Concurrent Initiation by Air in the Atom Transfer Radical Polymerization of Methyl Methacrylate

Nanda, Ajaya K.; Hong, Sung Chul; Matyjaszewski, Krzysztof

doi:10.1002/macp.200390088

Cited by 44 publications

(37 citation statements)

References 32 publications

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“…17 Zhu and coworkers mentioned that the Cu(II)-mediated reverse ATRP of styrene without thermal radical initiator could be successfully carried out via spontaneous generation of radicals from styrene by a Mayo-type process at higher temperature (above 110 C). 17 Zhu and coworkers mentioned that the Cu(II)-mediated reverse ATRP of styrene without thermal radical initiator could be successfully carried out via spontaneous generation of radicals from styrene by a Mayo-type process at higher temperature (above 110 C).…”

Section: Introductionmentioning

confidence: 99%

Facile iron(iii)-mediated ATRP of MMA with phosphorus-containing ligands in the absence of any additional initiators

et al. 2015

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A series of phosphorus-containing ligands was employed to establish a novel polymerization system for the iron(III)-mediated polymerization of methyl methacrylate (MMA) just using FeCl 3 $6H 2 O or FeBr 3 as the catalyst without any additional initiators and reducing agents. The polymerization results showed that this polymerization system involving MMA/FeX 3 (X ¼ Cl, Br)/phosphorus-containing ligand was a typical "living"/controlled radical polymerization process: first-order polymerization kinetics with respect to monomer concentration and a linear increase of the molecular weight of the resultant PMMAs with conversion while keeping a narrow molecular weight distribution. Chain end analysis of the obtained PMMA based on 1 H NMR, 31 P NMR were used to confirm the precise structure of the obtained polymers.The results showed that phosphorus-containing complexes acted as both ligand and thermal radical initiators in this process, which was consistent with a reverse atom transfer radical polymerization (reverse ATRP) mechanism.

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Section: Introductionmentioning

confidence: 99%

Facile iron(iii)-mediated ATRP of MMA with phosphorus-containing ligands in the absence of any additional initiators

et al. 2015

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“…Air-triggered reverse ATRP was suspected to be the culprit, as in the previously reported methacrylate polymerization in the absence of ATRP initiators. 45,46 To identify the suitable catalyst concentration for the reaction, we varied the concentration of CuCl in the catalyst mixture from 0.1 to 69 mM while keeping CuBr 2 at a fixed 30% molar ratio with respect to CuCl ( Figure 5B). For 5 h, the thickest film formed was from the reaction using 23 mM CuCl/6.9 mM CuBr 2 , whereas both higher and lower catalyst concentrations showed the formation of thinner films.…”

Section: Resultsmentioning

confidence: 99%

DNA-Accelerated Atom Transfer Radical Polymerization on a Gold Surface

Lou

2006

Langmuir

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A significantly increased polymer growth rate was observed during a surface-initiated ATRP reaction in the presence of DNA molecules. To investigate this phenomenon, thiolated single-stranded DNA molecules (ssDNAs) with ATRP initiators coupled at the distal point were used as the model molecule in the study. In comparison, a small molecule, HS-(CH(2))(11)NHCOC(CH(3))(2)Br, was used to provide a less-polar surface coating for polymer grafting. 2-Hydroxyethyl methacrylate (HEMA) and monomethoxy-capped oligo(ethylene glycol) methacrylate (OEGMA) were used as the ATRP monomers. The polymer growth rates were monitored by measuring the thickness of the polymer films formed at different times. Our results show that the presence of DNA molecules, although at a less-than-1% surface coverage, significantly accelerated the growth rates of both poly(2-hydroxyethyl methacrylate) (PHEMA) and poly(oligoethylene glycol methacrylate) (POEGMA) at the beginning of the ATRP reactions. This accelerating effect was suspected to be a combined result of the highly charged sugar-phosphate backbones of DNA molecules and the formation of Cu complexes with DNA bases. After the initial polymer growth, a smaller yet constant polymer growth rate was observed, suggesting the reduced influence of DNA molecules as the ATRP reaction centers moved farther away from the surface. Similar to conventional ATRP reactions, the polymer growth from surface-anchored DNA molecules was found to be strongly dependent on the composition and the concentration of the catalysts used. Specifically, a catalyst mixture of CuCl/30% CuBr(2)/bpy with 23 mM CuCl was found to provide the optimal reaction condition to yield the fastest polymer film growth among the conditions tested.

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“…In the deoxygenated system, the solution was purged with argon for 20 min; in the oxygen-added system, the addition of oxygen followed the Refs. [24,28]. The procedures were as follows: air was eliminated completely from the reaction mixture by three freezeepumpethaw cycles (high vacuum, pressure: 3 Pa).…”

Section: Raft Polymerization Of St In the Presence Of Oxygenmentioning

confidence: 99%

Reversible addition–fragmentation chain transfer (RAFT) polymerization of styrene in the presence of oxygen

Zhang¹,

Zhu²,

Cheng³

et al. 2007

Polymer

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Concurrent Initiation by Air in the Atom Transfer Radical Polymerization of Methyl Methacrylate

Cited by 44 publications

References 32 publications

Facile iron(iii)-mediated ATRP of MMA with phosphorus-containing ligands in the absence of any additional initiators

Facile iron(iii)-mediated ATRP of MMA with phosphorus-containing ligands in the absence of any additional initiators

DNA-Accelerated Atom Transfer Radical Polymerization on a Gold Surface

Reversible addition–fragmentation chain transfer (RAFT) polymerization of styrene in the presence of oxygen

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