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Патент USA US3041309

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United States Patent 0 cc
1
’ .
3,041,299
Patented June 26, 1962
2
latex, particularly one of those produced by emulsion
polymerization processes, in admixture with an asphalt
cutback is subjected to conditions of high shear such ‘as
3,041,299
PROCESS FOR PREPARWG SYNTHETIC RUBBER
A§PHALT CGMIPGSITIQNS AND CUMPOSITION
PREPARED THEREBY
in a colloid mill to produce a stable composition consist
ing of an emulsion in which the asphalt cutback consti
tutes the dispersion medium vfor the rubber and the water
that was contained in the latex. It has been found that
it is. not possible to produce stable compositions with
_
Felix C. Gzernski, Glen Mills, and Robert C. Taylor, King
of Prussia, Pa, assignors to The Atlantic Re?ning Com
pany, Philadelphia, Pa, a corporation of Pennsylvania
No Drawing. Filed Oct. 23, 1959, Ser. No. 848,232
3 Claims. (Cl. 260-285)
natural rubber latices even when using conditions ofvhigh
shear, hence this invention is limited to synthetic rubber~
asphalt cutback compositions.
The synthetic rubber latex emulsions contain various
This invention relates to a process for preparing syn
thetic rubber-asphalt cutback compositions and to the
novel composition prepared by such process. In par
~ conventional compounds such as surface active agents,
ticular, this invention relates to a process for preparing
polymerization catalysts such as cumene hydroperoxide,
synthetic rubber-asphalt cutback compositions by sub 15 short stop materials such as di-tertiary-butyl hydroqui
jecting a mixture of an asphalt cutback and a rubber
‘latex to conditions of high shear.
In recent years numerous advantages have been found
none and similar compounds, all of which are present in
small amounts. The surface active agents may consist of
emulsi?ers comprising the salts, or acids of natural esters
for incorporating rubber, particularly synthetic rubber,
such as potassium stearate, potassium-processed rosin,
int-o asphalts. The rubber gives the asphalt elasticity, 20 polyalkylene oxide‘dioleates, sorbitan triolea'te, and the
increases its ductility, and reduces its suscept1bility to
temperature changes. The extent to which these ad
like, or such surface active agents may be synthetics such
as the alkyl aryl sulfonates, particularly the alkyl-benzene
vantages can be realized, however, depends upon the ex
tent to which the rubber is dissolved or dispersed in the
asphalt. During the development of rubber-asphalt pav
25
ing compositions, crumb rubber was incorporated during
the mixing of asphalt and aggregate. This was such a
di?icult operation that the process did not advance much
beyond the experimental stage. Subsequently it was pro
sulfonates, condensed naphthalene-‘formaldehyde sulfoé
nates, alkylolamides and the like, or non-ionics such as
the ‘condensation products of nonyl phenol vwith ethylene
oxide or propylene oxide-ethylene ,oxideproducts. These
agents apparently not only aid in stabilizing the latex
emulsion but in, addition promote the stability of the
rubber latex-asphalt cutback composition.
posed ?rst to coat the aggregate with the, asphalt and 30 The latices may comprise from 15 to 70 weight percent
thereafter add latex to the hot mixture with constant
solids and 30 to 85 weight percent water. Latices hav
mixing in order to incorporate the rubber into the asphalt.
ingsolid contents higher and lower than these are occa
This process required exceedingly close temperature con-\
sionally found and are suitable for this invention. The
trol in order that the rubberized asphalt would retain its
>GRS-type rubber latices comprising copolymerized bu
desired elasticity ‘and, moreover, it was exceedingly di?‘i 35 tadiene and styrene may be either those produced by the
cult and required long mixing times to obtain a uniform
‘cold process or the hot process. ,GRS-2006 comprising
mixture of the asphalt and rubber with the aggregate.
approximately 24 percent styrene and 76 percent buta
In another method it was proposed to prepare asphalt
diene, the latex comprising ‘approximately 28 percent rub
rubber blends in the absence of a mineral aggregate by
ber and 72 percent water, has been found to be particu
adding a rubber latex to a molten supply of asphalt 40 larly suitable for the process of this invention.
under exceedingly carefully controlled conditions of tem
The asphalt cutback may be rapid, medium, or slow
perature and rate of addition such that foaming and
curing cutback made from 120-150 penetration at 77°
splattering would be minimized as the water from the
F. (ASTM Method D—,5) asphalt, 85-100 penetration
latex was ?ashed from the mixture by contact with the
asphalt (110° F.—12V5° F. softening point, ASTM Method
hot asphalt. This method also had many disadvantages 45 D-36), 150° F. softening point asphalt, 190° F. soften
inherently present whenever water is allowed to come into
ing point asphalt, and the like.” These asphalts are sepa
contact with hot asphalt.
rated from crude petroleum by well known conventional
A method now has been found, however, whereby syn
methods.
,The petroleum distillate solvent employed in
thetic rubber may ‘be incorporated‘ readily into asphalt
producing the asphalt cutback may be anyone of the
in the form of an asphalt cutback to produce a stable 50 conventional petroleum distillate fractions employed in
composition wherein the rubberized asphalt retains all
of its advantages of elasticity, increased ductility, and
reduced temperature susceptibility together with the un
producing cutbacks such as naphtha, kerosene, or gas oil
fractions. These fractions span a boiling range of from
about 180° F. to 600° F. For example, a conventional
expected advantage not heretofore realized of increased
rapidwcuring cutback is prepared from an 85400 pene
adhesivity to mineral aggregates. These properties ren 55 tration asphalt by dissolving it in a blending naphtha
der the compositions of this invention particularly useful
‘having a boiling, range from 190°, F. to 390° F. and a
in the manufacture of asphalt paving.
'
'
specific gravity of approximately 0;75. fThe quantity of .
,It' is an object of this invention to provide a process
‘aspha'ltconstitutes about 82 percent by weight of the blend
for preparing synthetic rubber-asphalt cutback compo
sitions.
.
It is another object of this invention to provide a proc
ess for preparing synthetic rubber-asphalt cutback com
positions from a mixture of a synthetic rubber latex and
an asphalt cutback.
‘_
and the naphtha 18 weight percent.
:
'
A medium curing cutback is prepared similarly from
an 85-100 penetration asphalt and a somewhat heavier
solvent, i.e., a petroleum distillate having a boiling range
betweeny'380" F. and 590° F. and a speci?c gravity of
approximately’ 0.85. Similarly, cutbacks can be made
It is another object of this invention to provide a 65 from the various asphalts and solvents
which have been
novel synthetic rubber-asphalt cutback composition
"wherein vthe rubberized asphalt has increased adhesivity
for mineral aggregates.
‘
_
_
.
Other objects and advantages of this. invention will be
apparent from the detailed description and claims that 70
i follow.
' In accordance with this inventionia synthetic rubber
mentioned, in various proportions, preferably, however,
the solvent should range from 10 to 50 percent by weight
and the asphalt from 5,0 to 90' percent by. weight.
..
g’ , It has been found that in order to impart. to the asphalt
the desired elasticity,‘ ?exibility, ductility, and toughness
properties it is, necessary to incorporate‘ at least 0.5 per
cent by weight of synthetic rubber based on the weight
4
3,.
v V of the asphalt.
Preferably, the amount of rubber should
range between 2 and 4 percent by weight based on the
' weight of the asphalt in the cutback and exceedingly
good results - have been obtained with compositions
wherein the rubber amounted to 3 percent by weight of
the asphalt contained in the cutback. Amounts ranging
up to 15 percent by weight of rubber based on the weight
of the asphalt may be employed. However, amounts in
excess of about 15‘ percent should not be used since the
back consisted of 82 percent by weight ofv an asphalt
having apenetration at 77° F. of 92 and a softening
point of 117° F ., and l8.percent by weight naphtha hav
ing a speci?c gravity of 0.754 and a boiling range of. a.
from 190° F. to 390° F. The rubber latex was GRS
2006 and consisted of a copolymer of 24 percent by weight
of styrene, 76 percent bygweight of butadiene. The latex
consisted of 28 percent by weight of the copolymer and
72 percent by Weight of water. Eight percent by weight
product becomes so highly viscous that it behaves as a 10 of the GRS'—2006 rubber latex was added to 92 percent
solid and cannot be admixed with paving aggregates or
utilized for other purposes in the manner of the ?uid cut
back.
by weight of the cutback at temperatures of 160° F. to
165° F. This amount corresponded to approximately
3 percent by weight of rubber based on the weight of
the asphalt in the cutback. Portions of this mixture
In accordance with the process of this invention the
asphalt cutback is heated to a temperature of from 130° 15 were subjected to three diiferent shear rates in a Model
G~3 Charlotte colloid mill. The variation in shear rate
F. to 190° F. The temperature should be selected such
was obtained ‘by adjusting the gap between the rotor and
that the cutback will be reduced in viscosity and be suf~
stator of the mill. The compositions thus prepared were
?ciently ?uid whereby its admixture with the latex is
allowed to stand for two weeks at a temperature of 175°
facilitated. If a low boiling solvent is employed in the
F. after which time the amount of phase separation, i.e.,
cutback it is preferred to use temperatures in the lower
the amount of latex phase separated, was determined by
end of the range to avoid rapid vaporization of the sol
decantation. The conditions and results of these experi
vent from the cutback. Since the latex is ordinarily suf
?ciently ?uid to permit thorough mixing it need not be
heated. The heated asphalt cutback and latex may be
premixed before being introduced into the zone of high 25
shear or they may be introduced separately togthe high
shear zone and admixed therein.
_
Since the latex constitutes the minor portion of the
composition it is usually unnecessary to. heat the’ mixture
prior to introducing the mixture into the zone of high
shear in order to subject the mixture to the high shearing
action at the desired temperatures ranging from 130° F.
ments are set forth in' Table I.
-
Table I
Shear
I
Colloid
Experiment Number
Separation
Rate
after 2
Mill Gap, Reciprocal
Inches
1 _______________________________ __
.wks. at
175° F.,
wt. percent
Seconds
0.001
1X106
0.5
2 _______________________________ __
0.01
_ lXl05
1.3
3 _______________________________ __.
0. ()3
3X10‘
1.6
' to 190° F. and preferably from 160° F. to 165° F. ‘In
the zone of high shear, the asphalt cutback and synthetic
rubber latex are subjected to shear rates ranging from
104 reciprocal seconds to 5X106 reciprocal seconds and
preferably the shear rate should range from 3><l0* re
ciprocal seconds to 106 reciprocal seconds. In order to
obtain these high shear rates it is preferred to employ
It will be noted that as the shear rate decreases the
amount of phase separation during storage increases
slightly. In each ‘of these cases, however, the material
which separated was very readily redispersible bygmerely
stirring the composition.
a colloid mill. Colloid mills which will attain these high
shear rates are available commercially. Two commer
cially available colloid mills have been found to be vpar
ticularly suitable for the process of this invention. These
'
'
EXAMPLE l1
'
’
Additional experiments were carried out to determine
the effect on the stability of the composition when the
composition’ Was recycled through the colloid mill. The
- ‘are a Model G-2 and Model G-3 Charlotte colloid mill
same mixture of asphalt cutback and GRS rubber latex
45
manufactured by the Chemi-Colloid Laboratories, Inc, , was used in these experiments as was used in Example
Garden City Park, New York.
It is a critical feature of this invention that the asphalt
cutback' and synthetic rubber latex be'subjected to high
I and the same colloidal mill also was employed. The
conditions, including the number of passes through the
shear rates since highpshear rates are required to produce ' v ' colloid mm and the stability of the resulting comppsi'
tions, are set forth in Table II.
stable emulsions of the latex in the asphalt cutback. If 50
’
~
> Table II
low shear rates are employed to incorporate the latex
in the asphalt cutback, the emulsion formed is very'un
,
Shear
stable and the latex phase will separate from the asphalt
. _
Rate,
cutback phase within a matter of days upon standing at ' 7
175° F. It then becomes necessary to reprocess the en
Experiment Number‘
.
Separation
vthe rubber-asphalt cutback composition prepared by the
high shear'rate process of this invention. This phase
separation, however, is very small and is usually only of
after 2
Through
wks, at
Seconds
Mill
175° F.,
'
tire mixture before it can be used. On prolonged stor
age a minor amount of phase separationmay occur with
the order, from 1 to 2 weight percent. Moreover, it is
unnecessary to reprocess the composition since the mate
N 0. of
Passes
Reciprocal
wt. percent
1X10B
1X10‘5
3X10‘5
1
2
1
1 3
O 5
2 2
3X105
5
0 9
‘These data show that the stability of the composition
rial which separates may be readily redispersed by stirring
is improved if the mixture is passed through the colloid
or other mild agitation.
mill more than once.
The following examples are provided solelyyfor the
purpose of illustrating, certain speci?c embodiments and
features of the instant invention. Accordingly it will be
understood ‘that the invention is not limited to these illusl V
'
' EXAMPLE III
In order'to demonstrate the desirability of ahigh shear
rate as compared with a low shear rate obtained by ordi
nary mixing, three mixtures of asphalt cutback and rub
tratlve examples.
_
.
a
70 ber latex were-processed in the Model G-3 Charlotte
colloid 'mill at a shear rate or 106 reciprocal seconds
_
1
EXAMPLE: 1
V
_
and
by ordinary mixing at shear rates well below 10*
In order to demonstrate the e?ect of shear rate on the
stability of the composition, three di?erent shear rates
were employed ‘to prepare compositions from a speci?c
asphalt cutback and GRS rubber latex." The asphalt'cut
reciprocal seconds with a commercial household mixer,
i.e., a “Mixmaster?‘operated at its maximum speed using
a one-quartcontairier. The processing-‘temperature in
.
~
7
3,041,299
5
.
.
-
7
6
each case ranged from 160° F. to 165° F. The ?rst mix
.
Table IV
ture employed GRS-2000 consisting of 46 percent by
weight of styrene, 5'4 percent by weight butadiene, hot
i
polymer Process, with 40 Percent by Weight .rubber and
Properties of Distillation Residue
60 percent by weight water in the latex.
The asphalt
I
5
cutback was the same as the cutback of Example I.
.
.
.
Asphalt,’ Asphalt
no rubber
133B’?
.
o (
_
Mixture No. 2 employed GRS-2l05 consisting of 46
i‘lifiii‘ié?t‘t? I“ (R &\B’ASTM’D 36)
116
121
percent by weight styrene, 54 percent by weight butadiene,
Ei§$% £1?’ $8 5'' 20533?’ '''
13;
iii
cold polymer process, with 62 percent by weight rubber
Temperature susceptibility, Pe'n. 3935-1531551‘.
and 38 percent by weight water in the latex. > The cuback 10 Dl7l7é-g;if;;5—t¢ ------------was the same as that of Example I.
.
Mixture No. 3 employed GRS-2006 consisting of 24
----- --
-26
~39
39.2°.F.,'cm. (5 cmjmin.) (ASTM, D-ll3)_____
10
150+
77~°° F" cm- (5 cIll/1111110 (ASTM. D—113)-.--
150+
150+
percent by weight of styrene, 76 percent by weight of buta
diene, hot polymer process, with 28 percent by weight
These data show that the asphalt-rubber composition
of the rubber and 72 percent by weight of water in the 15 has superior ductility and temperature susceptibility prop
latex and the same asphalt cutback as in Example I.
erties as compared with the base asphalt. Moreover, it
In each case the amount of rubber latex was selected
was found that the asphalt-rubber composition pulled out
so that the quantity of rubber in the latex corresponded
into nibbery‘strands that elastically retracted when re
to 3 percent by weight 'based on the weight of the asphalt
leased. The asphalt, of course, did not exhibit this prop
in the cutback. The results of these experiments are 20 erty in any manner. Impact’ tests on the rubberized as
set forth in Table III.
.
phalt showed it to have far less brittleness than ordinary
asphalt. During the ductility tests on the rubberized as~
Table III
phalt the composition pulled out into much thicker strands
Separation after Two Weeks at 175°
F., Weight Percent
Mixture Number
0 d_
1
8.!‘
,
h
OW
S
as compared with asphalt only showing that the rubber
ized asphalt has greater toughness.
Hi hsl 3
88.!‘
I m gliliillg
EXAMPLE VI
ie I‘,
l0igReciprocal SecFmdS
_
2. 5
3
1.7
6.2-.
7
.
. .
s
In order to determine the utihty of the synthetic rub
her-asphalt cutback compositions of this invention, por
30 tions of the composition prepared in Experiment No. 1
1 ------------------------------ -- 20")
(in ‘me week) ----- -10.0 (in one week) _____ __
2 .............................. ._
_
25
1'3
of g Example I were tested
for their ability to coat stone
_
_
aggregate (Pennsylvania sandstone) of the type used in
asphalt paving construction.
These tests were carried out
These data demonstrate that high shear rates must be
in accordance with the detailed procedure set forth in the
employed in order to produce a stable composition. in 35 publication of the Pennsylvania State Highway Depart~
"\taaggidance with the teachings of this invention.
ment “Special Speci?cations for Treated Bituminous Ma
'
terials, Supplementing Bulletin 25, Revised January
EXAMPLE IV
1957.” For comparison the same tests were carried out
on the asphalt cutback employedin the preparation of the
The cutback of Example I was mixed with a GRS-2004
latex consisting of 59 percent by weight of rubber, 41 40 rubber-asphalt cutback. The results of these tests are
set forth in Table V.
percent by weight of water, the\rubbe1- portion being
100 percent by weight butadiene polym\e.
'
Table V
of latex was selected such that the rubber amo
d to
3 percent by weight based on‘ the amount of asphal '
the cutback. This mixture was subjected to high shear
conditions at a temperature of approximately 160° F.
Percent of the Coating Retained on
and the resulting composition was found to have a good
stability. A second mixture was prepared similar to the
?rst mixture of this example except that Neoprene 735
the Aggregate
\XCOMPOSITION
\"\\
Static test Strtippting Wet Aggre
‘
gate Test
es
‘
Asphalt cutback ________________ __
latex consisting of 38 percent by weight’ of rubber, 62 50 Rubber'asphalt cutback """" "
.
_
90
10
30
99
7O
60
percent by weight of water were utilized instead of the
GRS latex. This composition after being subjected to
the high shear conditions likewise exhibited a satisfactory
stability.
EXAMPLE v
The physical properties of the composition prepared
according to experiment No. 1 of Example I were com
The results demonstrate that the synthetic rubber-as
phalt cutback compositions produced by the process of
this invention ‘are useful as paving compositions and are
55 markedly superior with respect to their adhesivity for ag
gregates as compared with asphalt cutbacks not contain
ing rubber. The synthetic rubber-asphalt cutback com
positions of this invention are also useful in the same ap
pared With the physical properties of the asphalt cutback
in which asphalt cutbacks without the rubber
employed to prepare the composition of experiment No. 60 plications
are employed, for example, as roo?ng coatings, pipe coat
l. The cutback had a speci?c gravity of 0.95 and a vis
ings, undercoatings for railway cars and automobiles and
cosity at 140° F. of ~127 Saybolt Furol seconds. The
the
like. In addition, various additives may be included
rubber containing composition had aspeci?c gravity of
in the synthetic rubber-asphalt cutback compositions of
0.969 and a viscosity at 140° F. of 223 Saybolt Furol
this invention including ‘stone coating additives and the
seconds. Thus, the rubber-asphalt cutback composition
like. These additives may be added to the latex, to the
‘ has a slightly higher speci?c gravity and. a considerably
higher viscosity than the original cutback.
The composition of Experiment '1 of Example I was
cutback or to the rubber-asphalt cutback composition.
We claim:
~
'
1.A process for preparing a synthetic rubber-asphalt
then distilled to remove the water ‘and naphtha solvent
cutback composition which consists of mixing an asphalt
leaving a residue comprising the rubber in the asphalt. 70 cutback consisting of from 50 percent to 90 percent by
The solvent naphtha was likewise distilled from a portion
weight of asphalt ranging in hardness from 150 penetra
of the same cutback employed in the preparation of the
tion at 77° F. to 190° F. softening point and from 10
rubber-asphalt cutback composition. rThe various physi-'
percent to 50 percent by weight of a petroleum distillate
cal properties of these distillation residues are compared /
boiling in the range from about 180° F. to 600° F. with
in Table IV.
’
75 a synthetic rubber latex, said rubber being selected from
3,041,599
8
'the group consisting of polymers of chloroprene, poly
it 3. A; process for preparing a ‘synthetic rubber-asphalt
,mers of butadiene, and copolymers of butadiene and
styrene, the quantity of the rubber in the latex ranging
from 0.5 to 15.0 percent by Weight based on the Weight of
weightiof asphalt r_'anging'in hardness from 150_.penetra
cutback composition which vconsists of mixing an asphalt
cutbackfconsisting of" frem?SO percent to 90 percent by
‘the asphalt in the cutback,’ and subjecting the mixture at V
temperatures ranging from 130° F. to' 190° F to condi
tions of high shear,- ranging in rate from "104 reciprocalv .
l
1
1
tion vat 7711:’; to’ 190° F. softening point‘ and, from 10
percent to '50‘percent by Weight off a‘ petroleum‘ distillate
inrthe-yrangei from about; 180§E§Ytqlf600°fli withv ‘
‘ boiling
I
‘ja‘synthetie'
bber late‘
.
..
.
‘
"Said"311121113:‘being:.sblsctédi?dm“'
~ he grew; acqnsisting"ofitiblymers"‘qféhlpropreneg ‘poly
tback consisting vef Qfrfom: 5.0., percent to 901percerit by
4107f e'i's “of butadi‘ene, aancijcopolyiners‘ of butadiene and
"styrendthe quantity 'ofjthe rubber ‘in the ‘latex ranging
‘from-2.011940 percent by ‘weight: based onrthe weight-of ‘
‘weight fof rasphzilt'grangingjinghardness from; 150. ,pelne raj- ‘
1101111713.}. 11701190? .F..qseftening_;p_oint_ and "from 10 ‘
percent :to .15 Opercent ‘bye/eight of a‘ ~‘petrQl'eum ~ distillate
“the-31115111111 in the cutback and-subjecting'the ‘mixture at
lteni'peratures ranging from 160°‘F. to 165° F. to condi
tboilingfinythe range frorn abQuttIBO-"H' E. to1600f’ .‘Rltwith ; ‘151‘ 'onst Qfjhigh shear. ‘ranging’ in rate from 3v>'<104'recip_ro
wé1_s_;ynt_hetie rubber latex; saidrubber ‘being s'elee'tedfrom
'cal‘seconidsito1108‘reciprecnl‘seconds;
;thej grqups consisting of polymers 1 of} chlorcprene,‘ poiy-- '
v rrners ofrbutadiene, and copolyniers-l.ofgbutadienel end.
V ‘ lieferences Citetl
'
’
s
the-‘?le of thi‘sipatenti ‘
styrene; ‘the quantity: of ‘the rubber ‘in the‘ latex ranging
'> - UNITED STATES PATENTS ;
‘
.tromOjyto, 15.0 percent by weightlbese'di. on the.i,veight__.
_
‘McMillan
et
a1.
'_
____
_‘_’_
May
30,
"
"5,509,711"
'7
tqpfrvthe asphalt in the cutback ancLsubjeéting the'mixture
2,537,190
Lankau et a1. __ _______ __ Jan. 9,
fat temperaturesranging from 160° Bite 1 65°- Ftfto'com
vditions of high shear ranging in rate_fro‘ri1.3>><104reeipro~
ical?secondsjq 106 reciprocal ‘seconds; I
>
_
‘2,921,313 7
1950
1951
Odasz ;_'__'._.; ________ _.. Jan. 12, 1960
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