US2812339A - Graft polymer-fortified bitumen additives - Google Patents

Description

United States Patent Ofitice GRAFT POLYMER-FORTIFIED' BrrUMEN ADDITIVES Mathew L. Kalinowski, Chicago, and Lowell T. Crews, Homewood, Ill., assignors to Standard Oil Company, Chicago, Ill., a corporation of Indiana N Drawing. Application July 30, 1954, Serial No. 446,965

' Claims. (Cl. 260-4045) The present invention is directed to improvements it bitumen compositions, and particularly to improvements in mineral aggregate coating compositions, and more particularly relates to bitumen compositions having improved adherence to damp or wet mineral aggregates, and to improvements in the method of making such compositions.

Residual oils and/or bituminous materials used in the preparation of pavements and roads do not coat and adhere well to mineral aggregates unless the-aggregate is substantially dry, and for this reason, in conventional pavements or road construction practice, it is customary to dry the mineral aggregate by suitable well known methods; Furthermore, water entering the road or pavement during service may have a detrimental etfect in that it may displace the oil or bitumen from the surface of the aggregate and thus diminish the bonding effect of the oil and/or bitumen. This materially shortens the life of the road or pavement requiring frequent repairs and is, therefore, uneconomical.

Mineral aggregates employed in road or pavement construction range in character from hydrophilic to hydrophobic. In general, siliceous and acidic minerals, such as sands and gravels, tend to be hydrophobic, while calcareous alkaline minerals, such as limestone, tend to be hydrophilic. It has been observed that the mineral aggregates appear to have a greater attraction for water than for oil or bitumens and that it is difiicult to obtain, by conventional methods, complete or satisfactory coating of aggregates by oil or bitumen when water is present. Furthermore, even though satisfactory coating is obtained by using dry aggregate, the oil or bitumen tends to be displaced if water enters the pavement or road.

It is known that the coating of damp or Wet mineral aggregates by oil or bitumen may be efiected and the resistance of the coating to displacement or stripping by water improved by treating the aggregate with small amounts of a water-soluble soap of a fatty acid in conjunction with a water-soluble salt of a polyvalent heavy metal or activator. For optimum results with these reagents, the relative amounts of the two reagents must be carefully adjusted. Thus, when a divalent heavy metal is used as activator, the amount of soap used should be substantially one mole per mole of activator; with a trivalent metal, between one and two moles of soap per mole of activator. Use of larger amounts of soap than this diminishes the eifect obtained, and this diminution of effect increases with excess of soap over the proportions given until, When the amount of soap becomes equivalent to the activator, i. e., two moles of soap per mole of divalent metal or three per mole of trivalent metal, the beneficial effect of the reagent substantially disappears.

The above method hasthe disadvantage that the relaare critical and must be carefully adjusted for optimum results. Use of an excess of soap over the optimum amount diminishes rather than enhances the eifect obtained; the use ofexcess heavy metal to avoid the danger of excess soap is not harmful but increases the cost. Furthermore, the two reagents must be weighed or measured out and added to each batch, as neither is soluble in the oil or bitumen; while this disadvantage may be partially overcome under favorable conditions by using, in place of the soap, a fatty acid dissolved in the oil or bitumen, this expedient is effective only under favorable conditions of low moisture content of the aggregate, adequate and eflicient mixing, etc. Under conditions which are not at all severe, such as appreciable amounts of water and/ or facilities for only moderately eflicient mixing, fatty acids appear not to be sufliciently soluble in water to reach and react with the heavy metal ion to the requiredextent, and if added directly to the mixture or dissolved in the oil or bitumen, are practically without effect.

Another important disadvantage of the above method is that a heavy polyvalent metal salt must be-used with the. soap. Furthermore, it has been found that while some limestones appear capable of adsorbing or reacting with polyvalent heavy metal ions and accordingly respond to some degree to the above method, a great many others do not, and with these it is diiiicult or impossible to obtain a good coating by the above method. Also, since the foregoing method is not in general satisfactory with limestone, a great many natural mixed aggregates such as gravels containing both siliceous and calcareous particles will have only a portion of the particles coated.

In addition to the use of polyvalent fatty acid soaps in bitumens as mineral aggregate coating agents, certain organic nitrogen compounds, such as those obtained by reacting a polyamine with a fatty acid under conditions to form essentially amides, have been used for this purpose. However, although the amide-type asphalt additives are effective coating agents for acidic mineral aggregates, such as sands and gravels, they are inefiective on alkaline mineral aggregates such as limestone. It is a primary object of this invention to avoid the formation of amides in the preparation of the fatty acid-amine type additive for bitumens and thereby retain the effectiveness of the additive in fortifying the coating material for application to acidic and alkaline aggregate. Another object of the present invention is to provide a coating composition for acidic and alkaline mineral aggregates which will not be stripped therefrom by aqueous liquids. Still another object of the invention is to provide a coating composition for acidic and alkaline mineral aggregate-s which can be applied without the necessity of drying the mineral aggregate and which will adhere thereto even in a wet condition. Another object of the invention is to provide a method of preventing stripping of the coating composition from acidic and alkaline mineral aggregates by water after the road and/or pavement is constructed. A further object of the invention is to provide a method of promoting the adherence of oil bituminous materials to siliceous and limestone aggregates without the necessity of drying the same. Other objects and advantages of the invention will become apparent as description thereof proceeds.

In accordance with the present invention, bitumens, such as for example, road oils and asphalts having improved mineral aggregate coating properties, especially with respect to wet acidic and alkaline mineral aggregates, are obtained by incorporating in such bitumens from about Patented Nov. 5,

3 0.25% to about and preferably from about 0.5% to about 3%, by weight, based on the bitumen, of the product obtained by reacting, in the presence of an ethylene oxide-propylene oxide graft polymer, an aliphatic polyamine having from 2 to about 20 carbon atoms per molecule with the propane-insoluble fraction obtained inthe propane extraction of crude fatty materials, such as animal, marine and vegetable fats, fatty oils or fatty acids split therefrom, under conditions which avoid the formation of amides so that a product essentially free of amido groups is obtained. Since amidation of amine soaps is brought about by the loss of water at high temperatures, the reaction of the aliphatic polyamine with the aforementioned propane-insoluble fraction is carried out at tempera tures below about 150 F., preferably below about 125 F and more preferably at substantially ambient temperatures of from about 60 F. to about 125 F., for example about 100 F. to about 125 F., and for a contact time of from about hour to 1.0 hour.

We have discovered that the addition to the mixture of alkylene polyamine and propane-insoluble fractions of a relatively small amount of an ethylene oxide-propylene oxide graft polymer corresponding to the general formula HO(C2H40)a(C3H60)b(C2H40)c-H of molecular weight within the range of about 1000 to about 4500 wherein a, b, and c are integers, the sum of a and 0 being within the range of about 2 to about 20, and b having a value of from about to 60, makes possible the production of very effective asphalt additive at relatively low temperatures.. Thisnonionic graft polymer is prepared as follows: polyoxypropylene glycol is made by condensing propylene oxide in the presence of moisture or by con densing propylene glycol in the presence of a catalytic amount of sodium hydroxide. The polyoxypropylene glycol is then reacted with ethylene oxide to produce the ethylene oxide-propylene oxide graft polymer. These products are known commercially as Pluronics and are produced by the Wyandotte Chemical Company.

Stripping properties of bitumen coating material containing reaction product prepared from the propane-insoluble material-aliphatic amine reaction product in the presence of the nonionic polymer are excellent. The reaction mixture containing the nonionic polymer is less viscous than reaction mixtures containing the propaneinsoluble fraction and aliphatic polyamine reaction prodnot without the added nonionic polymer and hence the processing and transfer of the additive product by pumping and incorporation of the product in the asphalt coating material is greatly facilitated when the nonionic polymer is present in the additive. The nonionic polymer is incorporated in the reaction mixture in amounts to correspond to about 0.5% to about 10% by weight of the propane-insoluble (Ebony Fat as defined below)- alkylene polyamine reaction product. The addition of the nonionic polymer may be made to the heated dispersion of Ebony Fat in hydrocarbon oil diluent or to an aromatic hydrocarbon-rich hydrocarbon oil dispersion of the aliphatic polyamine. The presence of the polymer at the time of initial contact of the propane-insoluble component with the polyamine makes possible the substantial completion of the reaction at substantially ambienttemperatures in a relatively short time, usually less than 30 minutes when temperatures. of about 125 F. are employed, thus avoiding amide formation.

The propane-insoluble fraction'obtained in the propane extraction of crude fatty materials of the type above described contains, inaddition to fats and fatty acids, esters of fatty acids and sterols. These propane-insoluble fractions which are obtained as residue of the order of about 0.2% to about 10%, by weight, contain most of the color bodies which are present in the crude fatty materials, and because of their very dark color, are referred to in' commerce as Ebony Fats. The properties of representative samples of thepropane-insoluble residues obtained from animal fats and from vegetable oils, on a water-free basis, are approximately as follows:

Residue Residue Property from from Animal Vegetable Fat 011 Viscosity, Seconds Saybolt at 100 F. 6, 500 930 Viscosity, Seconds Saybolt at 130 F. 1, 860 430 Viscosity, Seconds Saybolt at 210 F. 300 100 Ash. Weight percent 1. 3 06 A.P.I. Gravity, degrees 10 1G Acidity, A.S.T.M. (D4364) Mg. KOH/gm.. 41 G3 Pentane Insoluble, Weight pereent 2. 6 4.2 Benzene Insoluble, Weight percent .7 1.0 Sapomfication Number 190 170 Fatty Acid 31 Iodine Number 58 106 The above properties are, of course, merely illustrative,

and it should be understood that both the amount and the 5i vegetable fatty materials with propane to obtain Ebony Fat" is well known to those skilled in the art and one example thereof is commonly referred to as the Solexol Process, currently and commercially used and described in Industrial and Engineering Chemistry" of February 1949, page 280. The system for effecting such extractive fractionation is described in detail in U. S. 2,505,338 and U. S. 2,521,234. For most crude animal fats, marine oils and vegetable oils, and similar fatty materials including acids split from such fats, the fractionation conditions are employed which givea propane-insoluble residue of about 1%, i. e., about 0.2% to about 2%, although in some cases such residues may be as large as 5% or even 10%. i The amine reactant employed in preparing the additive of the present invention is an aliphatic polyamine, particularly an alkylene polyamine containing at least two primary amino nitrogen atoms. Examples of alkylene polyamines suitable for the herein-described purpose are ethylene diamine, propylene diamine, diethylene triamine diamylene triamine, triethylene tetramine, tripropylene tetramine, diethylenepropylene tetramine, tetraethylene pentamine, tetrabutylene pentamine, diethylenedipropylene pentamine, butylene diamine, dihcxylene triamine, and the like, or mixtures thereof. For example, a suitable polyamine product is a crude diethylene triamine containing minor amounts of ethylene diamine and triethylene tetramine. Other suitable polyamines include those having the general formula RNH( CH2 sNHz in which R is preferablya Cw to C18 aliphatic chain, and which are obtained by condensing the suitable amine with acrylonitrile andhydrogenating to the corresponding diamine. Commercially available polyamines of this type are those marketed by Armour and Company as Duomeens, which are prepared by the condensation of a dodecyl (coco) amine or an octadecyl (tallow) amine with acrylonitrile, followed by hydrogenation to the corresponding diamine product; these products are marketed as Duomeen C and Duomeen T, respectively.

In the preparation of the Ebony Fat and polyamine reaction product, it is, preferable, although not essential, that the Ebony Fat be first dehydrated to obtain an essentially water-free product, or a product having not more than about 0.5% water. This can be readily accomplished by diluting the Ebony Fat with from about 10% to about 200% of a suitable hydrocarbon solvent,

by heating the diluted mixture at a temperatureof about" 210 F. to 290 F. while stirring and/or blowing with air or other suitable gaseous medium until the water content has been reduced to the desired value. Following the dehydrogenation step the Ebony Fat-graft polymeroil mixture is cooled to a temperature below about 150 F., preferably by the continued inert gas blow such as for example a passage therethrough of cold air. If the Ebony Fat contains an undesirable amount of contaminants, they can be removed by permitting the hot dehydrated solution to settle, and decanting the di-' luted solution of purified Ebony Fat. If desired, the diluent may be removed from the dehydrated Ebony Fat by suitable means, such as by distillation under vacuum; however, we prefer to react the diluted Ebony Fats with the polyamine. As indicated above, this dehydration of the Ebony Fat may be carried out in the presence of the added nonionic polymer or if the Ebony Fat contains undesirable contaminants the polymer may be added .to the decanted solution? of dehydrated Ebony Fat. 7

Aromatic-rich hydrocarbon solvents suitable for this purpose are preferably those having boiling points, above about 220 F. at atmospheric pressure, for example, from about 220 F. to about 600 F., and includesmononuclear aromatic hydrocarbons or condensed ring arm matics, such as naphthalenes and mixtures of the higher boiling mononuclear aromatic hydrocarbons and polynuclear aromatic hydrocarbons. A preferred source of mixed aromatic hydrocarbons, suitable for the purpose, is a light catalytic cycle stock obtained from a powdered or a'fluid-type catalytic-type hydrocarbon cracking operation in which gas oil or heavier hydrocarbons are cracked at a temperature of 800 F. to 1050 F. under a pressure of about atmospheric to 50 pounds per square inch, in the presence ofsuitable fluidized powdered catalyst, such as for example silicaalumina, silica magnesia, and other well-known cracking catalysts. A method of conducting a fluidized cracking operation is described in U. S. 2,341,193, issued to Fred W. Scheineman, February 8, 1944. Fractions from the process heavier than gasoline, depending upon their boiling range, are commonly referred to as light catalytic cycle stock, heavy catalytic cycle stock and catalytic recycle resid, which usually are cycled to cracking. A li ht catalytic cycle stock particularly well suited as a diluent for the dehydration of the Ebony Pat is a fraction having an aromatic content of at least about 40% and a distillation range between about 425 F. and 560 F. A typical analysis of a suitable light catalytic cycle stock shows the material to be composed substantially of about 10% normal C12 to C20 parafiins, about 45% of other parafiins, and naphthenes, about mono-nuclear aromatics, which are mainly monoto hexa-alkylated benzenes, and about 40% polynuclear aromatics, which are mainly alkyl naphthalenes, largely methylated naphthalenes. While we prefer to use a light catalytic cycle stock of the type described, hydrocarbon fractions from other catalytic conversion processes or thermal hydrocarbon conversion processes are suitable, provided they have an aromatic content of at least about 20%, and a distillation range of above about 220 F. If desired, a part of the bitumen coating material, if a road oil, may be used as diluent for the Ebony Fat for the dehydrating operation either in the presence or absence of the nonionic polymer.

The dehydrated Ebony Fat preferably containing the nonionic polymer and preferably, but not necessarily, in solution in the light catalytic cycle stock or other suitable diluent, is reacted with the polyaminein the ratio of from about 20:1 to about 5:1, and preferably in a ratio of from about 12:1 Ebony Fat to the polyamine, at a temperature of about 60 F..to about 150 F., for example from about 100 F. to about 125 F., for not more than about one hour. If desired, the polyaminemay be added to the Ebony Fatin the form of a dispersion in a hydrocarbon oil, preferably an aromatic hydrocarbonrich hydrocarbon oil containing dispersed therein the nonionic ethylene oxide-propylene oxide polymer. By conducting the reaction in the manner herein described, and maintaining the finished product, until ready for use, at a temperature below about 150 F. and preferably below about 125 R, an eflicient stable coating agent essentially free of amido groups is obtained.

The preparation of polyamine-Ebony Fat reaction products is illustrated by the following examples:

EXAMPLE I A hydrocarbon oil solution of Ebony Fat consisting of 61 partsby weight of Ebony Fat and 39 parts by weight of light catalytic cycle stock was dehydrated according to the above procedure. The equivalent weight of the dehydrated solution was 1212. To 303 grams of the dehydrated solution, that is, equivalent weight, was added a mixture of 17.5 grams of crude diethylenetriamine (equivalent weight 56) diluted with 71 grams of light catalytic cycle stock. The reaction mixture was intimately contacted by mechanical stirring at 120 F. for a period of 15 minutes. The reaction mixture was used as a control sample in comparing the performance of the reaction product prepared in Example II.

As indicated in Example I, a 25% excess of the polyamine over that required to react with the Ebony Fat was used. In general, we use from about 5% to about 50%, preferably about 25%, excess amine in preparing the Ebony Fat-alkylene polyamine reaction product containing the associated nonionic graft polymer.

EXAMPLE II To 303 grams of the Ebony Fat stock solution prepared as in Example I was added a dispersion of 17.5 grams of crude diethylene triamine in 66 grams of light catalytic cycle stock containing dispersed therein 5 grams of Pluronic-62 having a molecular weight of about 2900, and showing by analysis an oxygen content of about 29.8%, that is, the apparent value of (a+c) of this product in the above general formula is about 13 and of b is about 40. The mixture was intimately contacted for a period of 15 minutes at a temperature of 120 F.

Samples of the products produced in Examples 1 and II were used in the tests described below.

While we have not been able to definitely determine the composition of the Ebony Fat-polyamine reaction product, we believe the reaction product comprises essentially the amine soaps of the fatty acids contained in the Ebony Fat, together with unreacted esters and alcohols, i. e., sterols. The presence of from about 0.25% to 10% 1 by weight of the nonionic polymer (based on the weight of the reaction product) improves the stripping properties of the coating material to which the reaction product is added. The reaction mixture, exclusive of diluent oil, will usually consist essentially of from about 65% to about by weight of Ebony Fat, as defined hereinabove, from about 5% to about 25% by weight of polyamine reactant, and from about 0.2% to about 10% by weight of the nonionic polymer.

The asphalt component of the herein described composition may be any bitumen which is useful for the coating of mineral aggregates used in the making of roads, highways, etc., or for the coating of other materials or surfaces where a water-resistant bond between the surface and the asphalt is advantageous or necessary. The term asphalt as employed herein is intended to be synonymous with bitumen and to cover a liquid, semi-solid, or solid plastic bituminous material of the type employed in making or surfacing of highways and/or pavements, caulking agents, sealing compounds, water impervious paints, roofing materials, etc. Such asphalt or bituminous materials are mixtures of hydrocarbons of natural or pyrogenous origin, and are usually derived from petroleum or coal but may occur as such in nature. Asphalts V may be derived as distillation resids or cracking resids with or without oxidation by air-blowing or by catalytic A specific example of a liquid asphalt of oxidation.

the type commonly employed in the preparation of highways,.etc., is a petroleum residuum fiuxed with a light aromatic diluent boiling in the range of 400 'F. to 700 F. to give a cut-back product of the following specifi Tests on distillation:

Residue- ASTM penetration at 77 F 120-300. ASTM ductility at 77 F NLT 100. S01. in CCl4, percent NLT 99.5. Oliensis spot test Negative.

' Not less than.

I Not more than.

Normally solid paving asp halts of the 40 to 200 penetrations grades commonly used in road building fallwith in the following specifications:

40-200. Not less than 100. 7 Negative.

Not less than 99.5. Not less than 0.9901.000. Not less than 475.

Not more than 0.5.

Not less than 70-75.

The effectiveness of the herein described Ebony Fatpolyamine reaction products in enhancing the adhesion of asphalts to wet mineral aggregrates is determined by subjecting blends of asphalts and the described reaction products to one or more of the following tests:

A. Modified Colorado Coating Tests Twenty grams of Ottawa sand or 20 grams of a 20 to 35 mesh limestone are weighed into a 2 oz. container and covered with one-half inch of distilled water.

One

gram of the additive-containing asphalt is floated on the water, the mixture then shaken for thirty seconds, and the extent of coating determined by visual'inspection; the results are expressed as Percent Coated.

B. Wyoming Stripping Test Approximately 25 grams of Lander chips, allpassing the in. sieve and retained on the No. 4 sieve, is mixed by hand with 1.0 gram of fortified asphalt until the best possible coating is obtained.

The mix is placed in an oven at 140 F. for 18 to 24 hours after which it is thoroughly remixed and is allowed to cool to room temperature. The

sample is then immersed in distilled water at a temperature of 120 F., and is maintained at this temperature. for a period of 24 hours. At the end of this period the area of the aggregate remaining coated is determined visually while the sample is still under water. Any thin or translucent areas are considered to be coated. The Wyoming Highway Department requires that 80% or greater coat-.

ing be retained in this test.

Samples of the above-described liquid asphalt designated as MC (medium curing)-2 asphalt containing sufiicient diluted additive, as described in Examples I and II above, to provide 1.0% and 2.0% by weight of the active additive based on the medium curing asphalt (MC-2),

were tested in the Modified Colorado Coating Test and Wyoming Stripping Test. The results are given in Table I below:

TABLE I Coating Additive Strip- Additlve in MIC-2 Cone, ping, percent San Limepercent percent stone. 10 percent None 0 0 10 I 1 25 90 40 2 60 90 80 H 1 50 90 50 2 85 90 95 PluronicL-GZ 1 2 5 5 10 The results in Table I show the superiority of the asphalt containing the nonionic polymer associated with the Ebony Fat+alkyleneaminereaction product additive particularly at the 2% level additive concentration.

The concentration of nonionic polymer in the additive was about 2.5% based on the weight of the reaction product in the asphalt and about 0.025% and 0.05% by weight respectively in the asphalt at the 1.0% and 2.0% levels of concentration of active additive in the asphalt.

Heat stability of the additives prepared in Examples I and H were tested by heating and stirring these samples of additive for varying lengths of time at 210 F. and retesting asphalts containing the reheated additive for coating ability and stripping resistance. The results are shown in Table II. v

TABLE II Time Sand Limestone Stripping Additive in MC-2 Slllll;8%&t

minutes 1% 2% 1% 2% 1% 2% Per- Per- Per- Per- Per- Percent cent cent cent cent cent 0 25 so 90 90 so 90 a0 90 no 95 3o 85 120 30 95 so 95 so 05 150 25 9s 85 no as 0 50 90 so as 30 75 05 so 00 05 90 75 95 so 95 so 05 75 95 s5 9s 70 95 75 100 so 95 0s 95 1 Percentages indicate percent surface remaining covered by coating material.

The coating ability and stripping qualities of the asphalt containing the reaction product and associated nonionic polymerwas not adversely affected by the heat treatment at the 2% concentration level and coating ability for sand at the 1% concentration level was much better than the coating shown in Example I. On the other hand, the heat treatment of the reaction product containing no associated nonionic polymer resulted in lowering the coating ability of the asphalt to which the additive was added below that of non-heated additive and the stripping properties of the asphalt were inferior to the stripreaction product containing the nonionic polymer.

Having thsu described our invention, we claim: 1. In the process for preparing. an additive suitable for use in bitumen comprising reacting at least one alkylene ping properties of the asphalt to whichthe heat treated polyarnine, having from 2 to about 20 carbon atoms, with Ebony Fat, which Ebony Fat is the propane-insoluble residue obtained in the solvent extraction of a crude fatty material selected from the class consisting of crude animal fats, fatty oils and fatty acids, crude vegetable fats,

fatty oils, and fatty acids, and mixtures thereof with action product being essentially free of amido groups, the improvement which comprises incorporating in the reaction mixture of said Ebony Fat and alkylene polyamine from about 0.5% to about by weight based on the weight of said Ebony Fat and alkylene polyamine in said reaction mixture, of an ethylene oxide-propylene oxide graft polymer corresponding to the general formula HO(C2H40)a(c3H60)b(C2H40)cH and having a molecular weight of about 1000 to about 4500 wherein a, b, and c are integers, the sum of a and c being within the range of about 2 to about 20 and b having a value within the range of about to about 60, and maintaining said reaction mixture at a temperature of from about 60 F. to about 150 F.

2. The improvement as described in claim 1 wherein the Ebony Fat is dehydrated to a water content not more than about 0.5% before contact with the alkylene polyamine to form said mixture of Ebony Fat with said alkylene polyamine.

3. The improvement as described in claim 1 wherein the reaction of the Ebony Fat with the alkylene polyamine containing said incorporated graft polymer is carried out in the presence of an aromatic hydrocarbon-rich hydrocarbon diluent.

4. The improvement as described in claim 1 wherein the alkylene amine component of the reaction mixture is crude diethylene triamine containing minor amounts of ethylene diamine and triethylene tetramine.

5. The improvement as described in claim 1 wherein the ratio by weight of Ebony Fat to alkylene polyamine in the reaction mixture is within the range of :1 to about 5: 1.

6. In the process for preparing an additive suitable for use in bitumen comprising reacting at least one alkylene polyamine, having from 2 to about 20 carbon atoms, with Ebony Fat, which Ebony Fat is the propane insoluble residue obtained in the solvent extraction of a crude fatty material selected from the class consisting of crude animal fats, fatty oils, and fatty acids, crude vegetable fats, fatty oils, and fatty acids, and mixtures thereof with liquified propane, said insoluble residue being insoluble in 6 to volumes of propane at a temperature of from about 140 F. to about 190 F. and constituting from about 0.2% to about 10% of the crude fatty material from which said insoluble residue is extracted, said reaction product being essentially free of amido groups, the improvement which comprises the steps of (I) blowing with an inert gas at a temperature of about 210 F. to 290 F. an intimate mixture of a hydrocarbon oil diluent containing said Ebony Fat and an ethylene oxide-propylene oxide graft polymer corresponding to the general formula HO(C2H40)a(c3H60)b(C2H40)cH and having a molecular weight of about 2900 wherein a, b, and c are integers, the sum of a and 0 being about 13 and b being about 40 to reduce the moisture content of said Ebony Fat to a value not greater than about 0.5%, (2) cooling the product of step 1 to a temperature below about 150 F., (3) adding to the dried, cooled product of step 2 sufficient alkylene polyamine to provide a reaction mixture containing an excess of the alkylene polyamine over that required to react with said Ebony Fat" and (4) intimately contacting the Ebony Fat" and alkylene polyamine of the reaction mixture at a temperature below about 150 F.

7. The improvement as described in claim 6 wherein the amount of graft polymer in the hydrocarbon diluent is within the range of from about 0.5 to about 10% by 10 weight of the Ebony Fat plus alkylene polyamine reactants in said diluent.

8. The process of claim 6 wherein the diluent is a hydrocarbon oil rich in aromatic hydrocarbons.

9. The method of preparing a hydrocarbon oil-diluted reaction product suitable for use as a bitumen additive comprising the reaction product of at least one alkylene polyamine, having from 2 to about 20 carbon atoms, with Ebony Fat, which Ebony Fat is the propaneinsoluble residue obtained in the solvent extraction of a crude fatty material selected from the class consisting of crude animal fats, fatty oils, and fatty acids, crude vegetable fats, fatty oils, and fatty acids and mixtures thereof, with liquified propane, said insoluble residue being insoluble in 6 to 30 volumes of propane at a temperature of from about F. to about 190 F. and constituting from about 0.2% to about 10% of the crude fatty material from which said insoluble residue is extracted, said reaction product being essentially free of amido groups, which method comprises the steps of (1) forming a mixture of said Ebony Fat in an aromatic hydrocarbonrich hydrocarbon solvent boiling in the range of from about 220 F. to about 600 F., (2) suspending said alkylene polyamine in an aromatic hydrocarbon-rich hydrocarbon solvent containing mixed therein nonionic graft polymer corresponding to the general formula HO(C2H40)a(C3H60)b(C2H40)cH and having a molecular Weight within the range of about 1000 to about 4500 wherein a, b, and c are integers, the sum of a and c being Within the range of about 2 to about 20 and b having a value within the range of from 15 to about 60, the amount of said graft polymer mixed in said aromatic hydrocarbonrich hydrocarbon solvent being sufiicient to provide in the reaction mixture of step 3 below from about 0.5% to 10% by Weight of said reaction product of Ebony Fat with alkylene polyamine, (3) intimately mixing at a temperature within the range of about 60 F. to about F. the suspension of step 2 with the mixture of step 1 to provide a stable graft polymer-dispersed reaction mixture containing Ebony Fat and alkylene polyamine in proportions to provide a ratio by weight of Ebony Fat to alkylene polyamine within the range of from about 20:1 to about 5:1 in said stably-dispersed reaction mixture, and (4) maintaining said stably-dispersed reaction mixture ata temperature not in excess of about 150 F. for a period of time sutficient to complete the reaction of Ebony Fat with alkylene polyamine not in excess of one hour.

10. The bitumen additive consisting essentially of Ebony Fat-alkylene polyamine reaction product, ethylene oxide-propylene oxide graft polymer and hydrocarbon diluent produced as described in claim 6.

References Cited in the file of this patent UNITED STATES PATENTS 2,438,318 Johnson Mar. 23, 1948 2,521,234 Leaders et al. Sept. 5, 1950 2,525,771 Cook et al. Oct. 17, 1950 2,663,648 Jelling Dec. 22, 1953 2,679,462 Monson May 25, 1954 2,728,682 Kalinowski et al Dec. 27, 1955 2,736,658 Pfohl Feb. 28, 1956 OTHER REFERENCES Schwartz et al.: Surface Active Agents, 1949, pages 202-207, 501.

Claims (1)

1. IN THE PROCESS OF PREPARING AN ADDITIVE SUITABLE FOR USE IN BITUMEN COMPISISING REACTING AT LEAST ONE ALKYLENE POLYAMINE, HAVING FROM 2 TO ABOUT 20 CARBON ATOMS, WITH "EBONY FAT", WHICH "EBONY FAT" IS THE PROPANE-INSOLUBLE RESIDUE OBTAINED IN THE SOLVENT EXTRACTION OF A CRUDE FATTY MATERIAL SELECTED FROM THE CLASS CONSISTING OF CRUDE ANIMAL FATS, FATTY OILS AND FATTY ACIDS, CRUDE VEGATABLE FATS, FATTY OILS, AND FATTY ACIDS, AND MIXTURES THEREOF WITH LIQUIFIED PROPANE, SAID INSOLUBLE RESIDUE BEING INSOLUBLE IN 6 TO 30 VOLUMES OF PROPANE AT A TEMPERATURE OF FROM ABOUT 140*F. TO ABOUT 190*F. AND CONSTITUTING FROM ABOUT 0.2% TO ABOUT 10% OF THE CRUDE FATTY MATERIAL FROM WHICH SAID INSOLUBLE RESIDUE IS EXTRACTED, SAID REACTION PRODUCT BEING ESSENTIALLY FREE OF AMINO GROUPS, THE IMPROVEMENT WHICH COMPRISES INCORPORATING IN THE REACTION MIXTURE OF SAID "EBONY FAT" AND ALKYLENE POLYAMINE FROM ABOUT 0.5% TO ABOUT 10% BY WEIGHT BASED ON THE WEIGHT OF SAID "EBONY FAT" AND ALKLYLENE POLYAMINE IN SAID REACTION MIXTURE, OF AN ETHYLENE OXIDE-PROPYLENE OXIDE GRAFT POLYMER CORRESPONDING TO THE GENERAL FORMULA HO(C2H4O)A(C3H6O)B(C2H4O)C'' AND HAVING A MOLECULAR WEIGHT OF ABOUT 1000 TO ABOUT 4500 WHEREIN A,B, AND C ARE INTEGERS, THE SUM OF A AND C BEING WITHIN THE RANGE OF ABOUT 2 TO ABOUT 20 AND B HAVING A VALUE WITHIN THE RANGE OF ABOUT 15 TO ABOUT 60, AND MAINTAINING SAID REACTION MIXTURE AT A TEMPERATURE OF FROM ABOUT 60*F. TO ABOUT 150*F.