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Publication numberUS2514954 A
Publication typeGrant
Publication dateJul 11, 1950
Filing dateOct 31, 1947
Priority dateOct 31, 1947
Publication numberUS 2514954 A, US 2514954A, US-A-2514954, US2514954 A, US2514954A
InventorsJohnson James M, Mark Francis L, Murray Jelling
Original AssigneeNostrip Inc
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Surface active composition and method of making
US 2514954 A
Abstract  available in
Previous page
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Claims  available in
Description  (OCR text may contain errors)

Patented- Julyll, 1950 SURFACE ACTIVE COMPOSITION AND METHOD OF MAKING James M. Johnson and Francis L. Mark, New

York, and Murray Jelling, Brooklyn, N. Y., assignors to Nostrlp Inc., a corporation of Delaware NoDrawing. Application October 31, 1947,

Serial No. 783,444

8 Claims. 1

This invention relates to a surface active agent and the method of making it. It relates also to asphalt and like bituminous compositions including the agent as an additive.

The invention is particularly useful in mak ng improved paving compositions, as, in improving the coating of wet stone by bituminous materials, bonding of the materials to the stone, and resistance to separation after long soaking in water. It will be illustrated, therefore, by description in connection with such use.

The invention relates to additives of the class described in the following patents to James M. Johnson: No. 2,426,220, issued August 26, 1947; No. 2,386,867, issued October 16, 1945; and No. 2,419,406, issued April 22, 1947.

- Our new product is fiowable, as first made. When cold it remains flowable when mixed with only a small proportion of solvents such as relatively inexpensive petroleum or coal tar distillate products while maintaining effectiveness of the additive in asphalt compositions.

Briefly stated, our invention comprises the" method of making an amido-amino-amine soap by reacting a polyamine containing at least 3 amino groups with an acid mixture consisting essentially of higher fatty acids and rosin acids, in proportion to leave unreacted at least one amino group of the amine, and then heating the resulting amine soap at an elevated temperature causing decomposition of the soap group of the higher fatty acid with the amine, so as to form an amido group and leave the soap of the rosin acid in undecomposed condition.

The invention includes also the amido-aminoamine soap in which the amido group includes the acyl radical R.CO. of a higher fatty acid and in which the acid radical represented in the amine soap is that of a rosin acid such as abietic.

The invention comprises, in addition, compositions of bituminous paving material including the above mentioned product as additive, as, for instance, an asphalt composition including 0.2 to 0.7 part of the soap to 100 parts of the asphalt, preferably with a diluent of kind to be described.

The invention will be illustrated in greater detail by description in connection with my preferred surface active agent, namely, oleyl amidoamino-amine abietate, the amine serving as the base for this compound being diethylene .triamine. 1

In making this compound, 1 mol of diethylene triamine is mixed with 1 mol of oleic acid and 1 mol of abietic acid. The mixture is then heatheating (2) (A) R.CO.NH.C1H4.NH.C1H4.NH3.OOC.R' (B) amido-amlno-amine soap In the first of the above reactions, there is formed the disoap (A) of the oleic acid and the abietic acid. In the second reaction, which is produced by controlled heating, water is evolved from the oleic acid soap group at the left in the formula as written. This group is decomposed to the amide group R.CO.NH. We have discovered that the abietate soap is not decomposed at a temperature as low as that which is "adequate todecompose the oleic acid soap; we select such temperature for this heating that the abietate soap remains in undecomposed condition. This gives a finished product that contains the oleic acid amide, the abietate soap, and a freeamino group such the .NH. shown the Formula B above. The decomposition of the disoap first formed into the amido-amino-amine soap desired is followed by titration of specimens of the mixture being heated. This titration is made .with a standard aqueous solution of sodium hydroxide with phenolphthalein as the indicator. The soap 1 groups which remain, as for instance, .NH3.OOC.R', titrate as so much free acid whereas the amido group R.CO.NH. is not saponifiable. The decomposition reaction is considered to be complete to the desired step when 1 mol of the sodium hydroxide will neutralize, that is, saponify, 1 mol of the amido-amino-amine soap.

The reaction may be followed approximately by the proportion of water eliminated, although this control is not entirely accurate and may be misleading, because the escape as vapor of the liberated water is retarded by retention of the water in the soap, possibly by hydrate formation. The presence and the proportion of the amino and soap groups remaining in the formula for the product are shown by titration of the soap with standard hydrochloric acid or like acid with methyl orange as the indicator. One mol of the product which includes 1 unreacted or free amino group (.NH.) and 1 soap group (.NH3.OOC.R) will, in this titration, require 2 mols of hydrochloric acid.

- The Formula B above may be considered as the type formula for our improved product, RCO.

' shown in' Equation 1 above.


In this formula, RC0. and R'.C00. have the same meaning as above; X represents the residue of a polyamine containing originally 3 to 6 amine groups, the residue being the amine less 2 amine groups and preferably less 2 primary amine (.NHz) groups. resented by X are Examples of higher fatty acids that may be used as the R.COOH of Equation 1 above and to furnish the acyl radicals R.CO. of compound (B) are oleic,-l inoleic, linolenic, and lauric acid.

As the rosin acid to furnish the molecule R'COOH in Equation 1, we used abietic acid, rosin, the rosin acid fraction of talloil, or the like.

As the amine used, diethylene triamine is In place of this amine, we may substitute, on either a mol for mol or an equal weight basis, triethylene tetra- Examples of such residues repused in proportion less than that required theoretically to react with all of the amine groups of the selected amine. Whenthe amine used is a triamine, as, for instance, diethylene tri-- acid is not over'4 mols and preferably about 3.5

to 3.8. In the case of talloil having an acid value of 168 and an average molecular weight of 334, we use 6.5 parts by weight. to'l part by weight of diethylene triamine. With the tetramine and pentamine, we keep this same, weight ratio of 6.5 parts of the selected mixed organic acids to mine, tetraethylene pentamine, dipropylene trlamine, tributylene tetramine, pentaethylene hex-. amine and the like polyamines containing 3 to 6 or so amine groups to the molecule.

As the diluents we prefer light petroleum fuel oil such as No. 2 having a relatively high aro- Theselected organic acids and the polyamineused in forming the soaps as shown in Equation 1 are mixed in liquid condition at room temperature or at elevated temperatures as required to melt any normally solid ingredient, say at 80-100 C.

For effecting the partial dehydration according to Equation 2, there is used a temperature adequate to decompose the fatty acid soap without decomposing the rosin acid soap group. Thus there is used to advantage temperatures within the range 90 to 120 C. and preferably about 110 to 150 C. At the lower temperatures within the above ranges the reaction is slow and is difficult to complete in a period of time that is satisfactory commercially.

It is to be understood that reactions (1) and (2) may be made to occur at the same time. In fact, we preferably make these two reactions si multaneously. Thus we mix the selected higher fatty and rosin acid with the amine at a temperature of about 90 to 100 0. Under these conditions, the heat of reaction of the organic acids with the amine raises the temperature to about 120125 C. or so, the exact temperature depending upon the size of the batch and other commercial conditions afiecting heat loss. At this higher temperature the disoap, formed as in Equation 1 above, undergoes decomposition to the amido-amino-amine soap of Formula B.

As to proportions, the organic acid mixture s 1 part of the amine.

Except as specifically stated to the contrary, all proportions are expressed herein as parts by weight.

It will be noted that, in our method and composition, the acid used consists essentially .of the higher fatty acid and rosin acid. It is not required to use any other acid in addition. With only a very limited dilution of our product with petroleum fuel oil or other suitable liquid diluent, we make homogeneous, readily flowable solutions that may be withdrawn from tank cars or drums without applying any externalheat and that are readily incorporated into" heated. or cut-back bitumen. v

' By contrast we have made from the polyamine' .and the acid mixture consisting essentially of the higher fatty acids and rosin acids, surface active agents in which there was not the combination of unreacted amine group, fatty acid amide, and a rosin acid soap. The product so made did not give a readily flowable liquid unless there was present an additional large excess of acids as diluent.

Example 1 rial is in the fluid state. Then 1 mol of diethylene' triamine at 25? C. is added and the three reactants are mixed thoroughly. During the reaction the temperature rises to to C. and the disoap is formed.

The material is then heated to C. over a period of-2 to 10 hours and held at 150 C. for about 1 hour. While the temperature is bein raised, the oleic acid soap is decomposed and water is evolved, the oleic acid soap portion of the molecule being converted to the oleic acid amide.

The product is soluble in liquid hydrocarbons. .When 6 to 9 parts of it are dissolved in 1 to 4 parts of fuel oil No. 2, the resultant product is a homogeneous liquid having an A. S. T. M. pour point of about 40 F. maximum. This solution also is effective as a surface active agent in asphalt, tar, and like bituminous composition, at a. concentration of 0.2 to 1 part for 100 parts of the said composition, the exact proportion required depending on the type and condition of the bitumen and of the mineral aggregate and also the method and type of construction in which the mixture is to be used.

Example 2 The procedure of Example 1 is followed except that (a) 1 mol of linoleic acid is substitutf r e 1 mol of oleic acid and (b) rosin is august 1 8 Substituted on the chemically equivalent basis for the abietic acid.

Example 3 The procedure of Example 1 is followed except that an amount of crude tall oil equivalent to 2 mols of acid is substituted for the oleic acid and abietic acid.

The crude tall oil or refined tall oil, the com position of which has not been radically changed in the refining process, is a particularly satisfactory material for the reaction. It consists of approximately 50% fatty acids and 50% rosin acids, thus supplying fatty acids and rosin acids known to contain substantial proportions of abietic acid.

Example 4 The procedure of Example 1 is followed except that the 1 mol of oleic acid is substituted by an equivalent weight of the mixed fatty acids of vegetable and animal oils as, for instance, cottonseed, cocoanut, linseed, or fish oil.

Example 5 In place of the fatty acid used in any of the numbered examples above, we substitute an equivalent weight of a fatty oil. Thus we may use in place of a mol of oleic or like acid, onethird of a mol of a vegetable or animal fatty oil such as cottonseed, cocoanut, linseed, or a fish oil. When such oils are used they are saponified by the amine, with the production of the compound shown in the Formula B above and glycerine as a by-product. It should be understood that one mol of rosin acids in used along with the fatty oils, to provide the acid shown in the Equation 1 a R'COOH.

Example 6 Any one of the surface active agents made as described herein or more particularly as described in Example 1-5 above is mixed with a flowable bituminous material in proportion to improve the adhesion of the material to sand, gravel, slag, stone, or like paving aggregate in either wet or dry condition. Thus there is used V4 to 1 part of the surface active agent to100 parts of asphalt, the exact proportion required depending upon the condition and type of aggregate which is to be bonded with the asphalt.

In any case, the bituminous material used is flowable, that is flowable at somewhat elevated temperatures or when out back with a solvent. Examples of such fiowable bituminous materials are native lake asphalt, asphalt cutback with a hydrocarbon diluent, petroleum still residues, and heavy coal tars.

When incorporated in such bituminous materials, our additive increases the adhesion of the bitumen to the aggregate whether the latter is incorporated wet or dry and in a pavement increases the stripping resistance and stability on long exposure to the weather. As compared to additives used heretofore, the product is cheaper for a'given level of eflectiveness in coating wet aggregates, resistance to stripping, and long range stability in the presence of moisture. It is flowable at summer temperatures. and on very slight dilution down to temperatures of 40 1".

It will be understood also that it is intended to cover all changes and modifications of the examples of the invention herein chosen for the purpose of illustration which do not constitute departures from the spirit and scope of the invention.

What we claim is:

1. In making an amido-amino-amine soap in which the amide group is essentially derived from fatty acids and the soap group from rosin acids, the method which comprises forming a mixture of one mol of a polyamine containing 3 to 6 amino groups with organic carboxylic acids, the number of mols of acids used being at least 2 mols and not more than the number of amino groups less 1 and the acids consisting essentially of higher fatty acids and rosin acids, maintaining contact between the said acids and the amine until the acids are substantially completely reacted with the amine, with the production of fatty acid and rosin acid soap of the amine, and then heating the soap at a temperature of C. to 180 C. until decomposition with the liberation of water converts a substantial part at least of the fatty acid soap present to an aliphatic amide, the rosin acid soap portion rema' 'ng in the product. i

2. The method described in claim 1, the amine used bein diethylene triamine and the acids used being, higher fatty acids and rosin acids, the proportion of higher fatty acids used being approximately 1 mol to 1 mol of the rosin acids,

3. The method described in claim 1, the temperature of heating being to C.

4. The method described in claim 1, the heating with the liberation of water being discontinued when titration with alkali shows that only approximately 1 mol of the 2 mols of acid originally used is titratable by the alkali.

5. As a. new compound, an amido-amino-amine soap of the type formula R.CO.NH.X.NH3.OOC.R' in which RCO. represents the acyl group of a higher fatty acid, R'.COO. represents the radical of a rosin acid, and X represents a polyamine containing normally 3 to 6 amino groups less 2 of the said amino groups.

6. As a new compound, an amido-aminoeamine soap of the type formula in which R.CO. represents the acyl group of a higher fatty acid and R'.CO0. represents the radical of a rosin acid.

7. As a new compound an amido-amino-amine abietate of the type formula REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,191,295 Dohse et al Feb. 20, 1940 2.317359 Johnson Apr. 27, 1943 2,371,212 Bassford et a1 Mar. 13. 1945 2,386,867 Johnson Oct. 16. 1945 2,419,404 Johnson Apr. 22, 1947 2,428,220 Johnson Aug. 26, 1947

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2191295 *Nov 27, 1936Feb 20, 1940Ig Farbenindustrie AgBituminous materials
US2317959 *Mar 1, 1941Apr 27, 1943Nostrip IncBituminous composition
US2371212 *May 28, 1942Mar 13, 1945 Shellac modified with primary
US2386867 *Dec 8, 1942Oct 16, 1945Nostrip IncBitumen treating agent
US2419404 *Mar 9, 1943Apr 22, 1947Nostrip IncMethod for higher fatty acid polyamine soaps
US2426220 *Sep 2, 1942Aug 26, 1947Nostrip IncBituminous composition having increased adhesion to mineral aggregate
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US2663648 *Nov 21, 1950Dec 22, 1953Jelling MurrayThermally stable bituminous bonding compositions
US2679462 *Dec 18, 1951May 25, 1954Petrolite CorpStrip-resistant bituminous composition
US2724700 *Jul 3, 1951Nov 22, 1955Atlas Powder CoSolid compositions containing urea and polyoxyethylene ethers of resin alcohols
US2737509 *Nov 19, 1953Mar 6, 1956Jelling MurrayCarboxylic acid salts of n-dialkylaminoalkylamides
US2772966 *Jul 28, 1954Dec 4, 1956American Cyanamid CoCationic rosin sizes
US2863785 *Nov 19, 1953Dec 9, 1958Jelling MurrayThermally stable bituminous bonding materials
US2874174 *Mar 15, 1955Feb 17, 1959Cincinnati Milling Machine CoBituminous bonding compounds
US2875219 *Mar 15, 1955Feb 24, 1959Cincinnati Milling Machine CoBituminous bonding agents
US2891873 *Feb 14, 1957Jun 23, 1959Maguire Ind IncAsphalt additives
US2937106 *Sep 11, 1957May 17, 1960American Cyanamid CoDialkylpolyaminopolyalkalene amides as asphalt antistripping agents
US2996398 *Apr 18, 1958Aug 15, 1961Cincinnati Milling Machine CoBituminous compositions
US2996399 *Apr 18, 1958Aug 15, 1961Cincinnati Milling Machine CoBituminous compositions
US3030219 *Aug 18, 1958Apr 17, 1962Olin MathiesonAsphaltic composition
US3047414 *Aug 28, 1957Jul 31, 1962Katz JacobAsphalt compositions and wetting and anti-stripping agents for use in connection therewith
US3284388 *May 31, 1963Nov 8, 1966Grace W R & CoImidazoline-amine soap-rubber mixtures as asphalt additives
US3322706 *Jun 11, 1962May 30, 1967Continental Oil CoAsphalt compositions and method of improving spot testing to select asphalts
US4234414 *Sep 28, 1978Nov 18, 1980The Dow Chemical CompanyPhosphate beneficiation process
US4450011 *Sep 20, 1982May 22, 1984Westvaco CorporationCationic bituminous emulsions
US4537762 *Nov 14, 1983Aug 27, 1985Bernel Chemical Co.Hair compositions containing mixtures of quaternary ammonium compounds and tertiary amine salts of long-chain acids
US4548810 *May 8, 1981Oct 22, 1985Albert ZofchakMethod of lubricating the skin
DE1060858B *Nov 19, 1954Jul 9, 1959Carlisle Chemical WorksVerfahren zur Herstellung von hitzebestaendigen Bitumenbindemitteln
U.S. Classification530/221, 106/232, 106/269, 554/59, 106/219, 106/284.4
International ClassificationC11C3/00
Cooperative ClassificationC11C3/00
European ClassificationC11C3/00