Patent GB-1510728-A (GB)
Title: Stable phenolic resoles
IPC: C08J9/04
Filed: 1975-08-12
Abstract: 1510728 Deionized phenolic resoles and foams thereof UNION CARBIDE CORP 12 Aug 1975 [13 Aug 1974 14 July 1975] 33512/75 Headings C3R and C3C A phenolic resole which is free of ionic species removable by the free acid form of a cation exchange resin and the free base form of an anion exchange resin is prepared by reacting an aldehyde, preferably formaldehyde, and a phenolic compound, preferably phenol itself, generally in a molar ratio of from 1 : 1 to 3 : 1, in the presence of an alkaline catalyst such that an aqueous alkaline condensate is formed, and deionizing the alkaline condensate by treatment thereof with the said cation and anion exchange resins. Part or all of the water may be removed from the aqueous condensate before or after the ion-exchange treatment and an organic solvent may be added, so that the condensate contains at least 10% wt. of diluent for the ion-exchange treatment. The resoles have improved stability towards self-condensation and improved shelf-life. Suitable alkaline catalysts are the hydroxides, oxides, carbonates and bicarbonates of alkali metals and alkaline earth metals, the preferred one being potassium hydroxide of mercury cell grade. Other phenols and aldehydes which can be used include p-substituted-alkyl phenols and/or polynuclear phenols, glyoxal, acetaldehyde, chloral, furfural and benzaldehyde. The ion-exchange treatment may be carried out batchwise or continuously, generally at 20-75 C., using either a mixed bed of the 2-types of ion-exchange resins, wherein the alkaline condensate is contacted with the exchange resins until the pH of the treated liquid stabilizes to a value of 4-7, or using individual beds of exchange resins wherein the alkaline condensate is first treated with the cation exchange resin until its pH stabilizes to a value of 1À5 to 4, and is then treated with the anion exchange resin until its pH stabilizes to a value of 4-7. The H<+> ions of the cation exchange resin may be provided by -COOH or -SO3H groups, and suitable resins include sulphonated phenol- HCHO, benzene - HCHO and divinyl - benzene resins; acrylic polymers and copolymers of methacrylic acid and divinyl-benzene. The anion exchange resin contains OH or free amino groups and may be a copolymer of styrene and divinylbenzene containing quaternary ammonium hydroxide substituents. The deionized resoles can be used for the manufacture of phenolic foam by polymerizing in the presence of an acid catalyst and a blowing agent and optionally a surface active agent, filler, pigment or non-punking agent, the water content of the resole as well as the content of any added organic diluent, generally having been reduced to a level of not more than 10% wt. prior to foaming. The density of the cellular products may vary from 0À2 to 30 p.c.f. Suitable acid catalysts include HCl, H2SO4, fluoboric acid, HCOOH, and organic sulphonic acids. Suitable blowing agents include halogenated organic compounds having a boiling point of from - 40 F. to 200 F. and aliphatic ethers having a boiling point of 30-100 C. Suitable surfactants include condensation products of alkylene oxides and alkylphenols, and siloxaneoxyalkylene copolymers. A suitable non- punking agent is tetrakis (hydroxymethyl) phosphonium chloride. The deionized resoles may also be used in the manufacture of adhesives, coatings, films and cast thermosetting articles.