| 摘要 |
The monoethers produced by reaction of a phenol with a non-conjugated polyunsaturated hydrocarbon (see Division C2) may be used as high-temperature lubricants.ALSO:Phenols are substituted in the nucleus, or the hydroxylic H atom is replaced, by reaction in presence of an acid catalyst with a non-conjugated polyunsaturated hydrocarbon; the latter contains a main structure of 7-21 C atoms arranged either linearly with 3 or more C atoms between double bonds, or as a single ring of at least 8 C atoms with 2 or more C atoms between double bonds. The reaction of 1,5-cyclooctadiene with 1 mol. phenol is stated to give a monophenol and an ether in which the diene is converted to a saturated bicyclic structure; 1,5,9-cyclododecatriene with 1 mol. phenol, a monophenol and an ether in which the triene is converted to a saturated tricyclic structure, but with 2 mols phenol, the triene gives a bisphenol, a bis(phenyl ether) and a monophenolmonophenyl ether stated to contain a bicyclododecane structure, as in all these cases Br2 reacts by substitution instead of the expected addition. 1,5-Cyclooctadiene reacts with 2 mols phenol giving products in which the cyclooctane ring is retained, and linear polyenes (e.g. 1,7-octadiene) give the anticipated products. The monophenolic products stabilize trichloroethylene.ALSO:Novolac-type resins are derived by reacting a slight molar excess of a phenol with a nonconjugated polyunsaturated hydrocarbon. The latter may contain 7-21 carbon atoms arranged either linearly with 3 or more carbon atoms between double bonds, or as a single ring of at least 8 carbon atoms with 2 or more carbon atoms between double bonds. They may contain halogen, methyl, ethyl or phenyl substituents. Compounds specified include cycloocta-1,5-diene, cis, trans, trans- and trans, trans, trans-cyclododeca-1,5,9-triene and octa-1,7-diene. Phenols specified include phenol itself, mono-substituted phenols in which the substituents are OH, F, Cl, Br, C1- 18 alkyl, C5- 18 cycloalkyl, e.g. cyclopentyl, cyclohexyl, methyl cyclohexyl and butyl cyclohexyl, C6- 18 aryl or aralkyl, e.g. phenyl, a -methyl benzyl, benzyl and cumyl or one of these hydrocarbon groups in which a carbonyl group is present in the carbon skeleton or a carboxyl group is present and m-disubstituted phenols. Acid catalysts specified include BF3. The reaction may be effected by adding the unsaturated hydrocarbon to a hot mixture of the phenol and catalyst. The excess phenol may then be neutralized with for example NaHCO3. The product may be filled, e.g. with wood flour, mica or wax and crosslinked with hexamethylene tetramine, or paraformaldehyde. The resins also give polyesters by reaction with dibasic acids (or their anhydrides or halides). In examples unsaturated hydrocarbons are treated with a large excess of phenol, the 1:1 adduct is distilled off and the resin remains in the still.ALSO:The N-methyl carbamate of the monophenolic product of reacting phenol with cis, trans, trans-1, 5, 9-cyclododecatriene prevents the development of early blight disease on plant foliage.
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