An ESR Study of Oxidation in Uniaxially Deformed Polybutadiene and Polyisoprene

Mead, W. T.; Porter, Roger S.; Reed, P. E.

doi:10.1021/ma60061a011

Cited by 21 publications

(10 citation statements)

References 6 publications

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“…Thus, the allyl radical (-CaC-C%) is likely to be formed by the chain scission. If so, the ESR signal from allyl radical should show a clear hyperfine splitting [16,35,36]. Carstensen reported that the allyl radicals in polybutadiene and polyisoprene formed at liquid nitrogen temperature were easily transformed into polyenyl radical (-(CaC) n -C%) during heating [35,36].…”

Section: Esr Resultsmentioning

confidence: 99%

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Effects of rubber/filler interactions on deformation behavior of silica filled SBR systems

Suzuki

Ito

Yatsuyanagi

2005

Polymer

175

122

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Section: Esr Resultsmentioning

confidence: 99%

“…When rubber molecules are stretched, a carbon radical (-C%) is formed by a chain scission of rubber molecules [14][15][16]. Electron spin resonance (ESR) is a powerful technique to detect the carbon radical formed by the chain scission [17,18].…”

Section: Introductionmentioning

confidence: 99%

Effects of rubber/filler interactions on deformation behavior of silica filled SBR systems

Suzuki

Ito

Yatsuyanagi

2005

Polymer

175

122

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“…Thus, the allyl radical (CCC · ) is likely to be formed if the breakdown of chemical linkages happened in SBR. In that case, the ESR spectrum from allyl radical should show a clear hyperfine splittings 4–6. However, Carstensen reported5, 6 that the allyl radicals in polybutadiene and polyisoprene formed at liquid nitrogen temperature were easily transformed into polyenyl radical ((CC) n  · ) during heating.…”

Section: Introductionmentioning

confidence: 99%

ESR study of silica‐filled SBR with different rubber/filler interactions

Ito

Isago

Suzuki

2008

J of Applied Polymer Sci

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Silica-filled styrene-butadiene rubber (SBR) unvulcanizates and their vulcanizates with different rubber/filler interactions were prepared by using several kinds of coupling agents. Tensile tests and electron spin resonance (ESR) measurements were carried out for both unvulcanized and vulcanized samples to get information on the effects of filler/rubber interactions on the breakdown of carbon-carbon (CÀ ÀC) linkages in SBR and carbon-sulfur (CÀ ÀSÀ ÀC, CÀ ÀSÀ ÀSÀ ÀC) linkages at the crosslinked points between rubber and sulfur by a tensile force.The combination of ESR results and stress-strain data suggested that with increasing the mechanical energy applied to the samples by the stretching, the carbon-sulfur linkages around silica particles were broken first, followed by the breakdown of carbon-sulfur and CÀ ÀC linkages in the rubber matrix. The assignment of ESR spectrum was also discussed.

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“…Electron spin resonance (ESR) is a powerful technique to study the mechanochemical reactions in deformed polymeric materials including elastomers where mechanically produced free radicals exist. The application of ESR to monitor radical formation during mechanical deformation of elastomers in the glassy state has been reviewed 1–4. Mead et al4 studied an oxidation in uniaxially deformed diene rubbers and reported that radicals formed following tensile testing of polybutadiene and polyisoprene at 83 K in predominantly nitrogen atmospheres containing small amounts of oxygen were a peroxy radical and most probably an allyl radical arising from main chain rupture.…”

Section: Introductionmentioning

confidence: 99%

“…The application of ESR to monitor radical formation during mechanical deformation of elastomers in the glassy state has been reviewed 1–4. Mead et al4 studied an oxidation in uniaxially deformed diene rubbers and reported that radicals formed following tensile testing of polybutadiene and polyisoprene at 83 K in predominantly nitrogen atmospheres containing small amounts of oxygen were a peroxy radical and most probably an allyl radical arising from main chain rupture. The radical stability vs. temperature tests showed that the peroxy radical decayed at a temperature approximately 20 K lower than the allyl radical which, in turn, decayed rapidly in the vicinity of the glass transition temperature of the samples.…”

Section: Introductionmentioning

confidence: 99%

ESR study of vulcanizates under the deformed state

Funatsu¹,

Takagi²,

Ito³

2009

J of Applied Polymer Sci

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Electron spin resonance (ESR) measurements under the tensile deformation of cross-linked polyisoprene were examined by the combination of home-built stretching machine with commercially available ESR spectrometer. The changes of radical concentration during tensile deformation were successfully determined by this technique. It was found that the number of radicals produced by the stretching process decreased during the retraction of stretched sample. In addition, at a given strain, the decrease of radical concentration with time was accompanied by the increase of stress. Such changes were more prominent in the cross-linked sample by sulfur PS sample (PS) than by dicumyl peroxide (PCP), PD sample (PD). The tensile modulus of the samples after the one cyclic deformation increased with increasing the keeping time at room temperature after the cyclic deformation. The increase was larger for the PS than for the PD. These results suggest that the broken cross-linking structure induced by the stretching process was partly reconstructed during and after the retraction with this tendency more prominent in the PS than in the PD.

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An ESR Study of Oxidation in Uniaxially Deformed Polybutadiene and Polyisoprene

Cited by 21 publications

References 6 publications

Effects of rubber/filler interactions on deformation behavior of silica filled SBR systems

Effects of rubber/filler interactions on deformation behavior of silica filled SBR systems

ESR study of silica‐filled SBR with different rubber/filler interactions

ESR study of vulcanizates under the deformed state

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