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Патент USA US3096302

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t
1
3,096,292
ie
3,09%,292
Patented July 2, 1963
2
ily restored to its normal consistency and appearance
by simple stirring and pumping, it has often been ob
CATIONKC BITUMHNGUS EMULSEONF}
Edward W. Martens, El Cerrito, Calih, assignor to Qaii
fornia Research Corporation, San Francisco, Caiif., a
corporation of Delaware
No Drawing. Filed Aug. 21, 1959, Ser. No. 835,176
5 Claims. (Ci. 252—31l.5)
“sapamines” (products of acylation of unsymmetrical di
alkyl ethylene diamines with a ‘fatty acid chloride), tend
The present invention relates to oil-in-water type acidic
tank, coalescing into large particles or gobs, until ?nally
served that cationic emulsions prepared with the aid
of cationic emulsi?ers, such as hydrochloride or acetate
salts of amines derived from tallow fatty acids, or of
to settle out the bitumen at the bottom of the storage
bituminous emulsions and more particularly to acidic bi 10 a thick mass of bitumen accumulates as a lower phase.
tuminous emulsions characterized by excellent storage
It is impossible to restore the emulsion thus broken
stability with virtually no settlement of the bituminous
down to its normal state by the mere stirring and pump
phase, after being storedwfor {a period, of at least from .ing. If the particles of bitumen are not too large, col
snare? ‘two weeks, as contrasted with other acidic bi
loid mill treatment may sometimes be of help, but this
tuminous emulsions heretofore reported in the art.
treatment increases the costs considerably. When col
Acidic bituminous emulsions, more commonly referred
loid mill treatment is no longer possible, the manu
to as cationic bituminous emulsions, have made their
facturer or applicator has to resort to scraping out the
appearance as materials suitable for road-paving con
settled asphalt which adheres to the inside of the tank,
struction and repair, and for other paving treatments
and this represents a highly annoying, laborious and
20
of all kinds of surfaces, at a relatively recent date. These
costly operation, whatever he the size of the tank in
emulsions are prepared by emulsifying bitumen in wa
volved.
ter with the aid of cation-active (cationic) emulsi?ers,
It has now been found that cationic oil-in-water bi
such as quaternary ammonium salts, amines, heterocyclic
tuminous emulsions, and in particular, cationic asphalt
N-bases, and the like. The main advantages of these
in~water emulsions, characterized by an excellent storage
cationic emulsions are their compatibility with acidic, 25 stability at conventional storage temperatures of from
siliceous types of aggregates that are unsuitable ‘for use
about 120 to about 160° F., may be produced with the
with the conventional basic (anionic) emulsions, and
aid of e?'ective cationic emulsi?ers, selected among a
also their quicker set, Le, a more rapid coating of the
speci?c group of hydrohalide salts of a particular kind
stone surface, which circumstance makes the paving work
of high molecular weight amino amides and employed
less dependent on adverse weather conditions often en 30 in amounts from about 0.1 to about 2.0% by weight,
countered. A further discussion in the present descrip
based on the ?nished emulsion.
tion of the various properties and advantages of cationic
The organic acids employed to prepare the amides,
emulsions would be redundant, since they have been al
whose hydrohalide salts constitute eifective cationic emul
ready amply described in the art, a particularly thorough
si?ers in accordance with the invention, are tall oil acids,
exposition having been published by Dr. Hans Kresse 35 i.e., mixtures of fatty acids and rosin acids derived from
in “Bitumen, Terre, Asphalte und Verwandte Stoife,” No.
waste liquor of wood-pulp manufacture. The high mo
7, 1956.
lecular weight amides of these tall oil acids (Swedish
Despite their successes of cationic bituminous emul
rosin acids) are prepared by reacting the acids with
sions in the art of paving treatment of various road sur
tetraethylene pentamine: (1) to form monoamides of
faces, certain shortcomings have been soon noted by 40 tall oil acids, tetraethylene pentamine is reacted with
their manufacturers and applicators.
tall oil acids in the mol ratio of 1:1; (2) to form di
Thus, when amidoamine salts, such as amidoamine hy
amides, the pentamine is reacted with tall oil acids in
drochlorides of stearic acid, tall oil acids, etc., are em
the mol ratio of 1:2. The two kinds of amides thus
ployed as the emulsifying agents to prepare these emul
have from 3 to 4 basic nitrogen atoms available for the
sions, the product of emulsi?cation lacks mechanical 45 formation of hydrohalide salts with halogen acids.
strength (is unstable) and breaks down, while being trans
The availability of basic nitrogen atoms depends on
ported to the construction or repair site, or while being
the choice of the ?nal pH of the salt solution to be used
pumped or otherwise handled prior to the actual appli
for emulsifying bitumen in water. Among the hydro
cation on the aggregate. Furthermore, the adhesion
halide salts, hydrochlorides and hydrobromides are pre
property of the emulsion is often found to be lower than
ferred for practical applications. These hydrohalide salts
that desired and to be ?uctuating from one type of ag
gregate to another. This unpredictable behavior, ac
cordingly, requires a very careful selection of the ag
gregate type in order to be sure that a satisfactory bond
would be provided between the stone surface and the
?lm of bitumen.
are employed as the cationic emulsi?ers for bitumens in
accordance with the invention in amounts which range
from about 0.1 to about 2.0% by weight based on the
weight of the ?nished bituminous emulsion.
In the following description, the monoamides formed
by reacting one mol of tetraethylene pentarnine with 1
mol of tall oil acids will be designated hereinafter as “N
salts as the cationic emulsi?ers, e.g., cetyl trimethyl am
talloyl amide of tetraethylene pentamine,” while the di
monium bromide, the emulsions, although having as a 60 amides formed by reacting 1 mol of the same pentamine
rule satisfactory mechanical strength, stability and ad
with 2 mols of tall oil acids will be designated as “N,N
hesion, are found to be de?nitely too viscous. To parry
ditalloyl amides of tetraethylene pentamine.”
this last drawback and to permit ready pumping and
The aforementioned salts of mono- and ditalloyl amides
distribution, the emulsions have to be prepared using
of tetraethylene pentamine (or of mixtures of these
low ‘concentrations of bitumen, so that the actual quanti
amides) serve to provide satisfactory oil-in-water type
ties of the emulsions required for satisfactory coating
cationic emulsions characterized by a satisfactory degree
of the aggregate by the bitumen become unduly high.
of adhesion to the aggregate, a low viscosity, a good me
A particularly annoying drawback lies, however, in
chanical strength, and, particularly, an exceptional de
the poor storage stability of the cationic emulsions.
gree of stability while in storage. Bituminous materials
While during storage a certain degree of thickening of 70 suitable for the preparation of these emulsions using
the emulsion at the bottom of the storage tank or con
cationic salts of talloyl amides of tetraethylene penta
On the other hand, in using quaternary ammonium
tainer is to be expected, and the emulsion can be read
mine, include natural asphalts, asphalts obtained by the
3,096,292
4
a 200—3 00 penetration asphalt of Venezuelan origin and
distillation of petroleum residues, air-blown petroleum
asphalt, coal-tar, coal-tar pitch, gilsonite, etc., and, in
particular, paving grade asphalts characterized by a pene
diiferent concentrations of the cationic amide salt emulsi
?ers in accordance with the invention. These emulsions
Were then tested ‘for various properties (viscosity, appear
ance, stability in storage, and also adhesion to the ag
tration from about 300 (and higher) to 0, and prefera
bly from 250 to 150 (ASTM D-S).
gregate). Coarse acidic siliceous aggregate (%-%”)
The emulsions prepared by emulsifying any one of the
was employed in the “stone-coating” (adhesion) tests.
aforementioned bituminous materials in water with the
For the purposes of contrasting and emphasizing the
aid of cationic salts of talloyl amides of tetraethylene
uniqueness of the salts or talloyl amides of tetraethylene
pentamine in accordance with the invention may be either
rapid-setting (RS——1 and RS-2) or medium-setting, and 10 pentarnine of the invention as the emulsi?ers for cationic
bituminous emulsions, corresponding salts of talloyl
are preferably characterized by a high enough residue
amides ‘of diethylene triamine have been likewise em
ployed to prepare the emusions, and the various prop
erties of these latter have been observed. The adhesion
for paving purposes.
After a particular bituminous binder material has been 15 was determined in ‘all tests in accordance with the follow
ing procedure:
selected and the monoamide or the ‘diamide of tall oil
(50 to 75%, and in particular from 55 to 68%) so as to
be useful as road binders and the like materials suitable
A wetted (2% Water, based on dry aggregate) sample
of coarse, siliceous, hydrophilic aggregate (465 g.) was
acids, and tetraethylene pentamine made available, the
preparation of the emulsion is carried out in a simple,
treated with a predetermined amount of the emulsion
straightforward manner. The following example illus
20
trates such a preparation.
(35 g.) by mixing vigorously the emulsion and the ag
gregate together for about 2-3 minutes. After that, the
mixing was stopped and the percentage of the aggregate
surface, from which the emulsion stripped off at the end
of mixing, was estimated visually.
The viscosity was determined in accordance with the
recommended ASTM practice for testing emulsi?ed
21.8 g. of talloyl amide of tetraethylene pentamine
(corresponding to 0.5% by Weight based on the ?nal
emulsion) is added to a 2 liter vessel containing 1300 g.
of distilled water and is thoroughly dissolved in the Water
with the ‘aid of a magnetic stirrer. The pH selected in
this instance is 3.5 and a 3.7% solution of hydrochloric
acid is added until the electrodes of a pH meter, placed
in this aqueous solution, indicate a pH of 3.5. There
asphalt (ASTM D244) in seconds Saybolt-‘Furol at 77°
F.
The appearance of the emulsions was observed
visually for the formation of large gobs or “shot,” skin
upon, the solution is made up to a total of 1475 g., and
‘or ?lm formation, and settlement of the emulsion either
as such (by thickening) or as a separate homogeneous
the pH is ?nally adjusted to 3.5. The resulting aqueous
phase is then added into the water cylinder of a colloid
asphalt phase. Particle size was determined in microns
mill and is heated to 120° F. At the same time, a suf
by means of a microscope.
The results of the several series of representative com
parison tests ‘are given below in Table I. in all tests, the
aggregate used was a siliceous sandstone of Pennsylvania
origin, known in the trade as White Haven Sandstone.
?cient quantity of a 200-300 penetration asphalt is in
troduced into the preheated asphalt cylinder of the same
colloid mill so as to provide a 65% residue in the ulti
mate emulsion. The mill is operated ‘at 3,600‘ r.p.m., the
two phases being forced into the mill head over a 30
second period, and the asphalt emulsion is discharged into
l-gallon glass jar. This jar is immediately covered, after
being ?lled with the emulsion, and is stored in an oven 40
overnight at 120° F. After 16 hours of overnight stor
rage, the several properties of the emulsion, such as vis
cosity at 77° F. (SS-F), adhesion in percent, appearance,
and settlement of the asphalt phase, are determined. Fol
lowing an additional storage of the emulsion for two
weeks at 140° F., viscosity, appearance and asphalt settle
ment are again observed.
The ?nished emulsion contained: 65 % by weight of an
asphalt ‘of Venezuelan origin: 0.5% of the cationic salt
emulsi?er, suf?cient HCl to give a pH of 3.5; and water
to make 100% by weight.
In the ‘table, the following abbreviations are employed:
Salts of N-talloyl amides of tetnaethylene pentamine are
designated as salts of N-talloyl amides of TEPA; salts
of N-talloyl amides diethylene thiamine as salts of N
talloyl DETA; mM. refers to millimoles of the amide salt;
SSF refers to seconds of Saybol-t-Purol scale. One gal
lon of the emulsion is assumed to weigh approximately
A number of cationic bituminous oil-in-water type
emulsions have been prepared in a similar fashion, using 50 3600 grams.
Table I.—C0mparison Tests of Cationic Emulsions
Concentration of
Inspection after
of Emulsi?er
Predominant
Run
No.
Emulsi?er Salt
Percent mM/3600
by Wt.
1 ____ __
N-Talloyl TEPA, hydro-
chloride.
5
__d0 _ _ _ _ _ _ .
_ _ _ _ _ _ _ __
6 ____ __ N-Talloyl DETA hydro-
chloride.
__
_ _____do__
___
Particle
Size in Viscosity,
Microns
________ __
SSE at
77° F.
0.2
13.8
1. 5
0.3
0.5
0.7
20.6
34. 3
48. 5
1. 5
1. 5
1. 5
1. 0
68. 8
1. 5
5
45
0.15
13.8
1.5
10
124
9
8
120
105
7
5
5
20.6
34. 3
1.5
1.5
0.525
48.5
1.5
________ __
06
____
0.75
68.8
1.5
________ __
87
l3_____ _____d0 ____________ __
____
Viscosity, 8813‘
Settlement
at 77° F.
Asphalt
65
0.225
0.375
N-Talloyl TEPA hydrochloride.
Adhcsion in
Percent
56
49
5O
____
12 ________ __do __________________ __
14 ________ "do _____ _-
pH
g.
Inspection after 2 Weeks at 140° F.
16 Hrs. at 120° F.
0.2
13.8
3. 5
4
0.3
20.6
3. 5
5
35
42
0.5
34.3
3. 5
5
43
0.7
48. 5
3. 5
5
48
_
15 ________ __(lo __________________ __
1.0
68.8
3.5
5
46
90
50____
16_____ N-Talloyl DETA hydrochloride.
0.15
13.8
3. 5
10
58
10
Emulsion partly
broken.
____
0.225
0.375
20. 6
34. 3
3. 5
3. 5
10
10
68
115
0.525
48. 5
3. 5
________ __
105
0.75
68. 8
3. 5
________ __
115
D0.
Very heavy.
D0.
. Minch layer.
D0.
3,096,292
Table 1-~Conti11ued
Concentration of
No.
Emulsi?er Salt
‘
.510 ____________ __
28_____ N? ’-ditalloyl DETA hydro chloride.
(1
Predominant
pH
21_____ N,N’-ditall0yl TEPA hydrochloride.
22
(10.
I“-..
Inspection alter
of Emulsi?er
Run
_
Percent nM/3600
Particle
Size in Viscosity,
by Wt.
Microns
.
Adhe-
Viscosity, SSF
Settlement
SSF at
sion in
at 77° F.
Asphalt
77° 1?.
Percent
0. 314
13. 8
3. 5
6
8O
0.472
20. 6
3.5
6
80
0.783
34. 3
3. 5
6
83
l. 10
48. 5
3. 5
6
65
1. 57
68.8
3.5
6
61
0. 258
13.8
3. 5
10
180
O. 386
0. (1'45
0. 906
1. 29
20. 6
34. 3
48. 5
68. 8
3. 5
3. 5
3. 5
3. 5
10
10
10
10
270
352
330
184
The results of the comparison tests presented in Table
I bring out conclusively the unique characteristic of sea
bility in storage of the cationic bituminous emulsions pre
pared with the aid of the particular salts of talloyl acid
amides of tetraethylene pentamine as the emulsi?ers. in
all test runs with these emulsions, after 2 weeks (14 days)
of storage at a temperature of about 149° F., the emul
sions appeared substantially unchanged, smooth or only
slightly grainy in texture, with practically no formation
of “shot,” and with no settlement of a separate asphalt
phase at the bottom of the storage vessel. The viscosity
of the emulsion, when determined after two weeks in
storage, did not increase inordinately as compared with
the viscosity originally observed after the emulsion was
prepared and left to stand overnight for 16 hours at 120°
F. The average particle size of the emulsion ranged from
about 4 to about 7 microns, indicating the high quality
Inspection alter Z'Weeksat 140° F.
16 Hrs. at 120° F.
and the test data are intended solely to illustrate the in
vention and are not to be interpreted in limitation thereof,
except as de?ned in the following claims.
I claim:
1. A cationic oil-in-water type bituminous emulsion
consisting essentially of from about 50 to about 75% by
weight of asphalt, as the disperse bituminous phase; from
about 50 to about 25% by weight of water, as the con
tinuous aqueous phase; and, as the emulsi?er for said
asphalt in said water, from about 0.1 to about 2.0% by
weight of a hydrohalide salt of an amino~amide of tetra
ethylene pentamine and tall oil acids, said salt being se
lected from the group consisting of hydrochloride and
hydrobromide salts of mono-talloyl and ditalloyl amides
of tetraethylene pentamine, said amides being character
ized by the presence of from 3 to 4 basic nitrogen atoms
Adhesion was excellent as
reactive with halogen acids, and said emulsion being
characterized by stability in storage at temperatures from
compared with the adhesion displayed by the emulsions
prepared with the aid of the emulsifying salt derived
about 120 to about 160° F. and by the absence of settle
ment of the asphalt, when so stored for at least two
of the emulsi?ed material.
from diethylene triamine. As a matter of fact, these lat
weeks.
ter emulsions prepared from the same asphalt, using iden 40
2. A cationic bituminous emulsion as de?ned in claim 1
tical quantities (in millimoles per 1 gallon of the ?nished
wherein the emulsi?er salt is a hydrochloride salt of a
emulsi?ed material) of the salt emulsi?ers derived from
tetraethylene pentamine monoamide of tall oil acids.
diethylene triamine, invariably possessed grainy struc
ture, and, on being stored for two weeks at 140° F, dis—
played separation of “shot” and heavy settlement of an
asphalt phase at the bottom of the storage vessel. The
viscosity of these emulsions after storage also lay outside
the limits speci?ed by ASTM.
In addition to the basic components of the cationic
emulsions, i.e., bitumen, water, and the salt of talloyl
acid amide derived from tetraethylene pentamine act
ing as the emulsi?er, the emulsions of the present inven
tion may contain conventional additives known in the
art to improve certain desirable characteristics of such
emulsions.
These additives include, e.g., anti-stripping
agents, thickening agents, etc., provided, of course, they
do not impair the bene?cial effect of the cationic salt
emulsi?er on the storage stability and other desirable
properties of the emulsions.
it is to be understood that the foregoing description 60
3. A cationic bituminous emulsion as de?ned in claim 1
wherein the emulsi?er salt is a hydrochloride salt of a
tetraethylene pentamine diamide of tall oil acids.
4. A cationic bituminous emulsion as de?ned in claim 1
wherein the emulsi?er salt is a hydrobromide salt of a
tetnaethylene pentamine monoarnide of tall oil acids.
5 . A cationic bituminous emulsion as de?ned in claim 1
wherein the emulsi?er salt is a hydrobromide salt of a
tetraethylene pentamine diamide of tall oil acids.
References Cited in the ?le of this patent
UNITED STATES PATENTS
2,317,959
Johnson et al ___________ __ Apr. 27, 1943
FOREIGN PATENTS
792,648
1,132,352
Great Britain _________ __ Apr. 2, 1958
France ______________ ._ Nov. 5, 1956
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