US1896467A - Johannes scheibek - Google Patents

Description

Patented Feb. 7, 1933 UNITED STATES :orrammsscnarana, or murzrc, onimamr PROCESS FOR THE TREATMENT OF FATTY OILS Io Drawing. Application fled July 19, 1829, Serial No. 879,581, and in Germany Lugust 4, 1928.

Among the natural fatty oils, which are used for the reparation of varnish roducts, printing co ors, paints and the ike, the China wood-oil takes an exceptional position,

I inasmuch as-the unsaturated fatty acid contained therein, the elaeostearinic acid, possesses three double bonds in a neighbouring osition, the so-called conjugated position. En all other fatty oils which here come in question, like linseed-oil, perilla-oil, poppy seed-oil, nut-oil, soya-oil, traino1l and so forth only such unsaturated fatty acids are 1 resent, which have their double bonds in isolated ositions. That fact accounts for great di erences between the manner in which wood oil dries as compared with the manner in which oils such as linseed oil dry. There is no doubt that the film formation -must be regarded as the consequence of Q0 polymerization processes. Amon all natural fatty oils, however, only wood 011 is enabled by its particular structure to undergo such reactions directly, while all other 0118 must be previously converted before to a considerable degree by oxidation. Therefore only wood oil shows a quick dry ng with formation of a film which is resistant to water. On the contrary the drying properties of all other oils gradually decrease, and the resistance of their films to water will be diminished. Practically, from the point of view of varnish-makers, these properties of the wood oil give it its superiority over all other fatty oils.-

possible, in products of the latter kind to shift the isolated double bonds in such a man ner, as to arrive in conjugated positions to each other. In other wordseif it were possible to realize the reaction CH=='GH-CH,-CH '==CH -CH CH=CH-CH=CH by a rational and economical process the typi- The differences between wood-oil and the other fatty oils should become less, if it were cal properties of wood-oil could be transferred to the conversion products of other fatty oils. Even if an oil, like linseed-oil or poppy seed-oil could never be changed into wood-oil, the transfer of the characteristic 59 properties of wood-oil to linseed-oil or poppy seed-oil would be a very great 1m rovement in the art. The oils converted y an artificial process would even be superior to the natural wood-oil, inasmuch as they would be less sensible to certain influences, which have an injurious effect on wood-oil.

It is known, for example, that wood oilis easily converted by light to a solid product (the so-called y-glyceride). The same effect 80 is obtained by certain atmosphericinfluences, as by oxygen or. sulphur or sulphur-compounds, and even by certain pigments" (as red ead etc.). Furthermore, the great activity of the accumulated treble conjugated double bonds which is advantageous with respect to .rapid drying of the wood oil mustbe regarded as detrimental with respect to the durability of the wood-oil-films which, after a certain time, become brittle and lose their adherence to to the surfaces upon which theyhav' been produced. In consequence of this, glycerides with only double or but few treble conjugated groups must be regarded as better film-formers than the wood oil itself, because such products have all the good qualities of the wood oil (i. e. rapid drying power, great resistance against water), and lack the faults of that oil. i

With respect to the film-forming-power of 3 I such products, itis of no importance in what special position the conjugated groups may be produced so that positions such as 9, 11 or 10, 12 or any similar positions within the acid groups of the glycerides must be re arded 8 as equal. Inconsequence of this, it 1s possible to produce wood-oil-like products (i. e. products of the conjugated type?l from fatty oils of isolated character by s ifting,

to a certain degree, the double bonds of such 9 i is, furthermore, different in degrees in'difoils from their originally isolated places into a conjugated position.

The shifting of double bonds is in itself a known fact. It was, however, not known heretofore that in substances with a plural number of double'bonds such shifting processes may produce conjugated systems from originally isolated systems.

It is a feature of the present invention that especially fatty acids, such as linolenic acid or linolic acid, undergo such shifting processes easily and to a suflicient degree to proeither with the fatty oils (i. e. to the glycerides of unsaturated fatty acids) directly or with the separated acid-mixtures from the corresponding oils. The latter course is preferred if the conditions for the shifting processes are such that a j ellyin of the glycerides would occur. The reason or this is that the molecules of a natural glyceride are suflicient (ca 880) to allow a formation of colloidal particles at a time rendering the product unfit for the purposes of varnish-making and the like. When using the acid mixture such risk can be avoided with certainty. Of course it is necessary to combine the said acids after their shifting with glycerol etc. Such reconversion of the fatty acids into triglycerides or other suitable esters of polyalcohols, for instance glycols, offers no difficulties and can be effected by any process well known in the art.

One may also combine both methods by using triglycerides or their mixtures as well as mixtures of different fatty acids of various kinds, e. g., derived from difierent fatty oils, and mixtures of fatty oils and suitable For carrying those reactions in practice'a large number of substances appear suitable. For instance, chlorine and other halogens, hydrochloric acid, hydrobromic' acid, hydroiodic acid, sulphuric acid and derivatives of sulphuric acid, like alkyl-sulphuric acids, etc., hypochlorous acid, hydrogen peroxide, oxygen, metallic halogenides, metallic oxides, metallic salts and so forth. All those compounds are suitable which have the power of combining with a double bond of splitting off a ain more or less easily with formation of ot or compounds.

It must be understood that the general reaction given above in reality covers several processesof a more complicated nature which are not at'all clear in all cases. For purposes of the present invention, however, such lack of explanation is of no importance.

The effect of the several shifting substances ferent cases.

Some of those substances show such a great. power of reaction, that they can be applied 1n minute quantities, so that a catalytic reaction sets in, as it were. With other substances it is necessary to use great quantities, so that for each double bond which should be shifted, one molecule of the addition compound must be taken. Within that range there are many degrees, in which the conditions of reaction play an important part. Apart from that, one is not bound to work with one single type of an addition product,

:- inasmuch as one may combine several of the substances mentioned with each other.

The different substances suitable for the shifting processes may be caused to react fatty acids.

The shifting effects may be ascertained by with a pluralitypf isolated double bonds will give the right iodine value immediately, while substances with conjugated systems first show first too low iodine figures which will increase with time and will not be right until after several days. Another possibility of recognizing conjugated systems is given by their behavior in the presence of stannic chloride which will jelly such products very quickly while substances with isolated double bonds remain unchanged.

The following examples may serve for illustrating my process which are to be regarded as in no way exhaustive or limitative.

E wample 1 Refined linseed-oil is treated with asmall' quantity of sulphuric acid (1% or less) of the specific gravity of 1.5 and is then thickened in a nickel boiler by heating to to 300 C. Whereas under ordinary circumstances temperatures exceeding 300 C. are required for 8 to 10 hours, one now succeeds in attaining a satisfactory'thickening in about half the time. The product possesses a higher drying power than the usual thickened oil and also shows figures of its iodine value, which are typical for conjugated double bonds.

Example 2 Soya bean-oil is mixed with 2% of ferrous iodide and boiled at first for three to four hours at 250 C. and afterwards for 2 to 3 hours at 300 C. After that time a thick oil has been produced which will show all- Ewample 3 The commercial mixture of linseed oil fatty acid-mixtures is treated with air at about 200 C., until the iodine value has dropped to about one half. The temperature is then raised to about 260 C., passing carbon dioxide through the mass all the time, the temperature being maintained, until water no longer is condensed in the receiver. By these processes double bonds are shifted as follows -cn,-cn=cacH,-(:H=cn

-ca,-cmom -ca oa) -cn,-cn=cn CH(IH--CH=-=CH -CH-=CH. Therefore the remaining acid mixture, after its esterification with glycerol in known manner will produce an oil of decided wood-01lproperties.

Example 4 Example 5 Soya bet-n oil is emulsified by the addition of Turkey red oil (sulphonated castor oil) or a salt of an alkyl substituted naphthaline sulphonic acid in about 2 or 3 times its quantity of water. I then introduce into the mixture a solution of sodium hypochloride in a quantity necessary for the saturation of 2 to 3 double bonds, and-the combination is supported by the addition of sodium carbonate. I then decompose the mass with a mineral acid, and the oil is separated and dried. The splitting off of water or hydrochloric acid respectively is effected by the addition of ignited alumina (fulleirs earth) and facilitated by the use of a vacuum.

Ewample 6' A mixture of linseed-oil fatty acids and ten times as much water is warmed with such a quantity of alkali with stirring, until a solution is obtained which remains clear in a hot state. I allow the mass tocool down and add with energetic stirrin at a temperature of about 15-20 C. slight y less of a dilute permanganate solution (say 3%) than is theoreticallyrequired for the addition of two 011- roups to a double bond. After separating t e manganese mud the mass is acidified whereby a more or less solid product separates. The further treatment is effected b heatin in a current of carbon dioxide until the splitting off of water ceases and by subsequent esterification with glycerol.

The products obtained in the manner described are superior to the fatty oils which form the basis of the products made therefrom in the usual'way. Above all, the power of dryin is greatly enhanced. Furthermore the dry lms show only a very small swelling power in water. The eas change in the properties of the films, which is disliked in the use of wood-oil, is not to be feared with the new products. On the contrary, the films are distinguished by a lon life, a good adhesion-beingmaintained an a good elasticity.

The new products can be employed by themselves or in combination with each other or with. any other products. We may use them in combination with natural fatty oils and products therefrom, as well as with resins of natural or artificial provenience, with pitch, asphalt, esters and ethers of cellulose, caoutch'ouc, depolymerized caoutchouc, and so forth. That means practically, that the new products may be used in the same manner as is usual for ordinary fatty oils. I have in mind to apply the process for all kinds of applying paints, lacquers, varnishes or printing colours. The manufacture of cements, plastic compounds, linoleum etc. may also come into the question.

Taken all together, the a plication of the present process can be consi ered for all fatty oils, which exhibit sufficient proportions of double or treble or even more unsaturated fatty acids, the'double bonds of which occupy isolated positions in the molecule. .Wood oil excepted, all fatty oils of a dryin or semidrying character may be useful, in tire process described, like oils from the character of linseed-oil, poppy seed-oil and train-oil.

What I claim is:--

1. As a new article of manufacture, a derivative of an oil selected from the class consisting of linseed oil, poppy seed oil and train oil, said derivative being a fatty oil with a shifted double bond and having the drying properties and water resistance of Chinese wood oil.

2. A process for treating fatty oils of the linseed oil, poppy seed oil and train oil type, consisting in acting upon the multiple unsaturated fatty acids of the said oils in the manner employed forshifting a single double bond in carbon chains, characterized by treating the said oils directly.

3. A process for treating fatty oils of the In testimony whereof I affix m si ature.

J OHANNES