Alkyl halide/tertiary amine as novel initiators for free radical polymerizations of methyl methacrylate, methyl acrylate and styrene. Issue 5 (4th May 2019)

• Record Type: Journal Article
• Authors: Zhang, Panpan; Yuan, Ming; Xu, Cheng; Jia, Kan; Zhu, Yifeng; Tang, Huadong
• Is Part Of: Journal of macromolecular science. Volume 56:Issue 5(2019)
• Page Start: 476
• Page End: 483
• Publication Date: 2019-05-04
• Subjects: Alkyl halide -- tertiary amine -- free radical polymerization -- initiation -- mechanism; Polymers -- Periodicals; Polymerization -- Periodicals; 547.7
• DOI: 10.1080/10601325.2019.1581577
• Languages: English
• ISSNs: 1060-1325

Abstract

Abstract: A series of combinations of alkyl halide with tertiary amine such as ethyl α-bromophenylacetate/tris[2-(dimethylamino)ethyl)]amine (αEBP/Me6 TREN), ethyl 2-bromoisobutyrate/triethylamine (EBiB/TEA), and ethyl 2-chloropropionate/ N, N, N′, N′, N′′ -pentamethyldiethylenetriamine (ECP/PMDETA) have been developed as novel free radical initiators and used for the polymerizations of methyl acrylate (MA), methyl methacrylate (MMA) and styrene (St). The effects of the structure of alkyl halide and tertiary amine on the polymerization of MA were investigated. Gel permeation chromatograph (GPC) and proton nuclear magnetic resonance ( 1 H NMR) have been utilized to analyze the end group of the obtained poly(methyl acrylate). Electron spin resonance (ESR) spectroscopy was employed to identify the structure of the radicals produced by αEBP/Me6 TREN, and the results indicated that αEBP reacted with Me6 TREN via a single electron transfer (SET) nucleophilic mechanism to produce corresponding ethyl α-phenylacetate radicals which subsequently initiated the polymerization of MA. As both alkyl halide and tertiary amine are commercially available at low cost, non-explosive, and ease of use and storage in comparison with conventional azo, peroxide or persulfate initiators, the combination of alkyl halide and tertiary amine as a free radical initiator is promising for large-scale practical applications.