Patented Mar. 2, 1937 2,072,825. UNITED STATES PATENT OFFICE 2,072,825 CONDENSATION PRODUCTS FROM HYDROXYLATED CYCLIC COM PoUNDs AND ACETYLENE Walter Reppe and Ernst Keyssner, Ludwigs hafen-on-the-Rhine, Germany, assignors to . G. Farbenindustrie Aktiengesellschaft, Frankfort-on-the-Main, Germany No Drawing. Application June 30, 1933, Seria No. 678,478. In Germany July 9, 1932 12 Claims... (C. 260-2) The present invention relates to condensation for example ethyl acetate or butyl acetate, or products of hydroxylated cyclic compounds and hydrocarbons of the aliphatic, aromatic or hydro acetylene and process of producing the same. aromatic Series, such as benzine, benzene, toluene It is already known that the treatment of or tetra- or deca-hydronaphthalene; further phenol, cresols or other phenolic bodies with more, substances which form liquid or solid solu acetylene in the presence of inorganic mercury tions with the initial materials and/or the con salts or mercury oxide and strong inorganic acids, densation products or which serve merely as fillers if desired in the presence of Organic solvents, leads may also be added during the condensation, as for to the formation of resinous products which Con example Waxes, oils, resins, resin esters, asbestos, 10 tain the components in the ratio of 1 molecular cellulose and its derivatives, gypsum and like O proportion of acetylene to 2 molecular proportions fillers. of phenol. In this reaction acetaldehyde is The reaction may be carried out at atmos formed as intermediate product. It has also pheric Or, advantageously, at increased pressure, been proposed to fix the mercury salt or Oxide discontinuously (in stirring autoclaves) or con 5 and the strong inorganic acid, for example Sul tinuously (in a pressure tower) and may either 5 phuric acid, on inert porous Substances, such as be carried to complete saturation or interrupted diatomaceous earth Or active carbon, in Order to prematurely. When Working under increased render more easy the removal of the catalyst pressure, it must be kept in mind that acety from the resinous products obtained. The field lene under pressure is liable to explode. It is, of employment of these resins is, however, re therefore, advisable when Working under in 20 stricted if they are not subsequently subjected creased pressure to dilute the acetylene with an 20 to a hardening With aldehydes. Under the same inert gas, for example nitrogen. conditions, resorcinol does not yield a resin but Depending on the temperature, amount of cata Crystalline products. lyst and duration of reaction employed, viscous, We have now found that valuable condensa semi-hard or hard products are obtained which tion products are obtained by causing acetylene are readily soluble, partly soluble or only capable 25 to act at temperatures between about 100 and of SWelling in Organic Solvents, such as acetone, about 300° C., preferably at from 170° to 220 C., . alcohol, ether and benzene, and in oils and aque on mono- or polyhydric hydroxy compounds of ous caustic alkalies. 30 the mono- or poly-, iso- or heterocyclic Series, The condensation products obtainable in the 30 or mixtures of such compounds, in the presence said manner may be employed either directly or of organic zinc or cadmium salts, as for example after previous purification in the preparation of Zinc or cadmium salts of acetic acid, propionic lacquers and insulating agents and in the arti acid, butyric acid, oleic acid or abietic acid. Since ficial material industries. For the purpose of water retards reaction, it is advisable to carry purification, the resin may be dissolved in a sol out the reaction in the absence of water or at vent, as for example alcohol or benzene, the least to keep the Water content of the reaction Solution treated With bleaching earth, active car mixture low. bon or a chemical bleaching agent, as for ex As suitable cyclic hydroxy compounds may be ample hydroSulphite, filtered and distilled at at 40 mentioned aromatic compounds such as phenols, mospheric or reduced pressure, any phenol which 40 the cresols, xylenois, polyhydric phenols, as for has not been converted being distilled off at the example resorcinol, naphthols and other isocyclic Same time. The product purified in this manner compounds, such as partially hydrogenated aro is practically free from Zinc or cadmium com matic or cycloaliphatic compounds containing pounds. Alternatively, any unconverted phenol hydroxyl groups, as for example tetrahydronaph present may be expelled by means of wet or super thol and cyclohexanol, or heterocyclic compounds heated steam before the dissolution in organic such as hydroxylated pyridine, quinoline and solvents. In cases when the products are still methyl quinoline, or halogenation and Sulpho soluble in aqueous alkali, it is possible to purify nation products of said hydroxy Compounds, such them by dissolution in alkali and precipitation as for example chlorinated phenol or Sulphonic by means of acids. The soluble and the insoluble acids of phenol. products may also be purified in a finely ground If desired the reaction may be carried out in the condition by treatment with acids or alkalies, presence of solvents, as for example alcohols, such dilute aqueous Solutions of caustic alkali being as methanol, ethanol or butanol, or ketones, such employed for purifying products which are in i5 as acetone or methyl ethyl ketone, or esters, as Soluble in caustic alkali solutions, and aqueous 55 2 2,072,825 solutions of alkali metal carbonates being suit hol and benzene, and in caustic soda, but insol able for the treatment both of the insoluble and uble in benzine and oil of turpentine. of the soluble products. In order to remove zinc from the reaction prod The condensation products may be subjected uct the latter is dissolved in 3000 parts of benzene 5 to a subsequent hardening with aldehydes or sub while heating and stirred with 160 parts of stances which split off aldehydes, as for example bleaching earth. The bleaching earth is then hexamethylene tetramine. Catalysts, such as filtered off and the benzene distilled at first at a sulphuric acid, organic sulphonic acids from all slightly reduced pressure and finally in a Wac phatic or aromatic compounds, resinic acids, uum of from 15 to 20 millimeters (mercury 10 fatty acids, aqueous caustic alkalies or organic gauge), the temperature being raised slowly to O bases, such as cyclohexylamine may be added 230° C. Towards the end of the distillation, the during this process if desired. Similarly sol unconverted phenol contained in the crude prod vents of low or high boiling point may be pres luct passes Over. The resin is poured out from ent during the hardening, in which case the em the distillation vessel while still hot. After cool 15 ployment of organic bases as catalyst is especially ing it forms hard clear pieces having a soften favorable, the solvents of high boiling point being ing point of from 100° to 130° C. depending on left in the hardened products if desired. More the periods of heating applied in the process. over filling materials, such as asbestos fibres, Subsequent hardening of the product may b gypsum or wood powder, may be, added before effected as follows:- 20 the hardening which remain finely divided in A mixture of 100 parts of the powdered resin 20 the finished product; or substances may be added With 10 parts of hexamethylene tetramine is which enter into solid solutions with the finished slowly heated to 200° C. When the evolution of product, for example cellulose ethers, polymeri gas which takes place has subsided, the prod zation products, as for example polymerized vi uct is allowed to 20ol. A very hard difficultly 25 nyl esters, polymerized styrene, polymerized acryl fusible resin is obtained which is 'insoluble in 2 5 ic acid and their derivatives, artificial or nat alkali and the usual organic solvents. ural resins and resin esters, a far reaching influ The esterification of the said resin having a ence on the properties of the final products thus melting point of from 100° to 110° C. may be being possible. 'effected as follows. 30 New products are also obtained by a complete 120 parts of the resin are mixed with 94 parts or partial esterification of the condensation of linoleic acid and slowly heated to 200° C. , products with organic, Saturated or unsaturated, The water split off distils off. When the reaction lower or higher acids, such as fatty acids, aro is completed the whole is allowed to cool. A soft matic acids, hydroxy acids, ether acids, as for ex resin is obtained which is still soluble in alkali 3 5 ample diglycollic acid, amino acids or polybasic since only one third of the theoretical amount of acids, as for example phthalic acid, succinic acid, linoleic acid has been employed for the esterifica adipic acid, suberic acid, citric acid or tartaric tion. The aqueous alkaline solutions of the prod acid or mixtures of these acids. act have great foaming power. The condensation products may also be sul the following is an example of the reaction 40 phonated (products having the character of tan of the alkali metal salt of the phenol resin: 40 ning agents being obtained), nitrated, chlori 120 parts of the purified resin having a soften nated, coupled with diazo compounds or con ing point of 110° C. are dissolved together with verted into the corresponding glycol ethers by 40 parts of caustic soda in 320 parts of alcohol treatment with ethylene oxide. while heating. 80 parts of ethylene chlorhydrin 45 For calising the phenol groups to react, the are then introduced. Sodium chloride separates 45 alkali salts of the phenol resins may be em immediately and is filtered off.