Phenol depolymerization

The xylenes, e.g., yield a lai er percent weight increase than does phenol and yet no significant solubilization of the coal results. In order to compare the products from depolymerization with m-xylene to those using phenol, products from these reactions were extracted with pyridine for 24 hours using a soxhlet extractor. The phenol depolymerization product proved... 

Solvent Fractionation. To facilitate later structural analysis, we separated the coal into structural types by solvent fractionation. Some other workers using the phenol depolymerization method to solubilize coal have used gas chroma-tography/mass spectroscopy (GC/MS) techniques to identify individual compounds (11, 13). However, with material containing large amounts of phenol and other polar groups, elaborate preparation and separation schemes have to be used to avoid contamination of the chromatography columns. As the emphasis of the present work was on structural characterization of the whole coal rather than on detailed examination of small parts of it in order to elucidate the chemistry of the phenolation reaction, we used the relatively simple scheme shown in Figure 1. 

Zavitsas et al. account for the effects of water in their calculations. Water promotes depolymerization of the paraformaldehyde as well as the hemiformals. Their modifications correct for the apparent reduction in methylolation rate as the extent of reaction proceeds, in that the hemiformals remove formaldehyde reactivity from the reaction mixture. Their rate constants look large because they are written for phenate concentrations rather than phenol and because of the formaldehyde equilibrium adjustments. They note that unsalted phenol is a by-... 

Polymerization occurs very quickly and the process is controlled via kinetic effects rather than thermodynamic ones. The net result is that the molecular weight distribution of the product does not match the thermodynamically stable one. If the chains were not capped with monofunctional phenols, the polymer chains would depolymerize, allowing the monomers to rearrange themselves at elevated temperature to approach the thermodynamically stable... 

Depolymerization techniques that cleave ester bonds release the indicated aliphatic monomers and phenolic components from suberin. 

While "conventional positive photoresists" are sensitive, high-resolution materials, they are essentially opaque to radiation below 300 nm. This has led researchers to examine alternate chemistry for deep-UV applications. Examples of deep-UV sensitive dissolution inhibitors include aliphatic diazoketones (61-64) and nitrobenzyl esters (65). Certain onium salts have also recently been shown to be effective inhibitors for phenolic resins (66). A novel e-beam sensitive dissolution inhibition resist was designed by Bowden, et al a (67) based on the use of a novolac resin with a poly(olefin sulfone) dissolution inhibitor. The aqueous, base-soluble novolac is rendered less soluble via addition of -10 wt % poly(2-methyl pentene-1 sulfone)(PMPS). Irradiation causes main chain scission of PMPS followed by depolymerization to volatile monomers (68). The dissolution inhibitor is thus effectively "vaporized", restoring solubility in aqueous base to the irradiated portions of the resist. Alternate resist systems based on this chemistry have also been reported (69,70). 

Three component, aqueous-base developable, positive-tone resists utilizing the chemical amplification principle have also recently been reported (81,82). In these systems, irradiation of a phenolic resin/inhibitor/acid generator resist generates an acid which upon mild heating, catalyzes either depolymerization or deblocking of a... 

Most lignin is now burnt for heat and power, but process options are available to depolymerize the phenolic material by thermal cracking or using base treatments [7]. In consecutive steps the products can be converted into aromatic hydrocarbon feeds. 

Transalkylation involves the transfer of alkyl groups between aromatic nuclei, usually in the presence of strong Lewis acids. Heredy and Neuworth used this reaction to "depolymerize" coal. As a result of the reaction of coal with BF3 and phenol, the solubility of coal in phenol or pyridine increased substantially. Various modifications of this reaction have since been reported . Transall lation reactions in the presence of trifluoromethane sulfonic acid and aromatic hydrocarbons have recently been used by Benjamin et al. and Farcasiu et al. to identify structural features in coals and heavy petroleum ends, respectively. 

A possible reductive role for veratryl alcohol oxidase is proposed in Figure 5. Laccases from C. versicolor can produce both polymerization and depolymerization of lignin (29). In phenolic lignin model dimers, laccase can perform the same electron abstraction and subsequent bond cleavage as found for lignin peroxidase (30). The phenolic radical is however likely to polymerize unless the quinoid-type intermediates can be removed, for example by reduction back to the phenol. Veratryl alcohol oxidase, in... 

The second, catalytic liquefaction process is similar to the first except that there is a catalyst in direct contact with the coal. ZnCl2 and other Friedel-Crafts catalysts, including AICI3, as well as BFj-phenol and other complexes catalyze the depolymerization-hydrogenation of coals, but usually forceful conditions (375 t25°C, 100-200 atm) are needed. Superacidic HF-BF3-induced liquefaction of coals8 involves depolymerization-ionic hydrogenation at relatively modest 150-170°C. 

Laszlo A. Heredy There is NMR spectroscopic evidence for the presence of both a- and /3-CHa groups in coal, based on depolymerization work with phenol-BF.3 reagent. For example, isopropyl groups were shown to be present in a high volatile bituminous coal. Is there a distinct difference in the behavior of these two types of CHs groups with respect to the reagent used in wet analytical methyl group determination ... 

Jhe distribution of hydrogen types in coals continues to be a subject of considerable interest in coal structure studies. Published data indicate that the fraction of aromatic hydrogens usually increases with increasing rank, but the absolute values depend on the specific analytical method used (7). Hydrogen type analysis of a single coal based on the application of NMR spectroscopy to the soluble fraction from depolymerization with phenol-BFa has been reported by us (3). The conversion of coal to soluble fragments in substantial yields under very mild conditions permits a reliable determination of the hydrogen types by NMR analysis, and these results can be extrapolated to the parent coal with considerable confidence. 

Details of the depolymerization, solvent separations, and product analyses were described previously (3, 4). Molecular weights of the benzene-, methanol-, and phenol-soluble fractions were determined cryoscopically using sulfolane as the solvent (li). 

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