Practical Radical Additions under Mild Conditions Using 2,2‘-Azobis(2,4-dimethyl-4-methoxyvaleronitrile) [V-70] as an Initiator

Kita, Yasuyuki; Gotanda, Kentoku; Murata, Kenji; Suemura, Miki; Sano, Atsunori; Yamaguchi, Takahiro; Oka, and Masahisa; Matsugi, Masato

doi:10.1021/op970059z

Cited by 48 publications

(24 citation statements)

References 14 publications

(14 reference statements)

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“…In particular, r-AMDV and m-AMDV produced the PMMA with the narrowest MWD. r-AMDV had a higher [P] and IE than m-AMDV, being in good agreement with the fact that r-AMDV has a higher reactivity than m-AMDV [67]. As a result of doubling MTEMPO to the initiator, all the initiators produced PMMA with a MWD below 1.7, and the resulting PMMAs showed sharp GPC curves.…”

Section: Effect Of Initiatorssupporting

confidence: 79%

“…In fact, the formation of a significant amount of hydroxylamine lowered the yield of CMTMP in its preparation by the reaction of MTEMPO and AIBN. The molecular weight distributions of the resulting polymers were somewhat broadened as compared to those of the polymers obtained by the photopolymerization by AIBN and 4-methoxy-TEMPO in the presence of BAI [36,67]. This broad molecular weight distribution was probably due to the slow initiation by CMTMP having a low photo activity.…”

Section: Mechanismsmentioning

confidence: 89%

“…Racemic-(2RS,2'RS)-azobis(4-methoxy-2,4-dimethylvaleronitrile) (r-AMDV) and meso-(2RS,2'SR)-azobis(4-methoxy-2,4-dimethylvaleronitrile) (m-AMDV) were obtained by separation from their mixture by recrystallization from ether [67]. 4-Methoxy-TEMPO was prepared as reported previously [80].…”

Section: Methodsmentioning

confidence: 99%

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Controlled Photoradical Polymerization Mediated by 2,2,6,6-Tetramethylpiperidine-1-Oxyl

Yoshida

2012

Polymers

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Abstract:In recent years, controlled photoradical polymerization has been established using 2,2,6,6-tetramethylpiperidine-1-oxyl as a mediator. This review article will describe the molecular weight control, polymerization mechanism, influence of initiator structure, effect of substituents supported on photo-acid generator, stability of the propagating chain end, photo-latency of the polymerization, molecular design, and an application to heterogeneous polymerization in an alcoholic medium.

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Section: Effect Of Initiatorssupporting

confidence: 79%

Section: Mechanismsmentioning

confidence: 89%

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Controlled Photoradical Polymerization Mediated by 2,2,6,6-Tetramethylpiperidine-1-Oxyl

Yoshida

2012

Polymers

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“…Materials: (2RS,2'RS)-Azobis(4-methoxy-2,4-dimethylvaleronitrile) (r-AMDV) was obtained by separation from a mixture of the racemic and meso forms of 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) [38]. MTEMPO was prepared as reported previously [39].…”

Section: Methodsmentioning

confidence: 99%

Selective Controlled/Living Photoradical Polymerization of Glycidyl Methacrylate, Using a Nitroxide Mediator in the Presence of a Photosensitive Triarylsulfonium Salt

Yoshida

2012

Polymers

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Abstract:The controlled/living photoradical polymerization of glycidyl methacrylate (GMA) was attained using 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl (MTEMPO) as the mediator and (2RS,2'RS)-azobis(4-methoxy-2,4-dimethylvaleronitrile) as the initiator in the presence of (4-tert-butylphenyl)diphenylsulfonium triflate ( t BuS). Whereas the polymerization in the absence of MTEMPO yielded a gel-containing polymer, the MTEMPO-mediated polymerization produced poly(GMA) bonded at the vinyl site, and retained the oxirane ring structure. No occurrence of the cationic ring-opening photopolymerization of the oxirane ring even in the presence of the photosensitive onium salt indicated that t BuS served as the photoelectron transfer agent between MTEMPO in their excited states at the propagating chain end. The resulting polymers had comparatively narrow molecular weight distributions of M w /M n = 1.46-1.48. The living nature of the MTEMPO-mediated polymerization was confirmed on the basis of a linear increase in the conversion-molecular weight plots and gel permeation chromatography (GPC) analysis.

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“…(2RS, 2'RS)-Azobis(4-methoxy-2,4-dimethylvaleronitrile) (r-AMDV) was obtained by separation from a mixture of the racemic and meso forms of 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) [56]. Methyl methacrylate (MMA) was washed with 5 wt.% sodium hydroxide solution and water, then distilled over calcium hydride.…”

Section: Methodsmentioning

confidence: 99%

Elucidation of Acceleration Mechanisms by a Photosensitive Onium Salt for Nitroxide-Mediated Photocontrolled/Living Radical Polymerization

Yoshida¹

2014

OJPChem

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The acceleration mechanisms by a photosensitive onium salt for the nitroxide-mediated photocontrolled/living radical polymerization (photo-NMP) were determined. The photo-NMP of methyl methacrylate was performed by irradiation at room temperature using 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl (MTEMPO) as the mediator and (2RS, 2'RS)-azobis(4-methoxy-2,4-dimethylvaleronitrile) as the initiator. The polymerization was accelerated in the presence of (4-tertbutylphenyl)diphenylsulfonium triflate ( t BuS) to produce a polymer with a molecular weight distribution as narrow as the polymerization in its absence. (±)-Camphor-10-sulfonic acid or 2-fluoro-1-methylpyridinium p-toluenesulfonate had no effect on the polymerization speed, suggesting that t BuS did not serve as the photo-acid generator for the photo-NMP. It was found that the acceleration of the polymerization was based on the electron transfer from MTEMPO into t BuS in the excited state to temporarily generate a free radical propagating chain end and an oxoaminium salt (OAS), the one-electron oxidant of MTEMPO. This electron transfer mechanism was verified on the basis of the fact that the photo-NMP in the presence of t BuS was still accelerated by triphenylamine, the electron transfer inhibitor, to partly produce a polymer with an uncontrolled molecular weight. The formation of an uncontrolled molecular weight polymer indicated the generation of a free radical propagating chain end due to the deactivation of the OAS by the triphenylamine. It was deduced that t BuS served as the electron acceptor from MTEMPO in the excited state to temporarily produce a free radical propagating chain end along with OAS, resulting in the acceleration of the polymerization.

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Practical Radical Additions under Mild Conditions Using 2,2‘-Azobis(2,4-dimethyl-4-methoxyvaleronitrile) [V-70] as an Initiator

Cited by 48 publications

References 14 publications

Controlled Photoradical Polymerization Mediated by 2,2,6,6-Tetramethylpiperidine-1-Oxyl

Controlled Photoradical Polymerization Mediated by 2,2,6,6-Tetramethylpiperidine-1-Oxyl

Selective Controlled/Living Photoradical Polymerization of Glycidyl Methacrylate, Using a Nitroxide Mediator in the Presence of a Photosensitive Triarylsulfonium Salt

Elucidation of Acceleration Mechanisms by a Photosensitive Onium Salt for Nitroxide-Mediated Photocontrolled/Living Radical Polymerization

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