Patented Nov. 21, 1939 2,180,418 UNITED STATES 2,180,418.PATENT OFFICE RESINIFICATION of oxIDIZED TERPENE HYDROCARBONS - Joseph Hidy James, Pittsburgh, Pa., assignor to Clarence P. Byrnes, Sewickley, Pa., trustee No Drawing. Application October 1, 1935, Seria No. 43,082 1 Claim. (C. 260-2) In various patents and pending applications, of the large naval stores companies, this showed I have described my vapor or gaseous phase par a composition of: tial oxidation process, preferably in the presence Alpha and beta pinene of a catalyst, for making partial Oxidation prod Limonene 5 ucts from aliphatic hydrocarbons whether sat Dipentene urated or unsaturated, as well as from hydrocar The terpinenes bons containing cyclated bodies of naphthenic Borneo type; see for example, my re-issue Patent No. Fenchy alcohol 18,522 dated July 12, 1932, and other of my Other compounds of the terpine group in small O patents, and . Copending applications Ser. No. amounts 0 272,567 filed January 22, 1919, Patent No. Of these bodies, alpha pinene has the following 2,085,221; Ser. No. 435,355 filed January 6, 1921, cyclic structure: Patent No. 2,054,571, and Ser. No. 310,437, filed October 4, 1928. - gh, 15 The partial oxidation product so produced C . Y contains groups of oxidized bodies in the range 15 from alcohols to organic acids, each group or class containing similar bodies of different molecular weights. For example, there are al- . CH-C-6, 20 coholic groups, ketonic groups, aldehydic groups, HC c-H, 20 acidic groups, etc. I have found that excellent resins may be produced by combining the par tially oxidized products or portions thereof with This cyclic structure has more of the ali polyhydric alcohols, such as glycerol or glycol; phatic than of the aromatic characteristics and , and I have also found that even where the acid its double bond acts like an olefin, in my vapor 25 content is not of a dibasic type, but of an phase process of oxidation. Oxygenated type, the reaction with such poly The double bond in alpha pinene offers 8, hydric alcohols occurs. This, therefore, opens point of oxygen attack, the result being the up a field for a large number of resin com opening of the chain and, on a less degree of 80 pounds which may be cheaply prepared, and Oxidation, forming a carboxyl group on One car especially from the liquid products produced by bon atom at the rupture and a ketOne group On. applying my vapor phase catalytic oxidation the other. Still more vigorous oxidation would process to aliphatic or naphthenic hydrocarbons, break the bond between the central carbon atom and to terpenic hydrocarbons such as pine oil. and the ring carbon to which it is attached, like I have further discovered that my process wise introducing a hydroxyl ketonic group at 35 is peculiarly adapted to the partial Oxidation of the other. The process may be applied to other terpenic hydrocarbons which are specially adapt terpene hydrocarbons, producing intermediate : ed therefor. The structure of such terpenic hy oxidation products of the alcoholic, acidic, ke drocarbons is a ring type body having, however, tonic and aldehydic types. The resulting oxi 40 a double bond so located that in my process the dation mixtures may either be subjected to terpenes act more like aliphatic compounds than methods of group separation or may be used in 40 like aromatics. This double bond is so located toto. ' ' w that the structure, is peculiarly open to oxygen attack by my vapor phase process. Consequently - Comple 45 the process may be carried out at relatively lower Taking Georgia pine oil of a specific gravity 45 temperatures than when applied to straight aii. 55%at 60°=936, (by voine Engler assing distillation; over 2006.initial and190 aC. phatic hydrocarbons for example, at 200 C. or end point of 226 C. lower. Furthermore, the product thereof is pe The partial oxidation apparatus was of my 50 cularily adapted for certain purposes such as triple-screen type, with molybdenum oxides as the resins. The process may be applied to all va catalyst, this being of the type which was non porizable...terpenes, and especially to the tur volatile at the temperatures used. In such case pentine and pine oil products of the Southern air was added in front of the first screen and be ; Pine Naval Stores Industry. Taking pine oil tween the first and second screen and again be 55 as an example from the Georgia plant of one tween the second and third screen. The rate of 2 4,180,418 feed into the vaporizer was 8 liters per hour and hydrochloric acid solution as a condensing cata the air rates 62 liters of air per hour at the first lyst. The temperature was gradually, raised to. screen; 50 liters of air per hour at the second l10 C. in the course of an hour, and the heat screen, and 50. liters of air per hour at the third ing continued at this temperature for about four screen. The temperatures were maintained be hours. The liquid mass (liquid from excess of low the ignition point for such mixture and below glycerol) was poured into 300 cc. of hot water that of continuous self-sustained complete com to dissolve the unreacted glycerol. The washing bustion and in this case were about 430° C. in was repeated until all the free glycerol was re the vaporizer; 460° C. at the first screen, 460 moved. The resin thus produced was of a brown 10 C. at the second screen, and 500' C. at the third color, showed darkening at 120° C. and on a melt io screen. During the run, 58 liters of oil were fed 1ng point determination, it showed no fusion up into the apparatus and 42 liters of oxidized prod to 240° C. It was insoluble in benzol, but dis uct were obtained, giving a volume recovery of solved in a solvent prepared from the vapor 68%. The condensed and recovered liquid prod phase catalytic oxidation of naphthenic gasoline, 5 uct had the following properties: specific gravity such solvent containing alcohols, aldehydes, ke S at 60° F =.948 Engler distillation; initial distill tones and esters (1 part. resin to 5 parts of sol lation at 90°. C. 50% (by volune), passing over vent). On evaporation an excellent film which at 196° C. Decomposition of the residual liquid was hard and tough resulted. . in the distilling flask started at about the 90% Eacample 2-5 grams of the oxidized product 20 point where the temperature was 236 C. So including oxygenated acids was combined with 20 diurn hydroxide saponification removed 50% by cc. of denatured alcohol to aid in initial Solution volume from the total oxidation mixture, show and reaction. A mixture was then made of this ing the presence of a large amount of carboxylic with 20 cc. of glycerine, using as a catalyzer acids. The sulphuric acid test gave a contrac one gram of anhydrous aluminum chloride. The 28 tion of 64% by volume, while the sodium acid mixture was gradually warmed up to 100° C. dur sulphite test for aldehydes and methyl ketones ing one hour and heating continued at that tem showed 10%, perature for about four and one-half hours. The Further proof that the greater part of the oil treatment with water and Washing to remove ex fed had been converted into partial oxidation cess water and glycerol was the same as in Ex 30 products was shown by the fact that the total periment 1. A resin was obtained which dark product dissolved nitrocellulose without any con ened at 210°C. and did not melt up to 250° C. centration of said oxidized product. It was not soluble in benzol or amyl alcohol. It The partial oxidation product thus obtained dissolved (1 part to 20 parts) in the oxidized may be used for several purposes. Among these gasoline solvent above referred to and formed a would be the preparation of cellulose solvents Very hard and tough film On evaporation. and plasticizers; solvents for synthetic resins; . Eacample 3-Here used a mixture of dibasic using the oxidized product as raw material for acid produced by a secondary oxidation of the the production of synthetic resins, either by poly partial oxidation product obtained by vapor phase merizing the product itself, or by combining it or oxidation of Pennsylvania spindle oil, nitric acid products thereof with phenols or with polyhydric being used for this, further oxidation. 5 grams 40 40 alcohols, or with combinations of them. of the dibasic acid thus obtained was combined Changes may be made in the terpenic hydro with 20 cc. of denatured alcohol to dissolve the carbon used as raw material; one or more cata acids and then mixed with 20 cc. of glycerol and lytic layers or screens may be used; a gaseous one gram of anhydrous aluminum chloride as a catalyst may be used or no catalyst at all pure catalyst. The mixture was heated gently, for 20 5 45 oxygen may be used instead of air; the process minutes to start the reaction and to evaporate may be carried out at subatmospheric, atmos the alcohol. The heating was . continued at pheric or superatmospheric pressures; partial ox 110° C. for five hours. The remainder of the idation products may be recovered by condenser process was the same as in Example 1. Light scrubber systems after each reaction and before brown resin was obtained with a melting point so the exit stream passes to another reaction cham of about 48° C. This resin was readily soluble ber; in the plural-screen type; and other changes in benzol and on evaporation left a tough film, may be made in this step. - but not having the hardness of the film left by One of the important products obtained from the evaporation of the oxidized gasoline solvent. such partial oxidation product or terpenes is the Eacample 4-5 cc. of oxidized pine oil was 55 production of resins. I will now give examples mixed with 5 cc. of glycerine, using 1 gram of of the production of resins from my partial ox anhydrous aluminum chloride as a catalyst. The idation products, and particularly as to three mixture was gradually heated up to 150° C. dur groups of resins, the first group being formed by ing three hours, and the heating continued at the reaction between my partial oxidation prod about that temperature for about three hours ucts of aliphatic or terpenic hydrocarbons and longer. A brown resin resulted which separated polyhydric alcohols such as glycerol; the second from the glycerine which had not entered the group relating to the formation of resins by the reaction. A melting point determination of the reaction of the terpenic partial oxidation prod resin showed an initial softening at 84 C. and ucts. with phenols and the third group to resins complete liquefaction at 95° C. In the solvent formed by adding the oxygenated acids to cer test, it was found easily soluble in benzol, form tain carbohydrates preferably in the presence of ing a hard and brittle film on evaporation. It a catalyst. - - - was also easily soluble, in the Oxidized gasoline First group: In this group, the oxygenated above referred to, leaving a hard and tough film 70 acids formed by my vapor phase catalytic air ox on evaporation. In this example, glycol may be 70 idation of Pennsylvania gas oil were combined used. .with glycerol to form resins. V Eacample 5-In this case 5 cc. of the oxidized Eacample -5 grams of oxygenated acids ex pine oil was resinified by heating with 1 gram , tracted from an oxidation mixture were heated of anhydrous aluminum chloride as a catalyst. with 20 cc. glycerol, using 2 cc. of concentrated This was gradually brought up to 150°.C. in one sieo41s. hour and heated at that temperature for about. ... four hours longer. A hard brown resin resulted. in the third group, resins are prepared by add A solvent test showed it was readily soluble in ing the oxygenated acids separated from my par benzol, leaving on evaporation a non-uniforn tial oxidation product, or the liquid product it film of poor characteristics. In the oxidized gas self or part of it, to certain carbohydrates, pref one above referred to, this resin dissolved read erably in the presence of a catalyst. Here, as in ily, leaving a tough film which was somewhat the glycerine reaction, the polyhydric alcohol tacky. The melting point determination of this groups of the carbohydrates react at the points resin showed initial softening at 90 C. and com in the oxygenated acids as before noted. 10 plete liquefying at 120 C. . . cample 9-5 grams of my oxygenated acids made from gas oil and 5 grams of glucose were O second group: In this group, resins were pre dissolved in 20 cc. of ordinary commercial alcohol - pared by reacting on oxidized pine oil produced with one-half gram of anhydrous aluminum by catalytic vapor phase oxidation of terpene added as a catalyzer... The solution was allowed hydrocarbon with phenol, using different cata to stand for 24 hours at room temperature and - 15 lysts. I have found that these terpene oxidan - was then warmed to 50° C. and held there for 12 15 tion products condense of themselves to form res hours. A resin separated out and the alcohol ins, as shown in Example 5, and also readily was finally evaporated. The resin was washed condense with phenols making resins of remark with water and dried. ableemples-5 quality. cc. of oxidized pine oil was On test, the resin showed change in color at mixed with 5 cc. of phenol, using 1 gram of anhy 120° C. and completely blackened at 150° C. 20 : drous aluminum chloride as a catalyst. This without fusion. In 20 parts of benzol, solubility was heated to 180 C. for ten minutes, and then was difficult and the film was poor. In 20 parts at 150° C. for five hours. A dark brown resin of solvent made from oddized kerosene, there. resulted which, on melting point determination, tacky,was slow and solution. very tough. The film was brown, slightly 25 showed initial softening at 62 C. and complete The advantages of my invention result from liquefaction at 70° C. The resin dissolved read the cheapness and excellent qualities of the res- . ily in benzol, leaving a tough hard film. It dis ins produced. The polyhydric alcohols may be solved even more readily in the oxidized gasoline used with any of my products from the partial above referred to and left on evaporation a oxidation of mineral oil fractions and the prod gasoline film which was very hard and tough. ucts from the partial oxidation of terpenehy Scample 7-A mixture was made of 5 cc. of drocarbons give especially good resins in con pine oil; 5 cc. of phenol and 1 cc. of caustic bination with phenols, and may also be directly soda solution. This was heated for two hours polymerized with or without the use of a catalyst, 35 at 150° C. and produced a resin which was solid especially by continued heating. at room-temperature. It was a light brown color By the terms polymerizing or condensing as and softened at 89.5 C. and became completely used herein, I mean the aggregating or clotting liquid at 114 C. It dissolved with some difficulty together of molecules, producing a material which in benzol, leaving a hard tough film. It was is more like a resinous 40'. readily soluble in the oxidized oil solvent giving solid. a very hard tough film on determination. claim: cample 8-5 cc. of oxidized pine oil was In the treatment of a -Inixture of different mixed with 5 cc. of phenol and 1 cc. of aniline, terpene" hydrocarbons, the steps consisting of After two hours heating at 150 C., the resin was heating said mixture and treating it with a gas 45 sold at room temperature. It gave a sharp containing free oxygen under conditions produc melting point at 70° C. and the resin was brown ing a liquid formed mainly of a plurality of oxy- is in color. In benzol it dissolved readily giving resinifyinggen derivatives said product.of terpene hydrocarbons, and an excellent fin-hard and tough. It dissolved easily in the oxidized gasoline solvent, giving 5) an excellent film both as to hardness and tough JOSEPEEDY JAMCs.

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