Kinetics of Emulsion Polymerization

Hoff, B. M. E. Van Der

doi:10.1021/ba-1962-0034.ch001

Cited by 69 publications

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“…The data set of Ryabova et al [122] seems to show a plateau for X < 10% but this might also be a broad initial peak as expected after particle nucleation and clearly expressed by the data of van der Hoff [146] where f 1 increases initially and peaks at about a conversion of 10%. From all the data only the set of Stähler [123] also contains average particle sizes showing expectedly decreasing f 1 with increasing d p .…”

Section: Microscopic Modelingmentioning

confidence: 79%

“…Figure 14. A) Literature data of experimental values for styrene/polystyrene showing the change of the monomer volume fraction per latex particle (f 1 ) during emulsion polymerization of styrene in dependence on the monomer conversion (X); triangles, [146] squares, [122] and circles. [123] B) f 1 in dependence on average particle size (d p,u unswollen average diameter from turbidity measurements), experimental values from ref.…”

Section: Microscopic Modelingmentioning

confidence: 99%

“…The experimental determination of the monomer concentration inside the particles during polymerization is quite challenging. Three independently carried out studies [121][122][123] clearly show decreasing f 1 values over the whole polymerization, including the conversion range that is sometimes called stage 2 where a constant monomer concentration inside the particles is supposed within the frame of the Smith-Ewart theory of emulsion polymerization [124] (see Figure 14 later and discussion below).…”

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Molecular Aspects of Radical Polymerizations—The Propagation Frequency

Tauer

Hernández

2010

Macromol. Rapid Commun.

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The product of the propagation rate constant and monomer concentration is a central issue of radical polymerization. Both quantities are strongly interrelated as the determination of a reliable value of the propagation rate constant requires exact knowledge of the monomer concentration. Even for homogeneous polymerization conditions, exact knowledge of the monomer concentration at the reaction site from the molecular perspective is not trivial. For emulsion polymerizations the situation is additionally complicated by mass transfer events and colloid-chemical effects. Molecular modeling appears as an attractive alternative or complement to the deterministic kinetic description of radical polymerizations.

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Section: Microscopic Modelingmentioning

confidence: 79%

Section: Microscopic Modelingmentioning

confidence: 99%

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confidence: 99%

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Molecular Aspects of Radical Polymerizations—The Propagation Frequency

Tauer

Hernández

2010

Macromol. Rapid Commun.

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“…5,6,7 However, the kinetic behavior of emulsion polymerization using oil-soluble initiators has been reported to be similar to the kinetics obtained with water-soluble initiators. 2,7,8 Thus, the conclusion is there must be some mechanism for the formation of single radicals inside the polymer particles when oil-soluble initiators are used. The various mechanisms proposed can be divided into two categories:…”

Section: Introductionmentioning

confidence: 87%

“…Single radicals formed by desorption from the particle of one of the two radicals formed by initiator decomposition. 5,6,7 2. Radicals formed in the aqueous phase from the fraction of oil-soluble initiator dissolved in the water.…”

Section: Introductionmentioning

confidence: 99%

Miniemulsion polymerization of styrene using the oil-soluble initiator AMBN

Blythe

Klein

Phillips

et al. 1999

J. Polym. Sci. A Polym. Chem.

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Compartmentalized polymerization with oil‐soluble initiators. Kinetic effect of single radical formation

Mørk¹,

Makame²

1997

J. Polym. Sci. A Polym. Chem.

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ABSTRACT:The stationary state distribution of radicals in compartmentalized systems initiated by oil-soluble initiators have been calculated for various cases of single radical formation as well as a simultaneous generation of single radicals and pairs of radicals in the particles. The effect of a contribution from radicals produced by initiator dissolved in the aqueous phase has been considered. Desorption and reabsorption of radicals, aqueous phase termination, total rate of radical formation and the water-solubility of the initiator are quantified in terms of dimensionless parameters. The calculations predict that single radicals generated in the particles are kinetically indistinguishable from radicals produced in the aqueous phase over a wide range of variation of the parameters. It is shown that if the rate of generation of single radicals constitutes only about 10 per cent of the overall rate of radical formation in the particles, the former radicals account for the major part of the rate of polymerization. The mechanisms previously proposed to account for the similar kinetic behaviour observed with watersoluble and oil-soluble initiators are discussed. It is concluded that the present calculations support the view that this similarity is mainly due to radicals produced by the water-soluble fraction of the initiator.

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Kinetics of Emulsion Polymerization

Cited by 69 publications

References 0 publications

Molecular Aspects of Radical Polymerizations—The Propagation Frequency

Molecular Aspects of Radical Polymerizations—The Propagation Frequency

Miniemulsion polymerization of styrene using the oil-soluble initiator AMBN

Compartmentalized polymerization with oil‐soluble initiators. Kinetic effect of single radical formation

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