Radical polymerization of new functional monomer: Methacryloyl isocyanate containing 4-chloro-1-phenol

The free-radical copolymerization of m-isopropenyl-␣,␣Ј-dimethylbenzyl isocyanate (TMI) and styrene was studied with 1 H NMR kinetic experiments at 70°C. Monomer conversion vs time data were used to determine the ratio k p ϫ k t Ϫ0.5 for various comonomer mixture compositions (where k p is the propagation rate coefficient and k t is the termination rate coefficient). The ratio k p ϫ k t Ϫ0.5 varied from 25.9 ϫ 10 Ϫ3 L 0.5 mol Ϫ0.5 s Ϫ0.5 for pure styrene to 2.03 ϫ 10 Ϫ3 L 0.5 mol Ϫ0.5 s Ϫ0.5 for 73 mol % TMI, indicating a significant decrease in the rate of polymerization with increasing TMI content in the reaction mixture. Traces of the individual monomer conversion versus time were used to map out the comonomer mixture composition drift up to overall monomer conversions of 35%. Within this conversion range, a slight but significant depletion of styrene in the monomer feed was observed. This depletion became more pronounced at higher levels of TMI in the initial comonomer mixture.

Section: Introductionmentioning

confidence: 99%

Free‐radical copolymerization of styrene and m‐isopropenyl‐α,α′‐dimethylbenzyl isocyanate studied by ¹H NMR kinetic experiments

Barner

Barner‐Kowollik

Davis

2002

“…Methacryloyl isocyanate (MAI) has been successfully used for syntheses of new types of methacryl monomers, [1][2][3][4][5] where the isocyanate group of MAI is allowed to react with alcohols, phenols, thiols, and amines. The reaction of MAI with a hydroxylic compound yields a monomer carrying an alkoxycarbonylcarbamoyl group as a new conjugative substituent.…”

Section: Introductionmentioning

confidence: 99%

Kinetic and ESR studies on radical polymerization behavior of N‐(2‐phenylethoxycarbonyl)methacrylamide

Seno¹,

Fukui²,

Hirano³

et al. 2000

Polymerization of N-(2-phenylethoxycarbonyl)methacrylamide (PECMA) with dimethyl 2,2Ј-azobisisobutyrate (MAIB) was investigated in tetrahydrofuran (THF) kinetically and by means of electron spin resonance (ESR). The overall activation energy of the polymerization was calculated to be 58 kJ/mol. The initial polymerization rate (R p ) is expressed by R p ϭ k[MAIB] 0.3 [PECMA] 2.3 at 60°C. Such unusual kinetics may be ascribable to primary radical termination and to acceleration of propagation due to monomer association. Propagating poly(PECMA) radical was observed as a 13-line spectrum by ESR under practical polymerization conditions. ESR-determined rate constants of propagation (k p , 4.7-10.5 L/mol s) and termination (k t , 4.6 ϫ 10 4 L/ml s) at 60°C are much lower than those of methacrylamide and methacrylate esters. The Arrhenius plots of k p and k t gave activation energies of propagation (24 kJ/mol) and termination (25 kJ/mol). The copolymerizations of PECMA with styrene (St) and acrylonitrile were examined at 60°C in THF. Copolymerization parameters obtained for the PECMA (M 1 ) Ϫ St(M 2 ) system are as follows: r 1 ϭ 0.58, r 2 ϭ 0.60, Q 1 ϭ 0.73, and e 1 ϭ ϩ0.22.

“…Using the monomer reactivity ratios, Q and e values of PECMA were estimated to be Q 1 = 0.73 and e 1 = +0.22, where Q 2 = 1.0 and e 2 = −0.8 were used for St. Similar monomer reactivity ratios ( r 1 = 0.49 and r 2 = 0.66) were reported for the copolymerization of N ‐(4‐chlorophenoxycarbonyl)methacrylamide (CPCMA) ( M 1 ) with St ( M 2 ) at 60 °C in THF, where CPCMA carrying a phenoxycarbonylcarbamoyl group was prepared by the reaction of MAI with 4‐chlorophenol 4…”

Section: Resultsmentioning

confidence: 90%

“…Methacryloyl isocyanate (MAI) has been successfully used for syntheses of new types of methacryl monomers,1–5 where the isocyanate group of MAI is allowed to react with alcohols, phenols, thiols, and amines. The reaction of MAI with a hydroxylic compound yields a monomer carrying an alkoxycarbonylcarbamoyl group as a new conjugative substituent.…”

Section: Introductionmentioning

confidence: 99%

Kinetic and ESR studies on radical polymerization behavior ofN-(2-phenylethoxycarbonyl)methacrylamide

Seno

Fukui

Hirano

et al. 2000

Polymerization of N‐(2‐phenylethoxycarbonyl)methacrylamide (PECMA) with dimethyl 2,2′‐azobisisobutyrate (MAIB) was investigated in tetrahydrofuran (THF) kinetically and by means of electron spin resonance (ESR). The overall activation energy of the polymerization was calculated to be 58 kJ/mol. The initial polymerization rate (Rp) is expressed by Rp = k[MAIB]0.3[PECMA]2.3 at 60 °C. Such unusual kinetics may be ascribable to primary radical termination and to acceleration of propagation due to monomer association. Propagating poly(PECMA) radical was observed as a 13‐line spectrum by ESR under practical polymerization conditions. ESR‐determined rate constants of propagation (kp, 4.7–10.5 L/mol s) and termination (kt, 4.6 × 104 L/ml s) at 60 °C are much lower than those of methacrylamide and methacrylate esters. The Arrhenius plots of kp and kt gave activation energies of propagation (24 kJ/mol) and termination (25 kJ/mol). The copolymerizations of PECMA with styrene (St) and acrylonitrile were examined at 60 °C in THF. Copolymerization parameters obtained for the PECMA (M1) − St(M2) system are as follows: r1 = 0.58, r2 = 0.60, Q1 = 0.73, and e1 = +0.22. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4264–4271, 2000