2. Condensation of Phenols
Phenolsulphonic acids exhibit pronounced tendencies to condensation, for which purpose A. v. Baeyer (1872) employed aldehydes. The reaction is rather violent, and yields, in addition to well-defined crystalline substances, amorphous bodies resembling rosins. In addition to formaldehyde, paraformaldehyde, trioxymethylene, methylal, hexamethylene-tetramine, and other substances containing a reactive methylene group, as well as acetaldehyde, benzaldehyde and other aldehydes may be employed to induce reaction.
A number of these condensation products are derivatives of diphenylamine or hydroxybenzyl alcohols. When the latter are heated, either by themselves or in presence of acids, anhydrides and polymerisation products are formed producing hard, brittle, fusible substances, insoluble in water but fairly soluble in organic solvents. The same substances are formed when phenols are condensed with formaldehyde, especially in the presence of acid contact substances and excess of phenol by sufficiently long heating at certain temperatures. The substances referred to are termed "Novolak": similar to these are the so-called "Resols," insoluble and non-fusible substances, very resistant to chemical and physical action. Another member of the series is the so-called "Bakelite" or "Resitol," which does not fuse but softens when heated and swells in organic solvents. The ultimate product of this class of substances is "Resit" which is obtained when concentrated hydrochloric acid is allowed to act upon a mixture of phenol and formaldehyde; the temperature rises spontaneously, and a hard, porous, insoluble mass of great resistance is obtained. By heating resols, resitols are formed which, on further heating, are finally converted into resits. [Footnote: Ber., 1892, 25, 3213.]
Of all these products, bakelite (resitol) has found the greatest industrial application; in its purest form, this substance is a nearly colourless or light yellow body of sp. gr. 1.25 and, being a poor conductor of heat and electricity, constitutes an excellent insulating material; it is exceedingly resistant towards most chemical reagents even in concentrated forms of the latter. Its pronounced refractivity, and the ease with which it may be worked, makes bakelite a favourite substitute for amber (Ger. Pat, 286, 568). Similarly, the resols which can be easily moulded are used either as such or mixed with sand, pulverised cork, asbestos or wood, and the moulded substances then converted into the more highly resistant bakelite by heating.
The constitution of these bodies no doubt depends largely on their method of preparation; Baekeland [Footnote: Chem. Ztg., 1913, 73, 733.] considers resit a polymerised hydroxybenzylmethylene glycol anhydride; Raschig, a diphenylmethane derivative (e.g., dihydroxydiphenylmethane alcohol); Wohl [Footnote: Ber., 1912, 45, 2046.] considers them polymerisation products of methylene derivatives of tautomeric phenol.
CH===CH
H_2C:C{ }CO
CH===CH
[Note: Lower Right CH has double bond to CO]
This group possesses the characteristic property of being capable of converting animal hide into leather when suitably dissolved. The author has dissolved a number of these water-insoluble condensation products in alkali and alcohol and was able to demonstrate their tanning effects on pelt; bakelite is easily soluble in alkali; a faintly alkaline solution partially precipitates gelatine, and completely so when the alkali is neutralised. This latter solution gives a dirty brown precipitate with iron salts.
These condensation products gained extraordinary importance for the tanning trade when Stiasny [Footnote: Ger. Pat, 262,558; Austr. Pat, 58,405.] succeeded in preparing them in water-soluble form when they are enabled to directly exert their tannoid properties. This may be done by acting upon two molecules of concentrated phenolsulphonic acid with one molecule of formaldehyde, the temperature thereby not exceeding 35°C. By condensation, however, considerable heat is liberated, and hence the rise in temperature can only be limited by adding the diluted formaldehyde drop by drop, whilst stirring and cooling, to the phenolsulphonic acid. The original letters patent is worded as follows: 10 kilos each of crude phenol and sulphuric acid (66° Bé.) are heated with stirring for two hours at 105°-106°C., cooled to about 35°C., and 463 kilos 30 per cent. formaldehyde added during three hours, the temperature thereby not exceeding 35°C.; the stirring is continued for a couple of hours after the final addition of formaldehyde. This yields about 24 kilos of the crude condensation product. On a commercial scale, however, cresol (cresylic acid) is substituted for phenol. There are three isomers of cresol, viz., o-, m-, and p-cresol, and it was naturally of interest to investigate whether one or the other of the isomers exerted any particular influence on the properties of the final product. It was found, however, that condensation products from the three isomers were distinguishable from one another neither in physical nor in tannoid properties. It is hence possible to employ crude cresol, which contains varying quantities of the o-, m-, and p-compounds, in the manufacture of these tanning matters. [Footnote: Gen Pat, 291,457.]
The tar obtained from the Rochling coal-gas generator contains considerable quantities of phenols (B.P.=200°-250°C.), and the author has protected the use of these for the production of synthetic tannins by Ger. Pat, 262,558. A deep brown viscous mass is obtained which, when partly neutralised, yields similar results to those given by the product above referred to.
It may be anticipated that by analogy from the chemical reactions taking place in the condensation of phenols on the one hand and cresolsulphonic acid on the other, that all other homologues of phenol, its polyvalent derivatives, substitution products and acids, would yield similar condensation products.