Polymerization of 1,3‐dienes with functional groups. II. Free‐radical polymerization of N‐(2‐methylene‐3‐butenoyl)piperidine

Abstract

The free‐radical homopolymerization and copolymerization behavior of N‐(2‐methylene‐3‐butenoyl)piperidine was investigated. When the monomer was heated in bulk at 60 °C for 25 h without an initiator, about 30% of the monomer was consumed by the thermal polymerization and the Diels–Alder reaction. No such side reaction was observed when the polymerization was carried out in a benzene solution with 1 mol % 2,2′‐azobisisobutylonitrile (AIBN) as an initiator. The polymerization rate equation was found to be Rp ∝ [AIBN]0.507[M]1.04, and the overall activation energy of polymerization was calculated to be 89.5 kJ/mol. The microstructure of the resulting polymer was exclusively a 1,4‐structure that included both 1,4‐E and 1,4‐Z configurations. The copolymerizations of this monomer with styrene and/or chloroprene as comonomers were carried out in benzene solutions at 60 °C with AIBN as an initiator. In the copolymerization with styrene, the monomer reactivity ratios were r1 = 6.10 and r2 = 0.03, and the Q and e values were calculated to be 10.8 and 0.45, respectively. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1545–1552, 2003

Synthesis, Structural Characterization, and Thermoresponsivity of Hybrid Supramolecular Dendrimers Bearing a Polyoxometalate Core

“…With the literature value of 128 kJ/mol for E d ,9 one can calculate E p − E t /2 as 20.1 kJ/mol. This value was smaller than that of PiA (25.5 kJ/mol),7 indicating that the R p of DEA was higher than that of PiA.…”

“…Through the study of diene polymerizations, the Diels—Alder dimerization and thermal polymerization are not favorable because they may increase the apparent rate of monomer consumption and make the analysis of the polymerization kinetics complicated. In a previous article,7 we reported that a PiA containing piperidine amide function either had a strong tendency to form the Diels—Alder dimer or to undergo thermal polymerization during the polymerization in bulk. Therefore, the possibility of such a side reaction was also examined in this study.…”

“…AIBN, benzene, styrene, and chloroprene were purified according to a previously reported procedure 7. Other reagents were used without purification.…”

“…DEA was synthesized and purified according to a previously reported procedure;7, 8 yield: 55%, bp: 45–46 °C/2 mmHg, purity: >99% [gas chromatography (GC)].…”

“…Previously, we reported the free‐radical polymerization of N ‐(2‐methylene‐3‐butenoyl)piperidine (PiA),7 a kind of N,N ‐dialkyl‐α‐vinyl substituted acrylamide. Different from N,N ‐dialkylmethacrylamides, PiA gave high polymers of 1,4‐structure in good yield when heated with azobisisobutyronitrile (AIBN).…”