Polymerization Kinetics of n-Lauryl Acrylate

Scott, Gregory E.; Senogles, E.

doi:10.1080/00222337008061005

Cited by 51 publications

(41 citation statements)

References 17 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Intramolecular chain transfer, also termed backbiting, refers to transfer to the backbone of the same propagating polymer chain and not to another species. This kind of transfer can occur at elevated polymerization temperatures for some monomers (e.g., acrylic monomers) and a radical of reduced propagation reactivity can be generated (Scott and Senogles, 1970).…”

Section: Chain Transfer Reactionsmentioning

confidence: 99%

Biodiesel: a green polymerization solvent

Salehpour

Dubé

2008

Green Chem.

View full text Add to dashboard Cite

In an effort to use clean technologies, fatty acid methyl esters (FAME) produced from canola have been used as a polymerization solvent. Solution polymerizations of four commercially important monomers have been studied using FAME as a solvent. A series of methyl methacrylate (MMA), styrene (Sty), butyl acrylate (BA) and vinyl acetate (VAc) homopolymerizations in FAME were carried out at 60 • C at different solvent concentrations. Chain transfer to solvent rate constants were obtained using the Mayo method. The transfer constants increased in the order: MMA < Sty < BA < VAc. Under the conditions studied, the MMA solution polymerization in FAME was observed to behave as a precipitation polymerization. The estimated chain transfer to solvent rate constants were employed in a polymerization simulator to predict the polymerization rates and average molecular weights.

show abstract

Section: Chain Transfer Reactionsmentioning

confidence: 99%

Biodiesel: a green polymerization solvent

Salehpour

Dubé

2008

Green Chem.

View full text Add to dashboard Cite

show abstract

“…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%

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

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

show abstract

“…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

View full text Add to dashboard Cite

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.

show abstract

Polymerization Kinetics of n-Lauryl Acrylate

Cited by 51 publications

References 17 publications

Biodiesel: a green polymerization solvent

Biodiesel: a green polymerization solvent

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

Chain‐Length‐Dependent Termination in Radical Polymerization of Acrylates

Contact Info

Product

Resources

About