Effect of a π‐donor on the radical bulk polymerization of methyl methacrylate

Wunderlich, Wiebke; Benfaremo, Nick; Klapper, Markus; Müllen, Kläus

doi:10.1002/marc.1996.030170610

Cited by 12 publications

(3 citation statements)

References 13 publications

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“…[8][9][10][11] Additionally, it has been reported that aromatic solvents may play a role in mediating the radical polymerization of methyl methacrylate. 12 It has been established that radical cations can be directly stabilized by electronrich p-systems. 13,14 Anchimeric assistance in radical reactions is quite rare and reports have mostly been restricted to 1,3 neighbouring group effects.…”

mentioning

confidence: 99%

Remote aromatic stabilization in radical reactions

Cabellero

Croft

Nalli

2008

Tetrahedron Letters

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The rates of free radical reduction of a series of anthracene derivatives and 1-phenyl-4-bromodecane with tributyltin hydride are mediated by the remote aromatic substituent in an apparent through-space interaction. Density functional calculations suggest that this enhancement is not due to direct stabilization of the free radical intermediate, and is likely to be achieved through the interaction of the aromatic moiety with the polarized transition state leading to the intermediate.

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confidence: 99%

Remote aromatic stabilization in radical reactions

Cabellero

Croft

Nalli

2008

Tetrahedron Letters

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“…Thermal Stability of PGMA. The thermal stability of polymer is in direct relationship with the polymer structure, and therefore one could expect desirable information on the regioselectivity and the extent of termination reactions during the polymerization process. , Figure a shows the TG spectra of PGMA synthesized via five different initiating systems: (1) by conventional free-radical polymerization (FRP) using AIBN initiator ( M n = 91 850, M w / M n = 1.49); (2) by ATRP (a) CuBr/BPN ( M n = 6800, M w / M n = 1.30), (b) CuBr/ClPN ( M n = 15 750, M w / M n = 1.76), (c) CuCl/ClPN ( M n = 19 560, M w / M n = 2.14), and (d) CuCl/BPN ( M n = 8100, M w / M n = 1.35). The DTG spectra of PGMA synthesized via five different initiating systems is shown in Figure b.…”

Section: Resultsmentioning

confidence: 99%

Room Temperature Atom Transfer Radical Polymerization of Glycidyl Methacrylate Mediated by Copper(I)/N-Alkyl-2-pyridylmethanimine Complexes

Krishnan

Srinivasan

2004

Macromolecules

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The homogeneous controlled/"living" free radical polymerization of glycidyl methacrylate (GMA) by atom transfer radical polymerization (ATRP) using Cu(I)X/N-alkyl-2-pyridylmethanimine complexes with various initiators R-X (X ) Cl, Br) and solvents was investigated. Most of these systems display characteristics of a living radical polymerization as indicated by (a) linear first-order kinetic plots of ln[M] 0/[M] vs time, (b) an increase in the number-average molecular weight (Mn) vs conversion, and (c) relatively narrow polydispersities indicating a constant number of propagating species throughout the polymerization with negligible contribution of termination or transfer reactions. The dependence of the rate of polymerization on the concentrations of initiator, ligand, and temperature is presented. We observed comparable rates of polymerization linear increase of molecular weight with conversion and low polydispersities in polar solvents. No polymerization was observed in nonpolar solvents such as toluene and xylene at room temperature. The order of controlled polymerization with different initiator system is CuBr/BPN > CuCl/BPN > CuBr/ClPN, and the polymerization did not proceed with CuCl/ClPN initiator system at room temperature. The high functionality of bromine end groups present in the polymer chains was confirmed by ESI MS analysis. The thermal stability of PGMA prepared by the CuBr/PPMI/BPN initiation system is higher than by the other three systems, indicating the high regioselectivity and the virtual absence of termination reactions in the former case. The ligand alkyl chain length from R ) propyl to octyl did not affect the rate of polymerization. The molecular weight (M n) increases linearly with conversion, and these polymers showed narrow polydispersities.

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“…π-Effects have been noted as responsible for enhanced chain length seen in methylmethacrylate polymerisation in the presence of tetrathiofulvene (TTF). [70] and in the stabilisation of radical cations, [71,72] although the latter could be argued to be an extension of the already well-established phenomenon of cation-π stabilisation. [73] Easton's observations of rate accelerations in the bromination reactions of phenylalanine derivatives has led to recognition of remote intramolecular π-effects.…”

Section: Partial Protonationmentioning

confidence: 99%

Radicals by Design

Croft¹,

Lindsay²,

Renaud³

et al. 2008

Chimia

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Radical reactions offer many advantages over conventional chemical reactions, lending themselves to numerous bond forming processes and rearrangements that are, clean, rapid, and tolerant of a wide range of functional groups. This review provides a brief overview of the design concepts behind new reactions illustrating, in particular, their relevance for the efficient synthesis of biomolecules. Tw o general reactions are highlighted: single electron transfer (SET) using SmI 2 and hydrogen transfer using reagents such as those based on tin, thiols and phosphorous reagents. Intermolecular influences that may direct radical reactions, such as partial protonation and radical complexation, are also discussed.

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Effect of a π‐donor on the radical bulk polymerization of methyl methacrylate

Cited by 12 publications

References 13 publications

Remote aromatic stabilization in radical reactions

Remote aromatic stabilization in radical reactions

Room Temperature Atom Transfer Radical Polymerization of Glycidyl Methacrylate Mediated by Copper(I)/N-Alkyl-2-pyridylmethanimine Complexes

Radicals by Design

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