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Patented Aug. 27, 1946 2,406,337 ' UNITED STATES A PATENT OF’FICE ' ' 214116.337 MODIFICATION OF FATTY oILs V Laszlo Auer, South Orange,‘ N; J. No Drawing. Application januaryaz3, 1943,’v V > ' vSerial N0.47_3,396 ' ,, f _ I 22 Claims. (01. 260-407) _ 1 ~In addition, it should be noted that esters of fatty acids other than the natural glycerin esters (fatty oils) may be used, for example, synthetic glycerin esters of fatty acids, and fatty acid esters formed with other polyhydric alcohols, such ‘as GENERAL FIELD or INVENTION ANDMSTATEL MENT OF OBJECTS This invention relates to‘ the modi?cation of fatty oils’, and especially to dryin'g'and semi-'ldr'ya ing fatty oils. ‘ glycols, pentaerythritol, mannitol, sorbitol, etc. Fatty oils are employed in‘ a number of differ ent industries, such, for instance,‘ as the coatings and. plastics industries, and it is'a ‘general object For convenience, all such materials are herein re ferred to merely as fatty oils. The process may be ‘employed on fatty oils of this invention to modify and improve the prop erties of fatty oils for various industrial purposes. themselves or on various mixtures of materials Briefly, the invention contemplates treatment of a fatty oil, for instance, linseed oil, withpoly or varnish bases of oleo-resinous types, Whether used clear or pigmented. Reference herein to “varnish base” means all or part of the varnish containing fatty oils, ‘for instance, on varnishes hydroxy benzenes, such as dihydroxy and trihy- ' droxy benzenes, the mixture being heated to ele 15 solids or ?lm forming ingredients. ' vated temperatures. I have secured particularly - Fatty acids may be added to the'reaction mix good results with resorcinol, which isadihydroxy benzene. Full description ofthe treatment pro cedure is given hereinafter. I I ' According to the present invention, it is possi ture, if desired. formed with the treated oil. ‘Y ' > ' TREATMENT PROCEDURE AND CONDITIONS As above noted, the treatment process involves 20 heating the fatty oil, or the material containing ble to achieve a number of advantages in the treatment of fatty oils. For example, it is possi , ble to materially improve the drying character istics of the fatty oil, and also to improve water and alkali resistance of ?lm coatings or the like ' same,‘ in the presence of a polyhydroxy benzene, especially dihydroxyv and trihydroxy benzenes. Particularly good results have been secured by the " use of resorcinol which is a dihydroxy benzene; and with'pyrogallol, which is l, 2, 3‘trihydroxy - The foregoing and other objects and advan The quantity of treating agent employed ‘may i tages Will appear more fully hereinafter, espe be‘ varied over a considerable range, depending cially from consideration of examples given. Be fore proceeding with description of the treatment 30 upon the extent of'modi?cation desired, the tem benzene. ' ‘ y' ‘ ~ perature,.the particular fatty'oil being treated, procedure, reference is now made to the-fatty oil etc.‘ ‘From'a small fractional percentage,‘ for in materials to which the invention is applicable. stance, from about 0.05% or 0.1% up to about The process may be employed on fatty oils gen 30%, may be used, although ordinarily from erally, including drying oils, semi-drying oils, and about 0.5%-to about 5 or 10%,‘for instance, 2% non-drying oils. The following is a typical list 35 is quite effective. . . . of such oils: " ' Tung oil ‘ In connection with treatment temperature, it may be saidthat in general temperatures from about the lowest dissolution temperature of the 40. modifying agent up to about 350° C. are usable, although the temperature should not be above the pointgat which the fatty oil appreciably de Oiticica oil Dehydrated castor oil Linseed oil Perilla oil composes. Poppyseed oil Soya bean oil Walnut oil Rapeseed oil > a > r - , V 4,5, with other factors such astemperature. percent age of treating agent, etc. ' Ordinarily thev time ‘should be at least 30 minutes and mostvusually several hours,,for instance, from about 1 hour to. Pine seed oil Olive oil Corn oil Cottonseed oil Coconut oil Babassu oil about 50 Hydroxylated oils‘such as ‘castor oil, etc. Fish oils (train 'oils) ' Thetime of treatment will- vary in accordance , ‘ 5hours. » . » v , » it i In connection with treatment procedure, it is pointed out that the treatment of a'fatty oil may be effected by adding the treating agent and heat ing the oil under conditions mentioned above. If desired, the treating agent may} also be,.mixed 55 with a varnish base or other composite material I _ 2,406,887 4 3 'Wherever the two-stage type of procedure is incorporating a fatty oil material, such composite adopted, it may be advantageous to carry on the ‘ material then being heated under conditions such as those discussed above. ?rst stage, at relatively low temperature, under pre-condensation conditions, especially when em ploying certain of the treating agents contem Agitation may advantageously be used during any mixing procedure, in order to aid thorough dispersion of the treating agent. plated, such as resorcinol which displays a marked tendency to sublime. A reflux condenser will be found effective in reducing the eiiect of sublima The treatment may be carried out under vary ing atmospheric conditions, both with respect to pressure and also with‘ respect to the gas in con By proceeding in this‘ way (pm-condensation at tact with the reaction mixture. Thus, under some 10 . relatively low temperature followed by additional circumstances, the fatty oil or the mixture con heating at a higher temperature), loss of treat taining the fatty oil may be heated under vacuum, and under other conditions, atmospheric pressure p 7 ing agent is prevented or at least reduced. The term f‘pre-oondensation” (initial or pri may be used, and also superatmospheric pressure. It is frequently of advantage to exclude thelair mary'condensation) , as used herein, means treat- ‘ tion. ' , a merit under conditions of the type just mentioned from the reaction mixture, and this-may beldone - during any stage of treatment, either by employ-e I 1 at vtemperatures below the sublimation point and for a time suchthat upon subsequent heating of ing Vacuum or by blanketing the surface of the the treated oil to higher or heat bodying tem V‘batch with some non-oxidizingbr inert'gas, for instance, CO2, S02, HzS, or nitrogen. Still fur 20 peratures the resorcinol no longer tends to sub lime to any‘ great extent. ther, exclusion of air may be obtained by carry ing. out .thejreaction in a closed vessel (but not EXAMPLES necessarily under a positive pressure), in which ' . Inv order'to- demonstrate the process linseed oil event vapors or the like released from the reac tion' mass may‘ serve to dispel or exclude the air. ~ 25 and'resorcinolwere selected'as typical of the start ing materials and treating agents, these two being I, have found vacuum'treatment to. be particu usedin' mostJof the examples given below. larly effective, for instance, from about 100- m-ms. ‘ To determine the most advantageous treat Hg to about 450 mms. Hg internal pressure, al ment conditions, several comparative series of though higher or lower pressures ‘are also useable. experiments were? carried'out, all utilizing resor _ With regardto the foregoing atmospheric con cinol andhnseed oil. An analysis of these ex conditionsin the reaction vessel, it‘may be noted periments will aid in an understanding of the in thatcertainof the gases mentioned may be vem ployed for their supplemental effect on the: re . First, note that resorcinol has a boiling point action, in which event, if desired, the gases may of 27.615? 0;, and melts at 116° C. When molten, be bubbled through the reaction mixture. , vention. ' ' ' it. dissolves quite easily in fatty oils and even at temperatures below- its melting point, it is'sol In general, it may be‘pointed out that increas ing any one of the variables: temperature; time or percentage of modifying agent, usually in creases‘the rate and/or extent of the reaction. uble inv many fattyoils. ’ In‘ spite of the fact that the boiling point of is comparatively high, it sublimes out The modifying'agents herein claimed may be 40 resorcinol of‘ fatty oils at temperatures below its boiling employed (either simultaneously or sequentially) in combination with others disclosed, for instance, in- various of my 'copending applications and issued patents, some of which are mentionedhere inafter; . V ' , point. ‘Furthermore, its boiling point is below the usual and preferred temperature range for bodying fatty .oils or for cooking varnishes. 45 ‘In addition, supplemental treatments'may be , applied to the oil, either during or following the COMPARATIVE'EXAMPLES 1 T0 5 Because of the foregoing characteristics, it is 1 advantageous to adopt‘ some means or procedure reactionwith the agents here contemplated, many for‘ reducing loss ofv the treating agent by subli of‘ such supplemental treatments also being dis mation" or‘ boiling. With this in mind, a series cussed fully’in" copending applications and issued 60 of' experiments were carried out in one liter'alu patents below mentioned. For instance, the modi minum beakers provided.v with covers, using resor-' ?ed oil products may be vulcanized with sulphur cinol and alkali: re?ned linseed oil, in-400 gm. or sulphur chloride or similar vulcanizing agents. batches, each" being heated at a different tem Attention’ isv directed ~ to my copending applica perature, as? is'indicated in Table No. I-A here tion Serial No. 461,789, ?led October 12, 1942', 55 below, showingireaction conditions and the re which discloses treatment of fatty‘ oils- with sulting viscosities of‘ the treated oils. All vis cosities given herein are expressed in terms of the Gardner Holt scale. 7 phthalic anhydride and resorcinol; ‘ In all cases of this series 2% of‘ resorcinol was -Where a fatty oil is being treated to prepare it for incorporation in- a varnish base of the oleo 80 used and the temperature was maintained for 2 '?uorescein and also with a combination 0 resinous type, oneparticularly advantageous pro hours. ' ' cedure is as follows: In this case the treating Table No. I-A agent may initially be added to and dispersed in ALKALI REFINED LINSEED OIL WITH RE's'oRoiNoL IN COVERED KETTLE the fatty oil at relatively low temperature, for‘ in stance, fromwabout 75°;C. to about 200‘ CL; and’ 05 then when’ the oil is incorporated in’ the varnish Ex. No Temperature Viscosity sl??glgtgn A A 3+ Slight. Considerable. Do. or, varnish base, additional heating maybe ap plied‘ at higher temperatures; in order to. carry out the‘ full degree of modi?cation of the‘ oilv contemplated. _ Even when treating a fatty oil alone, itv may' be ' advantageous to divide the, treatment‘ into two stages, the ?rst of which is carried on at' a rela tively low temperature, and the latter of which is carried on at a higher temperature. . A _______ __ 75 (The same heating). oil without B+ Do. S Do. A The foregoing series‘ indicated thatv sublima 2,406,887 5 tion increased in general with increase in tem perature. Following the initial treatment of the several The cold water test was carried outby immers ing one half of each panel‘ (carrying the varnish ?lm) in cold water for 24 hours; and observing batches as mentioned above, varnishes were pre the milkiness of the ?lm and the rate of recovery pared with the treated oils, the several varnishes 5 t0 the original condition. The hot water test was then being subjected to drying and water tests Carried out in a similar manner, except that the with results indicated in Table No. I—B herebepanels Were immersed in boiling Water for 15 low. The varnishes were prepared with ester minutes; the milkiness and rate of recovery again gum, each being of 25 gallon length, and each being OhSBI‘W-Id.v varnish was cooked at 3009 C_ to a Viscosity Of 10 The columns under the “Cold water” and “Hot about C to D, at 50% solids when thinned with Water” headings indicate the following: mmera’l _spn:1ts' ,The e°°¥<mg rttme requlred to Con=arbitrary scale of condition of ?lm when reach thls vlsee‘slty 1s mdlea'ted m the table be‘ ?rst removed after the test, No. 1 indicating the 1°w- best condition, , _ \ - A1“ explanatlon of the deslgee'tiens under the 15 Rec=arbitrary scale representing rate of recov drymg an‘? other test eelu'mns 1S glven after the ery to original condition after withdrawing table, but it is here pointed out that the followfrom the test, No. 1 indicating the best rate_ mg as well as ‘other tables, appearing In the DI‘BSON==arbitrary scale of the condition of- the ?lm em specl?ea'twn’ Include (In addition to num' after standing overnight (following immersion sent bered‘examples) letteredmxamples which repre- 20 blank or “control’ experiments, 1. e., an period)’ No. 1 _indicating the best condition‘ _ _ experiment carried out with the same on’ under The alkali resistance test was carried out with exactly the Same treatment conditions as the numbered examples, except that no treating agent somewhat heavier ?lms than for the drying test, and cold Water entitle? Water tests- For, this PUT‘ was used. It may also be mentioned that state- 25 pose ?lms of 0003 , thlckness were apphed to test merits regarding comparisons of properties, such as drying characteristics, are always related to panels which were eheeimmersed in a aqueous sedlun? hydree?de selutlon' The eondltwn afterr’ ?lms formed with varnishes incorporating the hours lmmerslen, was Observed aed reeerded’ end same fatty oil treated under the same conditions also the co'ndltloh after Overnight immersion. (both prior to and during the formation of the 30 The results of these two, Observatlons are men‘ varnish itself) but without the presence of the Gated, m?the eorrespondmg columns wider the modifying or treating agent, In the table just below the example numbers correspond to those in Table No. I-A, the letter heading Alkali.” The key to the letters in these columnsls as fellows: H=hazy “v” following the example number indicating the 35 Sl.m=slightly milky varnish prepared with the treated oil. M=milky ' Table No. I—B VARNISHES PREPARED WITH TREATED OILS or TABLE No. I—A EL No’ Minutes cooking _ Vis- at 300° cosity C. Drying ’ Cold water ' Set Hot water . DF TF % ON Alkali . 48 Con Rec ON 164 A % 1 B A 3 2 o .... ._ 1 D A 2 1 1 5 2 1 o O D % % % 84 % 84 % M % B O o A B A 2 4' 2 1 2 1 1 1 1 5 5 5 1 2 1 1 1 1 190 o 1 2 2 D- A 1 1 1 5 3 2 cate the following: ' Set=time in hours to initially set. ‘ DF=time in hours for the ?lm to become dust free. 'I’F=time in hours for the ?lm to become tack free. ON=condition of ?lm after "overnight” drying, 7hrs. ON 2 Where appreciable dissolution of the ?lm took place, that fact is noted in the corresponding col- _ umns by ?gures, representing the approximate percentage of the ?lm remaining. For instance, M—40 indicates that the ?lm was milky and that ‘40% of the immersed part of the ?lm remained on the panel, 60% being destroyed. With the foregoing explanatory comments in mind, it will be seen from Table No. I—B that 60 The columns under the heading “Drying” indi 2 ON 207 ing a ?lm of 0.0015" thickness was employed. . 5 Bee 203 185 161 All varnish tests in the present series, as well as in other series of examples mentioned herein after, were carried out in the following manner. Initially the varnishes were stored for 48 hours after the addition of driers (0.3% lead, 0.03% cobalt and 0.02% manganese, based on the oil content of the varnish and added in the form of naphthenate driers). In order to test the char acteristics of the varnishes, a coating knife yield 2 0011 notwithstanding the appreciable loss in treating agent during the initial treatment of the oi1 (see Table I--A),'the varnish ?lms displayed consid erable improvement in a number of respects as compared‘ with a ?lm made from a varnish incor porating the same oil in untreated condition (compare Example Av with the others). The al kali resistance and drying characteristics both display considerable improvement. the letters representing an arbitrary scale to in COMPARATIVE EXAMPLES 6 T0 9 dicate the relationship between the several ex 70 In this series of examples alkali re?ned linseed amples, “and also their relation to the item just oil was also used and was treated with 2% re below (the letter A indicates the driest ?lm and sorcinol, as in the ?rst series. In each case a succeeding letters progressively decrease in batch of 400 gms. of oil was placed in a one liter Erlenmeyer ?ask equipped with a re?ux con 48=condition of ?lm after drying for 48 hours. 75 denser, so as to provide a condition of pre-con hardness). ' 2,406, 3.37 8 7 densatien and thereby reduce loss of the resor COMPARATIVE ExAMPLEs 10 To 12 V cinol. For the re?ux condenser, a ‘straight air condenser was used, since the ‘relatively high boil ing point of resorcinol does not necessitate water In a third comparative series of examples, al kali re?ned linseed oil was again used and the percentage of resorcinol was varied in order to indicate what percentages yielded the best re cooling. In all experiments of this series the re ?uxing time was two hours. ‘The temperatures tried di?ered as between different examples. the results being indicated in the Table II—A here below, sults. ~ ‘ _ Table No. I,I——A provided with an air condenser. In each case a ' blanket of CO2 was maintained at the surface ALKALI REFINED LINSEED OIL WITH RESORCINOL < UNDER REFLUX Ex’ N0’ 1 In the exampleslof this series 4,000 gm. batches of the oil were placed in stainless steel kettles v10 of three gallon size, the kettles being covered and of the oil and all of the oils were heated under Temperature Viscosity Extent .of sublimation Very little. 6. . W... l50° C _________________________ __ A 7.. _ -.- 200°C _____ __ B reflux preliminarily for two hours at 200° C. and thereafter for an additional period at 300° C. for a time suf?cient to increase the body to from 1 about Z4 to Z6 viscosity. Results of this series ’ of examples are indicatedin Table No. III-—A. Do. 8._ .__.,_ 250° C ..> -_ U DO. 9 _______ _, 300° C _________________________ __ 'I‘ Do. B ....... .. (‘The same 011 without heating and not re?uxed.) . A Table No. III-A ALKALI REFINE’D LINSEED OIL WITH VARYIN G . As in Examples 1 to .5, the treated oils .of Ex amples 6 to 9 were also‘ used in preparing ester gum varnishes of 25 gallon length, the formula tion being the same as described above. These varnishes were then tested and the results are PERCENTAGE OF RESORCINOL Ex. No. Percentage Time at 300° C. Viscosity 0.5% ______ ._ .8 hrs, 10 mins___-___ 2.0%., .... ._ 8 hrs, 40 mins___._.... . indicated in Table ‘II—B just below, incorporating columns and distinctions corresponding to those described above. Table No.’ II-B 4.0% ______ __ ‘Z5 Z4 7 hrs ______________ __ Z6 No agent_.__ 8,hrs., 20 mins _____ __ Z5 From the above it will be seen that lower than ‘VARNIS'HES PREPARED WYITH TREATED OILS OF TABLE NO. II-A Minutes Ex N0 ' - cooking ‘ _ Drying Vis- ‘ at 300° cosity ' C. , Set Cv V 189 Cold water Hot water Alkali V v a ‘ DF .. Tl?‘ ON 48 0011 Bee ON ' Con ____ __ V), % B A 3 1 1 l C % % 1 C A 2 2 2 5 2 1 210 D ____ _- % % B A ' 2 1 1 6 ' '1 1 105 190 D C _____ i. l 1A 2 A A l l 1 1 l l 5 5 l 3 l 2 ,7 hrs. ON about 4% of resorcinol does not materially ac celerate the rate of bodying. The faster bodying of the varnish of Example 911 may be partly'explained by the fact that the oil here employed (see Table II-A) had a much To demonstrate drying and other characteris tics of these treated oils, 25 gallon length ester gum varnishes were again prepared and cooked higher viscosity than the other oils, indicating that at least a portion of the bodying took place during re?uxing. 5 V ‘ ON 210 % D I 2 D- l - Rec in a manner similar to those described above, ' except that the viscosity attained was about from 50 C to E. The properties of these varnishes are in dicated in Table III-B just below. ance were quite satisfactory and further that Table No. III—B The foregoing table shows that cold and, boil ing water resistance and also the alkali resist VARNISHES PREPARED WITH TREATED OILS or TABLE NO. IIL-A _ Minutes ' EX N0 , cooking‘ ' ‘ at 300° C. 95 _ Drying Cold water Hot water Alkali Vis cosity Set DF TF ON 48 Con ‘Rec ON Con > Rec ON 7 hrs ON C 1% 3 4 B - A 2 2 1 6 5 5 116 C‘ 1% 2 3 B A~ 2 2 l 5 2 .2 S1. m_--_ 90 D 1% 3 - 8 D A 1 l 1 6 5 5 H _____ __ Do. 135 E V2 1% A 2 2 1 5 1 1 1-1 _____ __ Do. 2 'D— M_______ Gone. Do. From the foregoing, it may be noted that while the drying of the varnishes made with treated oils was distinctly improved. The drying of the 65 the resorcinol, When used in low percentages, does not appear to appreciably accelerate the rate of varnishes made with oil re?uxed at 150° C. (var bodying of the oils, nevertheless, considerable im nish 611) and at 250° C. (varnish 812') was the provement With'respect to rate of bodying is ob best, the former having a slight edge over the servable in preparing or cooking the varnishes latter. The drying of the varnishes containing the treated oils was in all cases extensively im 70 from the pro-treated oils. The varnishes made with oil containing 0.5% proved as'compared with the blank experiment resorcinol (1011i and 2% resorcinol (1112) both showed up quite well in various of the drying and From the above it appears that pre-condensa other tests. The varnish containing 2% resor tion by re?uxing between about 150° C, and 250“ cinol (1112) seems to yield the best results, C. gives the most ‘advantageous results. (B1)). _ a i 2.406.881 .9 i 10 ~ ing the oil under pre-condensation or re?uxing EXAMPLE 13 Further tests were made. employing different percentages of resorcinol with linseed oil, the dif at a temperature of about 150° C. and for a time ferent percentages having been obtained'b'y di of abouttwo hours. That these conditions con stitute about the most favorable balance, when luting a precondensed concentrate with addi tional'oil. These tests were carried out in the and properties, is further evidenced by the results of another comparative series of examples given following manner: . considering the various diiferent ‘characteristics ' justbelow. . ‘ > . Initially a batch of alkali re?ned linseed oil was treated with 2% of resorcinol ‘under pre 10 COMPARATIVE EXAMPLES 14 '1‘0 17. condensation conditions at a temperature of 150° p In this series of examples alkali re?ned lin C. for 2 hours. This treated batch was then dilut seed‘oilwas'again used and in each example 2% ed with additional alkali re?ned linseed oil in of resorcinoiwas employed as'the treating agent. order to secure test batches incorporating the fol lowing percentages of resorcinol, The batch of each example was preliminarily 15 Example N0. heated ‘under reflux‘for two hours, the re?uxing temperature being different aslbe't'we'en‘ the, sev eral examples. Thereafter, the 'ltreated oil "of ' ‘ Resorcinol 13a _________________________________________________ ._ each batch was heat bodied at 300° C. for a time ‘ Per cent ‘ 1.0 of about'31/4 hours. (The viscosities obtained in 20. the given time are indicated in Table IV—-A just 0.5 0.2 0.1 138 _________________________________________________ _. below. 0. 05 V " ' Heavy bodied oils were prepared'of each of the ,> v initially prepared, by bodying them to Z-4 to Z-6 . . , '_ ‘ J . H L Table ‘NO. IV-—A HEAT BODYING diluted oils, and also of a portion of the 2% batch-j, viscosity. '. . I - 0F BESORCINOL ‘TREATED 'ALKALI 'REFINED LINSEED OIL . Re?ux tem-_ perature ' Varnishes were then prepared with each of the '1' above heavy bodied oils. These varnishes were 150 prepared with ester gum iii'twenty-?ve ‘gallon V 3 hrs., 20 min ______ _. ‘200 . length, and each varnish was cooked to a stand ard All viscosity. of the varnishes ' were ‘ tested v I in i accordance > i The foregoing indicates that re?uxing at about with the methods set out above‘, and in general all batches showed improvements in at least cer tain respects, as compared with a similar varnish ; "150° 0. results in quite‘ rapid bodying during the subsequentwheat bodying.‘ The relatively high viscosity (Z-G) secured with.the:oil re?uxed at 300‘? C..(Exarr'1pl'e"1'7)w is apparently due to the. made in essentially the same way but not con taining resorcinol-treated oil. Some of the spe ci?c results were'as follows: factthatat least a portion: of the heat bodying gallon length‘were prepared‘ from 'thelfforegoing bodied oilsi',"the preparation being according to the form 1115. and process already‘ described above in con I " Ester place? gum‘ duringcthe varnishes re?uxing oi’ l'tWenty-?ve' itself.; " 40.took In cold water resistance, the 2% resorcinol con taining oil yielded the best results, although these results were approached by the varnish prepared with the 0.05% resorcinol containing oil., In the boiling water test, the results were similar to those in cold water. - v > 45 a In alkali resistance, the several batches may Minutes EX , No ' at 300° other properties of the varnishes thus prepared are indicated in the following table. > Drying cooking ' nection with ‘otheriexamples; ,The'drying and Goldwater Vis, . \ cosity ' Setx DF% TF7 1 14v _____ __ C. 60 O ON B A 48, 15v _____ __ 161; _____ -- 90 ' 90 D D M; 56 3A M 1 1 D C A ‘A 1 2 Y 1711 _____ __ 55 O 36 % 1 -B ,A 2 be graded in the following order of percentage, of resorcinol contained in the oil used, the ?rst ?gure showing the best results and‘ the others gradually decreasing in alkali resistance: .1%, 0.5%, 0.05%, 0.2%, 2%, and 0.1%. ‘ From this series'of tests it will be seen that . Hot water > ' ' j 0011v 1_' Rec1‘ ON1 .2 1 , l Alkali . ' 1 > 0on,5, ,gRec. 11 1 1 v ' ' ‘ 5 5 - 1 l v5- , ‘l ON1 H_' 7hrs ____ __ M. 0N ‘ . l 1 H _____ __ .M-70. . S1. m____ Gone. 1 M _____ __ ‘ M-20. The foregoing‘ tableilshows highly “ desirable‘ properties, especially with ‘the’ example‘. (Example 14)‘ employing; 2%,re_sorcinol,';re?uxed for two ' hours at _150°'C.‘ , A" varnish made with this par ticular oil (140) shows excellent cold water ’re--_ sistance,- good hot water resistance andv good certain of the properties of the treated oils and 65 alkali resistance. varnishes made therefrom are not necessarily proportional to the quantity of resorcinol present. Therefore, for individual uses and applications, the concentration most favorable to that purpose should be selected. - ' ~ , 7. Various of the foregoing comparativeexam ples, indicate that for an all roundtype- of product, an e?ective balance of desirable properties is secured by the employment of presorcinorl in an amount approximating 2% and by pretreate It is tack-free in one hour and really hard in forty-eight hours. _As hereinbefqre ‘mentioned, for certain pur poses it may betdesirable to' treat'the oil not only with resorcinol' orother polyhydroxy ben-. 70 zenes, but ‘also withsome other agent'or agents; This may beadraniegeoqswhereit ,i§"d,e§i,red to improve .eertainsnesifiq; properties, for instance. . alkali resistance; drying, speed of ‘varnish body ing, etc. Examples 0 f such composite treatment’ are siyenhamw'r‘; :- - ‘shoe-33'? il V 12 , was prepared in the manner already described, yielding in the short time of 60 minutes a viscosity _ of G at 50% solids (cut with mineral spirits). Although the alkali ‘resistance of the varnish A-batch of 4,000gms. of alkali re?ned linseed ’ oil‘ was heated with 0.5% sulpho-salicylic acid at 100° C., until the reagent dissolved. Theheating ' was somewhat reduced as compared with a var nish containing an'oil made with resorcinol alone,‘ bythe conjoint use of maleic anhydride-the body ing velocity was greatly increased, and in addi~ was carried out. in a ‘three gallon openrkettle with a blanket of CO2. After dissolution of the sulpho salicylic acid,2% of vresorcinol was added tothe tion, the drying, time,jcold water and boiling'wa oil and a cover applied, with are?ux condenser ~ on the kettle. The oil was then heated at 150° 10 ter ,res‘istancewereah very satisfactory. C,’ for two hours, to e?ect pre-ccndensation. } EXAMPLE 21 . For ‘ purposes of comparison two additional , Inllthis example-a ‘compound, treatment of still another type is illustrated. For this purpose a treated linseed oil was employed as a starting batches of‘ oil were prepared under similar con ditions, one such batchbeing alkali re?ned lin seed oil, without any modifying agent, and the material, the oilcontaining beta-methyl-anthra-v ' dtherbeing .alkali.re?ned linseed ‘oil containing 7 r ..2‘% resorcinol alone (without the‘sulphoesalicylic vAll three of'the above oils were then: heat bod ied to aviscosity of from 2-4 toZ-g? and.25 gal lon long ester gum varninshes were prepared with the bodied oils in the mannergdescribed above, _» the several varnishesbeing'tested in the manner ‘ quinone'as an agent for acceleratingheat body ing. This oil had a viscosity about the same as 20 alkali re?ned or raw linseed oil. ' Seventy pounds of the treated oil were heated in a 15 gallon kettle with 2% resorcinol under re flux for 2 hours at 15010. A 5,000 gm. batch of the ‘resorcinol treated oil was then bodied at described above, and giving the-following results? Table No.-fV-' .. I 713%‘. 7 Minutes Messages ‘ - ' _ Dz)"; Oil Without any agent-" ' __‘__'-__ . V Ev'___r_. 2% resorcino1__;___.-__=._ ,_ ____ __ .172‘ ' T135 ,lld ' ‘ _ Alkali » Fair-k--. VG00d___-_. Gopd______ GoneZhrs. Good_..__ ___do__-__>_ Fair_..r_.t__, Gone 3% hrs, 300".- Qior two hours and twenty minutes, under The ioregoing treated and heat bodied oil was then employed in the preparation of 25 gallon ' long varnishes prepared in the general manner describedabove. Y Three such varnishes were pre pared .using different resins, as follows: . (It may be men tioned that for the alkali tests in Table V ?lms a. Ester-gum. is in contrast tothe heavier ?lms (.0030) used in ' ‘ > a V I ~ - The'threevarnishes were then cooked to a vis cosity of ‘C to H,'at 50% solids ‘when diluted with ‘mineral spirits and when containing the drier '7 EXAMPLE 19 Arbaich' of‘ 1.200‘ gm. of alkali re?ned‘ linseed combination hereinabove described. The body; oil was re?uxed with 2% resorcinol at 150°’ C. Thereafter, 0.5% of naphthionic acid was added ing times and viscosities' are indicated in the z‘iollowingitablep to the cil'and the temperature raised to 300-’ -C. " U ' " ' ~ > 'Table VI ' for 51/2 hours, under a blanket of cog. This ‘Se-w ' . Cured a viscosity of Z—'5 and ‘from this "treated ' ' - pared in accordance with the above description; yielding after a 21/2- hour cookingatr300° C., a viscosity of'D,vv at 50% solids. The resulting‘var ' b. Paranol 1750 (a rosin in'odi?ed'plienolic resin). 0''. Amberol 801 (a rosin modi?ed maleic resin); of only 7.00.15 inch thickness were. employed, which oil a 25 gallon long'ester gum varnish was pre I a blanket of CO2, yielding a-viscosity of X. t contributes‘to very‘ good hot and cold’ water’ resistance ‘and. also greatly; in; ' V ' Fain-.. ‘Very goodT l‘v'eryrgooi ‘(iced after 7 hrs.; gone overnight‘ ' sulpho-salicylic acid > - O watt E 0 ‘Although; the above table indicates that‘ the creases the alkali resistance. wit’; E sulpho-salicylic acid slightly decreases the body ing speed and the drying velocity of the resorcinol treated oil, it isinotedrthat the presence orthe ' I ceglgliglff Xiii?tt Dwmg 18.-.“ 2% resorcinol-F595 sulpho-sal____‘_. V other examples.) » EXLNO. Resin 7 Viscosity 7 55 21a _________________ __ 2lb.- ________________ __ '2le. ________________ _. Ester gum ______ ._ Para11o1l750 _ Amberol 801... _. 315 35 K C 65 I nish, had substantially improved alkali resistance compared tovthat of a similar varnishmade with 60 vThe foregoing varnishes were subjected to tests a similar oil containing resorcinol alone.' The dry of the types describedrabove’, the results indicat ' ing velocity, cold water. and boiling water re- I ing that the vcold Water'and boiling water'resi'slh sistance Were somewhat better than that of the ance‘were somewhat improved-as compared to a similar varnish made with oil containing beta varnish made with an oil treated only with. resorcinol. , _ 65 methyl-anthraquinone, but not containing resor EXAMPLE 20 . V A batch of 4000 gins. of alkali re?ned linseed oil were: treated with. 5% maleic anhydride and: 2% resorcinol, by re?uxing'the reaction mixture for two hours at 150° C.’v After the precondensa 70 tion period-(there?uxicondenser was eliminated . ' . and thetemperatureiyof the'roil raised to 295° C.‘ cinol. The drying'properties and alkali resist-' fance were'both substantially improved as ‘com-v ,pared with» the varnishes not containing resor c-inol. ’ 1' r ' r a The most striking improvement, however, is V the increasein the rate of bcdyin'g, as compared" with linseed oil treated with resorcinol alone. , For purposes‘ of comparison between varnishes hours and 10 minutes yielding a viscosity 4 ‘ (or varnish bases) prepared withthe oil treated 1 Here again a 25 gallon long esterigiimwajrinish? ' only ‘with betaemethyleanthraquinone, and with 2,406,337 _ 13 1,4. , said all further treated‘ with resorcinol, it may be noted that, if properly pre-bodied to a viscous oil, it will be found that in the cooking of varnishes (or varnish bases) the oil (without resorcinol) will further body fairly rapidly. The addition of resorcinol to the treated oil (containing beta methyl-anthraquinone) imparts a slight but still further increase in bodying velocity. Such accel eration of bodying is noticeable, for instance with varnishes (or varnish bases) prepared with‘- ester hours, and the product at this stagewas a fairly‘ thin The clear treated oil.‘ oil ' > was thereafter further heated by continuing heating at 290°,to 310° C. for two. hours, after which heating the oil was consida erably thicker. 2% hours at the same temperature (290° to 310° C.), and during this timethe oil became grad-v 112113’ thicken Finally the oil Was of asemi-solid consistency when cooled to room temperature. gum. ‘However, the more important improve ment imparted Ito this treated oil by the further additionof resorcinol is the improvement in dry ing and also some of the other properties, for in stance alkali resistance. _ . 151 It, therefore, appears that such conjoint treat similar to that described above in connection being Pyrogallol (1, 2, 3, trihydroxy benzene) in stead of-resorcinol. The oil was heated between only achieves the advantages of resorcinol, but at the. same time secures other improvements in , Particularly .useful products may be secured ‘EXAMPLE 25 v A; batch of linseed oil was heated in a manner with Example 23, the treating agent, however, ment with resorcinol and certain other agents not properties, notably the velocity of bodying. After cooling overnight, the batch was again heated for a further period of 20: by conjoint treatment with a polyhydroxy ben zene and with other modifying agents such as or ganic acids (polycarboxylic acids), condensed 170 and 200° C. for 3 hours and then between 280and 300° C. for 4 hours, and ?nally kept at 320° C.»-for 507 minutes. No appreciablewbodying _ took place until the temperature exceeded about 300° 0., but thereafter the bodying was rapid and the ?nalproduct, when cold, was a gelat ring compounds and organic sulfonic acids, ex amplesof whichare given in my Patents 2,298, inous solid. 914, 2,298,915, and 2,298,917. ‘ CQMPARATIVE EXAMPLES 22v 'ro 25v In four examples referred to below, oils were treated in accordance with this invention, with The ?nal oil products of Examples 22 to 25 were somewhat diiferent procedures in each‘ case. 30 employed in the preparation vof batches of var Thereafter, comparative varnish formulas were nishes made of 25 gallon length with lime hard made employing these oils. The treatment of the oils is ?rst referred to just below under indi ened rosin, the varnishes being diluted to 50% solids with mineral spirits. These varnishes were tested for drying (and other properties and in. each case, the varnish was tested in four differ vidual example numbers, following which the varnish preparation and results are described. ent forms as follows: EXAMPLE 22 ' ‘ a. Varnish without drier. A batch of 150 gms. of linseed ‘oil was heated in a 500 cc. Erlenmeyer ?ask with 71/2 gms. of resorcinol for 5 hours at a temperature between Vb. Varnish plus cobalt drier (0.03 ‘cobalt metal on the basis of oil content). I c. Zinc oxide paint made with the varnish with about 200, and 220° 0., the batch‘ being kept un out drier der a vacuum of 26 to29 inches. The tempera ture was just below the boiling point and the . . (pigment to vehicle solids ratio=1 to 1 by Weight). treated oil was-a somewhat bodied clear mobile ' ' oil. Although no extensive changes Were visible 45 in the oil itself, improved properties were secured d. Zinc-oxide» paint as per‘ 0, with drier ‘as per b. in varnishes, as brought out below. varnishes ‘and paints were also made up from a medium bodied linseed oil not containing any < ' EXAMPLE 723 For comparative purposes, a blank series of modifying agent. . In the drying tests one of the most signi?cant results which showed up was the considerable 3 hours at a temperature from 180° C. to 200° C., improvement in all of the varnishes made with for the purpose of precondensation. Thereafter treated oils as compared with the blanks, with the temperature was raised to 285° C. and the respect to “after-tack.” The varnishes made product kept at or somewhat above that tem 55 with the treated oils were very much more “print-free” than is usual with soft oil'varnishes. perature for5-hours. In the ?nal ‘half of the In the varnishes not containing cobalt drier, bodying period, the temperature was between 300 the rate of drying of the varnishes containing the and 320° C. After about 21/2 hours of the heat treated oils was also improved as compared with bodying, the oil started to body very rapidly. the blanks, the several examples showing up A batch of 150 gms. of linseed .oil was heated in an open beaker with 71/2 gms. of resorcinol for nan/rm.- '24 A batch of 150 gms. of linseed oil was heated with 15 gins. of; resorcinol in a Pyrex ?ask under air re?ux. - Solution of the resorcinol had been attained when the temperature rose to 220° C. yielding an amber colored oil. At about 306° C.‘ the batch was simmering gently, but developed some vigorous bumping, so that for a-short time the refluxing was replaced by a distillation con 60 the following order, the best drying being placed at the top of the list and being far superior to the I following: ' - Varnish made with oil of Example 24, containing 10% resorcinol. ' Varnish made with oil of Example za'cnntain» ing 5% resorcinol. Varnish made'with oil ‘of Example 25, contain-_ - ing 5% Pyrogallol. nection; ‘Very little of the material distilled. The Varnish made with oil of Example 22, contain re?uxing was continued at 300° C. until, after ing 5% resorcinol. 11/2 hours, the re?ux condenser was taken o?’, In the varnishes containing cobalt drier, the Y heating being continued under open atmospheric drying results were also quite satisfactory, the conditions at 280° C. to 300° C. for 31/2 hours. varnishes made with oils of Examples 23 and 22 The total time between 280° and 306° C. was 6 75 (both containing 5% resorcinol) being the best. , 2,406,337 16' ' face coating materials-which process comprises In the ,paints. not containing cobaltdrier. the ' incorporating in the oil up to 30% of a polyhy droxy benzene as the sole active treating agent, and heating the mixture at a temperature be tween aboutv 75° C. and about310° C". for at least - results were similar to the varnishes, the four ex- amples maintaining the same order as above noted, and at least the first three ,(in that order being improved as compared with‘ the blank and the four being about equal to the blank). In thepaints containing. cobalt drier, the big gest improvement was indicated in the initial drying, the best resultin this regard being se 30 minutes. ' ' ' r 8. A process in accordance ‘with claim 7 in » which said polyhydroxy benzene is a dihydroxy . benzene. .9. A processin accordance with claim‘ '7 in cured with the paint made with thetreated foil 10 which said polyhydroxybenzene is a trihydroxy of Example 25 (containing 5% pyrogallol) . Another signi?cant improvement which showed I 10. A process in accordance with claim 7' in.‘ up in the tests of the foregoing "varnishes and which said polyhydroxy benzene is pyrogallol. paints was that notwithstanding the use of lime’ 11. A process for treating fatty oils having dry hardened rosin asthe resin ingredient; very good 15 ing properties, to improve their ?lm~forming water resistance was ‘secured, especially-in the characteristics when usedas varnish base mate paints made with the oils of Examples25, 23 and rials, which process comprises incorporating in, 24;,and with the clear varnish made with‘ the the oil up to 10% of resorcinol as the sole active benzene. treated oil of Example 25. /I claim: < c 7 . ‘I ' . 20 treating agent, and. heating the mixture at atem perature between about 75° C. and about r310° C. r 1.. A process for treating fatty oils having dry: ' for at least 30 minutes. ving properties to improve their ‘characteristics, as components of surface coating compositions,’ . ' i ' 12. A process in accordance withclaim 11 in which at least a portion of the heating is effected which process comprises incorporating in the oil . up to 30% of resorcinol as the sole active treating 25 under re?uxing conditions. agent, and heating the mixture at a temperature which an initial portion of the heating is effected at a relatively low temperature under re?uxing conditions, and in which a succeeding portion of the heating is eifected at a relatively higher‘ . > V . between the dissolution point of the resorcinol and about 310° C. for at least 30 minutes. 2. A process in accordance with claim 1 in which the heating of the oil containing resorcinol is effected in two stages,the ?rst of ‘which is con. tinued- for at least 30 minutes at a temperature 30 temperature su?icient to effect heatbodying. ' 14. A process ‘in accordance with claim 11 in which the fatty oil is'sele'cted from the class not exceeding about'200° Cr and the second of comprising drying fatty oils and semi-drying which is continued for at least 30 minutes at a temperature above about 200° C. ‘ ‘ 13. A process in accordance with claim 11 in 35 Y fatty 'oils. 7' ~ ' ' v 15. A process in accordance with claim 11 in 3. A process in accordance with'claim 1 in which the fatty oil is linseed oil. 1 which the heating of the oil containing resorcinol 16. A process in accordance with claim 11 in is e?ectedin two stages, the ?rst of which is which the fatty oil is 'soya bean oil. 7 ' ~continued for at least 30 minutes at a tempera 17. A process in accordance'with claim 11 in 40' ture not exceeding about 200° C; and the second which the fatty oil is a pentaerythritol ester con-i ‘_ ; of which is continued for at least‘ 30 minutes at taining linseed'oil jfatty'acids. ' a temperature above about 200°‘ C'., said ?rst stage g 18. A varnish comprising a fatty oil contain“ I - being carried out under refluxing conditions.‘ , ing from about _.05% to about‘30% of resorcinol as the sole added treating agent, a varnish resin ll. A process for treating'fatty oils having dry 7 ing properties, to improve their characteristicsas and components of surface coating compositions, which process ‘comprises incorporating in. the oil up to 10% of resorcinol as the sole active ‘ treating agent, and heating the'mixture under 50'. refluxing conditionsat a temperature between about 75° C. and about 250° C. for at least 3.0‘ minutes. ; .7 . ‘ ' ‘ I ' from about .05% to about 30% of pyrogallol' as’ the sole added'treating agent, a varnish resin. and aivolatile solvent. > ' r s -20. A process vfor treating fatty’ oils having prises incorporating in the fatty oil up‘ to 5% of ?uxed mixture ata temperaturev between about ' ' 250°’ C. and about 310° C. for at least 30 minutes. resorcinol asxthe sole active treating agent, ‘pre condensing the resorcinol with the oil at a tem 6. A process for treating fatty oils having‘jdry? ing properties, to improve their ?lm-forming. peratu're below about 250° C. and thereafter heat bodyingthe oil by heating the mixtureto a heat . characteristics when used as components oi'sur bodying temperature above about 250° C. , 21..'A process in accordance with claim 4, in which. the quantity of resorcinol used is between V V 1/2‘% and 2% of the weight of the oil, above the boiling 0r decomposition point of the oil, whichever is lower, for at least‘ 30 minutes. '7. A process for'treating'fattybils havingrdry-r , ,7 I characteristics when‘ used as components of sur-' 7 characteristics when used ascomponents of sur face coating compositions which process come 5. A process in accordance with. claim 4.-: and further comprising additionally heatingthe re ‘ing properties, to improve theiru?lm-formingf solvent. drying properties to improve their‘ ?lm-forming ' . face coating materials, which process comprises incorporating in the oil up to 30% of ‘a polyhy droxy benzene as the sole active treating vagent, and heating the mixture at'a temperature be tween about 75° C. and about 350°iC. but not a volatile 19. A varnish comprising a fattyloil-containing ' v22.' A process inaccordance with claim '11; in whichiat least a portion of the heating is effected under re?uxing conditions and the temperature of the re?uxing'being at; least 150° C. ‘and not more than 200°C. and there?uxing time. being at 1east30 minutesj ' ' ' ‘ Y’ Lemme.