Evaluation of individual rate constants from the chain‐length distribution of polymer samples prepared by intermittant (rotating sector) photo‐polymerization, 1. First experiences with styrene and methyl methacrylate

The chain transfer-to-monomer dominated regime of the molar mass distribution of lowconversion emulsion copolymers of styrene and methyl acrylate and of styrene and methyl methacrylate of various compositions, prepared with varying initiator concentrations, was analyzed with size exclusion chromatography. By extrapolation of the values of the slope of the natural logarithm of the number molar mass distribution to zero initiator concentration, it was possible to determine the average chaintransfer coefficient as a function of composition. By calculation of the ratio of the concentrations of styreneterminated radicals and methyl (meth)acrylate-terminated radicals with an appropriate propagation model, the values of the cross-chain transfer rate constants of styrene-terminated radicals to methyl acrylate and methyl methacrylate could be deduced. These values were interpreted in the light of newly gained insights into radical propagation and transfer reactions.

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“…Fortunately this also applies to the monomer systems used in this work [27][28][29][30] (see Results and Discussion).…”

Section: Methods For Determining the Rate Of Chain Transfermentioning

confidence: 82%

Cross-Chain Transfer Rate Constants of Styrene-Terminated Radicals to Methyl Acrylate and Methyl Methacrylate

et al. 1996

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“…Only two measurements are required, and there are no problems with the validity of the stationary state hypothesis or difficulties associated with chain termination rates or measurements of initiation rates. The method depends on the observation 17,18 that if a pulse in the nanosecond range is used to initiate polymerization, a normal statistical distribution of terminated polymer chains will be produced during the following dark period. If a second pulse is used before all the chains have terminated, it will create a high concentration of primary radicals that will terminate virtually all the remaining growing chains.…”

Section: Free-radical-initiated Polymerizationmentioning

confidence: 99%

Absolute propagation constants in vinyl polymerization

Bywater

1999

J. Polym. Sci. A Polym. Chem.

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“…12-14 Professor Olaj pursued a similar approach, and he also confirmed Fukuda's discovery. 15 Fukuda et al 16 then developed a kinetic model to explain their experimental observations, and this became known as the implicit penultimate unit model.…”

Section: Fukuda's Contribution and The Aftermathmentioning

confidence: 99%

The mechanism of propagation in free-radical copolymerization

Davis

2001

J. Polym. Sci. A Polym. Chem.

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Evaluation of individual rate constants from the chain‐length distribution of polymer samples prepared by intermittant (rotating sector) photo‐polymerization, 1. First experiences with styrene and methyl methacrylate

Cited by 64 publications

References 8 publications

Cross-Chain Transfer Rate Constants of Styrene-Terminated Radicals to Methyl Acrylate and Methyl Methacrylate

Cross-Chain Transfer Rate Constants of Styrene-Terminated Radicals to Methyl Acrylate and Methyl Methacrylate

Absolute propagation constants in vinyl polymerization

The mechanism of propagation in free-radical copolymerization

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