Radical polymerization of new functional monomers derived from methacryloyl isocyanate and urea

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.

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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

Seno¹,

Fukui²,

Hirano³

et al. 2000

“…The temperature was raised to 72 °C, and the polymerization was continued for 6 h under constant stirring. A large quantity of distilled water was added to the reactor, and the precipitated polymer was filtered; washed sequentially with distilled water, methanol, and acetone; and dried at room temperature under vacuum until a constant weight was reached 12. AN, MMA, and VAC homopolymers were synthesized under the same conditions as the corresponding copolymers.…”

Section: Methodsmentioning

confidence: 99%

Novel refreshable N‐halamine polymeric biocides containing imidazolidin‐4‐one derivatives

Sun

Chen

Worley

et al. 2001

A novel cyclic‐amine monomer, 1‐acryloyl‐2,2,5,5‐tetramethylimidazolidin‐4‐one (ACTMIO), was synthesized in a good yield through the reaction of acryloyl chloride with 2,2,5,5‐tetramethylimidazolidin‐4‐one and was fully characterized with Fourier transform infrared and 1H NMR studies. ACTMIO was copolymerized with several widely used acrylic and vinyl monomers under ordinary conditions. In the presence of triallyl‐1,3,5‐triazine‐2,4,6(1H,3H,5H)‐trione, ACTMIO was easily grafted onto most textile fabrics. After regular chlorine bleach treatment, N‐halamine derivatives of the corresponding polymeric materials exhibited antibacterial properties against Escherichia coli, and these properties were durable and refreshable with chlorine bleaching. The relationship between the structures and antibacterial properties of the samples is further discussed. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3073–3084, 2001

“…Methacryloylisocyanate (MAI) has been satisfactorily employed for syntheses of new types of methacryl monomers, where the isocyanate group of MAI is allowed to easily react with alcohols, phenols, thiols, and amines 1–6. The reaction of MAI with a hydroxylic compound yields a monomer carrying an alkoxycarbonylcarbamoyl group as a conjugative substituent involving urethane moiety.…”

Section: Introductionmentioning

confidence: 99%

Kinetic study of the radical polymerization behavior of N‐(1‐phenylethylaminocarbonyl)methacrylamide

Seno

Yamada

Wang

et al. 2005

Polymerization of N-(1-phenylethylaminocarbonyl)methacrylamide (PEACMA) with dimethyl 2,2Ј-azobisisobutyrate (MAIB) was kinetically studied in dimethyl sulfoxide (DMSO). The overall activation energy of the polymerization was estimated to be 84 kJ/mol. The initial polymerization rate (R p ) is given by R p ϭ k[MAIB] 0.6 [PEACMA] 0.9 at 60°C, being similar to that of the conventional radical polymerization. The polymerization system involved electron spin resonance (ESR) spectroscopically observable propagating poly(PEACMA) radical under the actual polymerization conditions. ESRdetermined rate constants of propagation and termination were 140 L/mol s and 3.4 ϫ 10 4 L/mol s at 60°C, respectively. The addition of LiCl accelerated the polymerization in N,N-dimethylformamide but did not in DMSO. The copolymerization of PEAC-MA(M 1 ) and styrene(M 2 ) with MAIB in DMSO at 60°C gave the following copolymerization parameters; r 1 ϭ 0.20, r 2 ϭ 0.51, Q 1 ϭ 0.59, and e 1 ϭ ϩ0.70.