M n polymers ( M n = ca. 100 000), although the yield was below 10%. The system is also effective in the copolymerization ofEDA withnHDA, BDA, and cyclohexyldiazoacetate (cHDA ), affording high M n copolymers in moderate yield. NMR spectra of the products obtained with the system suggest that the polymerization proceeds with significantly higher stereoregularity compared to that with previously reported Pd-based initiating systems.