Thermal oxidation of polybutadiene. Part 1: Effect of temperature, oxygen pressure and sample thickness on the thermal oxidation of hydroxyl-terminated polybutadiene

Coquillat, M.; Verdú, J.; Colin, Xavier; Audouin, L.; Nevière, Robert

doi:10.1016/j.polymdegradstab.2007.03.020

Cited by 53 publications

(64 citation statements)

References 22 publications

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“…Indeed, for a moderately oxidizable polymer such as PE, E a is quite high: E a ≈ 138 kJ mol −1 [22]. In contrast, for highly oxidizable polymers such as PP or unsaturated elastomers, E a is significantly lower: E a ≈ 92 kJ mol −1 for PP [23] and E a ≈ 84 kJ mol −1 for HTPB [24]. As feared, the presence of aromatic rings in the vicinity of the CH 3 groups greatly increases the oxidation sensitivity of these latter.…”

Section: Resultsmentioning

confidence: 99%

Multi-scale and multi-technical analysis of the thermal degradation of poly(ether imide)

Courvoisier

Bicaba

Colin

2018

Polymer Degradation and Stability

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is an open access repository that collects the work of Arts et Métiers ParisTech researchers and makes it freely available over the web where possible. A B S T R A C TThe thermal degradation of PEI has been studied in wide ranges of temperature (between 180 and 250°C) and oxygen partial pressure (between 0.21 and 50 bars). On one hand, the chemical ageing mechanisms have been analysed and elucidated by FTIR spectrophotometry and by differential calorimetry (DSC) on sufficiently thin PEI films (between 10 and 60 μm thickness) to be totally free of the effects of oxygen diffusion. As expected, and by analogy with other aromatic polymers of similar chemical structure, oxidation occurs preferentially on the methyl groups of the isopropylidene unit of the bisphenol A part, thus causing the disappearance of their characteristic IR absorption band at 2970 cm −1 and the growth of a new IR absorption band at 3350 cm −1 , attributed to alcohols. In addition, oxidation leads successively to a relative predominance of chain scissions and crosslinking, resulting in a non-monotonic change of T g . On the other hand, the consequences of oxidation on the elastic properties have been analysed and elucidated by micro-indentation on polished cross-sections of PEI plates of 3 mm thickness. The diffusion control of oxidation leads to the development of profiles of Young's modulus within the sample thickness, which correlate perfectly with the changes in chemical structure determined by FTIR spectrophotometry. However, the increase in Young's modulus in the superficial oxidized layer is not the direct consequence of oxidation but of a physical ageing.

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Section: Resultsmentioning

confidence: 99%

Multi-scale and multi-technical analysis of the thermal degradation of poly(ether imide)

Courvoisier

Bicaba

Colin

2018

Polymer Degradation and Stability

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“…From a kinetic point of view, the Diffusion Limited Oxidation means that oxygen diffusion is the limiting step. In the case of polybutadiene oxidation, it results in the existence of an oxidized layer with a thickness ca 20 mm at 120 C [11]. pDCPD displays a lower oxygen permeability (Table 1) together with a higher oxidation rate (Fig.…”

Section: On the Oxidizability Of Pdcpd And The Influence Of Oxygen DImentioning

confidence: 99%

Kinetic analysis of polydicyclopentadiene oxidation

Defauchy

Gac

Guinault

et al. 2017

Polymer Degradation and Stability

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is an open access repository that collects the work of Arts et Métiers ParisTech researchers and makes it freely available over the web where possible. b s t r a c tThe in situ thermal oxidation of thin unstabilized polydicyclopentadiene was studied by TGA to monitor mass gain, and DSC to characterize hydroperoxides concentration. Results were discussed using kinetic analysis, which allowed the estimation of activation energies for key reactions of the oxidation process. Activation energy for termination was shown to be higher than in hydrocarbon liquids, which was discussed from the theory of diffusion controlled reactions, and a possible link with local motions associated with sub-glassy transition. Activation energy of thermal decomposition of hydroperoxides was found lower than for model hydroperoxides, suggesting an accelerating effect of organometallic catalysts. Despite those two results that indicate a poor thermal stability of thin pDCPD films, measurements of oxygen diffusivity at several temperatures show that oxidation remains confined in a relatively thin surface layer which would allow the pDCPD properties to be preserved.

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“…From a symmetrically auto-catalytic model, induction time was chosen as reaction from the beginning to the conversion at about two percent (α = 0.02). The auto-oxidation reaction schemes have been proposed and discussed in the literature concerning the thermal oxidation and degradation of polybutadiene and ABS [5,[6][7][8]11]. The oxidation mechanism consisted of the initiation, propagation and termination.…”

Section: Thermal Oxidation Of Pb Phase In Absmentioning

confidence: 99%

“…The rubber segment has been demonstrated to be the initial vulnerability under the attack of oxygen, giving rise to an allylic hydroperoxide [6][7][8]. In addition, cross-linking destroys the elastic property of the rubber phase with less impact resistance of ABS polymer in photo-or thermal-oxidation of PB [9,10].…”

Section: Introductionmentioning

confidence: 99%

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Study on Exothermic Oxidation of Acrylonitrile-butadiene-styrene (ABS) Resin Powder with Application to ABS Processing Safety

Duh

Chen

et al. 2010

Polymers

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Oxidative degradation of commercial grade ABS (Acrylonitrile-butadienestyrene) resin powders was studied by thermal analysis. The instabilities of ABS containing different polybutadiene (PB) contents with respect to temperature were studied by Differential Scanning Calorimeter (DSC). Thermograms of isothermal test and dynamic scanning were performed. Three exothermic peaks were observed and related to auto-oxidation, degradation and oxidative decomposition, respectively. Onset temperature of the auto-oxidation was determined to be around 193 °C. However, threshold temperature of oxidation was found to be as low as 140 °C by DSC isothermal testing. Another scan of the powder after degeneration in air showed an onset temperature of 127 °C. Reactive hazards of ABS powders were verified to be the exothermic oxidation of unsaturated PB domains, not the SAN (poly(styrene-acrylonitrile)) matrix. Heat of oxidation was first determined to be 2,800  40 J per gram of ABS or 4,720  20 J per gram of PB. Thermal hazards of processing ABS powder are assessed by adiabatic temperature rise at process conditions. IR spectroscopy associated with heat of oxidation OPEN ACCESSPolymers 2010, 2 175 verified the oxidative mechanism, and these evidences excluded the heat source from the degradation of SAN. A specially prepared powder of ABS without adding anti-oxidant was analyzed by DSC for comparing the exothermic behaviors. Exothermic onset temperatures were determined to be 120 °C and 80 °C by dynamic scanning and isothermal test, respectively. The assessment successfully explained fires and explosions in an ABS powder dryer and an ABS extruder.

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Thermal oxidation of polybutadiene. Part 1: Effect of temperature, oxygen pressure and sample thickness on the thermal oxidation of hydroxyl-terminated polybutadiene

Cited by 53 publications

References 22 publications

Multi-scale and multi-technical analysis of the thermal degradation of poly(ether imide)

Multi-scale and multi-technical analysis of the thermal degradation of poly(ether imide)

Kinetic analysis of polydicyclopentadiene oxidation

Study on Exothermic Oxidation of Acrylonitrile-butadiene-styrene (ABS) Resin Powder with Application to ABS Processing Safety

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