Encyclopedia of Polymer Science and Technology 2003
DOI: 10.1002/0471440264.pst306
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Radical Polymerization

Abstract: The present article summarizes the fundamental principles and recent advances in free radical polymerization systems. Each individual reaction step in the polymerization process—initiation, propagation, transfer, and termination—is discussed in detail with regard to the underlying first principles and to the latest rate coefficient data. Novel methodologies, including living free radical polymerization, are also introduced within this context. In addition, the article gives an up‐to‐date overview of current st… Show more

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Cited by 11 publications
(14 citation statements)
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“…It may therefore be inferred that irreversible cross-termination alone cannot describe the rate retardation effect in RAFT polymerization of MA over the employed range of CDB concentration. On the other hand, CDB-mediated styrene polymerization in toluene solution can be well described by the concept of dominant cross-termination underlying Equation (4). This is demonstrated in Figure 7, where our recent polymerization rate data for the CDB-styrene system in toluene solution are plotted according to Equation (4), yielding a straight-line correlation.…”
Section: Rate Of Polymerizationmentioning
confidence: 87%
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“…It may therefore be inferred that irreversible cross-termination alone cannot describe the rate retardation effect in RAFT polymerization of MA over the employed range of CDB concentration. On the other hand, CDB-mediated styrene polymerization in toluene solution can be well described by the concept of dominant cross-termination underlying Equation (4). This is demonstrated in Figure 7, where our recent polymerization rate data for the CDB-styrene system in toluene solution are plotted according to Equation (4), yielding a straight-line correlation.…”
Section: Rate Of Polymerizationmentioning
confidence: 87%
“…The data for CDB-mediated styrene polymerization in solution with carbon dioxide, which are also contained in Figure 7, however, tells that no straight-line dependence is obtained when plotting the R p data according to Equation (4). The curvature of the R p À2 vs.…”
Section: Rate Of Polymerizationmentioning
confidence: 96%
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“…Among the vinyl monomers, styrene has shown high tendency for thermal self-initiation. The proposed mechanism is the formation of two monoradicals from two styrene monomers via self-Diels-Alder cycloaddition [13,14]. Monomer self-initiation strongly depends on temperature; styrene needs more than one year to self-polymerize to reach 50% conversion at 29 • C, however, the same conversion will be obtained after only 4 h at 127 • C. In addition to styrene, thermal self-initiation of acrylate and methacrylate monomers have been studied [15][16][17].…”
Section: Introductionmentioning
confidence: 99%
“…It is hence clear that a detailed knowledge of initiator efficiency is crucial for a quantitative description of radical polymerization kinetics, as it directly impacts the actual radical flux that propels the polymerization. [1] Initiator efficiency data is also of vital importance for technical polymerization processes, as it governs the costs for initiator consumption and reflects the level of sideproduct formation. The latter is, e.g., of serious concern in the case of initiation by 2,2 0 -azoisobutyronitrile (AIBN), which readily generates the highly toxic tetramethyl succinonitrile via in-cage recombination of the primary radicals.…”
Section: Introductionmentioning
confidence: 99%