Патент USA US2406338код для вставки
- Patented Aug. ‘27', 1946 ' 2,406,338 UNITED STATES I PATENT OFFICE 2,406,338 _ Rosm' TREATMENT Laszlo Auer, South Orange, N. 'J._ No Drawing. Application October 2'7, 1943, ' . Serial No. 507,895 3 Claims. (Cl. 260-106) 2 GENERAL FIELD or INVENTION AND STATEMENT or Owners used with the modi?ed products. This invention relates to treatment of rosin, and especially to treatment with certain modify ln-part of my copending application Serial No.‘ semi-drying oils in paints and other coating and ~ plastic compositions. tures of rosin acids, known today as abietic acid, 10 others. Such rosins commonly have an acid value of from about 145 to 185, usually from about 160 - to about 168, and in their ‘natural state they-are ordinarily hard, brittle materials, of melting point from about 70° C. to about 85° C. ' Rosin is a valuable raw material for a number - i?ed rosin products, such products may be em ployed as a replacement ingredient, in substan tial proportions, for linseed or other drying or rosin. The present application is a continuation~ pyro-abietic _ acid and d-pirnaric acid amongst . Because of the improved properties of the mod-7 ing agents promoting softening or liquefaction of 461,795, ?led October 12, 1942. As is known, gum or wood rosins contain mix - varnishes and the like. Usually, however, at least some drying or semi-drying oil is advantageously ' For certain special purposes in .the soap and paper sizing industries, the modi?ed rosin prod acts of the invention may also be of advantage, notwithstanding the'fact that the modi?ed prod ucts have a reduced acid value. . One of the most important modi?cations brought about by the process of the invention is the softening Or liquefying of the rosin. i.»e.. at least some reduction of’ brittleness or in melting point, or both. In addition, the process of the * and plastics industries. There‘ are, in fact, 2. 20 invention is notable in its e?'ect on the acid value, the invention providing for appreciable reduction number of examples in the art of use of various 1 in acid value, as will further appear. In referring rosin derivatives for purposes such as those men to changes of this type and in making compari tioned, Some of the most important and common sons of the modi?ed products with products not examples occur in the coatings industry, 1. e., use :11; rosin derivatives in paints, varnishes and the 25 treated with modifying agents, it is to be under of commercial purposes, such as in paper sizing, soap manufacture, and especially in the coatings stood that the statements regarding changes and e. comparisons are always made on the basis of a In its natural state, however, rosin is not well suited to many commercial purposes for which ‘ relation between the producttreated with a mod ifying agent and a product treated in exactly the it is potentially a valuable raw material. 30 same manner (heating, etc.) but/without a modi The primaryobiect of the present invention fying agent. , . , is to modify various physical properties of rosin, According to the invention, by appropriate con whereby to produce modi?ed rosin products trol of treatment conditions, and by appropriate which are better adapted to many uses for which selection of materials, the degree of softening or rosin or rosin derivatives are now employed. In addition, the modi?cations, brought about in ac 35 liquefaction and also of acid value may be regu lated to meet various different requirements, cordance with the present invention make it pos For instance, according to the invention, it is pos sible and advantageous to use the modi?ed rosin sible-to very extensively soften the rosin, or to products for many purposes for which rosin in very extensively lower the acid value, or both. its natural state and also various derivatives Although the invention is not limited thereto, thereof are not well suited. it is‘of especial importance and advantage in ac To illustrate, reference is made to coating com cordance with the invention to subject the rosin' positions, such as varnishes.- In its natural state, to treatment for a time and under conditions rosin is a brittle material and therefore yields a brittle ?lm when employed alone .as varnish 45 such as to change the physical character of the rosin ‘from its natural hard and brittle condition _ solids. Thus, rosin in its natural state does not to a consistency approximating the so-called have ?lm forming characteristics such that it "cold ?ow,” i. e., a consistency according to which \ may satisfactorily be employed alone as vehicle solids ‘in a. coating composition. ' According to . the material will gradually ?ow at normal room this invention, modi?cations’ are brought about 50 temperatures, so that if ‘a blob of .the modi?ed rosin is, placed on a ?at surface, it will more or in the rosin so as to secure a rosin product having less-gradually ?atten out, often at a rate which drying or ?lm forming characteristics which are is not observable withthe eye. For many pur well suited to the coating composition industry, poses a liquefaction at least to this degree is de thereby even making possible employment of the sirable. modi?ed rosin products alone as vehicle solids in For certain purposes it is- advantageous that ' 2,406,888 . ' 3 the rosin be lique?ed even to the extent of be coming a mobile‘ liquid, similar, for instance. to ' the consistency of certain oils. such as bodied linseed oil. » . \ 4' even more, although usually not more than about 10% .will be absorbed by the reaction mass. The percentage of other modifying agents pres ent during treatment with sulfurdioxide, such as the decarboxylation promoting agents above . My preferred range of liquefaction extends ' referred to, may be anywhere from a trace, for from about the consistency of a viscous oil to instance, from .0l% or .5% up to about 10% by‘ about the cold flow consistency above mentioned. weight of ‘the rosin being treated, and I have although it is to be understood that a greater or found a particularly advantageous range to be a lessor degree of liquefaction is also contem 10 from about 1%. or 2% up to about 5%. ' plated. > The effects of certain variations in tempera The modi?cation process ture, percentage of modifying agent and time will be pointed out more fully hereinafter. The process of the invention involves heating Thorough dispersion of the modifying agent in the rosin in the presence of sulfur dioxide,~the ‘the rosin is of importance and appropriate con duration of heating, temperature and other treat trol of temperature and ,time both contribute ment conditions,‘ being such as to vefl’ect. decar to bringing about such thorough dispersion. Ag boxylation or softening of the rosin, and being controlled in accordance with the extent and type itation may be employed as an aid to securing - thorough dispersion. Usually not more than a of modification desired. , In addition to sulfur dioxide other modifying 20 few hours treatment on temperature will be found suiilcient, for instance, from about one hour to about five hours, although in some cases, the re action proceeds very rapidly, requiring not more agents may be present, ‘such for example as the following inorganic acids which promote decar boxylation: . ' - - than about one-half hour. Hydrochloric Hydrobromic Hydriodio Sulphuric Chlorsulphonic , Sulphurous (H2803) ' Hydrosulphuric (HzS) Hydrosulphurous Thiosulphuric Boric- Phosphoric fying agent servejto exclude the air. tact of .air may be brought about by blanketing the surface of. the reaction mixture with some Thiocyanic 1 inert gas, such as CO2, or nitrogen. Where vacu um is-used, a pressure, for instance, of about 100 Moreover, any one of many other decarboxyla tion promoting agents may be present, such as organic acids, metal salts, and other groups and mms. Hg to about 45.0 mms. Hg will be found ef fective, although higheror lower pressure may be used, under various circumstances. .classes of ‘ agents as disclosed in various of my ' Some. more or less general considerations re prior patents including those patents mentioned for . Vacuum is also effective for the purpose of‘ excluding air and, in addition, reduction‘ in con ' Hydrocyanic elsewhere herein, - ‘ Another important consideration is that the ‘ reaction is preferably carried out in the absence of air, or out of contact with any substantial quantity of air. For this purpose the reaction may be carried out in a closed vessel, though not necessarily at a positive pressure, so that the gases or fumes of theréaction released from the modi-' 25 garding the process should be noted, as follows: Although the complete mechanism of modi? cation may not be fully understood, it may be mentioned that rosin ‘is an organic isocolloid, i. e.. a colloidal system in which the dispersed phase and the dispersion medium are both of the same example Patent No. 2,298,270. The treatment in the presence of sulfur dioxide is desirably carried out either under positive pres sure or by bubbling the gas through the reaction ‘ mixture. The bubbling may be employed under chemical composition, though present in different . By selection of modifying agents, and by ‘ap 50 vacuum. propriate variations in treatment procedure, time, temperature, etc.,. I am enabled to pro duce modi?ed rosin products having quite a wide range‘ of properties. In fact, according to the invention, it is possible to secure a modi?ed prod 55 physical states. ' or relative proportions of the dispersed Phase and dispersion medium may be altered. Moreover, the‘ ' modi?cation process apparently also involves de carboxylation, the extent of which is usually in- ' complete. I uct in which either the- acid value or melting . By modification I believe that the relationship 7 , Possibly also non-‘volatile aggregates or poly point is very extensively lowered, or in which both of these properties are simultaneously lowered to a great extent. Various of the decor mers are formed. Some of the foregoing effects or reactions (par boxylation promoting agents ‘are notable in mak-v 60 ticularly with respect to the physical consistency of the modi?ed product) may work in one direc- ing possible extensive lowering of meltingpoint, tion and others in the opposite direction. so that in many instances liquid products are ob In considering the nature of the modi?cations, it is to be noted that, While some small loss inv In carrying out the procesathe rosin i's-heat tainable. _ ' ed in the presence of the sulfur dioxide at tem - perature between about 100° c. and about 350° 0., depending upon the materials used and the degree of modification desired. Usually the tem at weight may occur by volatilization (usually not more than about 15-20%), no appreciable frac tional or destructive distillation takes place.’ With appropriate precautions to avoid distillation the process can usually be carried out without perature should be at least 250° C. and most fre quently above 270° C. in order to secure appreci 70 loss or .more than 5% or 10%, such small loss as does occur usually comprising‘ water, CO2, etc., able modi?cation of the properties of the rosin. at least in major. part. Asa precaution, the tem Throughout the heating period the percentage ' perature should be kept below the boiling or dis of sulfur dioxide bubbled through or otherwise tillation point of the main reaction product, under brought in contact with the rosin may be any by weight of the rosin or 75 the applied reaction conditions of the process. where up to about 30% 2,406,888 5 By this precaution, destructive distillation or cracking is positively avoided. ployed may be such that gases evolved from the reaction will serve to effectively exclude air, with out applying vacuum. Furthermore, certain - The modi?ed rosin product is quite'unique, since the rosin molecule retains almost as many carbon gases, such as CO2, or nitrogen can be either bubbled through the reaction mass or employed _ atoms as are present in the initial basic con stituents of the rosin, the number of carbon atoms as a blanket on the surface of the batch'under being reduced ‘only by, that number involved in the decarboxylation. Still further, the types of going ‘treatment; vExpedients of this type not onlyserve to exclude the air from the reaction but may also be utilized, for their supplemental constituents of the modi?ed rosin are very few in number, probably not more than two or three, and 10 effect on the material being treated,‘ this subject these constituents are characterized by boiling being more fully considered in my copending ap points all lying within a narrow and relatively plication Serial No. 318,650, ?led February 12, high temperature range, as can be demonstrated 1940 (now Patent 2,298,270) , ‘of which the present by subsequent distillation of the modi?ed prod application is a continuation-in-part. It is here ucts. The modi?ed products, for practical pur- ' 'further notedlthat certain features herein dis poses, are non-volatile when exposed to the air. closedare also disclosed in my‘ prior U. 5. ap It is of importance in securing various of the plication Serial No. 359,425 (now Patent 2,213, ' foregoing characteristics that the reaction take 944); and Serial No. 143,786 ‘(now Patent No. place without any appreciable concurrent distilla 2,189,772) .l ’ tion. In addition, the absence of air and/ or con 20 Moreover, as disclosed in the above mentioned trol of temperature are important in avoiding de applications, still other variations in process may structive distillation. be employed for a number of diiferent purposes, _ ‘I Whatever the exact nature of the chemical col but it is not throught necessary to discuss these loidal and/or physical changes which are brought fully herein, since reference may be made to the about, in general the treatment provided in ac copending applications for that purpose. In cordance with the present invention reduces the passing, however, it is noted that additional treat acid value of the modi?ed product and also sof ment agents, of a supplemental character, may , tens or lique?es the material. These changes, also be present during the reaction, among which together with others which usually take place, might be mentioned dissolution promoting agents such-as imparting drying characteristics to the 30 of the type disclosed in my issued Patent No. rosin, and improving ?lm forming properties of 2,293,038. Various combinations vof modifying the modi?ed products as compared with untreated agents may also be used for different purposes, rosin in the absence of other vehicle solids, for including combinations of the modifying agents instance, make possible or'practicable use of my above disclosed, as well as combinations of the modi?ed rosin products for many purposes for 35 modifying agents herein disclosed with agents‘; which rosin in its natural state is not suited, or at disclosed in other of my applications mentioned least not well adaptable, and for which many above as well as hereinafter. known rosin derivatives are likewisenot satis It is further to be noted that in general increas _ factory. ing any one or all of the variables: namely, tem By appropriate selection of modifying agent perature, time of treatment and percentage of and treatment conditions, such as temperature, modifying agent, increases the extent of modi time, vacuum, vetc., I am enabled to control various fication. It will be understood that the foregoing physical properties of the modi?ed products, and is a general rule normally applicable within the notably the acid value, saponi?cation value and ranges of operation above indicated, although, as physical consistency. In general, the most valu- , to at least some variables, there may be limits ' able modi?ed products have, for instance, a sa beyond which the general rule does not apply. poni?cation value not exceeding about 120.~ ' . For instance, excessive increase in temperature ' may substantially alter the character of the proo- - Examzs Example 1 hbatchofboogramsofwwwocdrosinwasv heated in a one-liter distilling ?ask for 5 hours at a temperature of 290-295’ C. and under a pres sure of 400 mm. Hz. 80: ass was bubbled through ' the molten rosin during the 5-hour treatment periodat a rate ‘of 17 grams per hour, 1. e., 3.4% per hour based on the weight of rosin treated. The acid number of the rosin at the end of the treatment was 131. Example 2 In this‘ example a batch of 300 grams of ww ,wood rosin was heated in a one-liter ?ask imder the same conditions as in Example 1. In this example, however, 80: was bubbled through the batchduring the 5-hour treatment period at a rate of 25gramsperhour. Thisisequivalentto a rate a little above 8% per hour. ess. On the other hand, in instances where a 50 soap forming metal is present in the modifying agent, excessive increase in percentage of modi fyin's asent'may not yield as soft a product as a lower percentage of the modifying agent. In considering the starting material on which the process may be employed, it is ?rst noted that the process brings about changes both of a colloidal and also of a chemical nature. It is , important, however, to bear in mind that the process essentially involves a' reaction with the rosin molecule. that is, with the type of molecules of which the basic constituents'oi natural rosin are composed. Therefore, while rosin itself, such mas‘ gum or wood resins, represents perhaps the most important starting material towhich the process isadaptable, it is noted that the process -may be employed on rosin which has been pre treated in various ways, or- on mixed or chemicals 1y condensed materials incorporating rosin, since The acid value of the final product was 114.5. the reaction will take place wherever the rosin Certain variations in procedure may be 70 molecule is present, provided, of course, that the adopted. , physical or chemical state or “environment” of For example, vinstead of using vacuum during the rodn- molecule 3 not such as to prevent the " the treatment period,‘ other procedure may be I reaction from taking place. adopted with a view to excluding air from the It may also be mentioned that there are other reaction. The form of the reaction vessel cm 75 natural resins, such as copnls, which act simi I larly to rosin by treatment in accordance with this invention. In fact, the reaction may be carried out on any of the natural resins con stances where the vulcanization is carried out in a varnish solution, the sulphur chloride treat ment is especially practical. equivalent. “iused" before becoming soluble in organic sol vents and miscible with iatty oil. When oopals are used in'the present process. they should ‘be employed in the fused state. - . _ the modi?ed rosin - roducts maybe subject to - erin or other polrhydric alcohols, such as glycols, . The modi?ed products 0! this invention may, pentaerythritohmannitol. sorbitol, etc. The vulcanized. lique?ed resin products made in accordance with the invention have valuable properties for a number of purposes including the marina of protective coatincs, some or these vul 15 caniaed products beina useful as plasticizers ior ing upon the use for which it is intended. Thus, eoetins compositions and plastics. ior'example, the modi?ed products may be vul-‘ I claim: ‘ canized with sulphur. The modi?ed resin prod l. Aprocess for treating rosin, which process ucts secured in-accordance with the foregoing, consists in heatinlr the main to a temperature of may be vulcanized as such, or in solutions, such at least 250° C. but not above about 350° 10.: 20 as varnish solutions, (in the latter case with sul under conditions promoting decarboxylation, and circulating sulphur dioxide gas into. through, and phur chloride). Further, they may be converted into emulsions out or the reaction vessel dunnr said heating. I _ and used for various purposes in that form. ' ii'desired, be'subject ' > v still other supplemental treatments, such- for in stance, as esterincation, as by treating with glyc , Copals are iossil gums which have to be ’ As is mentioned in my application Serial No. 386,371, ?ied April 1, 1941 (new Patent 2.311.200) , taining high molecular resin acids; Therefore, wherever any such other natural resin behaves similarly to rosin, it is. herein considered as an to other treatment, depend ' In the event sulphur or other sulphur-like vul canizing agents are used, vulcanization, for cer 25 tain purposes, is desirably carried out at tem peratures between about 120° C. and 200° C. For other purposes where vulcanization is to be ei rected at lower temperatures, for instance, at room temperature. sulphur chloride or similarly 30 acting vulcanizing agents should be used. In in 2. A process in accordance with claim 1 vin which the treatment temperature is‘ about 290-395’ C. v , . - 8. A process in accordance with claim 1 in whicrlgdtge sulphutggimgas is bubbled through the durin! , cut 4.