Depolymerization with phenol

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. 

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 ... 

Heredy and his co-workers (1,5) have attempted to Interpret the reaction with phenol and boron trifluoride as a depolymerization process followed by saturation of the fragments. In fact, they found that considerable quantities of phenol reacted with the coal. In low-rank coals, the tendency towards this reaction was greater than with coking coals which did not show any notable Improvement of extractablllty. 

Acid catalyzed depolymerization of coal with phenol affords a means for dissolution of coal under relatively mild conditions (185°C, ambient pressure). Once dissolved, separation of ash constituents and unreacted char is accomplished by filtration or centrifugation (also under mild conditions). Depolymerized coal recovered as a low ash product from excess phenol could be dissolved in a coal derived solvent and hydrogenated to stable liquids. It might be anticipated that access to hydrogen and contact with the catalyst would be more efficient in the case of the solubilized coal substance than for coal particle slurries. Hydrogenation might proceed more efficiently and with less... 

This study was conducted to assess the behavior of various coals with respect to solubilization by acid catalyzed depolymer-ization with phenol. Ash removal, phenol uptake, and reactions of other solvent systems were considered and the hydrogenolysis of a number of coals and of their depolymerized products were compared. 

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... 

Figure 1. Coal depolymerization via transaralkylation with phenol-BF (1)...

Table IV. Depolymerization of Coals of Different Ranks with Phenol-...

Phenol-p-Toluene Sulfonic Acid Depolymerization. The kerogens were treated with phenol-tosyl acid according to literature methods (24). After reacting, excess phenol was removed by steam distilling. The products were filtered, washed with water, and dried in vacuo. The products were then Soxhlet-extracted with toluene, methanol, and finally pyridine. Extracts were isolated,... 

Little is known about the overall mechanism of cyclic oligomer formation, although the mechanism of the initial stages of the sequence seems fairly clear. The first chemical event is the reaction of formaldehyde (formed in the Petrolite procedures by depolymerization of paraformaldehyde) with phenol to form 2-hydroxy-methyl- and 2,6-6w(hydroxymethyl)phenols in a base-catalyzed process, as shown in Fig. 3. Such compounds were characterized many years ago50), obtained from the action of aqueous formaldehyde on phenol in basic solution at room temperature. Subsequent condensation between the hydroxymethylphenols and the starting phenol occurs to form linear dimers, trimers, tetramers, etc. via a pathway that might involve o-quinonemethide intermediates which react with phenolate ions in a Michael-like reaction, as portrayed in Fig. 4. The condensation of hydroxymethyl-... 

This picture has been broadly validated, and in some respects refined, by other work in which coal was depolymerized by acid-catalyzed transalkylation [as by interaction of coal with phenol and BF3 (23-27)] or by similar, less clearly defined, phenolation reactions (28-31), or selectively degraded by specific oxidants, such as dichromates (32-34), hypohalites (35-38), or peroxy-acids (39-43). But these studies have also revealed some previously unsuspected features. Buffer-controlled oxidation with Na2Cr207 (34) and KMn04 (44) have indicated an occasionally significant presence of straight-chain (up to C21) and branched-chain (up to C8) aliphatic compounds in coal. Oxidation with performic acid (41-43) has yielded substituted compounds that are clearly related to the microbial or chemical degradation products of lignin or flavonoids. And when applied to supposedly very similar coals, virtually identical depolymerization or oxidation procedures often furnished distinctly different product slates (45). 

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... 

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). 

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. 

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. 

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