A highly active homogeneous ICAR ATRP of methyl methacrylate using ppm levels of organocopper catalyst

Guo, Ting; Zhang, Lifen; Pan, Xiangqiang; Li, Xiaohong; Cheng, Zhenping; Zhu, Xiulin

doi:10.1039/c3py00309d

Cited by 23 publications

(17 citation statements)

References 57 publications

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“…However, normal ATRP shows some limitations regarding large-scale production, for instance, a large amount of metal usage and difficulty in the deoxygenation of the large vessels for commercial production. designed as a new route in synthesizing polymer materials such as reverse ATRP, 169 simultaneous reverse and normal initiation (SR&NI) ATRP, 170 activators generated by electron transfer (AGET) ATRP, 17,171,172 activators regenerated by electron transfer (ARGET) ATRP, 77,173 initiators for continuous activator 5 regeneration (ICAR) ATRP, [174][175][176][177] supplemental activator and reducing agent (SARA) ATRP, [178][179][180][181][182][183][184] electrochemically mediated ATRP (eATRP), 79,82,96 photoinduced ATRP, 185,186 and the controversial ATRP systems without reducing agent and radical initiator. 38, 42, 43, 66, 187-192 10 …”

Section: Iron(iii)-catalyzed Atrpmentioning

confidence: 99%

Iron-catalyzed atom transfer radical polymerization

2015

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In the last two decades, metal-catalyzed controlled radical polymerization (CRP), or atom transfer radical 5 polymerization (ATRP) has become a ubiquitous tool for the facile synthesis of a wide of materials with specific macromolecular architectures. The complex plays an important role in ATRP, and for this purpose researchers put a great deal of effort on studying the effect of various complexes on polymerization. However, one of disadvantages of copper complex which is the most extensively studied catalyst system in ATRP is the contamination of polymers resulted from a high concentration of stable catalyst. 10 Efficiently and economically removing the catalyst from the resultant polymers will open the way to a wide variety of new functional polymers for specialty applications, especially for large-scale industrial manufacture. Iron-based catalysts have attracted particular attention because of their low toxicity, low cost, abundance, and environmental friendliness, and thus many iron catalysts have been designed for ATRP. This article reviews the preparation of polymers using iron-catalyzed atom transfer radical 15 polymerization, and is organized according to: (a) mechanistic considerations; (b) Iron complexes and ligand types.

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Section: Iron(iii)-catalyzed Atrpmentioning

confidence: 99%

Iron-catalyzed atom transfer radical polymerization

2015

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“…However, an undesired chain transfer/exchange reaction is likely to occur because of the existence of the -S 2 CN(C 4 H 9 ) 2 group in those cases when using the above organic catalysts. [9][10][11][12] In order to exploit a new organic catalyst with a non-DC group, very recently, Matyjaszewski et al successfully reported a reversible-deactivation radical polymerization of methyl methacrylate and styrene using copper(II) acetylacetonate (Cu(acac) 2 ) or copper(II) hexafluoroacetylacetonate (Cu(hfa) 2 ) as the catalyst, and it showed excellent control over polymerization when employing Cu(hfa) 2 (PDI ∼ 1.1). 17 However, there have been no reports on ATRP using an organic iron catalyst with a non-DC group.…”

Section: Introductionmentioning

confidence: 99%

“…6g,h,l,m,8 There have been only a few reports involving organic metal salts with DC groups (e.g., -S 2 CN(C 4 H 9 ) 2 group) as the ATRP catalysts. [9][10][11][12][13] For instance, Cheng and Zhu et al 9 proposed highly active homogeneous initiators for continuous activator regeneration ATRP (ICAR ATRP) of methyl methacrylate (MMA) using organic copper N,N-n-butyldithiocarbamate copper (Cu(S 2 CN(C 4 H 9 ) 2 ) 2 ) as the catalyst and AIBN as the reducing agent.…”

Section: Introductionmentioning

confidence: 99%

Bulk AGET ATRP of methyl methacrylate using iron(iii) acetylacetonate as a catalyst

Liu

Zhang

et al. 2014

Polym. Chem.

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In this work, polymerization of methyl methacrylate (MMA) was successfully conducted by atom transfer radical polymerization with activators generated by electron transfer (AGET ATRP) at 90°C, using iron(III) acetylacetonate (Fe(acac) 3 ) as a catalyst, ethyl alpha-bromophenylacetate (EBPA) as an initiator, ascorbic acid (AsAc) as a reducing agent and triphenyl phosphine (PPh 3 ) as a ligand. The polymerization kinetics showed that the polymerization rate (the conversion reached up to 98.1% after 60 min) was much higher than that mediated by inorganic iron salts and it was affected by the feed of the iron catalyst. Moreover, the kinetic plots were linear, and the molecular weights of the resulting polymers with molecular weight distribution around 1.2, increased linearly with monomer conversions, indicating good features of "living"/ controlled radical polymerizations. The end-functionality of the polymers was confirmed by 1 H NMR spectroscopy and a chain extension experiment.

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“…The representative improved ATRP techniques were developed by Matyjaszewski's group, such as activators regenerated by electron transfer (ARGET) ATRP, initiators for continuous activator regeneration (ICAR) ATRP, and e ‐ATRP . Among them, ICAR ATRP was proved as one of the most advanced ATRP techniques, which could be conducted by using a significantly lower concentration of catalyst and air‐stable catalyst, namely, higher oxidation state transition metal …”

Section: Introductionmentioning

confidence: 99%

A Novel Janus Initiator for ATRP: Initiator Design and Application in Polymerization

Zhang

et al. 2015

Macro Chemistry & Physics

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A novel Janus compound containing azo‐based thermal initiator and bromo‐based atom transfer radical polymerization (ATRP) initiator group is synthesized. Such compound can be applied in the living radical polymerization of alkyl methacrylate monomers, such as methyl methacrylate, tert‐butyl methacrylate, and 2‐(N,N‐dimethylamino) ethyl methacrylate. Polymers with controlled molecular weights and narrow molecular weight distributions are obtained. The structure of polymers is identified by 1H NMR spectroscopy and matrix‐assisted laser desorption ionization time‐of‐flight mass spectrum. A modified initiator for continuous activator regeneration ATRP mechanism is proposed according to the polymerization behavior, hydrolysis of chain backbone, and end group identification.

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A highly active homogeneous ICAR ATRP of methyl methacrylate using ppm levels of organocopper catalyst

Cited by 23 publications

References 57 publications

Iron-catalyzed atom transfer radical polymerization

Iron-catalyzed atom transfer radical polymerization

Bulk AGET ATRP of methyl methacrylate using iron(iii) acetylacetonate as a catalyst

A Novel Janus Initiator for ATRP: Initiator Design and Application in Polymerization

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