Atom transfer radical polymerisation (ATRP) of methyl methacrylate in the presence of radical inhibitors

Haddleton, David M.; Clark, Andrew J.; Crossman, Martin C.; Duncalf, David J.; Heming, Alex M.; Morsley, Stuart R.; Shooter, Andrew J.

doi:10.1039/a702166f

Cited by 90 publications

(89 citation statements)

References 8 publications

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“…[28] Indeed, a lower rate of polymerization has been reported for the polymerization of methacrylates with Cu I /NPPMI and Cu I /NOPMI systems than with a Cu I /bpy system. [29,30,32] In acetonitrile, the value for k app was 2 times higher when the ratio of [L]/[Cu I ] ¼ 2/1 (L ¼ NPPMI or NOPMI) compared to a ratio of [L]/[Cu I ] ¼ 1/1 (Figure 1, entry 1, 3 and 4, 5 in Table 1). This is also similar to the results observed with the Cu I /bpy system.…”

Section: Resultsmentioning

confidence: 99%

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Effect of [Pyridylmethanimine]/[Cu^I] Ratio, Ligand, Solvent and Temperature on the Activation Rate Constants in Atom Transfer Radical Polymerization

Tang

Nanda

Matyjaszewski

2005

Macro Chemistry & Physics

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Summary: The effect of [L]/[CuI] ratio, ligand, the choice of solvent and temperature on the activation rate constants in ATRP with catalyst complexes formed with two pyridylmethanimine ligands [PMI, i.e., N‐propyl‐pyridylmethanimine (NPPMI) and N‐octyl‐pyridylmethanimine (NOPMI)] were studied. Maximal values for the apparent rate constants were observed at an [L]/[CuI] ratio of ∼2/1 and 1/1 in polar and nonpolar solvents, respectively. This is similar to the results obtained with the CuI/bpy system and was attributed to the formation of [CuI/L2]+Br− and [CuI/L2]+CuIBr species. The CuI/NPPMI system was only soluble in polar reaction media; however, the CuI/NOPMI complex was soluble in both polar and less polar reaction media. The activation rate constants increased with increasing temperature and the value of activation energy (Ea) for CuI/NPPMI in the activation process was 58.1 kJ · M−1 · K−1.Arrhenius plot of ln ka versus 1/T for the activation process for NPPMI and bpy in acetonitrile; [CuIBr/NPPMI2]0 ([CuIBr/bpy2]0)/[EtBriB]0/[TEMPO]0/[TCB]0 = 20/1/10/2 × 10−3 M.magnified imageArrhenius plot of ln ka versus 1/T for the activation process for NPPMI and bpy in acetonitrile; [CuIBr/NPPMI2]0 ([CuIBr/bpy2]0)/[EtBriB]0/[TEMPO]0/[TCB]0 = 20/1/10/2 × 10−3 M.

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Section: Resultsmentioning

confidence: 99%

“…[29][30][31] These ligands coordinate with Cu I and follow kinetics in the activation process similar to that of complexes formed with bpy. Although equilibrium constants were evaluated from the rate of ATRP, [32] direct measurements of the kinetics of the activation process with these ligands systems have not been carried out.…”

Section: Introductionmentioning

confidence: 99%

Effect of [Pyridylmethanimine]/[Cu^I] Ratio, Ligand, Solvent and Temperature on the Activation Rate Constants in Atom Transfer Radical Polymerization

Tang

Nanda

Matyjaszewski

2005

Macro Chemistry & Physics

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“…16,18 So, p-nitrobenzyl α-bromoisobutylate was synthesized via the esterification of p-nitrobenzyl alcohol with 2-bromoisobutyroyl bromide and used as initiator for the ATRP of MMA to prepare PMMAs with nitrophenyl-terminals. Figure 10 shows the GPC curves of PMMAs obtained at different monomer conversions initiated by p-nitrobenzyl α-bromoisobutylate.…”

Section: Resultsmentioning

confidence: 99%

“…In conventional free-radical polymerization, aromatic nitro compounds, such as nitrobenzene, trinitrobenzene, nitrotoluene, etc, are well known inhibitor or retarder. The influence of traditional radical inhibitors on ATRP has not been studied extensively except Haddleton 16 reported that ATRP of MMA mediated by copper(I) bromide, alkyl bromides and N-pentyl-2-pyridylmethanimine was enhanced by the addition of traditional radical inhibitors, 2,6-di-tertbutyl-4-methylphenol or 4-methoxyphenol. Therefore, the *Corresponding Author.…”

Section: Introductionmentioning

confidence: 98%

Study on atom transfer radical polymerization initiated by p-nitrophenyl initiator and synthesis of amino end-functionalized polymers thereof

Cai

et al. 2010

Macromol. Res.

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Atom transfer radical polymerization (ATRP) of styrene initiated by p-nitrobenzyl bromide and ATRP of methyl methacrylate (MMA) initiated by p-nitrobenzyl α-bromoisobutylate were carried out using CuBr/2,2'-bipyridine as a catalyst system. Controlled radical polymerization processes were involved in both reactions resulting in polystyrene and PMMA with nitrophenyl ends. The nitro ends of the polymers were converted to the amino-terminals through reduction in acetone with Fe and hydrochloric acid used as the reducing agent. The effect of nitrophenyl compounds on ATRP was examined and weak retardation was observed in both ATRP systems.

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“…It has already been demonstrated to provide efficient atom transfer polymerization catalysts for methyl methacrylate. 31,34,35 In our study, we obtained N-(n-propyl)-2-pyridinylmethanimine ligand by the reaction of pyridine-2-carboxaldehyde with n-propylamine in a high yield (above 90%) at room temperature. The ligand was characterized by 1 H NMR (Fig.…”

Section: Synthesis Of N-(n-propyl)-2-pyridinylmethanimine (Ligand)mentioning

confidence: 97%

Synthesis and characterization of the hydrophobic diblock copolymers of poly(dimethylsiloxane)‐block‐poly(ethyl methyl acrylate) through atom transfer radical polymerization

Luo

2008

J of Applied Polymer Sci

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The poly(dimethylsiloxane)-block-poly(ethyl methylacrylate) diblock copolymers (PDMS-b-PEMA) were synthesized by atom transfer radical polymerization (ATRP). The chemical structure of the copolymers was characterized by nuclear magnetic resonance (NMR) and Fourier transform infrared (FTIR) spectroscopy. Thermal behaviors were observed via differential scanning calorimetry (DSC). In the DSC curve, the resulting copolymers appear two glass transition temperatures (T-g's), one at -123 degrees C corresponding to the PDMS block and the other at 65 degrees C ascribed to the PEMA segment. Moreover, the copolymer microstructure was investigated by transmission electron microscopy (TEM). The results show that the diblock copolymers are microphase separated if the bulk contains enough PEMA segment. The surface properties of the PDMS-b-PEMA diblock copolymers were searched by contact angle. The PDMS-b-PEMA diblock copolymers are of low surface energy. The polymerization kinetics was also investigated, and the results show that the reaction proceeds in a living manner. (C) 2008 Wiley Periodicals, Inc

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Atom transfer radical polymerisation (ATRP) of methyl methacrylate in the presence of radical inhibitors

Cited by 90 publications

References 8 publications

Effect of [Pyridylmethanimine]/[Cu^I] Ratio, Ligand, Solvent and Temperature on the Activation Rate Constants in Atom Transfer Radical Polymerization

Effect of [Pyridylmethanimine]/[Cu^I] Ratio, Ligand, Solvent and Temperature on the Activation Rate Constants in Atom Transfer Radical Polymerization

Study on atom transfer radical polymerization initiated by p-nitrophenyl initiator and synthesis of amino end-functionalized polymers thereof

Synthesis and characterization of the hydrophobic diblock copolymers of poly(dimethylsiloxane)‐block‐poly(ethyl methyl acrylate) through atom transfer radical polymerization

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Atom transfer radical polymerisation (ATRP) of methyl methacrylate in the presence of radical inhibitors

Cited by 90 publications

References 8 publications

Effect of [Pyridylmethanimine]/[CuI] Ratio, Ligand, Solvent and Temperature on the Activation Rate Constants in Atom Transfer Radical Polymerization

Effect of [Pyridylmethanimine]/[CuI] Ratio, Ligand, Solvent and Temperature on the Activation Rate Constants in Atom Transfer Radical Polymerization

Study on atom transfer radical polymerization initiated by p-nitrophenyl initiator and synthesis of amino end-functionalized polymers thereof

Synthesis and characterization of the hydrophobic diblock copolymers of poly(dimethylsiloxane)‐block‐poly(ethyl methyl acrylate) through atom transfer radical polymerization

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Product

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Effect of [Pyridylmethanimine]/[Cu^I] Ratio, Ligand, Solvent and Temperature on the Activation Rate Constants in Atom Transfer Radical Polymerization

Effect of [Pyridylmethanimine]/[Cu^I] Ratio, Ligand, Solvent and Temperature on the Activation Rate Constants in Atom Transfer Radical Polymerization