A modified asphalt composition is provided comprising at least one plastomer, at least one elastomer, at least one crosslinking agent and asphalt. More specifically, a modified asphalt composition is provided comprising an oxidized polyethylene, a styrene-butadiene-styrene block copolymer, sulfur, and asphalt. A hot mix asphalt composition is also provided comprising the modified asphalt composition and aggregate. processes for producing the modified asphalt composition and the hot mix asphalt composition are also provided as well as articles produced from these inventive compositions.
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43. A modified asphalt composition comprising at least one plastomer, at least one elastomer, at least one crosslinking agent, and asphalt, wherein said plastomer comprises oxidized polyethylene.
40. A pellet comprising at least one plastomer and at least one crosslinking agent for use as an asphalt modifier, wherein said plastomer comprises an oxidized polyolefin and wherein said crosslinking agent is at least one selected from the group consisting of elemental sulfur, hydrocarbyl polysulfides, peroxides, and transition metals.
31. A process for producing a modified asphalt composition said process comprising:
1) contacting at least one plastomer, at least one elastomer, and at least one crosslinking agent to produce a pellet, wherein said plastomer is oxidized polyethylene; and
2) adding said pellet to asphalt in a mixing zone to produce said modified asphalt composition.
3. A modified asphalt composition comprising at least one plastomer, at least one elastomer, at least one crosslinking agent, and asphalt, wherein said plastomer comprises an oxidized polyolefin and wherein said crosslinking agent is at least one selected from the group consisting of elemental sulfur, hydrocarbyl polysulfides, peroxides, and transition metals.
1. A pellet comprising at least one plastomer, at least one crosslinking agent, and at least one elastomer for use as an asphalt modifier, wherein said plastomer comprises an oxidized polyolefin and wherein said crosslinking agent is present in said pellet in an amount ranging from about 0.1% by weight to about 5% by weight based on the weight of the elastomer.
41. A modified asphalt composition comprising at least one plastomer, at least one elastomer, at least one crosslinking agent, and asphalt, wherein said plastomer comprises an oxidized polyolefin and is present in said modified asphalt composition in an amount from about 0.1% by weight to about 10% by weight based on the weight of the modified asphalt composition.
42. A modified asphalt composition comprising at least one plastomer, at least one elastomer, at least one crosslinking agent, and asphalt, wherein said plastomer comprises an oxidized polyolefin and wherein said elastomer is present in said modified asphalt composition in an amount from about 0.1% by weight to about 10% by weight based on the weight of the modified asphalt composition.
30. A process for producing a modified asphalt composition comprising contacting at least one plastomer, at least one elastomer, at least one crosslinking agent and asphalt, wherein said plastomer comprises an oxidized polyolefin and wherein said crosslinking agent is at least one selected from the group consisting of elemental sulfur, hydrocarbyl polysulfides, peroxides, and transition metals.
36. A process for producing a hot mix asphalt composition comprising contacting at least one plastomer, at least one elastomer, at least one crosslinking agent, asphalt, and aggregate, wherein said plastomer comprises an oxidized polyolefin and wherein said crosslinking agent is at least one selected from the group consisting of elemental sulfur, hydrocarbyl polysulfides, peroxides, and transition metals.
33. A process for producing a modified asphalt composition said process comprising:
1) contacting at least one plastomer and at least one elastomer in an extruder zone to produce a plastomer/elastomer pellet;
2) contacting at least one plastomer and at least one crosslinking agent in an extruder zone to produce a plastomer/crosslinking agent pellet;
3) adding said plastomer/elastomer pellet and said plastomer/crosslinking agent pellet to at least one molten asphalt in a mixing zone to produce a modified asphalt composition;
4) mixing said modified asphalt mixture in said mixing zone to disperse the plastomer and elastomer in said plastomer/elastomer pellet to produce the modified asphalt composition.
37. A process for producing a hot mix asphalt composition said process comprising:
1) contacting at least one plastomer and at least one elastomer in an extruder zone to produce a plastomer/elastomer pellet;
2) contacting at least one plastomer and at least one crosslinking agent in an extruder zone to produce a plastomer/crosslinking agent pellet;
3) adding said plastomer/elastomer pellet and said plastomer/crosslinking agent pellet to at least one molten asphalt in a mixing zone to produce a modified asphalt mixture;
4) mixing said modified asphalt mixture in said mixing zone to disperse the plastomer, elastomer, and crosslinking agent to produce said modified asphalt composition; and
5) contacting said modified asphalt composition with aggregate to produce said hot mix asphalt composition.
2. A pellet according to
4. A modified asphalt composition according to
5. A modified asphalt composition according to
6. A modified asphalt composition according to
7. A modified asphalt composition according to
8. A modified asphalt composition according to
9. A modified asphalt composition according to
10. A modified asphalt composition according to
11. A modified asphalt composition according to
12. A modified asphalt composition according to
13. A modified asphalt composition according to
14. A modified asphalt composition according to
15. A modified asphalt composition according to
16. A modified asphalt composition according to
17. A modified asphalt composition according to
18. A modified asphalt composition according to
19. A modified asphalt composition according to
20. A modified asphalt composition according to
21. A modified asphalt composition according to
22. A modified asphalt composition according to
23. A modified asphalt composition according to
24. A modified asphalt composition according to
25. A modified asphalt composition according to
26. A modified asphalt composition according to
27. A modified asphalt composition according to
28. A modified asphalt composition according to
29. A hot mix asphalt composition comprising said modified asphalt composition of
32. A process according to
34. A process according to
35. A process according to
44. A modified asphalt composition according to
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In the abovementioned formula, the monovalent C1-C20 hydrocarbon radicals, R1 and R2 and the divalent C1-C20 hydrocarbon radical, R3, are chosen especially from aliphatic, alicyclic, or aromatic radicals. When the radicals R1 and R2 are joined together to constitute a divalent C1-C20 hydrocarbon radical forming a ring with the other groups of atoms associated in the formula, the divalent radical can be similar to the radical R3 and may also be of the aliphatic, alicyclic or aromatic type. Preferably, R1 and R2 are identical and chosen from C1 to C20 alkyl radicals, such as, but not limited to, ethyl, propyl, hexyl, octyl, nonyl, decyl, linear dodecyl, tert-dodecyl, hexadecyl, octadecyl, and C6-C20 cycloalkene or arylene radicals, especially phenylene, toluene, and cyclohexane.
Examples of polysulfides include, but are not limited to, dihexyl disulfide, dioctyl disulfide, didodecyl disulfide, di-tert-dodecyl disulfide, dihexadecyl disulfide, dihexyl trisulfide, dioctyl trisulfide, dinonyl trisulfide, di-tert-dodecyl trisulfide, dinonyl trisulfide, di-tert-dodecyl trisulfide, dihexadecyl trisulfide, dihexyl tetrasulfide, dioctyl tetrasulfide, dihexadecyl tetrasulfide, dioctyl tetrasulfide, dinonyl tetrasulfide, di-tert-dodecyl tetrasulfide, dihexadecyl tetrasulfide, dihexyl pentasulfide, dioctyl pentasulfide, dinonyl pentasulfide, di-tert-dodecyl pentasulfide, dihexadecyl pentasulfide, diphenyl trisulfide, dibenzyl trisulfide, diphenyl tetrasulfide, ortho-tolyl tetrasulfide, dibenzyl tetrasulfide, dibenzyl pentasulfide, diallyl pentasulfide, tetramethyltetrathiane, and mixtures thereof.
Any peroxide known in the art capable of crosslinking with the elastomer of this invention can be utilized. Examples of such peroxides include, but are not limited to, hydroperoxides, dialkyl peroxides, peroxydicarbonates, diacyl peroxides, peroxyesters, and others.
Any transition metal compound known in the art capable of crosslinking with the elastomer of this invention can be utilized. Examples of such transition metal compounds include, but are not limited to, zinc compounds, such as, zinc oxide; nickel compounds, such as nickel(II) chloride; and titanium compounds, such as, titanium halides and titanium hydroxides. Other active metal compounds known to react with unsaturation can be used.
Although not necessary in this invention, if desired, crosslinking accelerators can be utilized. Crosslinking accelerators are disclosed in U.S. Pat. No. 5,314,935, which is herein incorporated by reference beginning in column 7, line 5 through column 8, line 58.
The modified asphalt composition can also comprise other additives known to those skilled in the art. Additives include nitrogen compounds of amine or amide which are used as promoters of adhesion for the asphalt and the elastomer.
The modified asphalt compositions can be used to form any suitable articles. More particularly, the modified asphalt compositions are used to form road pavement surfaces. To form a road pavement, the modified asphalt composition is applied to a surface, such as earth that has preferably been leveled, using any method, including any method commonly used in the road paving industry. While the modified asphalt composition provides excellent physical characteristics for road paving applications, these mixtures may also be used for other construction purposes, such as roofing applications.
In another embodiment of this invention, a process is provided to produce the modified asphalt composition. The process comprises contacting at least one plastomer, at least one elastomer, asphalt, and optionally at least one crosslinking agent. The contacting can be conducted by any method known in the art. Generally, the asphalt is heated to its molten state and the plastomer, elastomer, and optionally the crosslinking agent are then added and mixed into the asphalt to produce the modified asphalt composition. Preferably, the plastomer and elastomer are added simultaneously. Most preferably, the elastomer, plastomer, and crosslinking agent are added simultaneously.
In another embodiment of this invention, a process for producing a hot mix asphalt composition is provided. The process comprises contacting at least one plastomer, at least one elastomer, asphalt, aggregate, and optionally at least one crosslinking agent.
The term “aggregate” is a collective term denoting any mixture of such materials including, but not limited to, sand, gravel, and crushed stone, and the like used with asphalt. The type of aggregate and the amounts used vary depending on the use of the hot mix asphalt composition.
In yet another embodiment, a process for producing a modified asphalt composition is provided. The process comprises: 1) contacting at least one plastomer and at least one elastomer in an extruder zone to produce a plastomer/elastomer pellet; 2) adding the plastomer/elastomer pellet and optionally at least one crosslinking agent to at least one molten asphalt to produce a modified asphalt mixture; and e) mixing the modified asphalt mixture in a mixing zone to distribute the plastomer, elastomer, and optionally the crosslinking agent to produce the modified asphalt composition. Preferably, the plastomer/elastomer pellet and crosslinking agent are added simultaneously.
In still another embodiment of this invention, a process for producing a modified asphalt composition is provided. The process comprises: 1) contacting at least one plastomer and at least one elastomer in an extruder zone to produce a plastomer/elastomer pellet; 2) contacting at least one plastomer and at least one crosslinking agent in an extruder zone to produce a plastomer/crosslinker pellet; 3) adding the plastomer/elastomer pellet and the plastomer/crosslinker pellet to at least one molten asphalt in a mixing zone to produce a polymer modified asphalt mixture; and 4) mixing the modified asphalt mixture in the mixing zone to distribute the plastomer, elastomer, and crosslinking agent to produce the modified asphalt composition. Preferably, the plastomer/elastomer pellet and the plastomer/crosslinker pellet are added simultaneously.
The extruder zone comprises at least one extruder. The plastomer and elastomer are heated in the extruder zone to a sufficient temperature so they can be adequately mixed.
The mixing zone comprises any equipment suitable for mixing the asphalt, plastomer, elastomer, and optionally the crosslinking agent. Suitable equipment includes, but are not limited to, low shear mixing equipment and high shear mixing equipment.
By adding the plastomer, elastomer, and crosslinking agent in pellet form to the molten asphalt, dust and fumes can be significantly reduced.
An advantage of the use of the plastomer is that when the polymers are added to asphalt, the viscosity of the mixture is only slightly increased over the viscosity of asphalt alone. By increasing the viscosity only slightly, the mixture exhibits good hot-mix workability and no observable separation. This aids also in the mixing of the elastomer, which is typically very difficult to mix. Furthermore, the plastomers exhibit dispersibility with a large number of asphalts, resulting in mixtures that are storage stable, with no polymer phase separation.
The present invention will be more readily understood by reference to the following examples. There are, of course, many other forms of the invention which will become obvious to one skilled in the art, once the invention has been fully disclosed, and it will accordingly be recognized that these examples are given for the purpose of illustration only and are not to be construed as limiting the scope of the invention in any way.
Table 1 lists the test methods used to characterize the modified asphalt compositions of the examples.
TABLE 1
Test Name
Test Method
Performance Graded Asphalt Binders
AASHTO MP1
Kinematic Viscosity 135° C.
ASTM D 2170
Absolute Viscosity 60° C.
ASTM D 2171
Toughness and Tenacity
ASTM D 5801
Ring and Ball Softening Point
ASTM D-36
Dynamic Shear Rheometer (DSR)
AASHTO TP5
Penetration
ASTM D 5
Compatibility/Separation
ASTM D 5976
Elastic Recovery
ASTM D 6084
Rolling Thin Film Oven Test (RTFO)
ASTM D 2872
Pressure Aging Vessel
ASTM D 6521
Bending Bean Rheometer (BBR)
ASTM D 6648
Force Ratio
AASHTO T-300
One criterion for asphalt performance is the Superpave™ Performance Graded (PG) Binder Specification. These parameters, which indicate the visco-elastic and service performance related properties of asphalt compositions, were developed to classify materials based upon performance. The PG parameters measure the properties between the low temperature service rating for the material (generally based upon embrittlement cracking) and the high temperature service properties for the material (generally based upon heat softening) to determine a service temperature range. The greater the PG temperature range rating, the greater the service range for the material.
Another criterion to evaluate asphalt performance is a group of historical conventional protocols such as Softening Point, Penetration, Force Ratio, Elastic Recovery, Compatibility, Toughness, and Tenacity. These tests assess a variety of physical properties that through historical use and correlation to actual pavement performance are used to specify an asphalt by various agencies in addition to the Superpave criteria.
Inventive Examples 1-6, 8-14 and 16 and Comparative Examples 7 and 15 in Tables 2 and 3, a PG 64-22 asphalt was modified. The PG 64-22 was heated to about 370-380° F. to produce a molten asphalt. The Preblend Additives 1 and 2 and the Crosslinker Preblend Additive were added in pellet form to the molten asphalt, and these additives were blended into the asphalt at high shear for about 1 hour followed by paddle agitation (stirring) for two hours at 370-380° F. This procedure was necessary to adequately blend the SBS block copolymer into the asphalt in Comparative Examples 7 and 15 and Inventive Examples 8 and 16. As can be seen from the data, this 3 hour period of mixing is not necessary when adding preblended elastomer and plastomer at the same time.
Preblend Additive 1 in Table 2 consisted of a 50/50 by weight blend of Wingflex® 411 SBS block copolymer commercially available from Goodyear and oxidized polyethylene available commercially as Epolene® E-20 wax from Eastman Chemical Company. Comparative Example 7 and Inventive Example 8 utilized Kraton® D1184 SBS block copolymer. The Crosslinker Preblend Additive 1 in Table 2 and Table 3 is 25% by weight sulfur in Epolene® E-20 oxidized polyethylene.
Preblend Additive 2 in Table 3 consisted of a 25/75 by weight blend of Wingflex® 400 SBS block copolymer commercially available from Goodyear and oxidized polyethylene available commercially as Epolene® E-20 wax from Eastman Chemical Company. Comparative Example 15 and Inventive Example 16 utilized Kraton® D1184 SBS block copolymer.
The PG Rating and conventional data displayed in Tables 2 and 3 indicates the inventive modified asphalt compositions have comparable performance grades and equivalent or improved conventional properties as compared to that of an asphalt containing a similar concentration of elastomer (e.g. SBS block copolymer).
The presence of the plastomer allows a more efficient use of the elastomer in the asphalt to achieve improved properties without detrimental effects such as incompatibility and high process viscosities associated with elastomer usage at equivalent dosages.
In Examples 7 and 8, modification of the PG 64-22 asphalt with 4% Kraton® D 1184 SBS block copolymer increased the PG grade by 2 grades to a PG 76-22 grade. In Example 8, the addition of a small amount of crosslinking agent only slightly increased the performance grade of the modified asphalt. However, the Crosslinker Preblend Additive 1 (Example 8) was not added with the Kraton® SBS rubber, but was added after the rubber had dissolved. It took the full three hours for the Kraton® SBS rubber to disperse in the PG 64-22 asphalt. It was only after the Kraton® SBS rubber had dispersed that the Crosslinker Preblend Additive 1 (oxidized polyethylene and sulfur) was added.
Example 7 shows that 4% Kraton® SBS rubber was not very compatible with asphalt in that the softening point after 48 hours at 163° F. was very different at the top (198° F.) and at the bottom (138° F.) of the aged sample. This was not the case for the inventive examples. This is a common problem with elastomer use and most host asphalts. Incompatibility, also referred to as separation, can typically be caused by a compositional deficiency in the asphalt for elastomer modification. When separation occurs, the ‘dissolved’ polymer phase can separate and rise to the surface of the blend and the asphalt's higher molecular weight component fractions, asphaltenes, can precipitate from the asphalt matrix and sink to the bottom of the blend. This often results in process difficulties at a modified asphalt producing facility. This can be followed by process problems at the hot asphalt mix manufacturing facility, and if incorporated into the pavement structure, pavements that under perform. Compatibility is a key property and is incorporated in nearly all specifications involving asphalt modifiers world wide.
Inventive Examples 1-6 of Table 2 and 9-14 of Table 3 depict the benefits of modification of asphalt with PreBlend Additives 1 and 2, which are further enhanced by co-use of Crosslinking Preblend Agent 1. These examples, inclusive, displayed separation values of <2° F., as determined by the Ring and Ball Softening Point. It should be noted the addition of Preblend Additives 1 and 2 in pellet form had a significant improved effect on separation, which may not be realized if the components of the Preblend Additives (oxidized polyethylene and SBS block copolymer) were added separately. When an asphalt and additive system are prone to separation, the asphalt may be remedied through the use of ancillary technologies such as aromatic oil addition, source asphalt blending, use of lower viscosity asphalt, which requires more elastomer to achieve the desired high temperature requirements. All of these processes are costly and time consuming.
Inventive Examples 3 and 5 of Table 1 indicate the benefit of inclusion of the proper dosage of Crosslinking Preblend Agent 1 with Preblend Additive 1 on Toughness and Tenacity, a measure of the strength under strain of the modified asphalt. These data are compared with Inventive Examples 1 and 2 where sulfur was not used for crosslinking. Toughness and Tenacity is a parameter used by various State DOTs in their modified asphalt specifications to assure the correct type and proper quantity of elastomer is used to meet the modified asphalt's specified requirements.
Similar improvements are witnessed in the Elastic Recovery properties of Inventive Examples 3 and 5. The elastic recovery (%) ranged from 66-83 for the examples involving crosslinking, while Examples 1 and 2 had a elastic recovery ranging from 41-44.
Inventive Examples 1-6 and 9-14 of Tables 2 and 3 display substantially reduced process viscosities when compared to Comparative Examples 7 and 15 using Kraton® D 1184 alone as a modifier. When using Preblend Additive 1 containing a 50/50 blend of SBS block copolymer and oxidized polyethylene, the viscosities (centistokes) at 135° C. for inventive examples 1-6 ranged from 648 to 1,150 centistokes compared to comparative example 7 where the viscosity was 1,256 centistokes. When using Preblend Additive 2 containing a 25/75 blend of SBS block copolymer and oxidized polyethylene, the viscosity of the Inventive Examples 9-14 ranged from 540 to 802 centistokes, while Comparative Example 15 using only SBS block copolymer as a modifier had a viscosity of 988 centistokes. High process viscosities present problems to the contractor during mixing of the modified asphalt composition with the aggregates and subsequent compaction of the modified asphalt composition with aggregate.
Examples 2 and 5 in Table 1 correspond to the Comparative Example 7 and Inventive Example 8 in that each contains 96% asphalt. Example 8 is an inventive example, but is used here for comparative purposes to show the advantage of addition of the elastomer in a pellet with the oxidized polyethylene. In addition, Inventive Example 5 and Comparative Example 7 both contain 0.5% of Crosslinker Preblend Additive 1. Both of the inventive modified asphalt compositions upgraded the asphalt to the same PG 76-22 grade as the Comparative Example 7 and Inventive Example 8, but at half of the SBS block copolymer level as the comparative modified asphalt compositions. In addition, in Inventive Example 5, the Preblend Additive 1 in pellet form and the Crosslinker Preblend Additive in pellet form were added at the same time as a single blend of pellets. These additives had completely dispersed into the asphalt in 1.5 hours which was approximately one half of the time it took the Kraton® SBS block copolymer to disperse. The compatibility of the modified asphalt composition was greatly improved when the inventive additives were used. The Ring and Ball softening point differential on the aged samples after 48 hours at 163° F. was only 1 or 2 degrees. Thus, the combination of a plastomer with the elastomer allowed a much more efficient usage of the elastomer in the asphalt matrix which resulted in the same degree of reinforcement of the asphalt but at half the level of elastomer.
The asphalt was modified by simultaneously adding 4% by weight Preblend Additive 1 and 1% by weight Crosslinker Preblend Additive 1 with the weight percent based on the weight of the modified asphalt composition at 370-380° F. and stirring for 1.5 hours. As shown in Table 2, the asphalt PG grade increased by +3 grades to PG 82-22 without the loss of low temperature properties.
TABLE 2
Data for examples 1 to 8
I-1
I-2
I-3
I-4
I-5
I-6
C-7
I-8
Ingredient
Specification
Weight Percent
Asphalt, West Coast
97
96
97
97
96
96
96
96
Blend PG 64-22,
Preblend Additive 1
3
4
3
3
4
4
—
—
Crosslinker Preblend
0
0
0.5
1
0.5
1
0
0.5
Additive 1
Kraton ® D 1184 SBS
—
—
—
—
—
—
4
4
PROPERTIES:
Original Blend
Viscosity @ 135° C.,
3,000
max.
648
709
721
928
890
1,150
1,256
1,574
cSt
Viscosity @ 60° C. P
6,920
10,046
13,409
19,010
33,518
54,703
20,164
29,805
DSR @ 88° C. kPa
1.0
min.
—
—
—
—
—
0.689
—
—
(G*/sin d)
DSR @ 82° C., kPa
—
0.621
—
0.986
0.829
1.117
0.764
0.932
(G*/sin d)
DSR @ 76° C., kPa
0.935
1.071
0.976
1.657
1.361
1.826
1.286
1.519
(G*/sin d)
DSR @ 70° C., kPa
1.716
1.777
1.655
2.823
2.25
2.768
2.34
2.729
(G*/sin d)
Penetration @ °25 C.
46
45
42
38
43
40
44
41
dmm
Softening Point, ° F.
134.3
137.3
151
162.5
170
184
153.5
164.5
Force Ratio @ °4 C.,
0.30
min.
0.175
0.194
0.252
0.147
0.337
0.283
0.25
0.418
f2/f1 (0.55 cm/min,
24 cm)
Toughness & Tenacity @ 25° C.
Toughness, in-lbs.
110
min.
117.8
140.8
190.3
135.6
232.3
164
199.3
233.8
Tenacity, in-lbs.
75
min.
53
68.7
116.8
49.2
168
97.7
128.9
172
Compatibility @
163° C./48 hrs
Top 1/ Softening
136.5
143
142.5
155
164
178
198
167
Point, ° F.
Bottom 1/ Softening
136
144
143
157
166
180.8
138
170
Point, ° F.
Difference, ° F.
4.0
max.
0.5
1
0.5
2
2
2.8
60
3
Elastic Recovery,
60
min.
0.175
0.194
0.252
0.147
0.337
0.283
0.25
0.418
% @ 25° C.
RTFOT Residue
Mass Loss, %
0.5
max.
0.229
0.229
0.199
0.142
0.144
0.114
0.171
0.142
DSR @ 88° C. kPa
2.2
min.
—
—
—
—
—
1.245
—
—
(G*/sin d)
DSR @ 82° C., kPa
—
—
—
1.488
1.371
2.289
1.341
1.547
(G*/sin d)
DSR @ 76° C., kPa
1.508
2.061
1.577
2.639
2.323
3.854
2.598
2.623
(G*/sin d)
DSR @ 70° C., kPa
2.592
3.851
2.904
4.847
4.287
6.05
5.01
4.798
(G*/sin d)
Elastic Recovery,
50
min.
54
57
63
53
70
70
73
84
% @ 25° C.
PAV Residue (100 C., 300 psi, 20 hours)
DSR @ 28° C.,
5,000
3,923
4,023
3,458
3,972
4,896
3,500
3,597
3,973
G*.sin d, kPa
DSR @ 25° C.,
max.
5,677
5,733
5,107
5,595
6,929
5,016
5,150
5,684
G*.sin d, kPa
BBR @ −12° C.,
300
max.
231
233
198
240
216
229
210
192
Stiffness, MPa
m Value
0.300
min.
0.308
0.306
0.318
0.308
0.328
0.317
0.307
0.331
BBR @ −18° C.,
300
max.
441
457
415
485
419
421
401
374
Stiffness, MPa
m Value
0.300
min.
0.235
0.235
0.242
0.235
0.251
0.244
0.236
0.256
Performance Grade
70-22
76-22
70-22
76-22
76-22
82-22
76-22
76-22
“True” Performance
75-22
76-22
75-23
81-22
80-24
83-23
79-22
81-24
Grade
Effective Temperature
MP 1
97
98
98
103
104
106
101
105
Range, ° C.
Grade Change
+1
+2
+1
+2
+2
+3
+2
+2
Note:
I-1 through I-6 and I-8 are inventive examples.
C-7 is a comparative example.
In Inventive examples 9-14 and 16 and Comparative Example 15 of Table 3, a PG 64-22 asphalt was modified by blending the components at high shear for 1 hour followed by paddle agitation (stirring) for two hours at 370-380° F. The procedure was necessary to adequately blend the SBS block copolymer into the asphalt in example numbers 15 and 16. Preblend Additive 1 in Table 3 consisted of a 25/75 blend of Wingflex® 400 SBS block copolymer (Goodyear) and Epolene® E-20 oxidized polyethylene from Eastman Chemical Company. The Comparative Example 15 and Inventive Example 16 utilized Kraton® D1184 SBS rubber. The Crosslinker Additive 1 in Table 3 is 25% sulfur in Epolene® E-20 oxidized polyethylene.
Inventive Example 9 and Comparative Example 15 both have 3% by weight modifier added to the asphalt. It is expected that Comparative Example 15 would have greater toughness and tenacity than Inventive Example 9 since it contains 3 times the quantity of elastomer. The Preblend Additive 2 contained a 25/75 blend of SBS block copolymer and oxidized polyethylene. It is not expected, however, that both modified asphalt compositions containing 3% modifier would have almost the exact PG grade for the modified asphalt composition. As shown in Table 3, the “True” Performance Grade for Inventive Example 9 was 74-21 compared to 75-22 for Comparative Example 15. These two examples suggest that the elastomer and plastomer combination allows much more effective use of the elastomer to upgrade the asphalt. The plastomer facilitates the dispersal and ordering of the asphalt matrix to more readily take advantage of the elastomeric properties imparted to the modified asphalt composition.
Inventive Examples 12 and 13 show that at either higher preblend additive levels or higher crosslinker preblend agent levels further improvement, as evidenced by a higher PG grade of the modified asphalt composition, is possible. However, SBS block copolymers tend to begin to have compatibility issues at these higher loadings
Example #
I-9
I-10
I-11
I-12
I-13
I-14
C-15
I-16
Ingredients
Weight Percent
Asphalt, West Coast
97
96
97
97
96
96
97
97
Blend PG 64-22
Preblend Additive 2
3
4
3
3
4
4
—
—
Crosslinker Preblend
—
—
0.5
1
0.5
1
—
0.5
Additive 1
Kraton ® D 1184 SBS
—
—
—
—
—
—
3
3
PROPERTIES:
Original Blend
Spec.
Viscosity @ 135° C.
3,000
max.
540
548
609
619
660
802
988
1,037
C cSt
Viscosity @ 60° C. P
7,027
10,596
10,083
11,048
24,556
27,005
6,225
19,905
DSR @ 88° C. kPa
—
—
—
—
0.441
0.755
—
—
(G*/sin d)
DSR @ 82° C., kPa
—
0.725
—
0.866
1.003
1.378
—
0.677
(G*/sin d)
DSR @ 76° C., kPa
0.845
1.159
0.983
1.449
1.757
2.113
0.946
1.125
(G*/sin d)
DSR @ 70° C., kPa
1.0
kPa
1.528
1.993
1.85
1.827
—
3.357
1.746
1.937
(G*/sin d)
Penetration @ °25 C.,
47.3
45.3
44.5
44.1
36
38
44
43
dmm
Softening Point, ° C.
134.5
143
140
143.5
160.3
170
132
148
Force Ratio @ 4 C.,
0.300
min.
0.113
0.13
0.106
Broke
0.145
Broke
0.223
0.375
f2/f1 (5 cm/min,
24 cm)
Toughness & Tenacity @ 25° C.
Toughness, in-lbs.
110
min.
907.84
93.48
93.81
84.26
110.1
95.85
183.8
265.1
Tenacity, in-lbs.
75
min.
26.11
29.29
27.04
15.33
35.26
17.85
102.29
191.5
Compatibility @
163° C./48 hrs
Top 1/ Softening
137
147
140
144.5
152.5
161
136
155.5
Point, ° F.
Bottom 1/ Softening
136
147
140
144.5
152.5
161
136
155.5
Point, ° F.
Difference, ° F.
4.0
max.
1.0
0.0
0.0
0.0
0.0
0.8
1.0
0.3
Elastic Recovery,
60
min.
33.5
41
47.3
29.2
57
43
47.3
80.5
% @ 25 C.
RTFOT Residue
Mass Loss, %
0.5
max.
0.057
0.086
0.057
0.085
0.072
0.086
0.076
0.056
DSR @ 82° C. kPa
—
1.332
—
1.418
1.347
1.482
—
—
(G*/sin d)
DSR @ 76° C.
1.601
2.415
2.054
2.517
2.576
2.175
1.919
1.901
kPa (G*/sin d)
DSR @ 70° C., kPa
2.2
min.
3.23
4.47
3.749
3.32
—
4.48
3.856
3.53
(G*/sin d)
Elastic Recovery,
50
min.
41.5
47.8
43.8
32
51
36
66
77
% @ 25° C.
PAV Residue (100 C., 300 psi, 20 hrs)
DSR @ 31° C.,
3,195
3,024
3,153
3,167
3,190
2,912
2,634
2,074
G*.sin d, kPa
DSR @ 28° C.,
4,447
4,392
4,661
4,605
4,598
4,214
3,817
3,104
G*.sin d, kPa
DSR @ 25° C.,
5,000
max.
5,983
6,260
6,562
6,504
6,492
5,946
5,554
4,509
G*.sin d, kPa
BBR @ −06° C.
300
max.
117
124
117
128
—
—
—
—
Stiffness MPa
m Value
0.300
min.
0.344
0.345
0.343
0.344
—
—
—
—
BBR @ −12° C.
300
max.
260
272
254
274
249
244
211
188
Stiffness MPa
m Value
0.300
min.
0.298
0.297
0.302
0.304
0.301
0.301
0.309
0.332
BBR @ −18° C.
300
max.
—
—
413
464
413
423
386
381
Stiffness MPa
m Value
0.300
min.
—
—
0.244
0.245
0.246
0.246
0.248
0.266
Performance Grade
70-16
76-16
70-22
76-22
76-22
70-22
70-22
70-22
“True” Performance
M
320
74-21
78-21
75-22
80-22
82-22
84-22
75-22
74-24
Grade
Effective Temperature
95
99
97
101
104
106
97
101
Range, ° C.
Table 5 is a mixing time table and shows the progress of the modified asphalt compositions of Table 3 while they were blended. A PG 64-22 apshalt was modified by blending the components shown in Table 3 at high shear for 1 hour followed by paddle agitation for two hours at 370-380° F. The procedure was necessary to adequately blend the SBS block copolymer into the asphalt in Comparative Example 7 and Inventive Example 8. It is clearly shown in Table 5 that the blend times for the Preblend Additive 1 was significantly shortened compared to the SBS block copolymer addition in Comparative Example 7. The Preblend Additive 1 was dissolved in the asphalt in approximately 30 minutes while the SBS block copolymer took at least 120 minutes to dissolve. This reduced blend time translates into shorter batch times and increased production rates. Thus, the Preblend Additive of Table 3 is readily soluble in asphalts at useful levels. This solubility also results in reduced tendency for the modifiers to separate upon storage.
TABLE 5
Ingredient
−1
−2
−3
−4
−5
−6
−7
−8
Asphalt, West Coast Blend
97
96
97
97
96
96
96
96
PG 64-22
Preblend Additive 1
3
4
3
3
4
4
—
—
Crosslinker Preblend
0
0
0.5
1
0.5
1
0
0.5
additive 1
Kraton SBS, D 1184
—
—
—
—
—
—
4
4
Mix/blend: appearance and
texture
initial, after Crosslinker Pb
A1 addition
small Undissolved particles
particles present
15 minutes
nearly all dissolved and dispersed
particles present
30 minutes
smooth and homogeneous
nearly dissolved
60 minutes
smooth and homogeneous
and dispersed
120 minutes
smooth and homogeneous
smooth and homogeneous
Ease of blending
excellent
excellent
excellent
excellent
excellent
excellent
Good
Good
Separation/Film formation
No Visual
Draw Down, undispersed
all blends were smooth and homogeneous
polymer?
Grzybowski, Kenneth Francis, Stuart, Jr., Richard Kingsley, Presley, Jeffery Lynn
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