Thermal elimination reaction in polyparaphenylene vinylene synthesis from the soluble sulfonium salt precursor route

Massardier, V.; Hoang, Tran Van; Guyot, Alain

doi:10.1002/pat.1994.220051005

Cited by 6 publications

(7 citation statements)

References 9 publications

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“…Our conclusion that both an E1 and E2 mechanism may be operating with the shift from E2 to E1 being dependent on reaction temperature and stereochemistry of the polymer is to a limited extent in agreement with a study by Massardier et al Schlenoff and Wang 14 have reported an E2 mechanism, and Halliday et al have reported an E1 mechanism. This is now understandable in light of the fact that both mechanisms are operative.…”

Section: Resultssupporting

confidence: 93%

“…These defects limit the conjugation length and thereby affect the charge transport, conductivity, and luminescence in this polymer. 10 The thermal conversion of a sulfonium precursor has been investigated in the past with the aid of several different techniques including thermogravimetry (TGA), 11,12 differential scanning calorimetry (DSC), [11][12][13] thermogravimetry-mass spectroscopy (TG-MS), 14,15 thermogravimetry-infrared spectroscopy (TG-IR), 14 and even X-ray diffraction (XRD). 16 Earlier studies 11,17,18 were performed on a PPV precursor synthesized from a dimethylsulfonium salt.…”

Section: Introductionmentioning

confidence: 99%

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A Comprehensive Analysis of the Thermal Elimination Reaction in a Poly(p-phenylene vinylene) Precursor

Shah

Arbuckle

1999

Macromolecules

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Sulfonium precursor routes are the most popular synthetic routes to light-emitting poly(p-phenylene vinylene) (PPV) thin films. These routes involve a high-temperature solid-state thermal elimination reaction which yields PPV from its water-soluble precursor. The quality of PPV and hence its ultimate properties have a strong dependence on the polymerization parameters and thermal elimination conditions. The elimination reaction remains less understood. In this report, we have qualitatively and quantitatively analyzed the thermal elimination reaction using TGA, DSC, MTGA, TG-IR and transmission IR. The qualitative analysis focuses on identification of the underlying reactions and establishing the reaction sequence and reaction mechanisms. The quantitative analysis, on the other hand, focuses on the determination of the kinetic parameters of these reactions. The effect of heating rate and reaction environment on the luminescent properties of PPV have also been investigated.

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Section: Resultssupporting

confidence: 93%

Section: Introductionmentioning

confidence: 99%

A Comprehensive Analysis of the Thermal Elimination Reaction in a Poly(p-phenylene vinylene) Precursor

Shah

Arbuckle

1999

Macromolecules

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“…These data are in complete agreement with the previously published results obtained by conventional rapid-scan m ethods. 19,20 The band assignments It should be noted that the precursor has a very short half-life (approximately 3.5 days at room temperature) as determined by our previous kinetic studies, 21 and therefore the precursor may be visualized as a random copolymer consisting of precursor and PPV repeat units. Hence the precursor shows spectral features of PPV such as vinylene stretch and bend m odes, as well as those due to the presence of tetrahydrothiophenium (T HT ) pendant groups and aliphatic units on the backbone.…”

Section: Resultsmentioning

confidence: 91%

Dynamic Infrared Linear Dichroism Study of Poly(p-Phenylene Vinylene) and its Precursor

1999

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Poly(p-phenylene vinylene) (PPV) has many interesting electrical properties, particularly anisotropic conductivity upon uniaxial stretching, because of its delocalized π-electron system. In this study we have investigated the mid-infrared response of PPV and PPV-precursor films subjected to modulated uniaxial strain in order to study the degree of molecular motions and their time dependence during deformation. These studies have used a step-scan infrared spectrometer in conjunction with a piezo-driven in situ Polymer Modulator™. The viscoelastic properties are monitored simultaneously with the dynamic infrared vibrational response to the applied perturbation. The major molecular vibrations associated with the stretching of the precursor and of PPV have been identified and their time-dependence studied by using both phase-spectral and two-dimensional infrared (2D-IR) approaches. It has also been shown that the precursor, at ambient temperatures, is elastic in nature. However, after the introduction of conjugation on the backbone via conversion to PPV, the material becomes more viscous; the change is evident at both the microscopic and macroscopic levels.

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“…The reaction is a two-step process: the first step occurs around 100ЊC via the loss of water and tetrahydrothiophene (THT) while the second, near 200ЊC, is associated with the loss of halogen species and residual THT [9]. The temperature at which full conversion occurs has been studied by thermogravimetric [13] or optical measurements [14] but different values were reported. Determining the exact con-version temperature is particularly important for economic reasons since the cost of mass production depends mostly on the energy consumed.…”

Section: Introductionmentioning

confidence: 99%

Thermal conversion of poly(paraphenylene-vinylene) precursor films: XPS and ESR studies

Nguyen

Rendu

Tran³

et al. 1998

Polym. Adv. Technol.

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The conversion of the precursor into poly(phenylene–vinylene) (PPV) was studied by means of photoelectron spectroscopy (XPS) and electron spin resonance (ESR) on precursor films synthesized from the polymerization of pxylene‐tetrahydrophenium halides. The sulfonium precursor containing chlorine or bromine was thermally converted to PPV and analyzed in situ using the spectrometers. It was found by XPS analysis that both halide precursors were thermally converted into polymer in a range of 190–250°C but traces of bromine were still present at >300 °C in the precursor containing Br. Furthermore, a small amount of oxygen in a ketone structure was also present in fully converted films. The ESR results corroborated the XPS experiments, showing a progressive disappearance of the radical distribution related to sulfur sites in a comparable temperature range. A discussion of the conversion process is given in terms of the modification of the core level spectra from XPS and the g distributions from ESR experiments. © 1997 John Wiley & Sons, Ltd.

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Thermal elimination reaction in polyparaphenylene vinylene synthesis from the soluble sulfonium salt precursor route

Cited by 6 publications

References 9 publications

A Comprehensive Analysis of the Thermal Elimination Reaction in a Poly(p-phenylene vinylene) Precursor

A Comprehensive Analysis of the Thermal Elimination Reaction in a Poly(p-phenylene vinylene) Precursor

Dynamic Infrared Linear Dichroism Study of Poly(p-Phenylene Vinylene) and its Precursor

Thermal conversion of poly(paraphenylene-vinylene) precursor films: XPS and ESR studies

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