Modified phenol resole ether resins and their preparation

A process for the preparation of a modified phenol resin which is based on phenol resol ethers which are bonded via, o,o'-methylene ether groups and are obtainable from phenol or an m-alkyl-substituted phenol, and formaldehyde or a formaldehyde donor, in the presence of divalent metal ions, and modification with monoalkyl or monoalkoxycarbamate or asymmetric dialkylurea, wherein

• A. where the procedure begins with methylolation in an aqueous medium,
• a.sub.1. the methylolation is carried out in the presence of from 0.5 to 10% by weight, based on the phenol used, of divalent metal ions,
• a.sub.2. the divalent metal ions are then removed as sparingly soluble salt, and
• a.sub.3. the water present as a solvent in the reaction mixture is separated off in the presence of monoalkyl or monoalkoxycarbamate or asymmetric dialkylurea and in the presence or absence of an entraining agent at from 30.degree. to 80.degree. C., while the water of reaction formed by reaction of the phenol resol ethers (a.sub.1) with monoalkyl or monoalkoxy carbamate or asymmetric dialkyllurea is separated off at from 40.degree. to 120.degree. C.,
• and
• B. where the procedure begins with methylolation in a non-polar organic solvent,
• b.sub.1. the methylolation is carried out in the presence of from 0.1 to 0.3% by weight, based on the phenol used, of divalent metal ions, and
• b.sub.1. the modification is effected at from 60.degree. to 120.degree. C. in the presence of one or more compounds of monoalkyl or monoalkoxy carbamate or asymmetric dialkylurea,
• and, finally, the residual amounts of phenol from the preparation of the products according to A. or B. are removed by evaporation in a thin film evaporator, the phenol content being reduced to less than 1% by weight.