US2298919A - Modification of fatty oh - Google Patents

Description

Patented Oct. 13,, 1942 MODIFICATION OF FATTY OILS Laszl Auer, East Orange, J.

No Drawing. Application February 5, 1942, Serial No. 429,663

I 14 Claims. GENERAL FIELD OF INVENTION Thisinvention. relates to the modification of organic isocolloids. More particularly, the invention is concerned with the bodying of fatty oils.

The subject matter claimed herein is divided from my copending application Serial No. 318,650 of which the present application is a continuation-in-part, and said subject matter is disclosed not only in said application 318,650 but also at least in part in certain other prior applications, especially Serial No. 359,425 (now Patent No. 2,- 213,944), and Serial No. 143,786 (now Patent No. 2,189,772).

Organic isocolloids are colloidal substances in which the dispersed phase and the dispersion medium are both of the same chemical composition, although present in a different physical state. In the bodying of fatty oils (which are organic isocolloids) the relation between the dispersed phase and the-dispersion medium is altered, the dispersed phase'being increased and the dispersion medium correspondingly decreased.

In accordance with various of my prior applications, including those mentioned above, various different methods-are disclosed for modifying organic isocolloids, and especially for bodying fatty oils. In general, the modification is brought about by heating the isocolloid in the presence of a modifying agent.

In the prior applications, various different generic and sub-generic classes and specific modifying agents are disclosed; and, in addition, there are also disclosed variations in process. Different modifying agents or groups thereof, and also va-' riations in process, effect different results, some being of importance for certain purposes and some for other purposes.

The present application is particularly concerned with the modification of fatty oils by means of polar compounds, i. e., modifying agents containing a positive charge in one part of the molecule and a negative charge in another part of the molecule; or capable of orienting their different radicals in opposite directions on an interface of liquid-gas, liquidsolid, or liquid-liquid. More specifically, the invention is concerned with that class of modifying agents which I have termed Z-radical type, i. e., having within the molecule an acidic inorganic residue and an organic residue. By an acidic inorganic residue I mean a residue capable of yielding an inorganic acid upon the addition of one or more hydrogen atoms or OH groups.

The subject matter claimed herein relates to the use of 2-radical type modifying agents in which the acidic inorganic residue contains a halogen and is capable of yielding an inorganic halogen-containing acid upon the addition of hydrogen, this particular sub-group of agents having certain distinctiv characteristics distinguishing it from other modifying: agents in the general class, in which the inorganic radical does not contain a halogen. The distinctive char-- acteristics will be pointed out more fully hereinafter.

Tin. STARTING MATERIAL The fatty oils and similar materials with which the present application is especially concerned find one of their most important uses in the coat ing materials and plastics industries, especially the paint and varnish industry, where oils having good body and drying power are very important.

Th improved products produced in accordance with this invention also have may other uses.

A list of typical oils which may be advantageously modified by my invention is as follows:

Tung oil Rapeseed oil Castor oil Walnut oil Linseed oil Pine seed oil Fish oil (train oils) Corn oil Poppyseed oil Olive oil The ease of bodying or modification, under equal conditions, decreases in the order given. That is, the first mentioned oils are most extensively bodied or modified by my methods, while the oils at the end of the series are modified to a lesser body. However, it should be also mentioned that by the employment of suitable modifying agents in my methods, even the last mentioned oils (those at the end of this series) can be profoundly modified or bodied, as well as those oils appearing in the first of the series. 1

The foregoing listed, and other fatty oils may be classified as follows:

Drying oils Semi'drying oils 'lung oil Sunflower oil Oiticicn oi] Poppyseed oil insced oil Soya bean oil lvrilla oil Walnut oil Rapeseed oil Pine seed oil Non-drying oils Special oils Olive oil Hydro lated; castor oil, (10. Corn oil Fish oils (train oils) Cottonseed oil Coconutoil The fish oils are mixtures of non-drying and dry ing triglycerides.

In accordance with the invention, the oils referred to may be treated per se, or they may be treated in mixtures containing more than one such oil, or containing other materials. For in stance, synthetic resins containing natural resins or acids or acids of fatty oils and of resins, may be modified in accordance with the invention.

In addition, separated fractions of fatty oils (for instance, the better drying fractions) may be used as starting materials, either alone or mixed with other oils.

The process of the present invention may, in fact, be used in connection with fatty oils themselves, fatty acids, esters or fatty acids, and various materials containing the same, and it is to be understood in connection with the appended claims that where reference is made to treating fatty oils, the language is not to be understood as limited to treatment of fatty oils per se, since essentially the same reaction takes place in the case of treatment of the fatty acids, esters thereof, etc.

THE MODIFYING AGENT As hereinbefore mentioned, the present application is particularly concerned with the use of modifying agents having within the molecule an acidic inorganic halogen-containing residue, and an organic residue, the inorganic residue being capable, upon the addition of hydrogen, of yielding a halogen-containing acid.

-With reference to the yielding of a halogencontaining acid, it may be mentioned that although I believe that that reaction takes Place during the treatment of the oil, in some cases the reaction may not occur to any considerable extent. Nevertheless, the treating agents herein contemplated are effective, so long as they have the capability of yielding the corresponding halogen-containing acid, upon the addition of hydrogen to the inorganic residue. It may be noted that with some compounds in this group, the corresponding halogen-containing acid may merely be split-off from the compound, in which event application of heat alone may be sufficient to yield the acid.

The principal outstanding characteristic of this group of treating agents is their ability to improve the drying characteristics or power of the oils treated. This is an important consideration in the varnish and paint industry.

In treating with the agents herein contemplated, precautions should be taken to prevent excessive loss of the reagent before ample opportunity has been given for the oil to absorb it. This may be accomplished by employment of a reflux condenser or in certain other ways which are discussed more fully hereinafter in connection with specific examples.

In the modifying agents of the group herein claimed, good results are secured where the inorgan'ic residue contains chlorine, fromine or iodine, yielding, upon the addition of hydrogen, hydrochloric acid, hydrobromic acid or hydroiodic acid.

I The following specific examples are illustrative of this class of treating agents:

'o-Dichlorobenzene, p-Dichlorobenzene, Trichlorobenzene, Naphthalene tetrachloride, Naphthalene trichloride, Naphthalene monochloride, Naphthalene hexachloride, Chloral hydrate,

Iodoform,

Pinene hydrochloride, 4-chloro-o-anisidine, p-Nitro-chloro-benzene, Triphenyl chloro methane, Benzyl chloride,

Benzoyl chloride,

Acetyl chloride, Mono-chloroacetic acid, Trichloroacetic acid.

It will be noted that some of these are aromatic and some aliphatic.

Some of the inorganic salts of organic bases also have the important characteristics of the class of treating agents herein claimed. Examples are as follows:

Diphenylamine hydrochloride, Diphenylamine hydrobromide, m-Nitroaniline hydrochloride, Trichloroaniline hydrochloride, Aniline hydrochloride,

Diphenylamine trichloracetate.

, Nitro-chlorobenzene,

Dinitro-chlorobenzene.

Certain sulphonic acids and sulphonyl chlorides also have the important characteristics of the class of treating agents herein claimed. For example-- 2:5 dichlorobenzene sulphonic acid.

From the foregoing it will be seen that certain treating agents in the class herein claimed may be relatively complex compounds incorporating, in addition to the halogen-containing residue, other residues such, for instance, as a sulphur-containing residue capable of yielding a sulphur-containing acid upon addition of hydrogen or OH groups, or a nitrogen-containing residue capable of yielding a nitrogen-containing acid upon addition of hydrogen or OHgroups. In such cases, the treating agent partakes somewhat of the characteristics of the sulphur or nitrogen, as well as of the halogen-containing acid.

In this connection it is pointed out that in copending applications filed concurrently herewith (Serial Nos. 429,661 and 429,662), I have disclosed and claimed other 2-radical type treating agents having withinthe molecule a sulphurcontaining residue or a nitrogen-containing residue. In certain instances, therefore, some of the treating agents herein referred to also belong to a group of agents claimed in a copending application, although in this event such a compound treating agent manifests not only the distinctive characteristics of the group claimed herein, but also the distinctive characteristics of the group claimed in said copending application.

TREATMENT CONDITIONS In carrying out the process, the treating agent and the oil are first mixed together in any suitable way. Treating agents of different physical characteristics, such as consistency, naturally require different technique for mixing. These matters need not be considered in detail herein since they are fully disclosed in my copending application Serial No. 318,650.

The mixing may be effected in the cold, 1. e., at

- room temperature; or may be effected at elevated temperatures; for instance at some temperature in the preferred range of reaction temperature.

While the quantity of treating agent may range anywhere from a minor amount (for in"tance. a fractional percentage) up to about 30%, ordinarily the amount required is relatively small, not usually more than about 10%. In general, the degree of modification of the oil increases with increase in the amount'of modifying agent used.

. sulphurized products.

The lower limit depends somewhat on the particular agent, and also on the particular oil being treated, although at least some modification is observable from even minor fractional percentages, going down as low as .01%.

The treatment temperature may also be varied over a considerable range, depending upon the nature of the treating agent and of the oil, as well as on the character and extent of modification desired. In general, the temperature should be considerably above room temperature, but not above the boiling or decomposition point of the oil. A good working range is from about 100 to about 350 C., and preferably above about 200 C.

The time of treatment is also a variable, depending upon the treating agent, the starting material and the result desired. In general, increasing the time of treatment results in more extensive modification, and in most'instances the treatment at reaction temperature should be continued for at least 30 minutes, and preferably for several hours.

The reaction may take place either in an open or in a closed vessel; and either at sub-atmospheric, at atmospheric, or at super-atmospheric pressure. Different results are secured under various of these conditions, as is brought out more fully in my copending application No. 318,650.

With reference to the foregoing statement of treatment conditions, it is pointed out that these matters are discussed only briefly herein, since they are fully disclosed in my copending application Serial No. 318,650, to which reference may be had for further information. This is also true as to the supplemental matter discussed just below.

SUPPLEMENTAL TREATMENT CONDITIONS AND AGENTS My processes may be practiced in the absence of any additional material, other than the polar compound. However, I have found it is advantageous in some cases to incorporate the polar compound in the presence of additional materials which facilitate its incorporation and the modification of the organic isocolloid. For instance, the polar compound may be incorporated in the presence of various organic bodies such as the purely organic additions mentioned post or organic solvents. Again metal soaps may also be added; for instance siccatives (driers) such as the resinates and linoleates of metal compounds and metal oxides, commonly used in the varnish industry, as is mentioned in Serial No. 143,786. Further, sulphur or sulphur compounds, such as sulphur chloride, etc., may also be used in these processes and added in addition to the polar compound during the reaction or as an after treatment. The sulphur or sulphur compounds efiect further modification and produce The temperature usually employed for modification (above 200 C.) being substantially above normal vulcanization temperatures, the effect of the sulphur treatment at modifying temperatures is quite different from vulcanization.

However, I may also effect vulcanization of my modified products in an after treatment, so as to produce solid, coherent and elastic products, similar in some characteristics to ordinary rubber. Sulphur may be used for this purpose and may be added as such, or in the form of a sulphur compound, such as sulphur chloride, etc. The action of the sulphur is analogous to that which takes place in the vulcanization of rubber. Thus, accelerators or activators (zinc 236,800 (Patent No. 2,234,545).

oxide, etc.) or both, such as usually employed in the vulcanization of rubber, may be used in my processes to accelerate vulcanization when sulphur, etc., is added. The added sulphur vulcanizes or sulphurizes my modified products further changing their properties.

When making solid vulcanized rubber-like products, I employ temperatures between and C. for vulcanization, and from 5 to 50 parts of sulphur to 100 parts of the isocolloid under treatment. This vulcanization should be effected after modification, and accelerators and antioxidants may be added to the mix in known manner. I may produce liquid vulcanized products as well as rubber-like solids, by regulating the amount of sulphur and the time and temperature of heating. The liquid products are useful as varnish or paint bases.

Two step methods for making vulcanized, modified, heat-bodied fatty oil products are described and claimed in my application Serial No. As there stated, many of those products are useful as rubber substitutes. Others are useful for other purposes, for instance, in the manufacture of varnishes, lacquers and other liquid coating compositions, as well as in plastic compositions.

As noted above, the processes may be carried out in various ways, for instance, either in open or closed vessels as desired. In the latter case, the air can be entirely or partially displaced by another gas, such as hydrogen, CO2, S02, HzS,

nitrogen, etc., which influence the results obtained, these gases being used in supplement to the primary modifying agent employed. Again,

in both cases such gases may be passed through the material being treated. That is, the modification can be carried out during the passage of a gasp The gas pressure can be that of atmospheric. In many cases, however, a vacuum may be used with advantage. Again, even ahigher pressure of several atmospheres is to be recommended in certain cases, it being sometimes advantageous.

That is, I have further found that the results of' the process vary with the nature of the gas present and also with the physical condition (pressure) of this gas. Thus I have found that a certain given starting material which is initially liquid will become slightly viscous only as a result of the modifying treatment, if the latter is effected under atmospheric pressure (open vessel) but more viscous if the gas is rarefied by the employment of a partial vacuum. In other cases the converse applies. When plus pressure was used the results differ again. Air gives a different result from another gas or mixtures of gases such as mentioned ante. The modifying treatment may be carried out either in the total or partial absence of air, by replacing the same with another gas, such as those shown ante.

A pressure treatment followed by a vacuum treatment may be used, and I have found it to be advantageous to use alternately, atmospheric or plus pressure and vacuum treatment. Such alternate treatment increases the uniformity of the distribution of the polar compound in the organic isocolloid. In my processes, the gas may be blown or passed through the liquid mass or simply passed over the surface of the same during the heating. It is advisable in some cases, both when open or closed Vessels are employed to have a constant passage of the gas, such as those given ante, during the treatment with the polar compound.

It may be stated with reference to the action of gases, that generally speaking rareflcation of the gases present, by reduction of pressure in the vessel in which the treatment-is given, tends to intensify the action of the gases in my processes.

If desired, the polar compound may be produced in situ, that is, within the organic isocolloid under treatment,-by interaction within the organic isocolloid, of substances capable of reacting under the conditions of the process to produce the polar compound. The same applies to the gas in the presence of which the organic isocolloidis to be treated and a substance or substances may be added which evolve the desired gas during the processing. It has been found in certain cases that polar compounds and gases which are produced in situ, being in the nascent state, are somewhat more active than those added in the preformed state.

Likewise, the organic isocolloid itself may be formed in situ duringthe treatment. That is, if it is desired to modify an organic isocolloid which is not a naturally occurring material and which has .to be produced before it can be treated, the production of such artificial or manufactured organic isocolloid maybe advantageously combined with the treatment with the polar compound. For instance, in making modified heatbodied fatty oils, the oil may be both heat-bodied and modified in a single step by heat-bodying the fatty oil in the presence of the electrolyte or polar compound. To do this several hours heating at polymerization temperatures is required. Many of my polar compounds are advantageous for this purpose as they accelerate the heat-bodying and polymerization of fatty oils.

In addition to the action of polar compounds and the cooperating action of gases in effectin the colloidal transformations characteristic of my invention, an additional modification of the ultimate physical properties of the treated products can be effected by the addition to the material under treatment, of purely (i. e. metal-free) organic bodies, such as phenols, naphthols, naph thalene, chloroform, acetone, alcohols and their homologues and derivatives. These additions are supplemental to the use of polar compounds. Some of them are'solvents and assist in dispersing the polar compound in the organic isocolloid.

The use of solvents for this purpose is also shown r in my Serial No. 273,159 (Patent 1,985,230) and other prior applications.

I have also found that in my processes the colloidal transformations may be promoted by the use of rays of oscillating energy, such as ultraviolet rays, infra-red rays, X-rays. etc. That is, it is advantageous to irradiate the oil or other organic isocolloid, before or during the treatment with the polar compound. Sometimes a subsequent treatment with these rays is also helpful. Further, these rays influence and intensify the action of the gases in my processes.

EXAMPLES Example 1 150 parts of linseed oil are heated in vacuum to 280-300 C. for 5 hours with 10 parts by weight of diphenylamine hydrobromide. The product is a moderately dark viscous oil.

. Example 2 300 parts of linseed oil are heated to 290-310 C.- in vacuum with 30 parts of triphenyl chlormethane. The modified product so obtained is a medium viscous oil, suitable for lacquer manufacture.

\ Example 3 COMPARATIVE Tners Whereas profound changes in physical properties of fatty oils usually required modifying agents in quantities of 1% or more, gradual changes of properties, such as bodying velocity, may be brought about with smaller proportions of modifying agent. Several comparative tests were carried out, using .5% of modifying agent. In each instance the oil treated was alkali refined linseed oil.

In each test a batch of 300 grams of oil in a 1 liter aluminum beaker was heated at atmospheric pressure (the beaker being open) to 295 to 305 C. and'kept at that temperature for 5 hours. Two modifying agents were tried in this way and a blank control experiment was also carried out, following the same heating procedure, in order to secure a comparison between the linseed oil, heat bodied with and without modifying agent. Color and viscosity of the oils were as follows:

Reagent 0031(5- of Viscgislity of Beta-chloro-anthroquinone l0 Z6 Naphthalene tetrachloride. 12 2-3 ic or enzenes onic acid .18 Blank 3. 7 2

Readings of both color and viscosity are on the Gardner scale Each of the above oils was further used in preparing a varnish, as follows:

2 parts of oil product and 1 part of ester gum were heated to 300 C. and kept at that temperature for 1 hour. The mixture was cooled to 200 C. and thinned with 3 parts of mineral spirits to 50% solids. Naphthenate driers were added in the proportion of .0? cobalt metal, .02% mananese metal and .3% lead metal, based on the quantity of oils used.

The color and viscosity of the varnish in each case was as follows:

Color of Viscosity of Reagent varnish varnish Beta-chloro-anthroquinone. 13 A Naphthalene tetrachloride. 13 A Chlomlhydrate 10 A- 2:5 dichlorbenzene sulphonic acid l8++ A- Rlnnk 11 A The foregoing varnishes were stored for 2 days and then panels of steel were coated with a coating knife yielding heavy films of .003" thickness Various characteristics of the varnishes were tested, with the following results:

1 Nora-In all of these tests metallic driers were used in the varnishes, for the sake of uniformity as between tests. However, sulphonic acids yield oils which, in turn, yield varnishes which dry more slowly 1n the presence of metallic driers than in the absence thereof. Since the particular material here noted (2:5 dichlorbenzene clontams tsulphgrt 1iln addition to the halogen, it manion proper y, an is ac ex lams' wh varmsh dried very slowly. p y this particular The initial drying indicates an observation made after the first hours of drying. Overnight tackfreeness, of course, indicates the condition after overnight drying. Before subjecting the panels to the cold water, boiling water and alkali resistance tests they were left to throughdry for i=8 hours. All of the immersion tests were made in a manner leaving one-half of the panels exposed, for comparativ purposes The cold water test was made by immersing the panels for-24 hours in cold water and observing the appearance of the film.

The boiling water test was made by immersing the panels in boiling water for minutes, and comparing the results. In this case the degree of milkiness and softness of the films was observed as well as the speed with which the milky films returned to their original appearance upon air drying.

The alkali resistance test was made by immersing the panels in a 3% sodium hydroxide solution and noting the time when the alkali completely attacked and dissolved the films.

Examples 4-13 In another series of comparative experiments certain uniform treatment conditions were adopted, as follows:

In each case, the oil employed was linseed oil and 5% of the treating agent was used.

In each case, the heating time was in the neighborhood of 5 hours. In conducting these experiments the approximate reaction temperature was 300 0., although there were minor differences between various of the experiments. The treatment temperature was between about 290 and 310 C.

A control experiment was also conducted under the same heating conditions, but without treating agent, so as to secure comparative results.

Most of the experiments in this group may be divided into pairs, the two experiments of each pair employing the same treating agent. The difference between the treatment of the two members of each pair was as follows:

1. Heating 9. 300 gram charge in a one liter distilling flask under vacuum-identified herebelow by the letter (a) following the example number.

2. Heating a 150 or 300 gram charge in a 500 cc. open enameled beaker-identified herebelow by the letter (1)) following the example number.

Example 4(a) M onochloracetic acid Gas was evolved and some distillation took place during rise in temperature. Upon reaching reaction temperature the mixture boiled steadily, without distillation, although distillation later set in, but again gradually stopped.

The product was a thick dark brown oil with a strong green fluorescence. The distillate was a black oil with an obnoxious smell.

Example 4(b) M onochloracetic acid A sample taken after about one-half hourheating (296 C.) indicated a pale yellow color.

, The fully treated product was a rather mobile brown colored oil with a strong green fluorescence. Example 5 (a) p-Aminophenol hydrochloride The reagent dissolved slowly, meanwhile the oil darkening in color.

The product was brown and viscous with a green fluorescence.

Example 5 (b) p-Aminophenol hydrochloride Some frothing occurred in the early heating but shortly stopped. The color gradually intensified. The fully treated product was brownish black in color and almost solid.

Example 6 (b) o-Dz'chlorbenzol Considerable frothing occurred in early heating, but this subsided at about C.

The product was a dark reddish brown oil with a strong green fluorescence. Some reagent remained as a charred mass.

Example 7 (a) Diphenylamine hydrochloride Considerable frothing occurred in the early stages of heating and this subsided gradually. Some sublimation occurred between about 80 and C. Upon reaching about 290 C. the mixture began to boil steadily and remained steady throughout the treatment time, except during the last two hours, when the mixture bumped occasionally.

The product was a thick golden brown oil with a dull green fluorescence.

Example 7(b) Diphenylamine hydrochloride Serious frothing took place in the early heating but subsided upon reaching about 230 C. The mixture then remained steady up to the reaction temperature and throughout the reaction period.

The oil was thick and brown, with strong fluorescence.

Example 8(a) Diphenylamine hydrobromide Initial frothing occurred but this gradually subsided and boiling was then steady. After boiling for about 2V2 hours on temperature some distillation began and continued to the end of the treatment time.

The product was a thickish oil with green fluorescence.

Example 8(b) Diphenylamine hydrobromide A sample taken at about 294 C. indicated a deep chocolate brown color.

The product after complete treatment wa a very thick brown oil with no fluorescence. Some reagent remained as a charred mass.

Example 9 (b) Trichloraniline hydrochloride Considerable frothing occurred on initial heating but shortly subsided. An unusually extended length of time .was required to raise the temperature to reaction temperature and the batch was shut down for the night after 4 hours on temperature. On restarting the temperature quickly reached 300 C. and was kept there for the balance of the reaction period.

The product was a moderately thick golden brown oil with a strong green fluorescence.

Example 10(a1 Triphenylchloromethane Slight frothing occurred at about 108 C. but

this subsided and th mixture remained steady throughout.

The product was a rather mobile black brown 011 with a faint dark green fluorescence.

quickly restored and the heat maintained for the balance of the treatment period.

The product was a thickish rather dark brown oil with a green fluorescence.

Example 10(1)) Example 13m) Triphenylchloromethane p-Chlororthoamsidine The mixture remained steady throughout the Some frothing et in at about 87 C. and lasted entire heating. until boiling set in at aloout 280 C. During the The product was a thick 011 of brown color, treatment period the bOlllng gradually slackened with strong dark green fluorescence. and the oil darkened.

Example 11w) fiu'ghascrgoguct was a thin brown 011 with green Diphenylamine trichlm'acetate Example 13(1 Th mixture was steady throughout th treatp-Chlororthoam'sidine T l' ie product was a fairly thick brown oil with fi i gifiggi remamed steady throughout the strong green fluorescence The product was similar to that of Example Example 12 (b) 13(a), but thicker and slightly darker. Benwlchlofide 5.52%; ifv 'n fiiiioifi fiiifiiii $055. 50353.. he re wa heated 0n temperature for poses of ready comparison. The table also indiu s and then Shut wn for e nig t. O cates characteristics of the blank control exrestarting, reaction temperature was again periment.

Example 0 Viscosity Color Reagent solubility Mono-chloracetic Med. viscous (liquid). Med. greenwich brown Dissolves.

Mono-chloraeetic do Light med. greenish Part undissolved.

p-Aminophenol hydrochloride Thick viscous (fluid) Fairly dark Dissolves.

p'Aminophenol hydrochloride do do Do.

o-Dichlorbenzene Med. viscous (liquid). Med. greenish brown Diphenylamine hydrochloride do Dissolves.

Dlphenylamine hydrochloride.- do Light med. green Do.

Dlphenylarnine hydrobromide do Fairly dark Part uudissolved.

Diphenylamine hydrobromide Thick viscous (fluid).. do Do.

9(b)-B Trlchloraniline hydrochloride Med. viscous (liquid). do Do.

Triphenylchlormethane do Med. greenish brown sullggns in min. at

Triphenylchlormethane do do Part undissolved.

1l(b)-B Diphenylamine trichloracetate do Light med. greenish Do.

Benzyl chloride -.do do Dissolvcs at once.

l3(a)-V p-Chlororthoanisidine do Fairly dark Dissolvos.

l3(b)-B v p-Chlororthoanisidine do... do Dii giles in 10 min. at Blank Thin viscous liquid... Light Code explanation:

V==vacuum experiment. B ==open breaker experiment.

Viscosity=range from heavy to light. Color=rango from dark to light.

varnishes were made up employing the prodnets of Examples 4 to 13, the varnishes being without driers. The relative drying order of the varnishes is indicated in the following list:

Drying order of varnish Example No.

(no dricrs) The best drying were the varnishes made with the product of Examples 5(b) and 8(b), the others following in sequence as indicated.

Example 14 Comparative experiments A number of comparative experiments employing chloral hydrate as the modifying agent were carried out under various conditions. The percentage of agent varied from about .05% to 4%. Both alkali refined linseed oil and heavy bodied linseed oil were tested, and in all cases blank control experiments were carried out with both of these oils, in order to secure comparison of the treatment procedure as between treatment with and treatment without the chloral hydrate.

All experiments were conducted in one liter aluminum beakers, in batches of 300 grams of oil, the resulting oils being tested for color and viscosity.

From the modified oils and also; from the blank control oils. varnishes were cooked at 300 C., in the proportion of 25 gallons of oil to 100 pounds of ester gum. Driers were added to all varnishes-.03% cobalt, .02% manganese, and .3% lead (metal content based on quantity of oil); and the varnishes were tested for viscosity, color, drying, 'cold and boiling water resistance, and 3% alkali resistance.

Experiment A In this experiment 2% of chloral hydrate was employed and the reaction mass placed in an Erlenmyer flask, equipped with a reflux condenser. In different batches, the regent was heated or pre-condensed in the oil at several different temperatures, as follows: '75", 100, 150, 200 and 250 C. The most eflective temperature for precondensation was 200 C., and the time was 2 hours.

In this experiment (A), alkali refined linseed oil was precondensed under reflux for 2 hours at 200 C. and then one-half of the oil was used directly in cooking a varnish. the other half being further bodied at 300 C. for 3 hours to a viscosity of Z-5. This bodied oil was also used in a varnish, and both of the varnishes showed improvement in drying and in alkali resistance over the blank control varnish experiment.

Experiment B This experiment was conducted in the same manner as Experiment A with the exception that instead of precondensing under reflux, the precondensing was done in an open beaker without reflux. Some reagent was lost through fuming or sublimation, and the color of the oil was not as light as with Experiment A. However, as with Experiment A, the drying and alkali resistance were better than the blank control varnishes.

Experiment C Alkali refined linseed oil was directly cooked under a C02 blanket, without precondensation, to a viscosity of Z-S in 5 hours. The varnishes made in accordance with this experiment showed no improvements over the blank control varnishes in any tests.

Experiment D Alkali refined linseed oil was directly cooked under a vacuum of mm. of mercury, without precondensation, to a viscosity of Z-4 in 5 hours. The results were similar to those of Experiment C above.

Experiment E A group of tests was conducted with heavy bodied linseed oil, treatment being carried out in three different ways:

(a) The oil was heated at low temperature with the reagent so that the reagent was completely dissolved.

(b) The oil was heated at about 200 the reagent for 2 hours (without reflux).

(c) The oil was heated at about 250 C. with the reagent for 2 hours (without reflux). Some increase in viscosity over the original viscosity of the oil was effected.

varnishes were cooked with the products of (a). (b) and (0), but neither the oils nor the varnishes indicated improvement over the blank control experiments. It may be mentioned that (11) just above would have shown up better with the use of a reflux condenser.

From the various experiments of this example (14) it may be seen that Experiment A is superior to all of the others, both in regard to the bodying and color of the oil and with regard to the properties of the varnishes.

When concentrations of more than 2% reagent were used, readily.

I claim:

1. In the modification of fatty oils to improve their drying properties, the process which comprises mixing the oil with a minor amount and not more than 10% of a polar compound having within the molecule an organic residue, and an acidic inorganic halogen-containing residue, and heating the mixture to a reaction temperature between about 200 and 350 C. for at least thirty minutes.

2. A process in accordance with claim 1 wherein the fatty oil is linseed oil.

3. A process in accordance with claim 1 in the fatty oil is soya bean oil.

C. with of the charring occurred more where- 4. A process in accordance with claim 1 whereclaim 1 wherev 10. A process in accordance with claim 1 wherein the halogen is chloral hydrate.

11. A process in accordance with claim 1 in which the initial heating is efiected in a manner providing against loss of the polar compound.

12. A process in accordance with claim 1 in which the heating is efiected in a manner providing precondensation of the polar compound with the oil.

13. In the modification of fatty oils to improve their drying properties, the process which, comprises mixing the oil with a minor amount and not more than 10% of a polar compound having within the molecule an organic residue, and an acidic inorganic halogen-containing residue, heating the mixture to and maintaining the mixture at a temperature appreciably below the re- .between about 200 and 350 action temperature for a period of time sufficient to provide for absorption by the oil of at least a major portion of the polar compound, and thereafter heating the mixture to a reaction temperature between about 200 least thirty minutes.

14. In the modification of fatty oils to improve their drying properties, the process which comprises mixing the oil with a minor amount and not more than 10% of a polar compound having within the molecule an organic residue, and an acidic inorganic halogen-containing residue capable of yielding a halogen-containing acid, and heating the mixture to a reaction temperature C. for at least thirty minutes.

LAszLo AUER.

and 350 C. for at- CERTIFICATE OF CORRECTION. Patent No. 2,298,919. October 15, 191;,2.

LAs'zL6 AUER. It is hereby certified that error appears in the printed specification of the above numbered patentrequiring correction as follows: Page 1, second column, line 15, for the word "may" read many--; page 2, first column, line 5, for "'or" read --of--; line 52, for "fromine" read -bromine---; page 6, in the table, third column thereof,- Example L .(a)V, for "greenwich" read --greenish-; and last column thereof, Example 7(b)-B, strike o'ut "D0 and that the said Letters Patent shouldbe read with this correction therein that the same may conform to the record of the case in the Patent Office.

si ed and sealed this 24th day of November, A.'D. 19m.

Henry van Arsdale, (Seal) Acting Commissioner of Patents.