US2389453A - Amides - Google Patents

Description

Patented Nov. 20, 1945 2,389,453 mamas John Harold Perrine, Prospect Park, Pa., assignor to Sun Oil Company, Philadelphia, Pa., a corporation of New Jersey No Drawing. Application April 15, 1943,

Serial No. 483,171

4. Claims.

amides, having commercially valuable properties. The amides in accordance with this invention are those formed from a group or mixture of saturated acids containing cycloaliphatic rings and having the generic formula Calla-=02, in which n has a value between 13 and 30 and a: has a value between 4 and 10. More specifically the amides are those formed from a group or mixture of said acidsa large proportion, and usually most, of which individually have the generic formula Cullen-:02, in which 11. may vary from 13 to 30 and a: is an even number from 4 to 10. Still more fspecifically the amides are those formed from a roup or mixture of said acids which are derived, in various ways, from petroleum.

The acids forming the group in question are obtainable from petroleum and are present, for example, as alkali salts in the asphaltic still bottoms produced in the distillation of topped crude in the presence of caustic soda to produce lubricating oils '(see Pew Patent 1,761,153 and Angstadt Patent 1,931,880). tained commercially from the source as a mixture of the various acids by treatment of the still bottoms with a mineral acid to convert the alkali salts to free acids, followed by distillation to obtain the acids as a distillate fraction.

The acids are also obtainable from lubricating oil fractions of naphthenic base crudes distilled without the addition of caustic soda.

The acids are also obtainable from gas oil fractions distilled from Gui Coastal (and probably other) crudes. Such acids may be so recovered by, for example, the process disclosed in the application of McCorquodale, Magill and Easy. Serial No. 475,318, filed February 9, 1943. 50 to 70 per cent. of these gas oil acids are identical with acid obtainable from the still residue. Since such method for recovering the starting acids forms no part of the present invention, its description is unnecessary.

The starting acids also appear to be obtainable by oxidation of naphthenic oils, as, for example, by methods similar to that disclosed in the'application of Johnson and Bruun, Serial No. 415,910, filed October 21, 1941.

It may be. also, that acids of the class defined may be synthesized from pure compounds by (possibly) some known method or by some process that may be hereafter developed.

From a practical or commercial standpoint,

however, the starting acids may be said to be those either naturally occurring in petroleum, or which are formed in petroleum during conven- (Cl. 260-55'l) The invention is directed to a new class of" These may be obtional processes of refining or which may be produced from petroleum by some special process.

The mixture of acids may be separated into more or less pure individual acids by fractional distillation in vacuo. The acids distill between about 125 C.- and-330 C. at 2 mm. The commercial mixture solidifies at about 50 C. However produced, the mixture of acids will generally contain some hydrocarbons as impurities, reducing the acid number of the mixture, but the presence of these hydrocarbons does not generally prevent the use of the commercial mixture of acids inaccordance with the present invention.

It has been found that valuable industrial products may be obtained by treatment of the acids comprising this group, either in purified form or as the commercial mixture, with urea for the formation of their amides,

.In general the reaction between the petroleum acids and urea will be carried out at a temperature of 150 C. to 200 0., at atmospheric pressure, or at higher temperatures at superatmospheric pressure. The reaction will take from 10 to 20 hours at the temperature range given, less at higher temperatures under pressure. Optimum proportions of reactants are two moles of acid to one mole of urea. Details or a preferred procedure may be found in the DAlelio Patent No. 2,109,941.

' The amide or mixture (if-amides formed in the reaction may be purified by water-washing and drying the reaction product. or the unreacted urea may be removed by filtering the crude reaction product through glass wool at a temperature just below the melting point of urea. The urea will crystallize on the glass wool. Impurities such as CO: and water can be removed from v the product b mild heating in vacuo.

Thus, 126 g. of petroleum acids having an acid number of may be heated with 12 g, of urea in a sealed glass bomb tube at C. for 15 hours, The bomb tube may then be allowed to cool to room temperature, further cooled to about 0 C. to reduce gas pressure within the tube, and

ent invention. Thus, the acid chlorides or esters of the petroleum acids may be reacted with ammonia to form amides; the ammonium salt of the acids may be dehydrated at 100 C.-200' 0.: or

mamidesoipetrolcumacidsinaccordancewith this invention are viscous liquids, the properties oiwhich have not yet been fully investisated. They have the aroup formula crinza-z-icom where n and :2: have the same values given above for the acids, and. like the acids, are probably characterised by the presence 0! five-membe'red' rings.

Among other uses as intermediates, etc., the amides oi the present invention are valuable modifiers for use in production oi modified alkyd resins. Thus extremely satisfactory synthetic resins for use in lacquers ma be formed by heatin: together for one to two hours at about 225 C. 1 part by weight glycerine, 2 parts phthalic anhydride, and 2 parts of the amides produced from hydrocarbon-tree petroleum acids havin: a saponiflcation number of 1'10.

This application is a continuation in part c! an application filed by me- January 15, 1941, Ser. No. 374,557.

What I claim and desire to protect by Letters Patent is:

1. The mixture or amides iormed irom a mixture of saturated monocarboxylic acids containin from two to five cycloaliphatic rings per aaeaasa hasavalueransinsiromewhenthenumber of cycloaliphatic rinse is two to 10 when the number 0! oycloaliphatlc 111188 is five.

2. The mixture 01 amides Iormed from a mixture of saturated monocarboxylic acids containin: from two to five cycloaliphatic rings per molecule and havin: the generic formula cant-=01 3. The mixture of amides formed from a mixture oi saturated monocarbosylie acids containing from two to five cycloallphatic rinss 'per molecule individual acids of which have the generic formula Came-s02, wherein n is a number from 13 to 30 inclusive and a: an even number ranging (mm 4 when the number of cycloaliphatic rings is 2 to 10 when the number of cycloaliphatic rings is 5 inclusive.

4. The mixture of amides formed from a mixture of saturated monocarboxylic acids containins from two to five cycloaliphatic rings per molecule individual acids of which have the generic formula cant-:02, wherein n is a num-