D¢¢= 31, 1946» F. w. KRESSMAN- EI'AL 2,413,326 RESINOUS MATERIAL. AND PROCESS .OF PREPARING THE SAME Filed Jan. 5, 1942 @Zigi 4044/ - ' W / ATTORNEYS. Patented Dec. 31, 1946 2,413,326 ' UNITED ‘STATES 'PATENT' OFFICE 2,413,326 RESINOUS MATERIALS AND PROCESS OF , PREPARING THE SAME Frederick W. Kressman and Frederick W. Kress man. Jr., Laurel, Miss., assignors of one-half to Continental Turpentine & Rosin Corporation, Inc‘., Laurel, Miss., a corporation of Mississippi 1 Application January 5, 1942, Serial No. 425,700 ' 9 Claims. (Cl. 260-104) This invention relates to a resinous plastic material and a process of preparing the same 2 shown) extending about the outside thereof for receiving the heated vapor of a high boiling and more particularly to a process of reacting liquid. In this Way, the temperature of the drum rosin with a ligno-cellulosic materia1 at an ele and the material therein may be accurately con vated temperature and obtaining from the re trolled during the heating operation and the fur action a thermo-setting plastic. nace may be eliminated. An object of the invention is the preparation The container II is equipped with an inlet of a new and improved thermo-setting plastic opening M which receives the discharge-end of a or resin and the development of an ‘improved ' tubular conveyor IS, the opposite end of the con process of making the same. Another object is 10 veyor being in communication with the outlet to provide a process for utilizing wood and other I6 of a hopper H. The conveyor l5 preferably ligno-cellulosic materials particularly in the form carries a screw ?ight l8 on the shaft l9, the of residues such as those obtained from the acid shaft i 9 being driven by any suitable power hydrolysis of Wood and from the extraction of means. Preferably the screw ?ight l8 extends wood with steam and solvents. Still another ob 15 to a point closely adjacent the inlet opening 14 ject is to provide a process for reacting ?brous but is spaced slightly from the drum ll. ligno-cellulosic materials such as wood ?bers or Said drum H is equipped in the lower portion particles of relatively low density with rosin to thereof with a suitable outlet 24 controlled by form a resinous material. ' the valve 25. This outlet may be used to remove Another object of the invention is to provide 20 from the drum the liquid product of the reaction“.v a process for reacting ligno~cellulosic materials In the upper portion of the drum II is an outlet with heated rosin in varying proportions to ob 26 which permits' the escape of excess vapors tain resinous materials of different character from the container. _ istics. Another object is to provide a resinous Within the drum II is a scraper 20 which plastic material which is thermo-setting and 25 is carried by the rotatable shaft 2|, the shaft which may be used as a molding resin or as a being driven by any suitable power means. The coating resin. Yet another object is to provide scraper 20 may be equipped, as shown, with a a resinous plastic material which is highly re plurality of scraper blades 21 which pass along sistant to alkalies and acids and which is sol the inner periphery of the drum I I. uble in only a limited number of organic solvents. 30 In the operation of the apparatus, the drum A further object is to obtain a resinous product II is partially ?lled with rosin indicated at 22 of a relatively low melting point which is thermo and heated to a temperature of approximately setting and thus may be readily lique?ed and will 450° F. at which point the rosin in the drum form a solid product upon the further applica has lique?ed. Suitable ligno-ceilulosic material tion of heat. 35 such as wood ?bers or particles of relatively low Other features and advantages of the inven density are introduced into the hopper I‘! from tion will appear from the following speci?cation which they are advanced by the screw conveyor and drawing, in which Hi to the inlet M in the drum I l and pass into Figure 1 is a diagrammatic showing of ap the drum. The ligno-cellulosic particles form a paratus for carrying out the reaction and Fig. 40 plug 23 between the inlet Id of the drum H 2 is a sectional view taken along the line 2--2 and the end of the screw conveyor [8. The of Fig. 1. plug of ligno-cellulosic particles in the inlet M In the speci?c embodiment of the invention of the drum l i serves to seal the inlet to prevent described herein and referring particularly to escape of rosin vapor from the drum II through the drawing, a furnace or heater ll! of any suit the same. As the screw conveyor I8 is rotated, able construction is arranged with a container the plug of wood particles as a whole is advanced, or drum H of any suitable size and shape sup the particles at the discharge end being intro ported therein and adapted to be heated by the duced into the drum I I. furnace. The furnace is preferably equipped As the ligno-cellulosic material is fed into the with a suitable temperature control ( not shown) 50 drum, the temperature of the rosin is gradually which permits careful and accurate adjustment raised and substantially all of the ligno-cellulosic of the temperature within the furnace. A ?ue material is added by the time that the temper l2 extending from the furnace receives the ex ature of the rosin reaches 550" F‘. The raising haust gas therefrom. If desired, the drum or of the temperature of the rosin continues until container ll may be equipped with a jacket (not 55 the mixture of rosin and ligno-cellulosic material 2,418,826 3 in the drum reaches the neighborhood of 600° F. The scraper 20 is continuously operated dur ing the reaction and serves to intimately mix the particles of the ligno-cellulosic material with the rosin and continuously agitate the mixture. The reaction is continued for a substantial period of time in order to permit all of the ligno-cellu losic material to react with the rosin. The re action is an endothermic one and requires the addition of a considerable amount of heat to 10 carry it on properly._'After the materials are mixed the reaction begins and takes up a large quantity of heat. When the reaction mixture no longer takes up substantial quantities of heat the reaction may be considered as being complete or nearly complete. Ordinarily, the reaction will require a period of at least one-half hour and often as long as two or three hours. When the reaction is substantially complete the entire mass in the drum I I is in the liquid state, after which said mass may be removed from the drum ll cause local condensation of the rosin vapor on the same. It may be that the condensation of the rosin vapor on the wood ?bers to form liquid rosin facilitates the introduction of ?bers into the liquid rosin and the mixing of the same there with by increasing the density of the wood ?bers and by wetting the ?bers with the condensed liquid rosin to improve the blending of the ?bers with the liquid rosin.‘ V The wood particles or ligno-cellulose may be added continuously to the heated rosin by means of the screw conveyor until the proper propor tions of the reaction ingredients have been ob tained. At this point the temperature is prefer ably raised as rapidly as-possible to a tempera ture in the range of 600° F.-650° F., preferably between 625° F.—635° F. and the mixture main tained at this temperature and continuously agitated until the reaction is substantially com plete. Ordinarily, between one-half and two _ hours will be required for the reaction, the time through the outlet 24 controlled by the valve 25. By means of the invention it is possible to utilize ligno-cellulosic products such as wood varying substantially with the quantities of in gredients used and with the other conditions of the reaction. The reaction is preferably carried ?bers which may be in the nature of residues from other operations or processes. For ex~ out at atmospheric pressure. ample, the ?nely divided particles of wood ?bers which are obtained from the acid hydrolysis a The exact mechanism of the reaction is not completely known. Since the reaction occurs at a temperature to which both the rosin and the wood particles normally partially decompose, it of wood and the wood ?bers which have been may be that the reaction occurs between the processed either in steam or organic solvents to 30 decomposition products or partial decomposition remove therefrom the soluble organic -constitu products of the rosin and ligno-cellulose. At any ents thereof are particularly suitable for the rate, when the reaction is carried out under the process. Unprocessed ?ber or sawdust is not as conditions set forth, the materials readily react desirable as these materials but may in some in to form a resinous plastic thermo-setting prod stances be used in the process. It has been not. found that the reaction m'ay be carried out, for In carrying out the reaction, the temperature example, with pine shavings and alpha-cellulose. of the mixture in the reaction chamber should The ligno-cellulosic material should preferably be very carefully controlled. The rosin should be in the form of ?nely divided particles. How be heated before the ligno-cellulosic material is ~10 ever, if the reaction conditions are very care introduced. The temperature at which the rosin fully controlled, it is possible to carry out the is initially heated prior to the introduction of reaction using particles of a substantial size. the ligno-cellulosic ‘material should be in the By using the screw conveyor [5 to introduce neighborhood of 450° F. After the material has the ligno-cellulosic material into the reaction chamber, the mixing operation may be carefully - been introduced into the rosin the temperature of the mixture should be raised to approximately controlled. The material should be introduced. 600° F. and maintained in the neighborhood of slowly in order to permit the ligno-cellulosic this temperature until the reaction is substan material to become mixed with the rosin shortly tially complete. Preferably, the mixture should after it is introduced into the container. It is, be maintained at a temperature of between 625° 50 of course, desirable to introduce the material as F. and 635° F. as the reaction proceeds. vrapidly as possible without forming a doughy In carrying out the reaction various proportions mass in the rosin. If the material is introduced of the ingredients may be used. Preferably in too rapidly, this doughy mass will be formed and the neighborhood of equal parts of the ligno will prevent the proper mixing and reacting of cellulosic material and the rosin are used in the the ingredients. Nevertheless, in accordance reaction, the proportions being by weight. Since with the present invention the ligno-cellulosic the ligno-cellulosic material, when formed of light , material may be introduced in a very short time, wood ?bres, may be of a density as low as 1/20 or it being possible to completely mix a large batch Han of that of the rosin, the process in this in in a few minutes under ordinary conditions. stance serves to facilitate the incorporation of By following the reaction conditions set forth, the ?bres in the rosin. it is possible to readily incorporate the ligno The proportions in which the ingredients are cellulosic material in the liquid rosin without mixed will, to a certain extent, determine the type the formation of a doughy mass in the rosin and of product which is obtained in the reaction. without any substantial scorching or partial car 65 For example, a reaction between ?fty percent bonization in the mixture. ‘ ligno-cellulosic material and ?fty percent rosin Since rosin at a temperature of 450° F. or above results in a product which has a melting point possesses a substantial vapor pressure, the of 260° F. On the other hand, when forty-three chamber during the course of the reaction con percent ligno-cellulosic material is reacted with tains rosin vapor above the liquid rosin. When ?fty-seven percent rosin, the product has a melt the wood ?bers are introduced into the cham ing point of approximately 230° ,F., while the ber, they are brought into contact with this product of a reaction of forty-?ve percent rosin vapor before being introduced into the liquid rosin. The rosin vapor being maintained at an and ?fty-?ve percent ligno-cellulosic material elevated temperature serves to preheat the wood ?bers while, at the same time, the cooler ?bers melts at approximately 295° F. In each instance the proportions are by weight and the reaction is anaaac 5 . 6 , carried on until no Iurthendistillate is obtained be used as a coating resin particularly when from the reaction mixture v'at a temperature at treated with drying oils and the like. As a coat a range of 625° F. and 630° F. ing resin the product is particularly useful in pipe Each of the various products which is obtained and conduit coverings and the like. in the reaction is subject to a lowering of the Li The foregoing speci?c description has been melting point if the product is reheated at a given for the purpose of illustrating the inven higher temperature in the absence of air. For tion and the means of practicing it. Changes example, the product obtained by reacting parts and modi?cations, therefore, may be made in the of the rosin and ligno-cellulosic material, which process and product as set forth, particularly as melts at 260° F., may be reheated at 640° F. to to the quantities of the reagents used and as to 650° F. in the absence of air to obtain a product the conditions of the reactions without departing which melts at approximately 230° F. In each from the spirit and scope of the invention. case the heating at a higher temperature in the We claim: absence of air will result in the lowering of the 1. A process of forming a resinous plastic ma melting point. The operation need not be a re 15 terial comprising heating a body of rosin to a heating operation since the same effect may be temperature in the range of 450° F.—550° F., in obtained by heating the product or the original troducing into the heated body a solid ligno reaction mixture to 640° F. to 645° F. in the ab cellulosic material, agitating the mixture, and sence of air. The product of the reaction between then heating the same to a reaction temperature forty-?ve percent and ?fty-?ve percent ligno- ~ until the entire mass has lique?ed, said reaction cellulosic material, which normally melts at 295° temperature being at least approximately 600° F., may be changed to a 230° F. melting point and not substantially above 650°. product by heating the material in the absence 2. A process of forming a resinous plastic ma of air at a temperature in the range of 650° F. terial comprising, heating a body of rosin to a to 660° F. temperature in the range of 450° F.-550° F., in The products resulting from the reaction are troducing small particles of wood ?bre into the in the form of black plastic resins which are body of rosin, agitating the mixture, raising the liquid at the reaction temperature. If the prod temperature of the mixture to 600° F.-650° F., uct is withdrawn from the reaction chamber while and maintaining the mixture at the raised tem in the liquid condition, it will be found to have 30 perature until the entire mass has lique?ed. the melting point above stated when tested by the 3. A process of forming a resinous plastic ma ball and ring method. " terial comprising, heating a body of rosin at When the products of the reaction are heated atmospheric pressure to a temperature in the in the presence of air to a temperature above neighborhood of 450° F., introducing into the body 630° F., preferably in the neighborhood of 650° F. small ?brous particles of a‘ligno-cellulosic mate to 660° F., they will gradually solidify to form insoluble infusible masses. The products, there fore, are possessed of thermo-setting properties and are extremely valuable as molding com pounds. The thermo-setting resin which is normally ‘ obtained from the reaction in the liquid phase, may have a melting point of approximately 230° F. and is, therefore, normally solid. The solid resin possesses a black opaque lustrous appear ' ance and is quite brittle. When fractured the exposed‘ portions of the rosin are brilliant and rial, the particles being of relatively low density, intimately mixing the ligno-cellulosic material with the liquid rosin, increasing the temperature of the mixture to ,a temperature in the range of 625° F.-635° F., and maintaining the mixture at a temperature in’Hsaid range while continuously agitating the same until the entire mass has lique?ed. ’ 4. A process of forming a resinous plastic ma ' terial comprising, heating a body of rosin to a temperature in: the range of 450° F.-550° F., in troducing small particles of ?brous ligno-cellu lustrous. losic material of relatively low density into the The reaction product is substantially insoluble heated rosin, said particles being present in the in practically all organic solvents with the ex 50 proportion of approximately one part by weight ception of aromatic naphthas and carbon tetra to each part by weight of rosin, agitating the chloride. Such solvents as para?inic naphthas, mixture, raising the temperature of the mixture gasolines, greases, oils, etc., do not affect the to 600° F.-650° F., and maintaining the mixture material. In addition, the resinous material is at the raised temperature while continuously agi resistant to organic and mineral acids and to 55 tating the same for a period of at least one-half caustic solutions in concentrations up to ten per hour to "permit the ligno-cellulosic material to cent. react substantially completely with the rosin. The reaction product may be used in further 5. A process of forming a resinous plastic ma . reactions to obtain desired materials. It may, terial comprising providing a substantially closed for example, be reacted with drying oils .such as 60 container having therein a quantity of heated tung oil or linseed oil to form a new type of rosin, the rosin being in the liquid state and at coating plastic resin as distinguished from mold a temperature of approximately 450° F., grad ing plastics. For this type of reaction, a mixture ually raising the temperature of the rosin to 550° of twenty-?ve percent to thirty percent of the oil F. while slowly introducing into the same small with seventy to seventy-?ve percent of the res 05 ?brous wood particles of relatively low density, inous material is preferably used. The product of such a reaction is soluble in mineral spirits and will produce tough ?lms of high luster and jet black re?ection. Such products are extreme intimately mixing the wood particles with the liquid rosin, raising the temperature of the mix ture to a temperature in excess of 600° F., and below the decomposition temperature‘ of the res ly useful in the preparation of coating ?nishes. T0 inous reaction products and maintaining the mix The rer'.:ous plastic product of the reaction ture at a temperature in excess of 600° F. while between .116 rosin and ligno-cellulosic material agitating the same for a substantial period of ...ay be used as a molding resin and is particu ' time to permit the entire mass to liquefy. larly valuable because of its thermo-setting prop 6. A process of forming a resinous plastic ma erties. On the other hand, the product may also 75 terial comprising, providing a body of heated 8,418,826 7 . rosin at a temperature in the range of 450° F. ture being maintained at the raised temperature 550° F., introducing into the body small particles 01' ligno-cellulosic material, intimately mixing the ligno-cellulosic material with the rosin, raising the temperature of the mixture to 600° F.-650° F., and maintaining the mixture at the raised in the presence of air. substantially the melting point of pure rosin, mixing the resulting molten material with the ligno-cellulosic material .in approximately equal temperature for a period of at least several hours while simultaneously agitating the mixture. 7. A process of forming a resinous plastic ma substantially above 650‘ E, and maintaining the , 8. A process which comprises heating rosin to proportions by weight, then heating the mixture to a reaction temperature above 800° F. and not terial comprising, providing a body of heated 10 mixture at that temperature for a period oi at least approximately one-half hour. liquid rosin, introducing into said body small par 9. The method as set forth in claim 8, in which ticles of a ligno-cellulosic material, raising the the reaction is carried out at a temperature oi temperature of the mixture to a temperature in GOO-635° F., and the reaction product is then excess of 650° F., and below the decomposition temperature or the resinous reaction products, 15 heated in the absence of air at a temperature above 640° F. maintaining the mixture at the raised tempera ture for a substantial period of time until the reaction between the ligno-cellulosic material and the rosin is substantially complete, the mix- FREDERICK W. KRESSMAN. FREDERICK W. KRESSMAN, JR.