| 摘要 |
Resinous products are obtained by condensing, preferably in the presence of catalysts, aldehydes such as formaldehyde with phenolic bodies obtained by condensing phenols and terpene halides containing not more than two halogen atoms in the molecule in the presence of metal halide catalysts such as aluminium, zinc or ferric chlorides. The terpene halide may be formed in the presence of the phenol and metal halide or a small proportion of a terpene halide used in the presence of the terpene, the liberated hydrogen halide serving to convert further terpene into terpene halide. Excess of the phenol used as starting material may be removed or converted into particular substitution products as by alkylating with an alkyl halide or an olefine or by chlorinating with sulphuryl chloride. Suitable terpene hydrocarbons include American oil of turpentine rich in pinene and dipentene, limonene. The halides which may be used, which may be recrystallized, include mono- and di-chloro menthanes or bornyl chlorides. Acid or alkaline catalysts such as mineral acids, or ammonia may be used in the resin-forming condensation. Other phenols which may be employed in addition to the terpene phenols include those that have only two of the reaction-favourable positions unoccupied and which are substituted by aliphatic, hydroaromatic or mixed aliphatic aromatic residues such as p-tert-butyl phenol, o- or p-cresol, o- or p-chlorphenol. Alternatively, preformed resins derived from these phenols may be blended with the resins derived from the terpene phenols. Depending on the reaction conditions soluble or insoluble, hardenable or non-hardenable products may be obtained which may be worked up with drying oils, natural resins or their esters, waxes, coumarone resins, castor oil, with esters as described in Specification 334,572, [Class 2 (iii)], and acidic products may, if desired, be neutralized. The products which may be soluble in alcohol, acetone, benzene, xylene, aliphatic hydrocarbon, turpentine, may be used in the preparation of varnishes and enamels. In examples, (1) a substantially pure dihydrochloride obtained by distilling the crude product obtained by saturating dipentene with gaseous hydrogen chloride is reacted with phenol in the presence of aluminium chloride and the product or a solution of the product in benzene and alcohol is reacted with aqueous formaldehyde in the presence of hydrochloric acid, ammonia, or caustic soda; (3) American oil of turpentine is saturated with hydrogen chloride and the bornyl chlorides are separated into solid and liquid isomers, reacted with phenol in the presence of zinc chloride and condensed with formaldehyde in the presence of hydrochloric acid or together with tert-butyl phenol condensed with formaldehyde in the presence of sodium hydroxide, the products being blendable with drying oils and, in the latter reaction, with natural resins; (5) the phenol obtained in example 1 is condensed with formaldehyde in the presence of caustic soda, and the product may be blended with a condensate of p-cyclohexylphenol and formaldehyde, or p-butylphenol, or alternatively a mixture of the phenols may be condensed with formaldehyde; (8) a mixture of hydrochloride is added to phenol and a metal halide catalyst and when the reaction has started, dipentene is added, and the product worked up with formaldehyde after, if desired, treating any excess of phenol with tertiary butyl chloride to yield products that may be worked up with neutral resins or phthalic acid--fatty acid--glycerol esters. Specification 417,122 also is referred to. The Specification as open to inspection under Sect. 91 was not restricted to the use of terpene halides containing not more than two halogen atoms per molecule.
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