Asphalt compositions containing anti-stripping additives prepared from hydrocarbyl substituted nitrogen-containing aromatic heterocyclic compounds, aldehydes or ketones and amines

Asphalt compositions are improved by incorporating therein the reaction product of a hydrocarbyl substituted nitrogen-containing aromatic heterocyclic compound such as 2,4,6-trimethylpyridine, an aldehyde such as formaldehyde or ketone such as acetone and an amine such as a mixture of C.sub.10 -C.sub.18 aliphatic monoamides.

BACKGROUND OF THE INVENTION 
The use of petroleum residuum such as asphalt as a paving material and 
other construction material is well known. It is also well known that it 
is desirable to include in such compositions anti-stripping additives so 
as to reduce the tendency of the paving material which consists of the 
asphalt and an aggregate material from deteriorating during inclement 
weather conditions. During the winter months, the low temperatures tend to 
stiffen and reduce the flexibility of the asphalt binder in the paving 
material. Traffic loadings then cause the pavement to crack. When that 
happens, surface water can easily seep into the pavement. As the water 
goes through freeze-thaw cycles, it strips the asphalt from the aggregate 
surfaces, reduces the pavement's strength and accelerates deterioration. 
During the summer months, high temperatures can cause the asphalt pavement 
to become so soft that traffic can permanently deform the material and 
create shoving, rutting, bleeding and flushing problems. The incorporation 
of an anti-stripping additive into the asphalt composition employed in 
preparing the pavement increases the life of the pavement. It would be 
desirable to have anti-stripping additives for asphalt which improves its 
adhesion to the aggregate material. 
SUMMARY OF THE INVENTION 
The present invention pertains to a composition which comprises a blend of 
(A) bituminous material and 
(B) the product resulting from reacting 
(1) (a) at least one monoamine having a combined total of about 1 to 36 
carbon, nitrogen, oxygen or sulfur atoms and at least one reactive amine 
hydrogen atom; (b) at least one polyamine having at least one reactive 
amine hydrogen atom; or (c) a mixture of (a) and (b); 
(2) at least one aromatic heterocyclic material having one or more rings, 
at least one nitrogen atom located in the ring and at least one 
substituent group which has at least one reactive hydrogen atom attached 
to a heterocyclic ring carbon atom; and 
(3) at least one aldehyde, ketone or combination thereof; and wherein the 
components are employed in quantities which provide a mole ratio of 
(1):(2):(3) of from about 0.25:1:0.25 to about 5:1:5, preferably from 
about 1:1:1 to about 2:1:2 and the reaction is conducted at a temperature 
of from about 25.degree. C. to about 250.degree. C., preferably from about 
60.degree. C. to about 200.degree. C. for a time to essentially complete 
the reaction, 
wherein components (A) and (B) are employed in quantities which provide 
from about 0.05 to about 10, preferably from about 0.25 to about 5, more 
preferably from about 0.5 to about 2.5, most preferably from about 0.5 to 
about 1 percent by weight of component (B) based upon the combined weight 
of components (A) and (B). 
The present invention provides anti-stripping additives for asphalt which 
improves its adhesion to the aggregate material. 
DETAILED DESCRIPTION OF THE INVENTION 
The bituminous material employed herein in the practice of the present 
invention is not critical. Any bitumen, asphalt or crude residuum 
containing alphaltenes can be employed. U.S. Pat. No. 3,317,447 contains a 
good description of useful bituminous materials which are useful herein 
and is incorporated herein by reference. In general, the asphalts which 
can be employed include conventional petroleum asphalts, natural asphalts, 
gilsonite, air blown asphalts, coal tar and other similar materials. The 
asphalts are characterized by having penetration grades up to 300 
decimillimeter at 77.degree. F. as measured by ASTM Method D5. Preferred 
asphalts are the normal paving asphalts (e.g. AC5, AC10, AC20, and AC30. 
AC indicates asphalt cement and the number indicates the viscosity at 
140.degree. F. in poise divided by 100). 
The anti-stripping compositions employed in this invention are preferably 
prepared by reacting an aldehyde or ketone with a mixture of an amine and 
a hydrocarbyl substituted nitrogen-containing aromatic heterocyclic 
compound. Preferably, the reaction is carried out in an inert atmosphere 
or under reduced pressure. The reaction can be carried out neat or in the 
presence of a solvent. A solvent, particularly water, is preferred. It is 
desirable to conduct the reaction in the presence of a catalyst. The 
preferred catalyst is hydrochloric acid. The hydrochloric acid neutralizes 
the amine thereby forming amine hydrochlorides. The quantity of (1) the 
amine, (2) hydrocarbyl substituted nitrogen-containing aromatic 
heterocyclic compound and (3) aldehyde or ketone employed should provide a 
mole ratio of (1):(2):(3) of from 0.25:1:0.25 to 5:1:5, suitably from 
1:1:1 to about 2:1:2. The reaction of the aldehyde or ketone with a 
mixture of the amine and a hydrocarbyl substituted nitrogen-containing 
aromatic heterocyclic compound is carried out at a temperature between 
about 25.degree. to about 250.degree. C., preferably from 60.degree. to 
200.degree. C. for a time to essentially complete the reaction, usually 
about 1-24 hours (3600-86,400 s), especially about 2-8 hours (7200-28,800 
s). The aldehyde or ketone usually is added to a refluxing 
(100.degree.-125.degree. C.) aqueous solution of the amine and hydrocarbyl 
substituted nitrogen-containing aromatic heterocyclic compound at a slow 
rate in the course of 1-10 hours (3600-36,000 s), preferably 1-3 hours 
(3600-10,800 s). Solvent and reactants can be removed by distillation, 
sublimation or solvent extraction. The anti-stripping agent in the acid 
form (formed when employing an acid as a catalyst) can be neutralized with 
a base. 
Examples of an inert atmosphere in which the reaction can be conducted 
includes nitrogen, helium, neon, xenon, argon mixtures thereof and the 
like. 
Other suitable solvents besides water, include, any solvents in which the 
reactants and products are soluble such as alcohols, acids, amides, ethers 
and hydrocarbons. Particularly suitable solvents include, for example, 
ethanol, methanol, isopropanol, butanol, ethanediol, acetic acid, dioxane, 
tetrahydrofuran, dimethylformamide, toluene, xylene, combinations thereof 
and the like. 
Suitable bases for neutralizing the anti-stripping agent in the acid form 
include sodium hydroxide, other hydroxides of alkali and alkaline earth 
metals, ammonium hydroxide, ammonia and the like. The inhibitor can be 
extracted with a solvent from the base during or after neutralization 
and/or salt formed during the neutralization. Suitable solvents for the 
extraction include chlorinated solvents, ethers and hydrocarbons and the 
like. Particularly suitable solvents include chloroform, diethyl ether, 
tetrahydrofuran, benzene, toluene, xylene, combinations thereof and the 
like. 
Suitable aromatic heterocyclic materials having one or more rings, at least 
one nitrogen atom located in the ring and at least one substituent group 
which has at least one reactive hydrogen atom attached to a carbon atom 
which is attached to an aromatic heterocyclic ring which can be employed 
herein include, for example, pyrazines, pyridines, pyrazoles, imidazoles, 
pyridazines, pyrimidines, purines, pteridines, triazines, quinolines and 
quinoxalines. Particularly suitable such substituent groups include 
methyl, --CH(R).sub.2 or --CH.sub.2 R groups wherein each R is 
independently a hydrocarbyl group containing from 1 to about 10, 
preferably from 1 to about 2 carbon atoms. 
The hydrocarbyl substituted pyrazines, pyridines, purines, pyrazoles, 
imidazoles, pyridazines, pyrimidines, pteridines, triazines, quinolines, 
and quinoxalines employed herein are all aromatic compounds. The term 
aromatic as employed herein means that a compound must have a planar 
(lacking ring strain) molecule that contains cyclic clouds of delocalized 
pi (.pi.) electrons located above and below the plane of the molecule; 
furthermore, the pi clouds must contain a total of (4n+2) electrons. This 
definition of aromatic is given in "Organic Chemistry", 2nd Ed. by R. T. 
Morrison and R. N. Boyd, Allyn and Bacon, Inc. 1970, pp. 317-318 which is 
incorporated herein by reference. 
All pyrazines, pyridines, pyrazoles, imidazoles, pyridazines, pyrimidines, 
purines, pteridines, triazines, quinolines and quinoxalines are not 
necessarily aromatic compounds. For example, pyrazine hexahydride 
(piperazine), 5,6-dihydropyrazine, tetrahydropyrimidine and 
hexahydropyrimidine are not aromatic compounds since they are either 
non-planar, do not have a total of (4n+2) pi electrons or have a 
non-cyclic cloud of pi electrons. As a consequence, pyrazine hexahydride, 
5,6-dihydropyrazine, tetrahydropyrimidine and hexahydropyrimidine are not 
pyrazines and pyrimidines of this invention. 
The term heterocycle or heterocyclic as employed herein means that the ring 
must contain at least one nitrogen atom located in the ring. Although 
benzene and its substituted derivatives are aromatic they are not 
considered aromatics of this invention because they contain no nitrogen 
located in their ring. The nitrogen located in the aromatic ring is 
essential for activation of the hydrogen atom attached to the carbon atom 
of the substituent group attached to the carbon atom of the heterocyclic 
aromatic ring. The hydrogen atom attached to a carbon atom of a 
substituent group where the carbon atom is attached to a benzene ring is 
unreactive. 
The term hydrocarbyl as employed herein means any aliphatic, 
cycloaliphatic, aromatic, aryl substituted aliphatic or aliphatic 
substituted aromatic groups. 
Particularly suitable as the heterocyclic material which can be employed 
herein include the pyrazines such as, for example 2-methylpyrazine, 
2,3-dimethylpyrazine, 2,5-dimethylpyrazine, 2,6-dimethylpyrazine, 
2,3,5-trimethylpyrazine, 2,3,5,6-tetramethylpyrazine, 2-ethylpyrazine, 
2-ethyl-3-methylpyrazine, 2-ethyl-5-methylpyrazine, 
2-ethyl-6-methylpyrazine, 2-ethyl-3,5-dimethylpyrazine, 
3-ethyl-2,5-dimethylpyrazine, 5-ethyl-2,3-dimethylpyrazine, 
2-propylpyrazine, 2-methyl-3-propylpyrazine, 2-methyl-6-propylpyrazine, 
2,5-dimethyl-3-propylpyrazine, 3,5-dimethyl-2-propyl-pyrazine, 
2-(1-methylethyl)pyrazine, 2-methyl-3-(1-methylethyl)pyrazine, 
2-methyl-5-(1-methylethyl)pyrazine, 6-methyl-2-(1-methylethyl)pyrazine, 
2,3-diethylpyrazine, 2,3-diethyl-5-methylpyrazine, 
3,5-diethyl-2-methylpyrazine, 2,6-diethyl-3,5-dimethylpyrazine, 
2,5-diethyl-3,6-dimethylpyrazine, 2,5-bis(1-methylethyl)pyrazine, 
2,5-dimethyl-3,6-bis(1-methylethyl)pyrazine, 2-butylpyrazine, 
2-butyl-3-methylpyrazine, 2-butyl-6-methylpyrazine, 
2-butyl-3,5-dimethylpyrazine, 3-butyl-2,5-dimethylpyrazine, 
5-butyl-2,3-dimethylpyrazine, 2-butyl-3,5,6-trimethylpyrazine, 
2,5-dibutyl-3,6-dimethylpyrazine, 
2,5-dimethyl-3,6-bis(2-methylpropyl)pyrazine, 
2,5-diethyl-3,6-bis(2-methylpropyl)pyrazine, 
2-methyl-3-(2-methylpropyl)pyrazine, 
2,3,5-trimethyl-6-(2-methylpropyl)pyrazine, 2-methyl-3-pentylpyrazine, 
2-hexylpyrazine, 2-hexyl-3-methylpyrazine, 
2,3,5-trimethyl-6-nitropyrazine, mixtures thereof and the like. 
Particularly suitable pyridines which can be employed herein include, for 
example, 2-methylpyridine, 4-methylpyridine, 2-methyl-5-vinylpyridine, 
2,3-dimethylpyridine, 2,4-dimethylpyridine, 2,5-dimethylpyridine, 
2,6-dimethylpyridine, 2-ethylpyridine, 2,3,4-trimethylpyridine, 
2,3,5-trimethylpyridine, 2,3,6-trimethylpyridine, 2,4,5-trimethylpyridine, 
2,4,6-trimethylpyridine, 2-ethyl-3-methylpyridine, 
2-ethyl-4-methylpyridine, 3-ethyl-2-methylpyridine, 
3-ethyl-4-methylpyridine, 2-ethyl-6-methylpyridine, 
5-ethyl-2-methylpyridine, 4-ethyl-2-methylpyridine, 2,4-diethylpyridine, 
3,6-diethyl-2-methylpyridine, 2-ethyl-3,6-dimethylpyridine, 
3-ethyl-2,6-dimethylpyridine, 4-ethyl-2,5-dimethylpyridine, 
2-ethyl-4,6-dimethylpyridine, 2-methyl-4-propylpyridine, 
2-methyl-4-(1-methylethyl)pyridine, 
2-(1,1-dimethylethyl)-4-methylpyridine, 4-(1,1-dimethylethyl)-2-methylpyri 
dine, 2,3-dimethyl-6-(1-methylethyl)pyridine, 
3,6-dimethyl-2-(1-methylethyl)pyridine, 2,6-dimethyl-4-propylpyridine, 
3,6-dimethyl-2-propylpyridine, 2-ethyl-3,4,6-trimethylpyridine, 
3-ethyl-2,5,6-trimethylpyridine, 2-methyl-4-(1-methylpropyl)pyridine, 
4-butyl-2-methylpyridine, 5-butyl-2-methylpyridine, 
2,3,4,5-tetramethylpyridine, 2,3,4,6-tetramethylpyridine, 
2,3,5,6-tetramethylpyridine, pentamethylpyridine, mixtures thereof and the 
like. 
Other suitable aromatic nitrogen containing heterocycles which can be 
employed herein include, pyrazoles, imidazoles, pyridazines, pyrimidines, 
purines, pteridines, triazines, quinolines and quinoxalines having one or 
more substituents having a reactive hydrogen atom attached to a carbon 
atom which is attached to a heterocyclic ring. Such substituent groups 
include methyl, --CH(R).sub.2 or --CH.sub.2 R wherein R is as above 
defined. 
Suitable pyrazoles include 3-methylpyrazole, 4-methylpyrazole, 
3,5-dimethylpyrazole, 1-ethyl-3,5-dimethylpyrazole, 
3,4,5-trimethylpyrazole, mixtures thereof and the like. 
Suitable imidazoles which can be employed herein include, for example, 
2-methylimidazole, 4-methylimidazole, 1,2-dimethylimidazole, 
2,5-dimethylimidazole, 2,4-dimethylimidazole, 2,4,5-trimethylimidazole, 
2-ethyl-4-methylimidazole, mixtures thereof and the like. 
Suitable pyridazines include, for example, 3-methylpyridazine, 
3,5-dimethylpyridine, 3,4,5-trimethylpyridine, 3,4-tripropylpyridazine, 
mixtures thereof and the like. 
Suitable pyrimidines include, for example, 4-methylpyrimidine, 
2,4-dimethylpyrimidine, 4,5-dimethylpyrimidine, 4,6-dimethylpyrimidine, 
2,6-dimethyl-4-pyrimidinol, 2,4,6-trimethylpyrimidine, 
2,4-diethylpyrimidine, mixtures thereof and the like. 
Suitable purines which can be employed herein include, for example, 
6-methylpurine, 2,8-dimethylpurine, 2,6,8-trimethylpurine, mixtures 
thereof and the like. 
Suitable pteridines include 6,7-dimethylpteridine, 2,6-dimethylpteridine, 
2,4,7-trimethylpteridine, mixtures thereof and the like. 
Suitable triazines which can be employed herein include 
3,5-dimethyl-1,2,4-triazine, 3,6-dimethyl-1,2,4-triazine, 
2,4-dimethyl-1,3,5-triazine, 2,4,6-trimethyl-1,3,5-triazine, mixtures 
thereof and the like. 
Suitable quinolines include, for example, 2-methylquinoline, 
4-methylquinoline, 2,4-dimethylquinoline, 2,6-dimethylquinoline, 
2,7-dimethylquinoline, 8-ethyl-2-methylquinoline, 
4-ethyl-2,3-dimethylquinoline, 8-ethyl-2,3-dimethylquinoline, 
4-ethyl-2,3,8-trimethylquinoline, 4,8-diethyl-2,3-dimethylquinoline, 
2,3-dimethyl-8-propylquinoline, 2,3,4-trimethyl-8-propylquinoline, 
2,4-dimethyl-6-(1-methylpropyl)quinoline, mixtures thereof and the like. 
Suitable quinoxalines include 2-methylquinoxaline, 2,5-dimethylquinoxaline, 
2,3-dimethylquinoxaline, 2,6-dimethylquinoxaline, 
2,3,6-trimethylquinoxaline, 2,3,6,8-tetramethylquinoxaline, mixtures 
thereof and the like. 
The aromatic heterocyclic materials having one or more rings and at least 
one nitrogen atom located in the ring and at least one substituent group 
which has at least one reactive hydrogen atom attached to a carbon atom 
which is attached to an aromatic heterocyclic ring carbon atom can be 
mixed with each other. For example, 5-ethyl-2-methylpyridine can be mixed 
with 2-ethyl-3,5-dimethylpyrazine and used as the heterocyclic material in 
the present invention. 
Suitable aldehydes and ketones which can be employed herein include, for 
example, all of those having the formula: 
##STR1## 
wherein each R.sub.1 and R.sub.2 are independently hydrogen, hydrocarbyl 
or substituted hydrocarbyl groups having from 1 to about 30 carbon atoms. 
Such substituents include, for example, halo, nitro, alkoxy and amino 
groups. 
Particularly suitable aldehydes include, for example, formaldehyde, 
paraformaldehyde, acetaldehyde, 2-bromoacetaldehyde, benzaldehyde, 
propionaldehyde, butyraldehyde, caproaldehyde, crotonaldehyde, 
nicotinaldehyde, 2,2-dichloromalonaldehyde, gluteraldehyde, 
p-tolualdehyde, 3-chlorobenzaldehyde, naphthaldehyde, anthraldehyde, 
2-furaldehyde, malonaldehyde, phthaldehyde, 3,5-dibromophthalaldehyde, 
1-cyclohexene-1-carboxaldehyde, 3-quinolinecarboxaldehyde, 
3-aminobenzaldehyde, combinations thereof and the like. Particularly 
suitable ketones include, for example, acetone, methyl ethyl ketone, 
2-pentanone, 3-pentanone, 1-chloro-2-propanone, butyrone, 
1-bromo-7-nitro-4-heptanone, acetophenone, 
5,6,7,8-tetrahydro-1-isobutyronaphthone, capriphenone, 
1-cyclohexyl-2-methyl-1-propanone, 1-(2-furyl)-1-butanone, 
1-(5-quinolyl)-1-pentanone, 2-acetylchrysene, 4-bromobenzophenone, 
2,4-pentanedione, 3,4-diacetyl-2,5-hexanedione, 3-cyclohexene-1-one, 
2-acetonyl cyclohexanone, mixtures thereof and the like. 
Suitable amines which can be employed herein include saturated and 
unsaturated aliphatic monoamines, cycloaliphatic monoamines or aromatic 
monoamines having a combined total of from about 1 to about 36 carbons, 
nitrogen, oxygen or sulfur atoms and at least one reactive amine hydrogen 
atom. Such amines include ethanamine, propanamine, butanamine, 
3-buten-2-amine, N-hexyl-1-hexanamine, N-octyl-1-octanamine, 
N-nonyl-1-nonanamine (Di-n-nonylamine), isopropoxypropylamine, 
3-(2-methoxyethoxy)propylamine, N-(3-ethoxypropyl)ethylamine, 
4,4-diethoxybutylamine, cyclohexanebutylamine, cyclooctylamine, 
cyclododecylamine, N-methylcyclododedecylamine, octamethyleneimine, 
4-hexyloxyaniline, 4-pentyloxyaniline, 1,4-benzodioxan-6-amine, 
2-amino-4-tert-butylphenol, 2-biphenylamine, 4-biphenylamine, 
2-aminonaphthalene, 2-fluoroenamine, 1-anthramine, 4-phenylbutylamine, 
2-(benzyloxy)ethylamine, 2-(b-phenethylamino)ethanethiol, 
4-amino-1-benzylpiperidine, tall oil amine, soya amine, hydrogenated 
tallow amine, tallow amine, C.sub.8 -C.sub.15 ether amine, mixtures 
thereof and the like. 
Particularly suitable monoamines include 1-hexanamine(hexylamine), 
1-heptanamine, 1-octanamine, 1-nonanamine, 1-decanamine, 1-undecanamine, 
1-dodecanamine (dodecylamine), 1-tridecanamine, 1-tetradecanamine, 
1-pentadecanamine, 1-hexadecanamine, 1-heptadecanamine, 1-octadecanamine, 
N-methylhexanamine, N-methylheptanamine, N-methyl-1-decanamine, 
N-(1-methylethyl)-1-pentanamine, N-(1-methylethyl)-1-decanamine, 
N-methyl-1-octadecanamine, N-dodecyl-1-dodecanamine, 9-octadecen-1-amine, 
9,12-octadecadien-1-amine, 9,12,15-octadecatrien-1-amine, 
9-eicosen-1-amine, 11-eicosen-1-amine, mixtures thereof and the like. 
Particularly suitable monoamines are the aliphatic primary amines having a 
combined total of from about 10 to about 20 carbon, nitrogen, oxygen or 
sulfur atoms or a mixture thereof. 
Particularly suitable polyamines which can be employed in the preparation 
of the anti-stripping agents include, for example, those represented by 
the formulas 
##STR2## 
where each R.sup.1 and R.sup.2 is independently hydrogen or a hydrocarbyl 
group or hydroxyl substituted hydrocarbyl group or amine substituted 
hydrocarbyl group having from about 1 to about 36, preferably from about 1 
to about 24, more preferably from about 1 to about 10, most preferably 
from about 1 to about 3, carbon atoms; each R3 is independently a divalent 
hydrocarbyl group having from 1 to about 36, preferably from about 1 to 
about 24, more preferably from about 1 to about 10, most preferably from 
about 1 to about 3, carbon atoms; m has a value from zero to about 8; m' 
has a value from 1 to about 4; n has a value of 2 to 20, preferably 2 to 
3; n' has a value from 1 to about 10. The term hydrocarbyl as employed 
herein includes, alkyl, cycloalkyl, aryl, aralkyl, alkaryl, alkenyl and 
the like. Such amines include 1,2-ethanediamine, 1,2-propanediamine, 
1,3-propanediamine, N-(2-aminoethyl)-1,2-ethanediamine, 
N-(3-aminopropyl)-1,3-propanediamine, N-(3-aminopropyl)-1,4-butanediamine, 
bis-(2-aminopropyl)amine, 1-piperazineethanamine, 
2-(3-aminopropylamino)ethanol, 1-(2-aminoethylamino)-2-propanol, 
triethylenetetramine, tetraethylenepentamine, hexaethyleneheptamine, 
N,N-dibutyl-1,3-propanediamine, N,N'-dipropyl-1,7-heptanediamine, 
N,N'-dioctyl-1,2-ethanediamine, N,N'-dioctyl-1,3-propanediamine, 
N,N'-didecyl-1,3-propanediamine, N,N'-didecyl-1,3-propanediamine, 
1,10-dodecanediamine, 1,12-dodecanediamine, N-decyl-1,2-ethanediamine, 
N-undecyl-1,2-ethanediamine, N-tridecyl-1,2-ethanediamine, 
N-pentadecyl-1,2-ethanediamine, N-hexadecyl-1,2-ethanediamine, 
N-heptadecyl-1,2-ethanediamine, N-octadecyl-1,2-ethanediamine, 
N-decyl-1,3-propanediamine, N-dodecyl-1,2-propanediamine, 
N-tetradecyl-1,3-propanediamine, N-hexadecyl-1,3-propanediamine, 
N-heptadecyl-1,3-propanediamine, N-octadecyl-1,2-propanediamine, 
N-octadecyl-1,3-propanediamine, N-octadecyl-1,4-butanediamine, mixtures 
thereof and the like. Other suitable polyamines which can be employed 
herein include, for example, 5,11-pentadecanediamine, 
4,13-hexadecanediamine, 2,2,11-trimethyl-1,11-dodecanediamine, 
5,13-diethyl-6,12-heptadecanediamine, 3,4-diethyl-4,13-hexadecanediamine, 
12-ethyl-2-methyl-2-propyl-1,11-tetradecanediamine, 
5,15-diethyl-5,14-nonadecanediamine, 
6,9,12-trioxa-3,15-diazaheptadecane-1,17-diol, 
3,6,9,12,15-pentaoxaheptadecane-1,17-diamine, 
N-[3-(decyloxy)propyl]-1,3-propanediamine, 
1-[(2-aminoethyl)amino]-2-tetradecanol, 
1-[(3-aminopropyl)amino]-2-dodecanol, 
5-[(3-ethylamino)propyl]amino-1-pentanol, 1-piperazinepropanol, 
ether-1,3-propylenediamines, ether-1,2-ethylenediamines, mixtures thereof 
and the like. 
The monoamines or polyamines can be partially alkoxylated such as partially 
ethoxylated, partially propoxylated, partially butoxylated or partially 
polyethoxylated, partially polypropoxylated or partially polybutoxylated, 
provided that there remains at least one amine hydrogen atom per molecule. 
Also suitable are the aminated polyols. Suitable such aminated polyols 
include, for example aminated ethylene glycol, aminated polyoxyethylene 
glycol, aminated propylene glycol, aminated polyoxypropylene glycol, 
aminated glycerine, aminated reaction products of ammonia or an amine such 
as methylamine, ethylamine, propylamine, butylamine, ethylenediamine, 
propylene diamine, diethylenetriamine or the like with an alkylene oxide 
such as ethylene oxide, propylene oxide, butylene oxide, mixture thereof 
and the like, aminated reaction products of trimethylol propane with an 
alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, 
mixtures thereof and the like. Suitable such aminated polyols include 
those disclosed in U.S. Pat. No. 4,374,222. 
Suitable catalysts which can be employed include, for example, acids, Lewis 
acids, bases or salts. Particularly suitable acids include, for example, 
hydrohalides, sulfuric or glacial acetic acid. Suitable hydrohalides 
include, for example, hydrochlorides, hydrobromides, hydroiodides, 
combinations thereof and the like. Particularly suitable bases include, 
for example, alkoxides and hydroxides of alkali or alkaline earth metals, 
such as sodium ethoxide, magnesium ethoxide and sodium hydroxide. 
Particularly suitable Lewis acids include, for example, boron trifluoride 
and aluminum trichloride. Particularly suitable salts include, for 
example, zinc chloride. The use of such catalysts is not indispensable but 
it reduces the time required for the reaction. The preferred catalyst is 
hydrochloric acid. The catalyst can be reacted or complexed with the 
amine, the hydrocarbyl substituted nitrogen-containing aromatic 
heterocyclic material, a mixture of amine and hydrocarbyl substituted 
nitrogen-containing aromatic heterocyclic material and a mixture or 
reaction product of amine, hydrocarbyl substituted nitrogen-containing 
aromatic heterocyclic material and aldehyde or ketone. 
The catalysts can be added to the reactants separately or to any one or 
combination of the reactants prior to contact with the remainder of the 
reactants. 
The acid catalyzed reaction product of the hydrocarbyl substituted aromatic 
nitrogen heterocyclic material amine and aldehyde and/or ketone are 
believed to be those compounds or mixtures of compounds represented by the 
following formulas (II), (III), (IV), (V) or (VI): 
##STR3## 
wherein R.sup.1 and R.sup.2 are independently hydrogen or a hydrocarbyl 
group containing 1 to about 10, preferably from 1 to about 2 carbon atoms; 
each R.sup.3 and R.sup.4 are independently hydrogen, hydrocarbyl or halo, 
nitro, alkoxy or amino substituted hydrocarbyl group having from 1 to 
about 30 carbon atoms; each R.sup.5 is independently hydrogen, or a 
hydrocarbyl group having a combined total of from about 1 to about 36, 
preferably from about 10 to 20 carbons, nitrogen, oxygen or sulfur atoms; 
each X is independently hydrogen, methyl, --CH(R).sub.2 or --CH.sub.2 R 
groups wherein each R is independently a hydrocarbyl group containing from 
1 to about 10, preferably from 1 to about 2 carbon atoms; A is either the 
pyrazine, pyridine, pyrazole, imidazole, pyridazine, pyrimidine, purine, 
pteridine, quinoline or quinoxaline nucleus; m has a value of 3 when A is 
a pyrazole, imidazole, purine or triazine, 4 when A is a pyrazine, 
pyridazine, pyrimidine or pteridine, 5 when A is pyridine, 6 when A is 
quinoxaline and 7 when A is quinoline; n has a value from 1 to m. The 
compound represented by formula III is only formed when R.sup.1 of the 
substituent group of the aromatic nitrogen-containing heterocyclic 
compound is a hydrogen. Similarly, the compound represented by formula IV 
and VI are only formed when one of the two R.sub.5 groups of the amine is 
a hydrogen. 
In addition to the five compounds represented by formula II, III IV, V and 
VI, the reaction of the hydrocarbyl substituted aromatic nitrogen 
heterocyclic material, amine and aldehyde and/or ketone are believed to 
form a high molecular weight product or polymer of unknown composition. 
The presence of the high molecular weight product or polymer is suggested 
by gel permeation chromatography with tetrahydrofuran as the solvent. For 
example, some 2700 molecular weight material was found to be present in 
the reaction product of 2,4,6-trimethylpyridine, formaldehyde and Kemamine 
P-650. Molecular weight was based upon polystyrene standards. 
Compounds II and III each have at least one 
##STR4## 
linkage. The 
##STR5## 
linkage results from the condensation of the amine and the hydrocarbyl 
substituted aromatic nitrogen containing heterocyclic material with the 
aldehyde and/or ketone under conditions sufficient to form a molecule of 
water. The two hydrogens of the water molecular are believed to originate 
from the reactive amine hydrogen of the amine and the reactive hydrogen 
atom attached to the carbon atom which is attached to the aromatic 
heterocyclic ring, respectively. 
The asphalt compositions of the present invention can be blended with any 
of the aggregate materials known to the art in order to form pavement 
compositions. 
The following examples are illustrative of the invention, but are not 
intended to limit the scope thereof in any manner.

EXAMPLE 1 
51.44 grams (0.25 mole) of KEMAMINE.RTM. P-650 (a mixture of C.sub.10 
-C.sub.18 primary amines commercially available from Witco Chemical Corp. 
which consists primarily of 1-decanamine, 1-dodecanamine, 
1-tetradecanamine, 1-hexadecanamine, 1-octadecanamine and 
octadecene-1-amine) are added to a one-liter resin kettle equipped with a 
thermometer, mechanical stirrer, condenser, addition funnel and a nitrogen 
pad. The fatty amines are cooled to 19.degree. C. and 100 milliliters of 
37% hydrochloric acid are added in 54 minutes to form amine 
hydrochlorides. 40.2 grams of 2,4,6-trimethylpyridine (0.33 mole) are 
added while stirring over an 18 minute period. The temperature increased 
from 20.degree. C. to 60.degree. C. The mixture is heated to 108.degree. 
C. and a nitrogen sweep is employed to aid in the removal of water via a 
Barrett Trap. The light yellow viscous material is heated to 127.degree. 
C. at which point a minimal amount of water is collected. 97.55 grams (1.2 
moles) of 37% aqueous formaldehyde are introduced dropwise via an addition 
funnel in 135 minutes. The temperature increased from 125.degree. C. to 
170.degree. C. during the addition of formaldehyde. The reactants are then 
heated for an additional 75 minutes at 185.degree. C. 299.1 grams of water 
soluble leather brown product is recovered. 
EXAMPLE 2 
51.44 grams (0.25 mole) of KEMAMINE.RTM. P-650 and 13.3 grams (0.08 mole) 
of triethylenetetramine are weighed into a 250 milliliter 4-neck round 
bottom flask equipped with an immersion thermometer, mechanical stirrer, 
condenser and addition funnel. A nitrogen atmosphere is maintained 
throughout the reaction. 48.36 grams (0.49 mole) of 37% hydrochloric acid 
are added dropwise over an 18 minute period to the cooled and stirred 
amines. After 20.19 grams (0.17 mole) of 2,4,6-trimethylpyridine are added 
to the amine hydrochlorides, the reactor contents are heated to 
107.degree. C. and the resultant clear yellow liquid is allowed to reflux. 
54.23 grams (0.67 mole) of 37% aqueous formaldehyde solution are added 
dropwise over 40 minutes giving a dark reddish brown liquid. After the 
reactants are heated for 4 hours between 98.degree. C. and 100.degree. C., 
a Barrett Trap is installed to remove water. The reactor contents are 
heated an additional 77 minutes between 98.degree. C. and 182.degree. C. 
On cooling to room temperature, the reactor contents are a dark reddish 
brown waxy solid. 
EXAMPLE 3 
66.64 grams (0.33 mole) of KEMAMINE.RTM. P-650 are weighed into a reactor 
of the type described in Example 2. The fatty amines are stirred and 
cooled to 10.degree. C. in a nitrogen atmosphere. 38.62 grams (0.39 mole) 
of 37% hydrochloric acid are added dropwise over a 33 minute period to 
form the fatty amine hydrochlorides. After 25.82 grams (0.16 mole) of 
2,3-dimethylquinoxaline are added to the reactor contents, the reactants 
are heated to 103.degree. C. and allowed to reflux. Then 52.31 grams (0.64 
mole) of an aqueous 37% formaldehyde solution are added dropwise over a 
110 minute period. After a Barrett Trap is installed to remove water, the 
reactor contents are heated between 100.degree. C. and 125.degree. C. for 
an additional 147 minutes. A black waxy solid that is soluble in ethanol 
and xylene is recovered as the final product. The black waxy solid is 
ground to a fine powder and rotary evaporated under full vacuum at 
100.degree. C. Ethanol is added to the black powder and the ethanol 
removed by rotary evaporation under full vacuum at 100.degree. C. The 
infrared spectrum of the black waxy powder supported the presence of 
methylene group, amine salt, imine and quinoxaline. The presence of 
methylene groups is supported by absorption bands at 722 cm.sup.-1, 1467 
cm.sup.-1, 2850 cm.sup.-1 and 2925 cm.sup.-1. A combination of medium 
intensity bands between 2000 cm.sup.-1 and 2800 cm.sup.-1 are explained by 
the presence of an amine salt. A broad band between 1640 cm.sup.-1 and 
1690 cm.sup.-1 is assigned to the C.dbd.N stretch of an imine. Absorption 
bands at 765 cm.sup.-1, 1197 cm.sup.-1, 1205 cm.sup.-1 and 1382 cm.sup.-1 
supported the presence of quinoxaline. 
EXAMPLE 4 
52.47 grams (0.26 mole) of KEMAMINE.RTM. P-650 are weighed into a reactor 
of the type described in Example 2. The fatty amines are stirred while 
cooled to 19.degree. C. in a nitrogen atmosphere. 31.45 grams (0.32 mole) 
of 37% hydrochloric acid (0.32 mole) are added dropwise over a 14 minute 
period. After 31.6 grams (0.29 mole) of 2-methyl-5-vinylpyridine are added 
to the amine hydrochlorides, the reactor contents are heated to 99.degree. 
C. 40.91 grams (0.5 mole) of 37% aqueous formaldehyde solution are added 
dropwise over 18 minute period giving a reddish brown liquid. After the 
reactants are heated for 200 minutes at 100.degree. C., a Barrett Trap is 
installed to remove water. The reaction temperature is gradually increased 
from 100.degree. C. to 186.degree. C. over a period of 83 minutes. After 
cooling to room temperature, the reactor contents are a brown colored 
product. 
EXAMPLE 5 
The above prepared anti-stripping additives or agents are mixed with 
asphalt and the resultant blend is then mixed with an aggregate and 
subjected to a boil test and a freeze-thaw test. A description of the 
tests are as follows and the results are given in the Table. In these 
tests, AC-20 type asphalt obtained from Texas Cosden Oil & Chemical Co. is 
employed. Three siliceous aggregates which have shown signs of serious 
stripping problems are tested. The names and the origins and silicon 
contents of these aggregates are: 
Gifford-Hill (Bryan, Tex., 100% Si) 
Granite (Califoria, 61% Si) 
Helms (Nevada, 63% Si) 
BOIL TEST 
Preparation of Mixtures 
In order to minimize the effect of aggregate interlock while maximizing the 
bond between the aggregate and the asphalt cement, each individual 
aggregate is first wet sieved to obtain the portion that passes No. 8 
sieve and retained on No. 20 sieve (U.S. standard testing sieve series, 
ASTM E-11). Then 100 g of this size dry aggregate is heated to 160.degree. 
C. plus or minus 3.degree. C. for at least 2 hours. The asphalt cement (6 
g) with 60 mg of anti-stripping additive is heated and stirred at 
160.degree. C. for 5 minutes (300 s). At the appropriate time, the hot dry 
aggregate is poured into the asphalt and mixed manually on a hot plate as 
rapidly and thoroughly as possible for 5 minutes. This mixture is then 
allowed to cool at room temperature for at least 2 hours before testing. 
Test Procedure 
A 1-liter beaker is filled with 500 ml deionized water and heated to 
boiling. The prepared aggregate-asphalt mixture is added to the boiling 
water which temporarily lowers the temperature below the boiling point. 
The heat is then increased so that the water reboiled in approximately 2 
to 3 minutes. The water is maintained at the boiling temperature for 10 
minutes while stirring with a glass rod at 3-minute intervals. During and 
after boiling, the stripped asphalt is skimmed away from the water surface 
with a paper towel to prevent recoating the aggregate. The mixture is then 
poured onto a paper towel and allowed to dry. The amount of asphalt 
retained on the mixture is determined by visual rating expressed in terms 
of percent of retained asphalt. To standardize this evaluation, a set of 
10 sample mixtures representing a scale of from 0 to 100 percent asphalt 
retention is prepared. By referring to these standard mixtures, the 
percent of asphalt retained on the aggregate is determined. An additive is 
considered to pass the boil test when an aggregate retains more than 70% 
of the original quantity of the mixture of additive and asphalt previously 
coated onto the aggregate. 
FREEZE-THAW TEST 
Preparation of Mixtures 
In order to minimize the effect of aggregate interlock while maximizing the 
bond between the aggregate and the asphalt cement, each individual 
aggregate is first wet sieved to obtain the portion that passes No. 20 
sieve and retained on No. 35 sieve (U.S. standard testing sieve series, 
ASTM E-11). Then 46 g of this aggregate is heated at 160.degree. C. plus 
or minus 3.degree. C. for at least 2 hours. Three grams of asphalt cement 
containing 1% by weight of the anti-stripping additive is mixed at 
160.degree. C. for 5 minutes. At the appropriate time, the hot aggregate 
is added to the asphalt and manually mixed as thoroughly and rapidly as 
possible for 5 minutes. This mixture is then allowed to cool at room 
temperature for over 30 minutes before compaction of the specimen is 
begun. The specimen is then compacted by reheating the asphalt concrete 
mixture at 150.degree. C. for 20 minutes, then transferring the mixture to 
a steel molding cylinder with a 41.33 mm inside diameter and compacting 
by applying a constant load of 6200 lbs (2812.32 kg) which corresponds to 
a force of 27.6 kN for 7 minutes. Generally, 46 g of each individual 
aggregate will produce a compacted briquet with a uniform height of 19.05 
mm, plus or minus 0.127 mm. After compaction, the briquet is extracted 
from the mold and allowed to cool and cure at room temperature for two 
days before freeze-thaw cycling. 
Test Procedure 
The briquet is placed on a cone shaped stress pedestal with only the center 
of the briquet bottom touching the pedestal. This entire assembly is then 
placed in a jar with enough distilled water to fill the jar to about 
one-half inch (12.7 mm) above the test briquet. The jar is then placed in 
a freezer at a temperature of -12.degree. C. for 15 hours. After this 
period, the jar is then transferred to a 50.degree. C. oven for 9 hours. 
At the end of each complete freeze-thaw cycle, the briquet is carefully 
examined for the appearance of surface cracks. If no cracks are visible, 
the briquet is subjected to subsequent freeze-thaw cycles until cracks are 
observed or the test terminated. An additive is considered to pass the 
freeze-thaw test when the briquet with additive passes more freeze-thaw 
cycles than the briquet with no additive. A particularly useful additive 
is one whose briquet passes twenty-five or more freeze-thaw cycles. 
TABLE 
______________________________________ 
RUN ADDlTIVE AGGREGATE BOIL FREEZE- 
NO. TYPE TYPE TEST.sup.1 
THAW TEST.sup.2 
______________________________________ 
A* None Gifford-Hill 
40 6 
B Ex. 1 Gifford-Hill 
100 &gt;30 
C Ex. 2 Gifford-Hill 
100 &gt;30 
D Ex. 3 Gifford-Hill 
100 &gt;30 
E Ex. 4 Gifford-Hill 
100 &gt;30 
F* None Granite 90 13 
G Ex. 1 Granite 100 16 
H Ex. 2 Granite 100 18 
I Ex. 3 Granite 100 20 
J Ex. 4 Granite 100 12 
K* None Helms 80 9 
L Ex. 1 Helms 100 31 
M Ex. 2 Helms 100 &gt;30 
N Ex. 3 Helms 100 24 
O Ex. 4 Helms 100 26 
______________________________________ 
*Not an example of the present invention. 
.sup.1 Percentage of asphalt remaining on the aggregate after boiling. 
.sup.2 The number of freezethaw cycles the asphalt concrete withstood 
before cracking. 
Additives that pass the boil and freeze-thaw tests are considered to be 
useful anti-stripping additives for asphalt. The results in the above 
table clearly show that the reaction product of a hydrocarbyl substituted 
nitrogen-containing aromatic heterocyclic material and an amine with an 
aldehyde are particularly useful antistripping additives for asphalt with 
either Gifford-Hill, Granite or Helms type aggregates.