Kinetic parameters for polymerization of methyl methacrylate at 60°C

Carswell, Trudy G.; Hill, David J. T.; Londero, D.I.; O’Donnell, James H.; Pomery, Peter J.; Winzor, Catherine L.

doi:10.1016/0032-3861(92)90573-f

Cited by 71 publications

(60 citation statements)

References 18 publications

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“…It is known that in the later stage of bulk polymerization, an extremely viscous system, the propagation rate and the initiator efficiency decrease. 24,36,37 As the highly viscous polymerization solutions of PEG8000 and PEG1000 are comparable to the later stage of the bulk system, such negative factors would affect FRP results and make them inconsistent with the theoretical kinetics (Equations (1 and 3)). Therefore, we suggest that the viscosities of PEG8000 and PEG1000 are too high to effectively promote FRPs.…”

Section: Polymerization Resultsmentioning

confidence: 99%

“…At the monomer concentration of 3.0 mol l À1 , the FRP was accelerated in the region over B30% conversion, and completed in 3 h (run 8, Figure 1a). In contrast, the FRP mixtures in bulk [36][37][38][39][40] and in ionic liquids 34,35 Figure S2). Thus, the R p values under various polymerization conditions were evaluated from these kinetic plots.…”

Section: Polymerization Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Poly(ethylene glycol)-induced acceleration of free radical polymerization of methyl methacrylate: effects of highly viscous solvent and kinetic study

Matsuoka

Kikuno

Takagi

et al. 2010

Polym J

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Poly(ethylene glycol) with a molecular weight of 400 (PEG400) as an environmentally benign and highly viscous polymeric solvent was found to effectively accelerate the free radical polymerization (FRP) of methyl methacrylate and to afford a highmolecular-weight polymer. When the polymerization in PEG400 was performed at a monomer concentration of 3.0 mol l À1 and an initiator (2,2¢-azobis(isobutyronitrile)) concentration of 0.3Â10 À2 mol l À1 , the monomer conversion was completed for 6 h to afford a polymer with a number-average molecular weight (M n ) of 838 000. After polymerization, the PEG400 solvent was readily recovered and reused. The solvent effects of highly viscous PEG400 were kinetically analyzed. The polymerization rate (R p ) was proportional to the monomer concentration and the square root of both the initiator concentration and the viscosity of the polymerization media (g). For the FRP in the mixed solvents of PEG400 and toluene, both R p and M n values increased linearly with the square root of the g value. The kinetic study has shown that the highly viscous PEG400 solvent largely suppresses diffusion-controlled bimolecular termination.

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Section: Polymerization Resultsmentioning

confidence: 99%

Section: Polymerization Resultsmentioning

confidence: 99%

Poly(ethylene glycol)-induced acceleration of free radical polymerization of methyl methacrylate: effects of highly viscous solvent and kinetic study

Matsuoka

Kikuno

Takagi

et al. 2010

Polym J

View full text Add to dashboard Cite

show abstract

“…The initial polymerization rate was determined by approximation of experimental conversion dependencies of the study as well as the data published in [24][25][26][27][28][29] using the leastsquare method on the initial section of the curve x≤0.15 ( Table 3). The initial section of conversion curves is approximated by linear dependence with a high correlation coefficient r≥0.9964 (Pic.…”

Section: н-Andmentioning

confidence: 99%

“…Only one [29] There are four main sections in the kinetic curve: I -the initial section of the concentration increase up to the steady-state value, II -the sec tion with a constant concentration of macroradicals, III -the section on which there is a sharp increase in the macroradicals concentration, IVthe glass transition section. Note that the length of the first two sections is quite small compared to the polymerization time section.…”

Section: Macroradicals Concentrationmentioning

confidence: 99%

Concerning Chain Growth Specific Reaction Rate as a Part of the Process of Methyl Methacrylate Mass Radical Polymerization

Sultanova¹,

Yanborisov²,

Kolesov

2017

IJAS

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“…Among the k, values of a-substituted acrylates at 60oC summarized in Table II, the k, of MEA (k 1 =2.1 x 10 7 Lmol-1 s) is smaller than that of MMA (k,=4.2 x 10 7 L mol-1 s) 17 by a factor of two, and MMEA, M(DM)EA, and M(TE)EA have k 1 values much smaller than that of MEA. Comparison of the series of the k 1 values shows a decrease in the k, value with an increase in the bulkiness of the a-substituent.…”

Section: Polymerizationmentioning

confidence: 99%

Sterically Hindered Elementary Reactions in Radical Polymerization of α-Ethylacrylic Esters as Studied by ESR Spectroscopy

Kobatake

Yamada

1996

Polym J

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ABSTRACT:Radical polymerizations of methyl a-ethylacrylate (MEA) and cyclohexyl a-ethylacrylate (CHEA) in bulk were kinetically investigated on the basis of the absolute rate constants of elementary reactions evaluated by ESR spectroscopy. ESR spectra of the propagating radicals from MEA and CHEA were observed as five-line spectra by accumulation of a few scans during the slow polymerization of MEA and CHEA to low molecular weight (Mn= 1000---4000). The rate constants of propagation and termination (k 0 and k,) were determined based on quantification of propagating radicals from the a-ethylacrylates: k 0 = 8.6 and k, 2.1 x 10 7 L mol-1 s for MEA, and kP = 1.6 and k, = 1.8 x 10 6 L mol-1 s for CHEA. The steric hindrance of the ethyl group was found to bring about slower propagation and slightly slower termination rates of MEA in comparison with methyl methacrylate (MMA). The detailed structural analysis of the end group in the polymer indicates that replacement of the a-methyl group of MMA with the ethyl group of MEA results in termination involving mainly combination (76%). The steric hindrance seems to affect the termination mode.KEY WORDS Radical Polymerization I a-Ethylacrylate I a-Substituted Acrylic Ester I Propagation Rate Constant I Termination Rate Constant I Electron Spin Resonance Spectroscopy I Among 1, 1-disubstituted ethylenic monomers, a variety of IX-substituted acrylates except for the acrylates bearing a large alkyl group and functioning as a chain transfer agent through the addition-fragmentation are polymerizable. 1 Recent studies of radical polymerization of the IX-( substituted methyl)acrylates have drawn much attention because slight changes in the structure of the IX-substituent greatly affect the polymerizability. The IX-( substituted methyl)acrylates bearing alkoxymethyl, 2 acyloxymethy1,3 fluoromethyl, 4 and carboalkoxymethyl groups 5 as the IX-substituent readily polymerize to high molecular weight in spite of the presence of the bulky substituent. The absolute rate constants of propagation and termination (kp and k 1 ) for the alkoxymethyl, acyloxymethyl and carboalkoxymethyl derivatives have been determined based on quantification of the respective propagating radicals by the ESR method, 2 • 3 • 5 and it has been rationalized that the balance between the slow propagation and termination rates allows polymer formation from the IX-(substituted methyl)acrylates. Therefore, it is convinced that the steric hindrance of the IX-substituent provides steric hindrance-assisted polymerization of IX-(substituted methyl)acrylates.

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Kinetic parameters for polymerization of methyl methacrylate at 60°C

Cited by 71 publications

References 18 publications

Poly(ethylene glycol)-induced acceleration of free radical polymerization of methyl methacrylate: effects of highly viscous solvent and kinetic study

Poly(ethylene glycol)-induced acceleration of free radical polymerization of methyl methacrylate: effects of highly viscous solvent and kinetic study

Concerning Chain Growth Specific Reaction Rate as a Part of the Process of Methyl Methacrylate Mass Radical Polymerization

Sterically Hindered Elementary Reactions in Radical Polymerization of α-Ethylacrylic Esters as Studied by ESR Spectroscopy

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