Patent GB-835757-A (GB)
Title: Improvements in low ash phenolic resins of adjusted ph
Inventor: HYMAN JOSEPH BERNARD
IPC: C08G8/28
Filed: 1956-07-16
Abstract: Aqueous solutions of phenol-formaldehyde resins which have been catalysed with alkali or alkaline earth metals, the solutions being substantially free of such metal salts of an acid other than phenol and having a pH of 4-8 and an ash content of not over 0.9%, are prepared by reacting 1 mol. of phenol with 1.5-3.2 mols. of formaldehyde in the presence of a water-soluble alkali or alkaline earth metal to produce a water-soluble resin, passing the resultant alkaline solution through a mass of cation exchanger that is adjusted to the acid cycle and is insoluble in said solution, continuing such treatment until pH is less than 8, and either ceasing treatment while pH is 4-8, or, if pH is less than 4, adjusting pH to 4-8 by adding a soluble fixed metal alkali, ammonia or an amine.  Catalysts mentioned are sodium, potassium, barium and lithium hydroxides, and the phenol-formaldehyde reaction is preferably continued until there is less than 8% free formaldehyde.  Other phenols may be used with phenol, e.g. octyl phenol, cresol, phenol sulfonic acid, b -resorcylic acid, salicylic acid.  The phenol-formaldehyde resins may be modified, e.g. by propriolactone or epichlorhydrin.  The ion exchange treatment is usually carried out at 20-80 DEG  C.; ion exchangers specified include sulphonated styrene divinyl benzene products (Nalcite HCR), nuclear sulphonic acids (Dowex 50, "Amberlite" (Registered Trade Mark) IR120), phenolic methylene sulphonic acids (Dowex 30, "Amberlite" IR 105), carboxylic ("Amberlite" IRC 50), sulphonated coal ("Zeo Karb" (Registered Trade Mark)).  The pH adjustment may be made by adding fixed metal alkali, e.g. in the form of untreated alkaline phenolic resin, by ammonia, or by amines, e.g. methylamine, ethylamine, isopropylamine, diethylenetriamine, trimethylamine, triethanolamine or its hydrochloride.  Particularly ash-free resins (less than 0.02% ash content) are prepared by treating the resin until the pH is less than 3, and then adjusting to pH 4-8 with ammonia or amine. Optional ingredients include ethanol, phenol, glass wool, glass fibres, rock fibre: paper may be impregnated to form laminates and glass fibres impregnated to form insulating materials.  In examples: (1) a sodium hydroxide catalysed phenol-formaldehyde resin was mixed with "Amberlite" IRC 50 and concentrated in vacuo: the product, of pH 7.22, was then filtered to remove the "Amberlite."  (2) A similar resin was percolated through a column of "Amberlite" IRC 50 to give a solution of pH 7.1-7.8 which was also concentrated in vacuo.  (3) a similar resin was passed through a column of Nalcite HCR to give a solution of pH 3.5-4.8: when the filter was exhausted, the resin continued to run through at pH 8.1-8.5, to give a final blend of pH 7.1-7.8. (4) A similar resin was passed through a column of Nalcite HCR to give a solution of pH 2.4-2.7: ammonia was added to give a pH of 6, the solution concentrated, mixed with ethanol, and used to impregnate paper to form a laminate.  (5) A potassium hydroxide catalysed phenol-cresol-formaldehyde resin was mixed with Dowex 50 and filtered to give a solution of pH 2.6.  Ethylamine was added to give a pH of 6.3, the solution concentrated in vacuo, and ethanol added.  (6) A sodium hydroxide catalysed phenyl-octyl-phenol-formaldehyde resin was dehydrated under p vacuum, dissolved in ethyl alcohol and passed through a column of Nalcite HCR to give a pH of less than 3.  Isopropylamine was added to give a pH of 4.5.  (7) A sodium hydroxide catalysed phenol-formaldehyde resin was passed through a column of Nalcite HCR to give a pH of about 3.  Triethanolamine was added to give a pH of 5.5 and the mixture dehydrated.  (8) A similar resin was similarly treated with triethanolamine and HCl and dehydrated to give a pH of 7.4-7.7 and a product particularly suitable for impregnating glass fibres for insulation.  (9) A b -propiolactone modified similar resin was similarly treated to give a solution of pH less than 3.5; trimethylamine was added to give a pH of 4.6-5.4, the solution was dehydrated and was also suitable for glass fibres.  (10) A phenol-sulphonic acid modified similar resin was adjusted from pH 2.5 to pH 4.8-7.7 by triethanolamine.  (11) As (10) but b -resorcylic acid modified or salicylic acid modified resins were used and the products were suitable for impregnating glass fibres.  (12) An epichlorhydrin modified similar resin was adjusted from pH of less than 3.0 to pH 4.8-5.4 by triethanolamine.  Specification 796,515 is referred to.