Polymerization Kinetics of n-Alkyl Acrylates

Scott, Gregory E.; Senogles, E.

doi:10.1080/00222337408066396

Cited by 54 publications

(51 citation statements)

References 18 publications

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“…Only Scott and Senogles [8][9][10] foresaw the importance of backbiting also for acrylate polymerization. However, the significance of their findings was not fully appreciated by other researchers at the time.…”

Section: Introductionmentioning

confidence: 99%

“…From the abundance of quaternary carbons they deduced the branching frequency and concluded that the origin of these branches must be inter-and more notably intramolecular transfer to polymer reactions [17][18][19] giving a late confirmation for the backbiting theory. [8][9][10] Parallel to the investigations into the level of branching in acrylate polymerizations, difficulties in the determination of the propagation rate coefficient, k p , for alkyl acrylates became apparent. k p is determined by the IUPAC-recommended technique pulsed laser polymerization-size exclusion chromatography (PLP-SEC), in which the propagation rate is deduced from the characteristic molecular weight pattern that is produced upon laser initiation at a constant pulse rate.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

The role of mid‐chain radicals in acrylate free radical polymerization: Branching and scission

Junkers

Barner‐Kowollik

2008

J. Polym. Sci. A Polym. Chem.

213

326

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The past 5 years have seen a significant increase in the understanding of the fate of so‐called mid‐chain radicals (MCR), which are formed during the free radical polymerization of monomers that form highly reactive propagating radicals and contain an easily abstractable hydrogen atom. Among these monomers, acrylates are, beside ethylene, among the most prominent. Typically, a secondary propagating acrylate‐type macroradical (SPR) can easily transfer its radical functionality via a six‐membered transition state to a position within the polymer chain (in a so‐called backbiting reaction), creating a tertiary MCR. Alternatively, the radical function can be transferred intramolecularly to any position within the chain (also forming an MCR) or intermolecularly to another polymer strand. This article aims at providing a comprehensive overview of the up‐to‐date knowledge about the rates at which MCRs are formed, their secondary reactions as well as the consequences of their occurrence under variable reaction conditions. We explore the latest aspects of their detection (via electron spin resonance spectroscopy) as well as the characterization of the polymer structures to which they lead (via high resolution mass spectrometry). The presence of MCRs leads to the formation of branched polymers and the partial formation of polymer networks. They also limit the measurement of kinetic parameters (such as the SPR propagation rate coefficient) with conventional methods. However, their occurrence can also be used as a synthetic handle, for example, the high‐temperature preparation of macromonomers. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7585–7605, 2008

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

The role of mid‐chain radicals in acrylate free radical polymerization: Branching and scission

Junkers

Barner‐Kowollik

2008

J. Polym. Sci. A Polym. Chem.

213

326

View full text Add to dashboard Cite

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“…Most studies have concentrated on butyl acrylate (BA), [1][2][3][4][5][6][7][8][9][10][11][12][13] with this monomer being taken as typical of the entire family. Understanding of the polymerization kinetics of acrylate-type monomers is important not just for scientific reasons, but also because the industrial importance of these monomers makes it essential that their kinetic behavior can be well modeled.…”

Section: Introductionmentioning

confidence: 99%

Chain‐Length‐Dependent Termination in Radical Polymerization of Acrylates

Barth

Buback

Russell

et al. 2011

Macro Chemistry & Physics

147

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SUMMARY:The technique of SP PLP EPR, which is single-pulse pulsed-laser polymerization (SP PLP) in conjunction with electron paramagnetic resonance (EPR) spectroscopy, is used to carry out a detailed investigation of secondary (chain-end) radical termination of acrylates. Measurements are performed on methyl acrylate, n-butyl acrylate and dodecyl acrylate in bulk and in toluene solution at -40 °C. The reason for the low temperature is to avoid formation of mid-chain radicals, a complicating factor that has imparted ambiguity to the results of previous studies of this nature. Consistent with these previous studies, composite-model behavior for chain-length-dependent termination rate, is found in this work. However, lower and more reasonable values of α s , the exponent for variation of k t i,i at short chain lengths, are found in the present study.

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“…The calculations that follow thus do not include the range of very high conversions (x F 0.8). The kinetic parameters for MMA, styrene 11,26,27) and BA 28,29) polymerizations are given in Tab. 1.…”

Section: Calculations and Discussionmentioning

confidence: 99%

Modeling termination kinetics in free-radical polymerization using a reduced number of parameters

Buback¹,

Egorov²,

Kaminsky³

1999

Macromol. Theory Simul.

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SUMMARY: An approach for modeling chain-length dependent termination rate coefficients is presented. The method is based on the assumption that free-radical chain length may be considered as a continuous variable. As compared to discrete numerical methods, in continuous modeling the number of independent dimensionless parameters can be significantly reduced. As a consequence, for a wide variety of monomers the conversion dependence of k t can be predicted without extensive numerical calculations. The method may also be used to determine polymerization conditions under which simpler models of k t (which neglect effects arising from the dependence of k t on chain length) may be applied. Calculations for methyl methacrylate, styrene, and butyl acrylate bulk polymerizations up to high degrees of monomer conversion show that the impact of chain length on termination varies with conversion and strongly depends on the type of monomer.

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Polymerization Kinetics of n-Alkyl Acrylates

Cited by 54 publications

References 18 publications

The role of mid‐chain radicals in acrylate free radical polymerization: Branching and scission

The role of mid‐chain radicals in acrylate free radical polymerization: Branching and scission

Chain‐Length‐Dependent Termination in Radical Polymerization of Acrylates

Modeling termination kinetics in free-radical polymerization using a reduced number of parameters

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