Synthesis and monomer reactivity ratios of methyl methacrylate and 2‐vinyl‐4,4′‐dimethylazlactone copolymers

Abstract

We report the monomer reactivity ratios for copolymers of methyl methacrylate (MMA) and a reactive monomer, 2‐vinyl‐4,4′‐dimethylazlactone (VDMA), using the Fineman–Ross, inverted Fineman–Ross, Kelen–Tudos, extended Kelen–Tudos, and Tidwell–Mortimer methods at low and high polymer conversions. Copolymers were obtained by radical polymerization initiated by 2,2′‐azobisisobutyronitrile in methyl ethyl ketone solutions and were analyzed by NMR, gas chromatography (GC), and gel permeation chromatography. 1H NMR analysis was used to determine the molar fractions of MMA and VDMA in the copolymers at both low and high conversions. GC analysis determined the molar fractions of the monomers at conversions of less than 27% and greater than 65% for the low‐ and high‐conversion copolymers, respectively. The reactivity ratios indicated a tendency toward random copolymerization, with a higher rate of consumption of VDMA at high conversions. For both low‐ and high‐conversion copolymers, the molecular weights increased with increasing molar fractions of VDMA, and this was consistent with the faster consumption of VDMA (compared with that of MMA). © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3027–3037, 2003

Copolymers of 2,5‐bis[(4‐methoxyphenyl) oxycarbonyl]styrene with styrene and methyl methacrylate: Synthesis, monomer reactivity ratios, thermal properties, and liquid crystalline behavior

“…We noticed that the r MPCS ≫ r St (and r MMA ), so we calculated the reactivity ratios using the extended Kelen–Tudos (EKT) method when the effect of conversion is considered 18, 25. In the EKT method, the partial molar conversions for the two comonomers are defined as: where W is the weight conversion of polymerization, and μ is the ratio of molecular weights of monomer 2 to that of monomer 1, with X = F 1 /F 2 and Y = f 1 /f 2 .…”

“…For liquid crystalline copolymer, liquid crystalline behavior is also associated with copolymer composition 17. As one of the most important parameters for the composition equations of copolymers, the reactivity ratios can offer information such as the relative reactivity of monomer pairs, the monomer composition, and distribution in the copolymer 18–21. There was a report22 that preliminarily discussed the effect of composition of 2,5‐bis[(4‐methoxyphenyl)oxycarbonyl]‐styrene, MPCS (one of MJLCP's monomers), on the liquid crystalline behavior of copolymers, but the microstructure of the copolymers was still unknown.…”

Facile, efficient functionalization of polyethylene via regioselective copolymerization of ethylene with cyclic dienes

“…This may be best explained by both acceleration of chain propagation and chain transfer at higher reaction temperature. In contrast, for catalyst 1c, it is noteworthy that a significant increase is detected not only in the catalytic activity but also in the molecular weight of the resultant copolymers by raising temperature (Table 1, entries [14][15][16]. This may be owing to the enhancement of chain propagation without significant chain transfer at the elevated temperature, which is supported by the extremely narrow molecular weight distributions (PDI < 1.2) of the resultant copolymers.…”

Azlactone-functionalized polymers as reactive platforms for the design of advanced materials: Progress in the last ten years

“…22 In this latter context, 3M has reported extensively on the copolymerization of VDMA with methyl methacrylate (MMA), motivated, at least in part, by the potential utility of these copolymers for the design of reactive biomaterials. 23 …”