The effect of aromatic plasticizers on the photodehydrochlorination of poly(vinyl chloride). Part II: Dialkyl phthalates

Gerrard, D.L.; Bowley, H. J.; Williams, K. P. J.; Biggin, I. S.

doi:10.1002/vnl.730080204

Cited by 10 publications

(1 citation statement)

References 7 publications

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“…In the study of degradation from industrial PVC samples all three methods have been used (the direct method in refs 5a-d, 6,11, and 12, the THF method in ref 13, and the modified THF method in refs [14][15][16][17][18][19]. In this paper we report on several practical considerations for the methods mentioned.…”

Section: Introductionmentioning

confidence: 99%

Considerations for Raman spectroscopic determination of polyene length distribution in degraded poly(vinyl chloride)

Kip¹,

Aaken²,

Meier³

et al. 1992

Macromolecules

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Practical complications in the quantitative Raman spectroscopic determination of the polyene sequence length distribution in degraded poly(vinyl chloride) samples were found. If samples are measured directly, i.e. without dissolving them, the distribution of polyenes changes during the Raman experiment if power densities above 20 W/mm2 are used. Lower power densities or short exposure times (<1 min) must be used to avoid these effects. The direct method turned out to be an appropriate method for the quantitative determination of the polyene length distribution in lightly degraded poly(vinyl chloride) samples (<0.05 % HC1 loss). If the samples are dissolved in tetrahydrofuran, the influence of laser power is negligible. However, in that case other problems are encountered; solutions must be stored in a cooled state and in the dark in order to avoid disappearance of the polyenes. Moreover, the solution process results in an altered polyene sequence distribution. The tetrahydrofuran method turned out to be a quick and convenient way to obtain information about the polyene sequence distribution for samples with relatively high degradation levels (>0.05% HC1 loss).

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Section: Introductionmentioning

confidence: 99%

Considerations for Raman spectroscopic determination of polyene length distribution in degraded poly(vinyl chloride)

Kip¹,

Aaken²,

Meier³

et al. 1992

Macromolecules

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Photooxidation of poly(vinyl chloride) at 254 nm in the absence and presence of phthalate plasticizers

Denizligil

Schnabel

1995

Angew. Makromol. Chem.

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Irradiation of neat PVC at hinc = 254 nm under air induces the formation of conjugated double bonds, -(CH=CH)n-(quantum yield @ = 1.6for n = 3).Simultaneously, C-Cl bonds are split (@ = 8 * With the aid of FTIR spectroscopy the following oxidation products were detected:Irradiation of PVC plasticized with about 42 wt.-Vo phthalate results in similar chemical changes. However, to some extent the chemical alterations are due to an indirect radiation effect. PVC, isolated from plasticizer after irradiation, was found to contain phthalate fragments attached to the polymer. Moreover, in plasticized PVC the formation of carbonyl groups is enhanced as was evidenced regarding the generation of -CHCl-C(=O)-CHCl-groups. On the other hand, cleavage of C-Cl bonds and intermolecular crosslinking is retarded by phthalates. The exposure gel doses for unplasticized and plasticized PVC are 3 * and 2 .Einstein cm-2, respectively.

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UV resonance Raman spectroscopy using a quasi–continuous—wave laser developed as an industrial analytical technique

Williams

Klenerman

1992

J Raman Spectroscopy

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A resonance Raman method was developed for the study of a wide range of materials possessing UV chromophores with high sensitivity. The experimental arrangement, utilizing a low peak power yet high average power quasicontinuous-wave laser source, permits the study of both liquid and, for the first time, solid samples. Evidence for laser-induced sample degradation was observed from low levels of solid polycyclic aromatics dispersed in potassium chloride, but this was largely overcome by sample spinning. In addition, it was found that the Raman spectrum of individual components in a complex mixture can be selectively enhanced by a judicious choice of laser wavelength. Polyethylene and poly(viny1 chloride) were investigated and evidence for unsaturation was detected from both systems. This is attributed to the resonance enhancement of unsaturated moieties contained within the polymer.

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The effect of aromatic plasticizers on the photodehydrochlorination of poly(vinyl chloride). Part II: Dialkyl phthalates

Cited by 10 publications

References 7 publications

Considerations for Raman spectroscopic determination of polyene length distribution in degraded poly(vinyl chloride)

Considerations for Raman spectroscopic determination of polyene length distribution in degraded poly(vinyl chloride)

Photooxidation of poly(vinyl chloride) at 254 nm in the absence and presence of phthalate plasticizers

UV resonance Raman spectroscopy using a quasi–continuous—wave laser developed as an industrial analytical technique

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