Rate enhancement for nitroxide stable free radical polymerization of <i>n</i>‐butyl acrylate by dodecylbenzenesulfonic acid

Cheng, Kuo‐Chung; Chen, Jiun-Jeng; Chiu, Wen‐Yen; Wang, Lee Yih; Wang, Ping-Chieh

doi:10.1002/pola.20398

Cited by 11 publications

(9 citation statements)

References 22 publications

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“…Free radical polymerization mediated by nitroxide radicals such as 2,2,6,6‐tetramethylpiperidinooxy (TEMPO) and its derivatives has been investigated extensively 1–7. Nitroxide‐mediated polymerization is a simple route to synthesize well‐defined polymers.…”

Section: Introductionmentioning

confidence: 99%

“…Nitroxide‐mediated polymerization is a simple route to synthesize well‐defined polymers. Unfortunately, only styrene and its derivatives were found to be capable of controlled/living polymerization in the presence of TEMPO at 110–130 °C 2, 4, 5, 7. TEMPO‐mediated polymerization of acrylic monomers such as acrylic acid, n ‐butyl acrylate and methyl methacrylate (MMA) or other polar monomers has been considered a challenge, and now it can be achieved using special nitroxide radicals.…”

Section: Introductionmentioning

confidence: 99%

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Influence of DMF on the polymerization of tert‐butyl acrylate initiated by 4‐oxo‐TEMPO‐capped polystyrene macroinitiator

Kuo

Chiu

Cheng

2008

Polymer International

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BACKGROUND: In a number of studies it has been shown that 2,2,6,6‐tetramethylpiperidinooxy (TEMPO)‐mediated polymerization of acrylates is not facile. Therefore, the object of the study reported here was to prepare poly[styrene‐block‐(tert‐butyl acrylate)] (PS‐b‐PtBA) block copolymers using 4‐oxo‐TEMPO‐capped polystyrene macroinitiator as an initiator, in the presence of small amounts of N,N‐dimethylformamide (DMF). The kinetic analysis and the effect of DMF on the reaction mechanism are also discussed. RESULTS: PS‐b‐PtBA block copolymer was prepared through polymerization of tert‐butyl acrylate (tBA) initiated by 4‐oxo‐TEMPO‐capped polystyrene macroinitiator at 135 °C. The polymerization rate of tBA could be increased by adding a small amount of DMF, and the number average molecular weight of the PtBA block in PS‐b‐PtBA reached 10 000 g mol−1 with narrow polydispersity. The activation rate constant kact−tBA of alkoxyamine increased and the recombination rate constant krec−tBA decreased with increasing DMF concentration. CONCLUSION: DMF was shown to be a rate‐enhancing additive for the polymerization of tBA using a 4‐oxo‐TEMPO‐capped polystyrene macroinitiator. From the kinetic analysis, it was concluded that the improvement of polymerization with the addition of DMF was due to an increase in kact−tBA and a decrease in krec−tBA. Copyright © 2008 Society of Chemical Industry

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Influence of DMF on the polymerization of tert‐butyl acrylate initiated by 4‐oxo‐TEMPO‐capped polystyrene macroinitiator

Kuo

Chiu

Cheng

2008

Polymer International

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“…In the last few years, nitroxide‐mediated living radical polymerization has been widely used in the synthesis of controlled macromolecular structures 1–6. Also, previous limitations of this technique, such as slow reactions or poor control, have been successfully addressed and overcome to various extents by different authors 7–11. Because of its practical implications, considerable attention has been given to the mechanism and kinetics of the nitroxide‐mediated polymeri zation (NMP) of styrene,12–21 and a fair grasp of its general features seems to be well established, despite a still incomplete understanding of the mechanism of thermal styrene autoinitiation.…”

Section: Introductionmentioning

confidence: 99%

Incubation period in the 2,2,4,4‐tetramethyl‐1‐piperidinyloxy‐mediated thermal autopolymerization of styrene: Kinetics and simulations

Saldívar‐Guerra

Bonilla

Zacahua³

et al. 2006

J. Polym. Sci. A Polym. Chem.

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Mechanisms and simulations of the induction period and the initial polymerization stages in the nitroxide‐mediated autopolymerization of styrene are discussed. At 120–125 °C and moderate 2,2,4,4‐tetramethyl‐1‐piperidinyloxy (TEMPO) concentrations (0.02–0.08 M), the main source of radicals is the hydrogen abstraction of the Mayo dimer by TEMPO [with the kinetic constant of hydrogen abstraction (kh)]. At higher TEMPO concentrations ([N•] > 0.1 M), this reaction is still dominant, but radical generation by the direct attack against styrene by TEMPO, with kinetic constant of addition kad, also becomes relevant. From previous experimental data and simulations, initial estimates of kh ≈ 1 and kad ≈ 6 × 10−7 L mol−1 s−1 are obtained at 125 °C. From the induction period to the polymerization regime, there is an abrupt change in the dominant mechanism generating radicals because of the sudden decrease in the nitroxide radicals. Under induction‐period conditions, the simulations confirm the validity of the quasi‐steady‐state assumption (QSSA) for the Mayo dimer in this regime; however, after the induction period, the QSSA for the dimer is not valid, and this brings into question the scientific basis of the well‐known expression kth[M]3 (where [M] is the monomer concentration and kth is the kinetic constant of autoinitiation) for the autoinitiation rate in styrene polymerization. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6962‐6979, 2006

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“…18 However, the use of additives in controlled polymerization makes the process more expensive and/or complicates things further due to possible side reactions.…”

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confidence: 99%

Effect of initiator type and concentration on polymerization rate and molecular weight in the bimolecular nitroxide‐mediated radical polymerization of styrene

Nogueira¹,

Gonçalves²,

Lona³

et al. 2010

Adv Polym Technol

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ABSTRACT:To increase the polymerization rate in the bimolecular nitroxide-mediated radical polymerization (NMRP) of styrene, without using expensive non-commercial reagents, an experimental study using 2,2,6,6-tetramethyl-1-piperidinoxyl as a controller and tert-butylperoxy 2-ethylhexyl carbonate (TBEC) as the initiator was carried out. The basis for comparison was the bimolecular NMRP of styrene with dibenzoyl peroxide as initiator. It was found that faster polymerization rates and still relatively low polydispersities were possible using TBEC. C

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Rate enhancement for nitroxide stable free radical polymerization of n‐butyl acrylate by dodecylbenzenesulfonic acid

Cited by 11 publications

References 22 publications

Influence of DMF on the polymerization of tert‐butyl acrylate initiated by 4‐oxo‐TEMPO‐capped polystyrene macroinitiator

Influence of DMF on the polymerization of tert‐butyl acrylate initiated by 4‐oxo‐TEMPO‐capped polystyrene macroinitiator

Incubation period in the 2,2,4,4‐tetramethyl‐1‐piperidinyloxy‐mediated thermal autopolymerization of styrene: Kinetics and simulations

Effect of initiator type and concentration on polymerization rate and molecular weight in the bimolecular nitroxide‐mediated radical polymerization of styrene

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