Influence of the stereochemical configuration on the radical polymerization of methacrylic monomers:cis- andtrans-(2-cyclohexyl-1,3-dioxan-5-yl) methacrylate

García, Nuria; Guzmán, Julio; Riande, Evaristo; García, Félix C.; Peña, J. L. de la; Calle, Paloma; Jimeno, María Luisa

doi:10.1002/1099-0518(20001101)38:21<3883::aid-pola50>3.0.co;2-2

Cited by 11 publications

(8 citation statements)

References 38 publications

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“…The values of k p and k t determined at different temperatures in the polymerizations of CPDM and TPDM are compiled in Table 4, which also includes new values of k p and k t determined in the polymerizations of CCDM and TCDM. The values for CCDM and TCDM are higher than those previously reported 15 because our new method for correcting the baseline leads to lower values of the radical concentrations than those obtained by a simple baseline correction. Nevertheless, the conclusions 15 remain unchanged.…”

Section: Resultscontrasting

confidence: 70%

“…These results clearly show that the CPDM isomer is more reactive than the trans counterpart TPDM, as occurs in the polymerization of CCDM and TCDM methacrylate. 15 However, these results contradict those reported for the polymerization of trans-and cis/trans-4-tert-butylcyclohexyl methacrylate with cis content of 71%, which have similar polymerization rates. 21 Characterization of the Polymers.…”

Section: Resultscontrasting

confidence: 56%

“…Therefore, eq 1 can be transformed into eq 2. 15 Computer simulations of the absorbance data according to eq 2 can be used to determine A ∞ and k p /k t 1/2 . The values of k d (Table 1) for the calculations at each temperature were taken from the literature, [16][17][18][19] and those of f were determined as indicated below.…”

Section: Resultsmentioning

confidence: 99%

“…Previously, we studied 15 the radical polymerization at 60 °C of two new monomers bearing two bonded cycloaliphatic rings on the ester residue: cis-(2-cyclohexyl-1,3-dioxan-5-yl) methacrylate (CCDM) and trans-(2-cyclohexyl-1,3-dioxan-5-yl) methacrylate (TCDM). The termination rate constants were affected much more by the configuration of the monomer than the propagation rate constants.…”

Section: Introductionmentioning

confidence: 99%

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Radical Polymerization of Isomeric Methacrylic Monomers: cis- and trans-(2-Phenyl-1,3-dioxan-5-yl) Methacrylate

et al. 2002

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Two new monomers, cis-(2-phenyl-1,3-dioxan-5-yl) methacrylate (CPDM) and trans-(2-phenyl-1,3-dioxan-5-yl) methacrylate (TPDM), have been synthesized. The stereochemical configuration in both monomers was unequivocally assigned by correlation 1H−13C NMR experiments. The radical polymerization reactions of both monomers were studied by ultraviolet spectroscopy and electron paramagnetic resonance spectroscopy to determine the polymerization rate parameter k p/k t 1/2 and the absolute propagation and termination rate constants (k p and k t) at different temperatures. The values of k p/k t 1/2 lie in the range 0.40−0.55 L1/2/(mol1/2 s1/2) for CPDM and 0.29−0.37 L1/2/(mol1/2 s1/2) for TPDM at temperatures between 45 and 70 °C, showing that the polymerization rate of the cis monomer with the substituents in equatorial−axial positions on the dioxane ring is higher than that of its trans counterpart with the phenyl and ester residue in equatorial positions on the dioxane ring. Using EPR measurements of the polymer radical concentrations, similar values for k p were obtained for both trans and cis monomers, whereas the termination rate constant of the trans monomer was about twice that of the cis monomer at the same temperature.

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Section: Resultscontrasting

confidence: 70%

Section: Resultscontrasting

confidence: 56%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Radical Polymerization of Isomeric Methacrylic Monomers: cis- and trans-(2-Phenyl-1,3-dioxan-5-yl) Methacrylate

et al. 2002

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“…Figure 4 shows the ESR spectrum observed during the polymerization of PEACMA with MAIB at 60 °C in DMSO, where the concentrations of PEACMA and MAIB were 1.00 mol/L and 0.10 mol/L, respectively. The observed spectrum is closely similar to those of PECMA and also some methacrylate monomers,5, 16–19 and is assignable to the propagating polymer radical (II) of PEACMA. (See Scheme .…”

Section: Resultssupporting

confidence: 61%

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

Seno

Yamada

Wang

et al. 2005

J. Polym. Sci. A Polym. Chem.

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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.

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Determination of the Propagation Rate Coefficient of Vinyl Pivalate Based on EPR Quantification of the Propagating Radical Concentration

Kubota

Kajiwara

Zetterlund

et al. 2007

Macro Chemistry & Physics

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The propagation rate coefficient (kp) of the vinyl pivalate (VPi) has been determined from an EPR quantification of the concentration of propagating radicals. The polymerizations followed first‐order kinetics with respect to the monomer, and the concentration of propagating radicals did not vary with time. The chain lengths were estimated to be sufficiently large to not affect kp. The resulting Arrhenius parameters for kp of VPi in heptane are Ap = 1.39 × 107 dm3 · mol−1 · s−1 and Ep = 20.5 kJ · mol−1. They are very similar to those of vinyl acetate as previously determined by the PLP method. The present results thus indicate that EPR gives consistent kp values for vinyl esters.magnified image

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Influence of the stereochemical configuration on the radical polymerization of methacrylic monomers:cis- andtrans-(2-cyclohexyl-1,3-dioxan-5-yl) methacrylate

Cited by 11 publications

References 38 publications

Radical Polymerization of Isomeric Methacrylic Monomers: cis- and trans-(2-Phenyl-1,3-dioxan-5-yl) Methacrylate

Radical Polymerization of Isomeric Methacrylic Monomers: cis- and trans-(2-Phenyl-1,3-dioxan-5-yl) Methacrylate

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

Determination of the Propagation Rate Coefficient of Vinyl Pivalate Based on EPR Quantification of the Propagating Radical Concentration

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