High Conversion Diffusion-Controlled Polymerization

Marten, F. L.; Hamielec, A. E.

doi:10.1021/bk-1979-0104.ch003

Cited by 162 publications

(108 citation statements)

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“…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%

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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Section: н-Andmentioning

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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“…Therefore, any reduction in solvent quality should result in a reduced rate of polymerization. As the polymerization process continues, the presence of more polymer makes the solution a thermodynamically poorer one and, therefore, produces a slower rate and a lower degree of polymerization [24].…”

Section: Kinetic Modelmentioning

confidence: 99%

Micellar Aqueous Phase Polymerization of Acrylamide

Capek

Kocsisová

2011

Designed Monomers and Polymers

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The kinetics of aqueous phase radical polymerization of acrylamide initiated by ammonium peroxodisulfate (APS) and 2,2 -azobisizobutyronitrile (AIBN) were studied in the presence of the non-ionic hydrophilic Tween-20 and hydrophobic Tween-85. The polymerization rate vs. conversion curve is described by a curve with two or three rate intervals and the maximal rate is located at medium conversion. This behavior strongly deviates from the kinetic model of the ideal solution polymerization with the steady-state kinetics at low and medium conversions. On the contrary, the present data indicate the kinetics typical for the transparent heterogeneous-micellar or microemulsion polymerization. The associates of polyacrylamide and acrylamide play the role of active particles. Indeed, the light scattering measurements confirmed the presence of polyacrylamide nanoparticles in both polymerization systems with and without emulsifier. The intra-and intermolecular association of polyacrylamide with its monomer is suggested to be the dominant process which induces the formation of particles responsible for the kinetics typical for the micellar or microemulsion polymerization. The experimental data show that the dependence of the maximal rate of polymerization (R p,max ) vs. conversion is the result of polymerization within the nanoscaled polymer aggregates and not by the gel effect. R p,max decreases with increasing emulsifier concentration and the decrease is much more pronounced with hydrophilic emulsifier. Polymerization is faster for the APS-initiated system than for the AIBN-initiated one. The radical polymerization of AAm polymerization with and without emulsifier was discussed in terms of the formation of polymer chain aggregation (nanoparticle) into polymer chains as a main reaction locus.

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“…Several authors have proposed methods of incorporating diffusion resistance into free radical reaction kinetics, and have advanced mechanistic interpretations based on the concepts of molecular entanglement, 12 -14 free volume and the glass transition. 15 Chiu et al 16 and Huang et al 1 7 used film theory in which the diffusion and reaction resistances are combined in series.…”

Section: Curing Model Of Unsaturated Polyestermentioning

confidence: 99%

“…~l (dQ) dt Qtot dt T (15) In the use of DSC for studying the isothermal curing kinetics of thermosetting resins, one assumes that the amount of heat generated due to the curing reaction is directly proportional to the degree of cure ( or the extent of reaction) of the sample at that time and then one relates the rate of cure, doc/dt, to the rate of heat…”

Section: Glass Transition Temperature and Free Volume Fractionmentioning

confidence: 99%