Degradation model compounds

The isocyanurate reaction occurs when three equivalents of isocyanate react to form a six-membered ring, as shown in the fifth item of Fig. 1. Isocyanurate linkages are usually more stable than urethane linkages. Model compound studies show no degradation of the trimer of phenyl isocyanate below 270°C [10,11]. Catalysts are usually needed to form the isocyanurate bond. Alkali metals of carboxylic acids, such as potassium acetate, various quaternary ammonium salts, and even potassium or sodium hydroxide, are most commonly used as catalysts for the isocyanurate reaction. However, many others will work as well [12]. 

Thermogravimetric analysis and other studies made on low-molecular weight model compounds such as 1,3, 5,-trichlorohexane [7,8] corresponding to the idealized head-to-tail structure of PVC show these structures to be considerably more stable than the polymer. This abnormal instability of the polymer is attributed to structural irregularities or defects in the polymer chain, which serve as initiation sites for degradation. 

Studies of thermal degradation on low-molecular weight model compounds have shown that the structure [Eq. (7)1... 

Some Physico-chemical Interactions of Paraquat with Soil Organic Materials and Model Compounds. I. Effects of Temperature, Time and Absorbate Degradation on Paraquat Adsorption, I. G. Bums, M. H. B. Hayes, and M. Stacey, Weed Res., 13 (1973) 67 -78. 

Poly(CTTH) (Figs. 6 and 7) was also used as a model compound for the preliminary evaluation of the in vitro degradability of tyro-sine-derived poly(iminocarbonates) Solvent cast films of poly(CTTH)... 

Gierer, J. Opara, A. E. Enzymic degradation of lignin. Action of peroxidase and laccase on monomeric and dimeric model compounds. Acta Chem. Scand. 1973, 27,... 

For samples that meet the solubility requirements of the SEC approach, analyses were also reported for additives in polymers such as PVC and PS [28,29]. Direct SEC analysis of PVC additives such as plasticisers and thermal stabilisers in dissolution mode has been described [28,30,31 ]. In the analysis of a dissolved PS sample using a SEC column of narrow pore size, the group of additives was separated on a normal-phase column after elution of the polymer peak [21]. Column-loading capacity of HPSEC for the analysis of additives, their degradation products and any other low-MW compounds present in plastics has been evaluated for PS/HMBT, PVC/TNPP and PVC/TETO (glyceryl tri[l-14C] epoxyoleate) [31]. It was shown that HPSEC can be used to separate low-MW compounds from relatively large amounts of polymers without serious loss of resolution of the additives the technique has also been used for the group analysis of chlorohydrin transformation products of the TETO model compound [32]. 

Photochemistry of Model Compounds. Preliminary photochemical studies have been carried out on l,3-diphenoxy-2-propanol (3)8 as a model compound for bisphenol A-epichloro-hydrin condensates 1. The utilization of 3 as a model compound for thermal degradation of 1 has been reported. Irradiation (254 nm) of 3 in acetonitrile (N2 purge) provides two major volatile products, which have been identified as phenol and phenoxyacetone (4), by comparison of retention times (gas chromatography) with known samples. A possible mechanism for... 

Using l,8-diphenyloctatetra-l,3,5,7-ene, (DOT), as a model compound either in dilute, ( 10-5m), hexane or ethanol solutions or incorporated into a film of undegraded PVC confirmed that in the presence of HC1 it underwent a photochemical reaction which resembled that of the polyenes in thermally degraded PVC. The results indicated that the initial rates of reactions proceeding in either solvent showed a second order dependence on HC1 pressure and that the reaction was considerably slower in ethanol than in hexane. Further, when cast in PVC films, the characteristic absorption maxima of DOT were shifted about 16nm to longer wavelengths compared with their absorption in hexane and there... 

To correlate these changes in absorption with theory, the ultraviolet spectroscopic behavior of model compounds closely related to the degradation products isolated from bagasse native lignin, i.e., p-hydr-oxybenzaldehyde, vanillin and syringaldehyde, was determined. The compounds used were p-hydroxypropiophenone, vanillin, acetovanillone and acetosyringone and their derivatives. 

Complex 69 was prepared in about 60% yield with about 15% metallation and a small drop in molecular weight (from 73,000 for PMPS to 68,000 for 69), which, allowing for the increase in statistical repeat unit, indicates some degradation. Related model compounds based on the coordination of phenyl rings in phenyltrimethylsilane and 1,2-diphenyltetramethyldisilane were compared with 69. The UV absorption maxima (224 and 337 nm) were almost unchanged from those of the precursor PMPS (223 and 338 nm), which possibly reflects the low metal loading as... 

For each of the poly carboxylic acids investigated, the sum of the yields of carbon monoxide and carbon dioxide is much larger than the yield of radical products. This observation differs from that noted for the model compounds, where the two were of similar magnitude. This suggests that excited state processes may play a more significant role in the degradation of the poly acids than they do in the small molecule, model compounds. 

In the poly carboxylic acids, carbon dioxide is the major product of radiolysis, but the carbon monoxide yields are greater than they are for the aliphatic carboxylic acids. However, the radical yields are not greater than expected on the basis of the model compounds, which suggests that excited states play an important role in the degradation of these poly acids. 

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