Propagation rate coefficient of free‐radical polymerization of 1,3‐butadiene

Deibert, Stefan; Bandermann, Friedhelm; Schweer, Johannes; Sarnecki, Juergen

doi:10.1002/marc.1992.030130703

Cited by 48 publications

(23 citation statements)

References 15 publications

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“…reasonably well, with the recalculated value of 125 L -m o l -l -s -' for the k, of 1,3-butadiene in chlorobenzene at 50 "C from Deibert et al 34). However, the k, values for the bulk polymerization require further investigation.…”

Section: Discussionsupporting

confidence: 66%

Towards the propagation rate coefficient for the free‐radical polymerization of 1,3‐butadiene

Bandermann

Günther

Schweer

1996

Macro Chemistry & Physics

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The propagation rate coefficient k, for the free-radical polymerization of 1,3-butadiene was determined as a function of temperature in the range of 30-60°C in bulk and as a function of the concentration of 1,3-butadiene in chlorobenzene at 50°C using a combination of a UV flash-lamp induced polymerization and a measurement of the molecular weight distribution of the produced polymer by size exclusion chromatography. Differences of up to around45Vo resulted even for the same concentrations and temperatures when these measurements were compared with recent determinations of k, of 1,3-butadiene in chlorobenzene in which just such an experimental setup was used. This finding was essentially attributed to large differences in the radical termination rates which prevailed in the reaction volumes under the current conditions of the pulse-induced polymerization experiments. Moreover, in the vicinity of bulk concentrations of 1,3-butadiene in chlorobenzene, k, apparently decreases with concentration.

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Section: Discussionsupporting

confidence: 66%

Towards the propagation rate coefficient for the free‐radical polymerization of 1,3‐butadiene

Bandermann

Günther

Schweer

1996

Macro Chemistry & Physics

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“…This value agrees well with a value measured by laser flash photolysis reported by Deibert et aZ. 17 It must be noted that these authors did not mention how problems like branching and possible cross-linking of the polybutadiene could interfere with obtaining the necessary molecular weight data from sizeexclusion chromatography.…”

Section: Theorysupporting

confidence: 90%

Seeded emulsion polymerization of butadiene. 2. Effects of persulfate and tert-dodecyl mercaptan

Verdurmen¹,

Geurts²,

Verstegen³

et al. 1993

Macromolecules

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The kinetics of the emulsion polymerization of butadiene at 60 "C in Smith-Ewart interval I11 were investigated using sodium peroxodisulfate (persulfate) as initiator. The aim of this work was to elucidate and model the persulfate initiator efficiency. Monomer conversion was based on gravimetrically calibrated on-line densitometry. Plots of the product of the propagation rate coefficient, k,, and the average number of radicals per particle, a, versus initiator concentration showed minimal dependence on the initiator concentration if tert-dodecyl mercaptan (TDM) was present during polymerization. These results could not be modeled using normal emulsion polymerization theory. The model used in the absence of TDM fits two separate sets of data, a versus particle diameter and a versus initiator concentration. In the absence of TDM, a depends strongly on the initiator concentration. The significant effect of TDM is ascribed to a decrease in the radical desorption. A possible effect on the radical absorption is refuted on the basis of theory and experiment. IntroductionImportant papers on the butadiene emulsion polymerization have been published as a result of the synthetic rubber program' by Kolthoff et aL2 and by Morton et aZ

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“…[53,100] Furthermore pulsed lamps are applied as a cheaper alternative to a pulsed laser. [54,104] The question arises whether the principle of pulsed initiation/termination can also be applied on a preparative scale. [136,137] Certainly some companies are toying with the idea.…”

Section: Overview Of the Publications Up To The Beginning Of 2000mentioning

confidence: 99%

“…[143] The group of Schweer [54][55][56][57][58][59][60] also applied the MALDI-TOF technique to determine the molecular weight distribution. [60] The group of Moad [61,62,89,114] was able to determine the number of radicals generated per pulse in a PLP experiment by adding a TEMPO derivative and measuring the trapping of the radicals by the increase in fluorescence intensity with time.…”

Section: Overview Of the Publications Up To The Beginning Of 2000mentioning

confidence: 99%

Pulsed initiation polymerization as a means of obtaining propagation rate coefficients in free-radical polymerizations. II Review up to 2000

Herk¹

2000

Macromol. Theory Simul.

100

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Propagation rate coefficient of free‐radical polymerization of 1,3‐butadiene

Cited by 48 publications

References 15 publications

Towards the propagation rate coefficient for the free‐radical polymerization of 1,3‐butadiene

Towards the propagation rate coefficient for the free‐radical polymerization of 1,3‐butadiene

Seeded emulsion polymerization of butadiene. 2. Effects of persulfate and tert-dodecyl mercaptan

Pulsed initiation polymerization as a means of obtaining propagation rate coefficients in free-radical polymerizations. II Review up to 2000

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