United States Patent (19 11 Patent Number: 4,806,166

Schilling et al. 45) Date of Patent: Feb. 21, 1989

54). TALL OIL BASED AMINO ESTERS AS 3,607,773 9/1971 Pitchford et al. ................... 106/277
ANT-STRIPPINGAGENTS FOR ASPHALT E. 3. SE et a - a - - a - EN
st Avs chilling et al. .... -a
75 Inventors: Peter Schilling; Hans G. Schreuders, 4,494,992 1/1985 Schilling et al. ............... 106/273 N
both of Charleston, S.C. FOREIGN PATENT DOCUMENTS
73 Assignee: yraco Corporation, New York, 617466 2/1949 United Kingdom ........... 106/273 N
21 Appl.
w
No.: 97,687 Primary Examiner-Paul
Assistant
SSS. E 72-c.
Lieberman
Helene Kirschn
SSC
(22 Filed: Sep. 17, 1987 Attorney, Agent, or Firm--Terry B. McDaniel; Richard
51) Int. Cl." ...................... COSL95/00; C09D 3/24 L. Schmalz
52). U.S.C. ............................ 106/284.06; 106/2844;
208/44
37 ABSTRACT
58) Field of search. 106/281 N, 273 N, 273 R, An asphalt composition is disclosed having improved
106/277; 208/44 adhesion to aggregate comprising asphalt and an adhe
sion improving amount of an anti-stripping agent com
(56) References Cited prising the aminoester reaction product of at least one
U.S. PATENT DOCUMENTS tall oil fatty acid and triethanolamine.
3,114,649 12/1963 Katz ................................ 106/273 N
3,249,451 5/1966 Evans et al. .................... 106/273 N 12 Claims, No Drawings
 4,806,166
1. 2
taining a homogeneous mixture. There is also a danger
TALL OL BASED AMNO ESTERS AS since these amines are corrosive.
ANT-STRIPPING AGENTS FOR ASPHALT The patent literature sets forth a large number of
compounds which can be used to improve adhesion of
BACKGROUND OF THE INVENTION 5 aggregate and asphalt. These include fatty carboxylic
1. Field of the Invention chromites (U.S. Pat. No. 3,963,059), combinations of
This invention relates to the field of asphalt composi epoxy resins and onium borates (U.S. Pat. No.
tions, particularly compositions containing cationic 3,947,395), and ether amines in combination with alka
substances which improve the adhesion of the asphalt to 10 nolamines (U.S. Pat. No. 3,928,061). U.S. Pat. No.
mineral aggregate. 3,868,263 discloses a method of making a paving com
2. Description of the Prior Art position where the adhesion promoter is a primary,
In road construction, bitumen-aggregate mixtures are secondary, teritary or quaternary amine or imidazoline,
applied to the road surface. These bitumen-aggregate or reaction product of these with various acids includ
mixtures can be obtained by mixing anionic or cationic ing fatty acids, metal soaps, and several other com
asphalt emulsions with aggregate, such as stone chips, 15 pounds including rosin reaction products. Also known
gravel or sand, or by mixing free flowing heated asphalt are ethylene oxides condensates of long chain alkyl
(asphalt cement) with pre-dried aggregate, by a hot mix triamines (U.S. Pat. No. 3,615,797), alkoxylated fatty
process. The pre-dried aggregate can also be mixed amines and their salts (U.S. Pat. No. 3,347,690) and
with asphalt diluted with a hydrocarbon solvent, reaction products of ozonized unsaturated fatty acids
known as cutback asphalt. with polyalkylene amines (U.S. Pat. Nos. 3,246,008 and
The quality of the road surface is generally dependent 3,245,451).
upon the strength of the bonds between the asphalt and One promising class of compounds used as adhesion
aggregate after setting of the composition. Poor service promoters are aminoamines formed from the reaction of
performance is due to poor adhesion between the as tall oil fatty acid fractions and inexpensive polyamines.
phalt and aggregate, resulting in the stripping off of the 25 Since these low cost polyamines are scarce, the com
asphalt from the aggregate surface. mercial potential of these materials is quite limited.
Asphalt compositions have relatively poor adhesion A fatty aminoester has also become available for use
to aggregate in the presence of water. Since the aggre as an adhesion promoter under the name PAVEBOND
gate is preferentially wetted by water, even if the aggre AP sold by Carstab. This produce has low amine value
gate is dry at the time it is blended with the asphalt, the 30 (AV=56) and low viscosity. Low viscosity is important
eventual penetration of water into the composition in adhesion promoting agents, since no fuel oil or other
reaches the aggregate and interferes with the bond be diluent need be added in order to effectively mix the
tween the aggregate and the asphalt. The result of this adhesion promoter and the asphalt.
stripping is flaked pavement and pot holes. Stripping
problems also generally occur if the aggregate is poorly 35 SUMMARY OF THE INVENTION
dried, if sandy carbonate aggregate containing a large It is the object of the present invention to provide an
amount of quartz particles is used, if carbonate aggre asphalt composition of improved adhesion to aggregate.
gate is covered with dust or if igneous (silicate) aggre It is a further object of the present invention to pro
gates, such as granite, diorite, gabbro, diabase, or basalt, vide an asphalt composition with an anti-stripping agent
that strip in the presence of external water are used. formed from low cost and easily available materials.
To avoid such failures, adhesion improving agents It is an additional object of the present invention to
known as "anti-stripping agents' are commonly added provide an asphalt composition having an anti-stripping
to the asphalt. Before the mixing operation, these agents agent of low viscosity.
are added to the bituminous binder to reduce its surface To achieve these and other objects, the present inven
tension and to induce on the binder an electrical charge 45 tion provides an asphalt composition having improved
opposite to that of the aggregate surface. Lower surface adhesion to aggregate comprising asphalt and an adhe
tension gives improved wettability of the aggregate and sion improving amount of the aminoester reaction prod
charge reversal enhances bond strength by increasing uct of tall oil and triethanolamine.
Coulomb's attractive forces.
Cationic substances, particularly amines, have been 50 Triethanolamine is an inexpensive amine which is
traditionally used as anti-stripping agents. The cationic easily available and which easily reacts with tall oil to
substances increase the hydrophobicity of the aggre produce aminoesters.
gate, making the aggregate resistant to the penetration DETALEED DESCRIPTION OF THE
of water so that water seeping into the asphalt does not INVENTION
tend to destroy the bond between the asphalt and the 55 In contrast to polyethylene amines, triethanolamine:
aggregate. The addition of the cationic substances tends
to make the aggregate sufficiently water resistant that a N(CH2CH2OH)3 (1)
good bond with the asphalt is formed. Among the cati
onic materials which have been used as adhesion pro which is obtained by ethoxylation of ammonia, has only
moters with asphalt are primary alkylamines such as one nitrogen which is tertiary in nature. Except for salt
lauryl amine and stearyl amine, and the alkylene di formation to give triethanolammonium salts, this nitro
amines, such as the fatty alkyl substituted alkylene di gen is nonreactive when fatty acids are heated with
amines. Because these amines rapidly lose their activity triethanolamine. Instead, mono, di-, and triesters are
when combined with asphalt and stored at elevated formed upon heating in the presence of excess fatty
temperatures for an extended period, it has therefore 65 acid, according to the following reaction:
been necessary to combine the amine with the asphalt at
the work site when the asphalt is combined with the
aggregate, which in practice presents problems in ob
 3.
4,806,166
4.
known to have a history of stripping problems, and the
where x=1-3, y=0-2, x--y=3, laboratory standard asphalt is the viscosity grade 20
and R is a long chain saturated or unsaturated fatty acid (AC-20) asphalt cement normally used in the laboratory
radical. for mix design purposes. A "F" mix is prepared in
Compared to amidoamines and diamidoamines, which the aggregate is graded within E2 percentage
which are obtained by reacting fatty acids with poly points of that shown for each sieve in the following
amines, the fatty aminoesters are more fluid. Amidoa Table:
mines and diamidoamines often have the consistency of
paste or high viscosity liquids. O
For anti-stripping agents, the presence of a basic SIZE IN INCHES PASSING PERCENT
nitrogen is essential. In the case of the amidoamines, one 100
or two nitrogens per polyamine molecule are actually 95
wasted by amide bond formation. The amide nitrogen is 65
47
neutral and does not contribute to the basicity of the 15 1/50 20
molecule. 1/200 7
The aminoesters of the invention are generally stable
when added directly to hot asphalt. Stability is usually
only a problem if the asphaltis emulsified in solutions of The asphalt cement which is AC-20 in the following
low pH since ester bonds undergo hydrolytic cleavage 20 examples, is heated to 325' F. and 0.5% by weight of the
more readily than, for example, amide bonds. additive is thoroughly mixed in. The cement plus addi
The fatty acids used for reaction with triethanol tive is maintained at 325' F. until all stripping tests have
amine are those derived from tall oil, which is a by-pro been performed. The initial stripping test is performed
duct of the wood pulp industry and is recovered from within ten minutes after the treatment, a second test is
the black liquor of the sulfate or Kraft pulping process. 25 performed after 24 hours, and the final stripping test is
Tall oil fatty acids are chiefly oleic, 9-octadecenoic performed after 96 hours.
acid, and linoleic, 9,12-octadecendioic acid. The fatty The amount of treated asphalt cement initially pre
acids are reacted with triethanolamine in a conventional pared should be adequate but should not exceed the
ester reaction, such as by mixing the reactants in stoi quantity that can be properly mixed. In most cases, 900
chiometric quantities in a flask at 25 to 50 C., and 30 grams of asphalt cement and 4.5 grams of additive is
slowly heating to 200-250 C., while collecting reac adequate.
tion water in a trap. Heating is stopped after water The prepared mix of cement and aggregate is placed
formation is ceased and viscosity and amine value are in a container of boiling water and allowed to continue
determined. 35 boiling for ten minutes. The water is then drained off
The adhesion promoting agents of the invention are and the mix is dumped on a paper towel and remains at
useful by themselves, and also in combination with ambient temperature until dry, without moving or stir
other adhesion promoting agents such as amidoamines. ring. The mix is then visually inspected; a stripped parti
These combinations may be prepared by reacting the cle is considered to be one that visually appears to have
fatty acid with a mixture of triethanolamine and poly the asphalt cement totally or partially removed. The
amines, or by reacting the triethanolamine and poly visual inspection results are reported to the nearest 5%
amines separately with the fatty acids, and mixing the for each of the initial, 24 hours, and 96 hour tests.
reaction products. By mixing reaction products, agents Because of the variety of crude sources, which results
of lower viscosity are generally obtained. Another anti in changes to the chemical and physical consistency of
stripping agent can be obtained by reacting the fatty 45 the asphalt, coating results can change drastically when
acids with a blend of triethanolamine and triethylene a different asphalt, aggregate or evaluation test is used.
glycol to produce a product having low viscosity and In Examples 1 through 5 below, the anti-stripping
good coating performance.
The amount of anti-stripping agent used with the agents are evaluated with AC-20 asphalt from the
asphalt will vary, but will generally be in a range of 50 Young Refinery, Atlanta, Ga., which is the standard
about 0.1 to 2%, based on the weight of the asphalt or laboratory asphalt used by the Georgia DOT Labora
asphalt emulsion. 0.5 to 1% is generally the preferred tory for evaluation of anti-stripping agents. The aggre
range. The amount of mineral aggregate used will be gate used is 50% M-10 screening, 50% No. 89 stone
the amount generally used in conjunction with asphalt, 55 from Davidson Mineral Properties, Lathonia, Ga.,
typically 80 to 95% by weight of the total composition. which is a silicious type, granite aggregate.
The aminoesters are prepared by mixing the fatty
EXAMPLES acid and alkanolamine in a reaction flask at 25 to 50
In the following examples, asphalt compositions con C., and slowly heating to 200-250 C., while collecting
taining asphalt and an anti-stripping agent are prepared 60 reaction water in a Dean Stark trap. Heating is stopped
by mixing 251 grams of aggregate and 19 grams of after water formation ceases, and amine value is deter
treated asphalt cement, a proportion equivalent to 7% mined.
by weight asphalt. Mixing temperatures conform to Example 1
ASTM D-1559-76 (AASHTO standard T-245). The
mixing temperature or the temperature to which the 65 A number of anti-stripping agents prepared by the
asphalt cement is heated to produce a viscosity of reaction of tall oil fatty acids with treithanolamine are
280-30 centistokes shall be the compacting tempera tested against a commercially available low viscosity
ture. The laboratory standard aggregate is an aggregate product. The results are set forth below in Table I:
 5
4,806,166 6
TABLE I
Anti-stripping Agents Based on Tall Oil Acids and Triethanolamine
- Percent Coating -
Anti-Stripping Additive Amine Value 0.5%. 1.0% Dosage
COMMERCIAL PRODUCT 75 70-75 75-80
Ligrene D'-Triethanolamine
1.5:1 (W/W) 151.2 - 80
3:1 (W/W) 81.2 - 75
4:1 (W/W) 78.0 70-75 80-85
5:1 (W/W) 600 70-75 75-80
Liqro WTriethanolamine 2:1(W/W) 131.3 -- 80-85
Crude Tall Oil-Triethanolamine 2:1(W/W) 113.3 - 80-85

1.37:1 (W) 137.4 75-80

2.8:1 (W) 75.7 -- 70-75
4.66:1 (W) 9.6 -- 75
1483d Triethanolamine 4.66:1(W/W) 25.8 50 80
Liqrene D: Tall oil fatty acid heads.
Liqro W: Blend of tall oil fatty acid heads and bottoms.
L-5: Tall oil Fatty Acid (Westvaco), conjugated linoleic acid and oleic acids.
1483: Tall Oil Fatty Acid (Westvaco), oleic and elaidic acids,
The results above show that in general, the results Example 3
obtained from the TEA tall oil acid esters are compara
ble to that of the commercial product. As a comparison, tests were carried out with anti
EXAMPLE 2 stripping agents which are reaction products of tall oil
25 acids and N,N-dimethylethanolamine. In initial experi
Tests are carried out by reacting tall oil fatty acids ments, the tall oil fatty acid is mixed with the alkanola
with mixtures of triethanolamine and various poly mine in a ratio of 3:1 and 4:1 parts. By heating this
amines. The results are set forth in Table II below: mixture 170 C. most of the amine distills from the mix
TABLE II
Anti-stripping Agents Based on Reaction Products of Tall Oil
Acids and Blends of Triethanolamine and Polyamines
Anti-stripping Amine Percent Coating
Additive Value 0.5% 1.0% Dosage
Liqrene D. (TEA/AEP,1:1)2:1(W/W) 179 75-80 95 Glossy
4:1 (W/W) 108.3 70-75 70-75
Liqrene D - (TEA/AEP,2:1)4:1(W/W) 75.7 70-75
Liqro W-(TEA/AEP,1:1)2:1 161 - 90-95 Glossy
2:1 (W/W) 157.6 75-80 90-95 Glossy
Liqrene D. (TEA/G-100, 1:1)2:1(W/W) 84 --- 80-85
4:1(W/W) 19.5 . -- 80-85
Liqrene D - (TEA/AL-7, 1:1)2:1(W/W) 111 - 80-85
4:1(W/W) 75.1 - 80-85
Liqro W - (TEA/AL-7B,1:1)2:1(W/W) 151 -- 85-90
Slightly Gloss
Liqro W. (TEA/AL-7B,1:3)2:1(W/W) 157 -- 85-90
Slightly Gloss
Liqrene D - (TEA/Polaymine 142 - 85-90
H-Special, i:1) 4:1(W/W) 142 - 85-90
M28Bf- (TEA/AEP,1:1)2:1 (W/W) 137.4 -- 85-90
Slightly Glossy
AEP: aminoethyl piperazine (Union Carbide);
G-100.20% diethylene triamine, 80% aminoethylpiperazine (Dow);
AL-7: polyamine bottons product (Jefferson);
AL-7B: polyamine bottoms product (Jefferson);
PAHS: polyamine bottoms product (Union Carbide);
M28B; Tall oil fatty acid/rosin blend (Westvaco)
While the results above show generally excellent 55 ture before ester formation occurs. The fatty acid to
properties at a 1% additive level, the reaction products alkanolamine ratio is then increased to 7:1, at which
are generally of much higher viscosity than those of ratio fatty acid is by far in excess, and no alkanolamine
Example 1. distills from the reaction mixture. The final reaction
products, which are blends of fatty acids with fatty acid
salts of the aminoesters, are very fluid. The results of
testing with these materials are set forth in Table III:
TABLE II
Anti-stripping Agents Based on Reaction Products
of Tall Oil Acids and N,N-Dimethylethanolamine
Percent Coating
Amine 0.5% .0%
Anti-stripping Additive Value Dosage Dosage
Liqrene D - Dimethylethanolamine 7:1(W/W) 86.3 65 60-65
 4,806,166
7 8
TABLE III-continued
Anti-stripping Agents Based on Reaction Products
of Tall Oil Acids and N,N-Dimethylethanolamine
Percent Coating
Amine 0.5% 1.0%
Anti-stripping Additive Value Dosage Dosage
Liqro W - Dimethylethanolamine 7:1(W/W) 168.3 -- 6S-70
1483 - Dimethylethanolamine 7:1(W/W) 109.9 -
L-5 - Dimethylethanolamine 7:1(W/W) 86.4 60-65
M28B - Dimethylethanolamine 7:1(W/W) 88.6 65 70-75
T-3 - Rosin(1:1) - 813 70-75
Dimethylethanolamine 7:1(W/W)
Liqro W - Dimethylethanolamine - 102.2 -- 60-65
Triethanolamine 4:0.5:0.5(W/W/W)

It can be seen from Table III that the performance of reaction product of fatty acids with a mixture of trietha
the 7:1 reaction products is generally inferior at the 1% nolamine and triethyleneglycol which gives good per
dosage to TEA reaction products. This 7:1 reaction formance in a low viscosity product.
TABLE V
Miscellaneous Anti-stripping Agents
Amine Percent Coating
Anti-stripping Additive Value 0.5%. 1.0% Dosage
Liqro WO)-AEP(b)2:1 (W/W) 29.3 - 90-95(Slightly Glossy)
Licro W()-AL-7B(c)4:1 (W/W) 104.9 75-80 75-80(Slightly Glossy)
Liqrene D - AL-7B(c)4:1 (W/W) 115.6 85 80-85
Liqrene D - AL-794:1 (W/W) 103.2 70-75 85-90 (Glossy)
Liqrene D - HEP()-Mixture 114.4 - 75
Liqrene D - N,N-Dimethylethanolamine - 100 - 50
Liqrene D. CH3NH2-2 PO(2:1 (W/W) 130.1 - 60
Liqrene D - CH3NH2-2 PO(i)/AEP(50:502:1(W/W) 121.2 - 80-85CSlightly Glossy)
Liqrene D. EDA - 2PO3)3:1 (W/W) 132.3 - 85-90(Slightly Glossy)
M28B - AEP - 1 PO(h92:1 (W/W) 249.4 - 65-70(Slightly Glossy)
Liqro W() - (TEA/TEGG), 1:1)2:1 110 - 85-90
Liqrow: Blend of tall oil fatty acid heads and bottoms.
(AEP: aminoethylpiperazine (Union Carbide);
9AL-7, AL-7B polyamine bottoms (Jefferson);
(HEP. Hydroxyethylpiperazine blend (Union Carbide);
'91 mol N,N-dimethylethanolamine reacted with 1 mol propylene oxide;
01 mol dimethylamine reacted with 2 moles propylene oxide;
81 part ethylene diamine reacted with 2 parts propylene oxide (W/W);
91 part aminoethyl piperazine reacted with part propylene oxide (W/W); and
(TEG: triethylene glycol.
product is thought to be roughly a 1:1 blend of salt of
the aminoester and fatty acid.
E le 4 Example 6
xample Further testing is carried out with a different sample
Anti-stripping agents are prepared by blending a of Young AC-20 asphalt and two different aggregates
triethanolamine-fatty acid reaction product with other received from the Tennessee DOT Laboratory. These
fatty aminoesters or aminoamines. In Table IV below, aggregates are crushed limestone and crushed silicious
component A is the TEA reaction product, which is rivergravel and both samples are washed and screened,
blended with the other reaction product shown: passing a half inch screen and retained on a number 4
TABLE IV 50 sieve - o
Antistripping Agents Prepared by Blending Liqrene A 10 minute boiling test is carried out as described
D - Triethanolamine 5:1 (A) With Other Fatty above. In addition, an immersion test is carried out in
Aminoesters or Amidoamines which the coated aggregate is immersed in water for 24
Anti-stripping Additive
Percent Coating
1.0% Dosage
hours at 140 F. and judged visually as in the boiling
test,
50%. A - 50% (Liqrene D-AL 7, 4:1 75-80 The performance of the tall oil triethanolamine esters
50%. A - 50% (Liqrene D (TEA/AEP,1:1).2:1) 85-90 Shiny is very similar to that of commercial tall oil fatty acid
50%. A - 50% (Liqro W - (TEA/AEP,1:1).2:1) 80-85 amidoamines.
50%. A - 50% (Liqro W. (TEA/AL-7B,1:l).2:1) 75-80
50%. A - 50% Liqro W - AL 7B, 4:1) 80-85 TABLE VI
% Coating Retained
The products obtained according to this method gen Boiling Test - Immersion Test
erally have low viscosity and provided good results at No. Anti-Stripping Agent CaCO3 SiO2 CaCO3 SiO2
the 1% dosage. 1 Commercial Amidoamine 90 98 60 90
Example 5 (A)
2 Commercia Amidoamine 80 90 60 90
Testing is carried out on a number of anti-stripping (B)
3 TEA/Liqrene D 1:5 80 90 50 85
agents prepared by reaction of fatty acids with various 4 Liqrene D/TEA 3:1 88 90 65 90
amines. It is noted that the final agent in the table is the 5 Liqrene D/TEA 4:1 82 88 65 90
 9
4,806,166
10
TABLE VI-continued by a substantially anhydrous esterification reaction be
% Coating Retained tween a tall oil fatty acid and triethanolamine, wherein
Boiling Test - Immersion Test the weight ratio of tall oil fatty acid to triethanolamine
No. Anti-Stripping Agent CaCO3 SiO2 CaCO3 SiO2 added to the reaction is between about 1:1 and about 5:1
6 TEA/Liqro W 1:4 90 90 50 80
5 respectively.
7. In a process for preparing an asphalt composition
for combination with an aggregate material, the im
What is claimed is: provement of enhancing the asphalt composition's ad
1. An asphalt composition having improved adhesion hesion to the aggregate material comprising adding to
to aggregate comprising asphalt and an adhesion im 10 the composition an adhesion improving amount of an
proving amount of an anti-stripping agent comprising aminoester reaction product of a tall oil fatty acid and
an aminoester reaction product of a tall oil fatty acid triethanolamine.
and triethanolamine. 8. The process of claim 7 wherein the tall oil fatty
2. The asphalt composition according to claim 1, acid is selected from the group consisting of linoleic
wherein said tall oil fatty acid is selected from the group 15 acid, conjugated linoleic acid, oleic acid, and elaidic
consisting of linoleic acid, conjugated linoleic acid, acid.
oleic acid and elaidic acid. 9. The process of claim 7 wherein the reaction prod
3. The asphalt composition according to claim 1 uct is added in an amount of about 0.5% to about 1.5%
wherein said anti-stripping agent is present in the as by weight.
phalt composition in an amount of 0.5 to 1.5% by .20 10. The process of claim 9 wherein the reaction prod
weight. uct is added in an amount of about 1.0% by weight.
4. The asphalt composition according to claim 3, 11. The process of claim 7 wherein there is addition
wherein said anti-stripping agent is present in the as ally added to the asphalt composition a tall oil fatty
phalt composition in an amount of about 1.0% by acid.
weight. 25
12. The process of claim 7 wherein the reaction prod
5. The asphalt composition according to claim 1 uct results from a substantially anhydrous esterification
wherein said anti-stripping agent additionally comprises reaction of a tall oil fatty acid and triethanolamine in a
a tall oil fatty acid. weight ratio of between about 1:1 and about 5:1, respec
6. The asphalt composition according to claim 1, tively.
wherein said aminoester reaction product is produced 30 x 8 k .

35

45

50

55

65