On the Mechanism and Kinetics of TEMPO-Mediated Radical Copolymerization

Zaremski, M. Yu.; Plutalova, A. V.; Garina, E. S.; Lachinov, M. B.; Голубев, В. Б.

doi:10.1021/ma981753x

Cited by 21 publications

(16 citation statements)

References 6 publications

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“…As concluded by many studies, the main reason for the absence of a controlled nature of TEMPO‐mediated polymerization of acrylic monomers is not only a small equilibrium constant ( K = k act / k rec ) between the dormant and active polymeric species in the system, but also an increase in excess free TEMPO concentration during polymerization. The two effects could reduce the rate of TEMPO‐mediated polymerization of acrylates 3, 8, 14, 20, 21. As concluded in our previous study,22 4‐oxo‐TEMPO‐mediated polymerization of butyl acrylate at 165 °C is strongly influenced by the hydrogen transfer reaction of hydroxylamine (4‐oxo‐TEMPOH) to the growing radicals, which results in the accumulation of nitroxide radicals and a slow rate of polymerization.…”

Section: Introductionmentioning

confidence: 69%

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: 69%

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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“…[55][56][57] Copolymers in these systems displayed rather broad molecular weight distributions (M W /M n b 2), suggesting heterogeneity in both composition and molecular architecture (no precise composition data were reported).…”

Section: Gradient Copolymers From Controlled Radical Polymerizationsmentioning

confidence: 99%

Gradient copolymers by atom transfer radical copolymerization

Matyjaszewski

Ziegler

Arehart

et al. 2000

J. Phys. Org. Chem.

415

391

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“…For instance, the application of the spin traps has helped to solve a number of problems in complexradical polymerization and copolymerization (Golubev et al, 1978). They have also helped to address controversies related to spontaneous initiation and unusual inhibition of some polymerization systems (Zaremski et al, 1999). We hope that the results presented in this work will encourage the further development and application of these techniques for RAFT polymerization and other controlled radical polymerization processes.…”

Section: Resultsmentioning

confidence: 82%