Synthesis and reactivity ratios of regioisomeric vinyl‐1, 2, 3‐triazoles with styrene. Issue 16 (16th May 2013)

• Record Type: Journal Article
• Authors: Lartey, Michael; Gillissen, Martijn; Adzima, Brian J.; Takizawa, Kenichi; Luebke, David R.; Nulwala, Hunaid B.
• Is Part Of: Journal of polymer science. Volume 51:Issue 16(2013:Aug.)
• Page Start: 3359
• Page End: 3364
• Publication Date: 2013-05-16
• Subjects: click chemistry -- copolymerization -- Mayo–Lewis equation -- nonlinear least squares (NLLS) -- radical polymerization -- reactivity ratio -- vinyl‐1, 2, 3‐triazole; 547
• DOI: 10.1002/pola.26723
• Languages: English
• ISSNs: 0887-624X

Abstract

ABSTRACT: The free radical reactivity ratios between styrene and different vinyl‐1, 2, 3‐triazole regioisomeric monomers in 1, 4‐dioxane at 65 °C have been established using nonlinear least square method. The results obtained for the reactivity ratio between regioisomers show exceptionally different polymerization behavior, highlighting the effects of the electronic and steric factors of these regioisomeric monomers. The experimental results highlight the effects of the electronic and sterics on the copolymerization behavior. In case of 1, 4‐vinyl‐triazoles, it was found that without the steric effects, the reactivity is very similar to that of styrene and forms random copolymers. However, it was found that 1, 5‐vinyl‐triazoles are more reactive than 1, 4‐vinyl triazoles. In the case of styrene‐ co‐ 1, 4‐vinyl‐1, 2, 3‐triazoles, the reactivity ratios were calculated to be r styrene : r 1‐octyl‐4‐vinyl‐triazole = 1.97:0.54, r styrene : r 1‐benzyl‐4‐vinyl‐triazole = 1.62:0.50, and r styrene : r 1‐methyl‐4‐vinyl‐triazole = 0.90:0.87. On the other hand, reactivity ratios for styrene‐ co ‐1, 5‐vinyl‐1, 2, 3‐triazoles were found to be r styrene : r 1‐octyl‐5‐vinyl‐triazole = 0.13:0.66 and r styrene : r 1‐benzyl‐5‐vinyl‐triazole = 0.34:0.49. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3359–3364 Abstract : This work investigates polymerization behavior of regioisomeric vinyl triazole monomers with styrene. The results obtained for the reactivity ratio between regioisomers show exceptionally different polymerization behavior highlighting the effects of the electronic and steric factors of these regioisomeric monomers. In the absence of any steric effects or electronic effects, a random copolymer is formed.