US2300090A - Modifying fatty oils - Google Patents

Description

Patented Oct.27, 1942 UNITED STATES PATENT. OFFICE MODIFYING FATTY OILS Laszl Auer, "South Orange, N. J.

No Drawing. Application March 9, 1942,

Serial No. 433,875

15 Claims.

GENERAL FIELD OF INVENTION This invention 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 Serial No. 318,650 but also at least in part in certain other prior applications, especially Serial Nos. 359,425

(now Patent 2,213,944), 143,786 (now Patent 2,189,772), and 305,409.

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 ifying agents are disclosed; and, in addition, there are also disclosed variations in process.

Difierent modifying agents or groups thereof,

and also variations in process, effect difierentresults, 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 chargein'a'nother part of the molecule, or capable of orienting their different radicals in opposite directions on an interface of liquid-gas, liquid-solid, or liquid-liquid. More specifically, the invention is concerned with use of halogen salts as modifying agents. Examples of these salts are given hereinafter.

The fatty oils and similar materials with which the present application is especially concerned ing materials and plastics industries, especially in lacquers, where oils having good solubility and miscibility characteristics are very important. The improved products produced in accordance with this invention also have many 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 Sunflower oil The ease of bodying or modification, under equal conditions, decreases in the order given. That is, under equal conditions, 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 emp10yment 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.

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

Drying oils Semi-drying oils Tung oil Sunflower oil Oiticica oil Poppyseed oil Linseed oil Soya bean oil Perilla oil Walnut oil Rapeseed oil Non-drying OZZS Pine seedoil Olive oil com on Speczal 0118 Cottonseed oil Hydroxylated; castor oil, .etc.

Coconut oil Fish oils (train oils) The fish oils are mixtures of non-drying and drying 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 instance, synthetic resins containing natural resins 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 beused as starting materials, either alone or mixed with other oils.

Prebodied oils may also be used as starting mafind one of their most important uses in the coatb5 terials in accordance with the present invention.

THE Monrrvme AGENT As mentioned hereinbefore, the present application is particularly concerned with the use of halogen salts in the treatment of fatty oils.

-- Moreover, the invention especially contemplates use of salts of hydrochloric acid, hydrobromic acid and hydriodic acid. Such halogen salts are salts of mono-basic acids, and the salts may be used to advantage in modifying all types of fatty oils, including non-drying, semi-drying as well as drying oils, such as linseed oil.

Examples of such salts of halogen acids are:

Ammonium chloride Zinc chloride Ammonium bromide Sodium iodide Sodium bromide Magnesium chloride Zinc bromide Mercuric chloride Cadmium iodide Barium chloride Ammonium iodide Mercuric bromide Bismuth chloride Tin chloride (tetra) The foregoing listed salts all have relatively good solubility and miscibility characteristics. Sodium chloride may also be employed for some purposes, although this agent is difilcultly soluble in organic solvents.

Still further, barium thiocyanate, potassium 'thiocyanate and other thiocyanates of metals may be used, the thiocyanate salts being similar in action to the halogen salts. In view of this similarity, the thiocyanate salts, for the purposes of the present application, are considered as falling within the definition "halogen salts." The thiocyanate salts, particularly barium thiocyanate, like most of the halogen salts, impart good solubility to 0115.

Solubility characteristics (solubility in organic solvents) of certain of the foregoing salts are indicated in the following table:

Solvent Reagent Acetone Benzol Sodium iodide. S S. I. 1. Sodium bromide I. 81.8. I. I. Ammonium iodi e 81.8. S. S. SL8 Magnesium chloride I. S. B. I. Zinc bromide. B. S. I. 8.

Code explanation:

S.=soluble I.=insoluble S1. S.=slightly soluble Because of solubility characteristics indicated just above, and further because of certain other characteristics, the halogen salts herein contemplated are of importance in modifying fatty oils for use in lacquers andfor other purposes where similar characteristics are desirable.

The halogen salts impart to oils treated theremetal salts of the alkali metal class, because of with a high degree of miscibility with solvents the similarity in action. Moreover, the ammonium salts not only manifest the general characteristics of the other salts mentioned, but they are particularly effective from the standpoint of dispersion. Ammonium salts very readily disperse in the starting materials.

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 efiected 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 instance, a fractional petrcentage) up to about 30%, ordinarily the amount required is relatively small, not usually more than about 10%. In general, thedegree of modification of the oil increases with increase in the amount of modifying agent used. 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 .0l%.

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 200 to about 350 C., and preferably above about 250 C. A good practical range is from 280 to 310 C. Temperatures appreciably below 200 0., for instance from room temperature to C., produce entirely different effects, and are not useful for the present purposes.

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 gnoresfoully in my copending application Serial No.

With reference to the foregoing statement of treatment conditions, it is pointed out that these matters are discussed only briefly herein, since they are fullydisclosed 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 matters discussed just below.

SUPPLEMENTAL TREATMENT CONDITIONS AND AoEN'rs My processes may be practiced in the absence of any additional material, other than the polar compound. However, I have found it is advan tageous 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 asthe 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 inthe 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 effect further modification and produce sulphurized products. 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 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 120 and 180 C. for vulcanization, and from to 50 parts of sulphur to 100 parts of the isocolloid under treatment. This vulcanization should be efthe air can be entirely or partially displaced by another gas, such as hydrogen, 002, S02, E28, 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 gas. The gas pressure can be that of atmospheric. In many cases, however, a vacuum may be used with advantage. 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 fected 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 lacquer, varnish or paint bases.

1 Two step methods for making vulcanized, modified, heat-bodied fatty oil products are described and claimed in my application Serial No. 236,800 (Patent 2,234,545) 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,

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 com? pound.

- It may be stated with reference to the action of gases, that generally speaking rarefication 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 isocolloid is to be treated anda 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 during the 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 may be advantageously combined with the treatment with the polar compound. For instance, in making modified heat-bodied fatty oils, the oil may be both heat-bodied and modified in a single step by heat-bodying the Again, even a higher temperature and 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 effecting 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, naphthalene, 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 in my Serial No. 273,159 (Patent 1,985,230) and other prior applications.

I havealso found that in my processes the colloidal transformations may be promoted by the use of rays of oscillating energy, such as ultra-violet 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 To 100 parts of rapeseed oil are added parts of ammonium iodide. The mixture is heated in a vacuum for two hours to 300-350" C. At the end of this time, the vacuum is broken and the material poured out and allowed to cool.

In Example 1, other fatty oils, such as linseed oil, perilla oil, etc. (drying oils), poppy-seed oil, soya bean oil, etc. (semi-drying oils) and nondrying oils, such as castor oil, olive oil, etc., may be used in lieu of rapeseed oil. Further, fish oil and other mixtures of drying and non-drying fatty oils may be used. In modifying such oils, particularly castor oil, etc., I sometimes prefer to use somewhat lower temperatures, say between 200 and 300 C., and heat for a longer time, as illustrated post. I

Example 2 100 parts of castor oil are heated together with 5 parts of ammonium iodide in vacuo at 260 C. for 5 hours.

A dark-colored soft paste is obtained upon cooling. This modified castor oil product is soluble in acetone. It is useful in making nitrocellulose compositions, such as lacquers, plastics and the like.

By varying the amount of the salt and the time of heating in Example 3,

other modified castor oil products can be obtained. For instance, by heating for a shorter time or at a lower temperature (200-250 C.) or using a smaller amount of the salt, say 2% or less, or combinations of these, modified oils are obtained from castor-oil which are oils varying from thinly mobile liquids to thickened (bodied) viscous oils. All such oils have properties different from the original castor oil.

In fact, such modified castor oils may be readily obtained from castor oil by the method of Example 3, using other cadmium iodide, zinc bromide, and barium thiocyanate, in lieu of the ammonium iodide. Using those salts in the method of Example 3 to modify the castor oil, I obtain modified oils as follows:

Cadmium iodide: a viscous oil, soluble in actone; Zinc bromide: a thick oil, soluble in butyl acetate, as well as soluble in acetone; Barium thiocyanate: a brown mobile oil, soluble in butyl alcohol and in benzene.

The ammonium iodide and other salts of halogen acids mentioned ante in regard to Example 3, may also be used to modify other fatty oils, such as linseed oil, soya bean oil, etc.- as disclosed in my application Serial No. 446,174 (now Patent 2,180,342), to produce other modified fatty oil products also useful in the manufacture of lacquers, varnishes and other coating compositions. Such compositions containing my modified oil products, particularly those made from castor oil, are claimed in my Serial No. 305,409, filed November 20, 1939 as a continuation of said Serial No. 446,174 and earlier copending applications set forth ante in this application. In both of those applications, I have disclosed various methods of modifying castor oil and other fatty oils, such as linseed oil, soya bean oil, etc. and the various examples and illustrations given therein illustrate this invention.

Examples of the use of lows:

thiocyanates are as fol- Example 4 To parts of linseed oil are added 5 parts of potassium thiocyanate. The mixture is heated in a vacuum for two hours at a temperature between 300 and 350 C. At the end of this time, the vacuum is broken and the material poured into molds and allowed to cool.

Example 5 To 100 parts of rapeseed oil are added 5 parts of potassium thiocyanate. The mixture is heated in a vacuum for two hours at a temperature between 300 and 350 C. At the end of this time, the vacuum is broken and the material poured into molds and allowed to cool.

In the above examples, 5 parts of cobalt linoleate may be added to the oil in addition to the potassium thiocyanate. Cobalt linoleate is a well known siccative used in the varnish industry. In my processes, cobalt linoleate serves to further modify the oil products so produced. The following examples are illustrative of such embodiments of my invention.

Example .6

' into molds and left to cool.

halogen salts, namely Example 7 100 grams rapeseed oil, grams cobalt linoleate and 5 grams thiocyanate of potash are heated in a vacuum for two hours to 300350 C. the vacuum is then destroyed, the mass poured into molds and left to cool.

The modified oil product obtained in Example 7 is useful in the varnish industry, that is, it is useful in making varnishes and like compositions. It has increased drying velocity and increased body as compared with the original rapeseed oil.

The modified'oil product of Example 5 likewise has improved properties, such as increased body, etc. The same is also true of the modified oil products of Examples 4 and 6. Both of them have increased body (viscosity) as compared with the original linseed oil.

Thus. various oils may be used in the practice of my invention and other fatty oils, such as tung oil, castor oil, fish oil (train oils), sunflower oil, olive oil, etc., as disclosed in my Serial No. 359,425 may be used in the foregoing examples, in lieu of linseed oil or rapeseed oil.

Example 8 100 parts of castor oil are heated together with 5parts ammonium iodide in vacuo of 100 mm./Hg pressure for 5 hours at 260 C. A dark colored soft paste is obtained which is soluble in acetone. Ammonium iodide is soluble in acetone. Ammonium iodide causes good solubility in many lacquer solvents.

Example 9 100 parts of castor oil are treated with 5 parts of cadmium iodide as described in Example 8. A viscous oil is obtained which i acetone soluble (as is cadmium iodide itself).

Example 10 100 parts of castor oil are treated with 5 parts of zinc bromide at 250 C. in vacuum of 100 mmJHg pressure. After the heatin proceeded properly the oil gels in vacuum. Therefore, it is advisable to reduce the amount of zinc bromide, for instance to 2 parts, and to reduce the temperature and/or cooling time, for instance, by heating to 200 C., holding there for 2 hours, heating to 230 C., reaching that temperature in an additional minutes, and then holding there for 3 hours. The product is a viscous brown oil, soluble in aceton as well as in butyl acetate. The reagent itself is also soluble in these solvents. If the reaction is repeated in open containers under atmospheric pressure, the product is thicker and is in the cold an elastic solid. It still has good solubility properties in the solvents in which zinc bromide is soluble.

Example 11 100 parts of castor oil modified with 5 parts of barium thiocyanate under the conditions of Example 8 yields a brown mobile oil which is soluble in butyl acetate and benzol. Barium thiocyanate is soluble in butyl acetate and is moderately soluble in benzene. Increased temperature and duration of heating increases the viscosity of bases of coating materials and plastics, the process which comprises mixing the oil with a minor amount and not more than 30% of a. halogen salt, and heating the mixture to a temperature between about 200 and 350 C. but not above the boiling or decomposition point for at least thirty minutes.

2. A process in accordance with claim 1 wherein the quantity of halogen'salt employed is not more than about 10% V 3. In the modification of fatty oils for use as bases of coating materials and plastics, the process which comprises mixing the oil with a minor amount and not more than 10% of a salt of an acid selected from the class consisting of hydrochloric acid, hydrobromic acid, hydriodic acid and thiocyanic acid, and heating the mixture to a temperature between about 200 and 350 C. but not above the boiling or decomposition point for at least thirty minutes.

4. A process in accordance with claim 3 wherein said salt is a hydrobromic acid salt.

5. A process in accordance with claim 3 wherein said salt is a hydriodic acid salt.

6. A process in accordance with claim 3 wherein said salt is a thiocyanic acid salt.

7. A process in accordance with claim 3 in which said salt is selected from the class consisting of ammonium, zinc, cadmium, bismuth, magnesium, tin, barium, potassium, mercury and sodium salts.

8. A process in accordance with claim 3 in which said salt is an ammonium salt.

9. A process in accordance with claim 3 which said salt is ammonium iodide.

10. A process in accordance with claim 3 which said salt is zinc chloride.

11. A process in accordance which said salt is tin chloride.

12. A process in accordance which said oil is linseed oil.

13. A process in accordance which said oil is soya bean oil.

14. A process in accordance which said oil is a castor oil.

15. In the modification of 'fatty 'oils to improve the solubility thereof in organic solvents, the process which comprises mixing the oil with a minor amount and not more than 10% of a salt of an acid selected from the class consisting of hydrochloric acid, hydrobromic acid, hydriodic acid and thiocyanic acid, the cation portion of said salt being selected from the classconsisting of ammonium, zinc, cadmium, bismuth, magnesium, tin, barium, potassium and mercury, and heating the mixture to a temperature between about 200 and 350 C. but not above the boiling or decomposition point for at least thirty minutes.

LAszLo AUER.

with claim 3 CERTIFICATE OF CORRECTION. Patent No. 2,500,090. October 27,.19b,2. LixszLb AUEIL.

It is hereby certified that error appars in the printed specification of the above numbered patent requiring correctionas fdllows: Page 2, sec-- 0nd column, line 56, for "petrcentuge" head -perc'enta ge-; page 1;, first column, line 57, for "200-55 -rea d -500 5 50-; and that the said Letters Patent should be readwith this porrctipn therein that'thesame n 1 ay conform to the record of the case in the Patent Office. I

Signed and seal edgthis 5th day of Jnua ry,iA. 13-19145 Benny Arsdale; (sa 1).. Acting -.Oe:c n1. Batnts..