Patented May 1, 1945 2,374,969 UNITED STATES PATENT OFFICE

oF PREPARATION Ludwig F. Audreth, Dover, N. J., assignor to Hercules Powder Company, Wilmington, Del, a corporation of Delaware No Drawing. Application April 27, 1943, Serial No. 484,762 . 9 Claims. (C. 260-100) . This invention relates to a new composition of matter and to a method for its production, and cample 2 more particularly to a new rosin compound and to Example 1 was repeated except that the FF a method for its production. wood rosin was replaced by a hydrogenated wood In accordance with this invention acetone or rosin having a drop melting point of 76° C. and diacetone alcohol or mesityl oxide, is treated an acid number of 165. A precipitate formed in with annonia and a rosin acid at a temperature this case very shortly after adding the ammonia between about 0° C. and about 100° C., with the to the acetone-hydrogenated rosin solution. Nine ammonia in molali excess of the rosin acid present, parts of white crystalline salt were recovered. the excess being sufficient to insure an alkaline Eacample 3 condition, until a crystalline precipitate of the diacetoneamine salt of the rosin acid or rosin A 20% solution of wood rosin in acetone, similar acids present is formed. The crystalline precip to the solution utilized in Example 1, was satu itate is then recovered from the reaction mix rated at room temperature by gaseous ammonia ture, for example, by filtration and drying. If bubbled into the solution with agitation thereof. desired, the crystalline product may be purified The addition of the ammonia was continued for by redissolving and recrystallizing. A hour to insure saturation and the presence of The product obtained is a white crystalline salt an excess of ammonia. The heat of reaction. which has a melting point with decomposition be brought the temperature to the boiling point of tween about 145° C. and about 165° C. depending the mixture. The mixture was then permitted to upon the purity of the salt and also depending on stand A. hour and the precipitated crystalline the particular rosin acid utilized since rosin acids salt which formed therein was recovered by filter are almost universally mixtures of isomers. The ing and washing with acetone as in Example 1. exact melting point will depend on the particular The product was the same as that obtained in mixture of rosin acids present. In the case of 25 Example 1. . . ' products predominantly salts of abietic acid the Eacample 4 melting point will usually be between 154 C. and Twenty parts of N wood rosin were dissolved in 158° C. for crystals purified by a single recrystal 120 parts of acetone. Sixteen parts of liquid lization from absolute alcohol. ammonia were then added. A precipitate formed The crystalline product is substantially insolu 3) but redissolved. Upon cooling the mixture, to ble in acetone. It is somewhat soluble in hot ab well below. O C. a copious precipitate formed. solute alcohol or hot ethyl acetate and readily re Separation of this precipitate showed it to have crystallizes from both upon cooling. The crystal a vague melting range of about 85 C. to 110° C. line salt fuses to a light yellow liquid with evolu This precipitate was discarded and the filtrate tion of ammonia. When heated with strong sod 35 was permitted to stand for 24 hours at room tem ium hydroxide solution, acetone is evolved. . . . perature. Three parts of the crystalline product The preparation of the new compounds is ill obtained in Example 1 were then recovered from lustrated by the following examples in which the filtrate. Repetition of this procedure but per "parts' represent parts by weight unless otherwise mitting the solution to stand at room tempera indicated. 40 ture (actual temperature in solution rose to 40-50 Eacample it C.) caused the formation of the desired crystal line diacetoneamine abietate salt in a yield of 10.5 Into 100 parts of an acetone solution containing parts. This product in the unpurified state had 20% by weight of FF wood rosin were poured 15 a melting point of about 150° C. parts of liquid anhydrous ammonia. The mixture As shown in the examples, the ammonia may be was permitted to warm up by its own heat of . , added in the form of gaseous ammonia or in the reaction. A precipitate formed after about 4. form of liquid ammonia. However, it is essen hour. The mixture was permitted to stand about tial that the ammonia be in excess of the rosin 1 additional hour after which the Crystalline pre acid present. A large excess may be used, an cipitate was filtered from the mixture, washed excess from about.10% to about 300% of the the with acetone and dried in a vacuum desiccator to oretical amount which will react with the ace yield 10.7 parts of crystalline salt. This salt was tone and the rosin acid being preferred. The nearly white in color, having a faint tinge of reaction may be conducted at any temperature 1. 1 yellow. It had a melting point of about 150 C. between about 0° C. and about 100° C. It will be 1. with decomposition. 55 noted that although the ammonia may be added 1 2 2,874,969 as liquid ammonia at a low temperature the heat 1, he diacetoneanine salt of a rosin acid. of reaction soon brings the temperature into the 2. A diacetoneamine hydroalbietate. 0-100° C. range. Suficient ammoaia is retained 3. Diacetoneamine abietate. by an open reaction mixture to provide the ne 4. A process for the preparation of a diacetone cessary excess. If the reaction mixture is held 5 amine rosis 2Cid Salt which comprises subjecting at below about 0° C. little or none of the desired a compound selected from the group consisting of product is obtained but instead there may be acetone, mesity oxide and diacetone alcohol to formed undesired annonium abietate. Where treatment with a rosin acid and ammonia in mo the temperature is permitted to rise above about lal excess of the acid, at a temperature between 0° C., any initial precipitate of undesired ma 0. about 0°C, and about 00° C., until a crystalline terial will usually redissolve and react further ... precipitate of the diacetoneamine salt of the acid to form the desired product. Preferably the re used is formed, and recovering the precipitated action is initiated at room temperature or pers. Salt from the reaction mixture. initted to rise from the temperature of any liquid 5. A process for the preparation of a diace annonia added to room temperature. Ordi 15 toneanine rosin acid salt which comprises sub narily the resulting temperature will be between jecting a compound selected from the group con about 10° C. and about 56 C. sisting of acetone, mesityl oxide and diacetone 'The new salts may be prepared from abletic alcohol to treatment with abietic acid and an acid, pinnaric acid, sapinic acid or such acids in monia in molal excess of the acid, at a tempera hydrogenated form. Usually they will be pro 20 ture between aibout 0° C. and about 100° C., until vided as ordinary rosin or hydrogenated rosin. a crystalline precipitate of the diacetOnearmine Reat treated rosin, polymerized rosin and dehy salt of the acid used is formed, and recovering drogenated rosin are likewise suitable. The con the precipitated salt from the reaction mixture. centration of the rosin acid will usually be from 6. A process for the preparation of a diace about 0.03 to about 0.09 mois of rosin acid per toneanine rosin acid salt which comprises sub mol of acetone or other ketone formed from ace jecting a compound selected from the group con One, used. sisting of acetone, mesity oxide and diacetone It appears that the acetone forms diacetone alcohol to treatment with a hydroalbietic acid alcohol in the presence of the excess ammonia and, anmonia in molal excess of the acid, at a and that the diacetone alcohol then reacts with 30 temperature between about 0° C. and about 100° the annonia with replacement of the hydroxyl C., until a crystalline precipitate of the diace group by an amine group to form diacetoneamine. toneanine Salt of the acid used is formed, and re Simultaneously or subsequently this combines covering the precipitated salt from the reaction with the rosin acid to form the crystalline pre mixture. cipitated salt. It is possible that the diacetone 35 7. A process for the preparation of a diacetone alcohol believed to be formed dehydrates to mesi amine rosin acid salt which comprises subject tyl oxide which then adds ammonia to form the ing acetone and abietic acid to treatment with diacetoneamine. The diacetoneanine rosin acid annonia in molal excess of the acid, at a tem Salt may be prepared in the manner shown by . perature between about 0° C. and about 100° C., the examples when the acetone is replaced by di 40 until a crystalline precipitate of the diacetone acetone alcohol or by mesityl oxide or by mix amine Salt of the acid used is formed, and recov tures of these substances with acetone. ering the precipitated salt from the reaction mix The reaction of the ammonia with the inter ture. mediate acetone condensate occurs most readily 8. A process for the preparation of a diace under anhydrous or substantially anhydrous con 45 toneamine rosin acid salt which comprises sub ditions. It is, therefore, preferable to start with jecting acetone and a hydroabietic acid to treat Substantially anhydrous reactants so that the ment with ammonia in molal excess of the acid, at a temperature between about 0° C. and about water present in the reaction mixture is little or 100 C., until a crystalline precipitate of the di no more than that formed in the reaction. 50 acetoneamine salt of the acid used is formed, The products of this invention find use as ac and recovering the precipitated salt from the re celerators in rubber vulcanization and also as in action mixture. hibitors, preventing the oxidation of oils, rosin 9. A process for the preparation of a diacetone size and other materials which deteriorate read amine rosin acid salt which comprises subject ily on oxidation. They also have value as dis 55 ing diacetone alcohol and abietic acid to treat persing agents, for example, in dispersing pig ment with ammonia in molal excess of the acid, ments in paint vehicles. at a temperature between about 0° C. and about This application is a continuation in part of 100 C., until a crystalline precipitate of the di my copending application, Serial No. 438,899, acetoneamine salt of the acid used is formed, filed April 14, 1942. and recovering the precipitated salt from the re What I claim and desire to protect by Letters action mixture. Patent is: LUDWC. F. AUDRETH.