Activation of stable polymeric esters by using organo‐activated acyl transfer reactions. Issue 9 (24th February 2014)

• Record Type: Journal Article
• Authors: Kakuchi, Ryohei; Wongsanoh, Kwanjira; Hoven, Voravee P.; Theato, Patrick
• Is Part Of: Journal of polymer science. Volume 52:Issue 9(2014:May)
• Page Start: 1353
• Page End: 1358
• Publication Date: 2014-02-24
• Subjects: functionalization of polymers -- organo‐activated acyl transfer reactions -- organo‐catalysis -- polyamides -- poly(methacrylamides) -- post‐polymerization modification -- radical polymerization; 547
• DOI: 10.1002/pola.27124
• Languages: English
• ISSNs: 0887-624X

Abstract

ABSTRACT: In this study, we succeeded in the in situ activation of nonactivated ester moieties embedded in polymer structures. Although poly(pentafluorophenyl methacrylate) (PPFPMA) can react with 2‐ethylhexylamine at 50 °C in the presence of proton scavenger such as NEt3, such conditions were not suitable for poly(phenyl methacrylate) (PPhMA). Nevertheless, the combination of organo‐activating agents, namely 1, 8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU) and 1, 2, 4‐triazole (TZ) led to a facile conversion from ester to amide for PPhMA. The reaction between PPhMA and 2‐ethylhexylamine was conducted at 120 °C in the presence of one equivalent of TZ and three equivalents of DBU and yielded >99% ester conversion to afford corresponding polymethacrylamide derivatives as confirmed by FT‐IR and 1 H NMR measurements. In addition, poly(2, 2, 2‐trifluoroethyl methacrylate) (PTFEMA) and poly(methyl methacrylate) (PMMA) were also allowed to react with amines in the presence of the organo‐activating agents with dramatically increased conversions (>70%). © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 1353–1358 Abstract : Facile activations of stable polymeric esters such as poly(methyl methacrylate) (PMMA) are demonstrated by using a newly developed organo‐activation method. Even PMMA showed fairly high reactivity toward amines in the presence of organo‐activators comprising of 1, 8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU) and 1, 2, 4‐triazole (TZ).