AP167A - Process for preparing bituminous compositions. - Google Patents
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- AP167A AP167A APAP/P/1990/000214A AP9000214A AP167A AP 167 A AP167 A AP 167A AP 9000214 A AP9000214 A AP 9000214A AP 167 A AP167 A AP 167A
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- block copolymer
- bitumen
- carbon black
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
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Abstract
The invention provides a process for preparing a bitumen composition,
Description
This invention relates to a process for preparing bituminous compositions.
Bitumen, also referred to as asphalt, or as flux, is used in paving, roofing, joint compounds and adhesives. Bitumen is an inexpensive material for these uses, but has certain shortcomings, including low flexibility, low tensile strength and poor resistance to degradation due to exposure to oxygen, sunlight and water. Some of these deficiencies in 1θ physical properties may be at least partially overcome by including in the bitumen composition various elastomeric polymers and reinforcing fillers such as carbon black. However, the usefulness of these bitumen-polymer compositions is seriously limited by the tendency of elastomeric polymers to be incompatible with the bitumens and to separate in to a polymer rich phase and an asphaltene rich phase upon storage.
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U.S. Patent No. 3,699,913 (Ral.ey) discloses a blend of bitumen and a random copolymer of propylene and ethylene. The composition is said to have good low temperature elasticity and good high temperature impact strength. The process disclosed to blend the polymer and the bitumen consists of placing the
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polymer in a hot-roll mill and adding bituminous material portion-wise until the desired proportion of bitumen has been added. Alternatively, the copolymer is fluxed into a portion of the molten asphalt, and when a homogenous mixture is obtained, the balance of the asphalt is added. Raley does not disclose a method to combine bitumen, carbon black and elastomeric polymers.
U.S. Patent No. 3,265,765 (Holden) provides elastomeric block copolymers A-B-A which may be dispersed in bitumen to improve high temperature viscosity and low temperature ductility and flexibility. The elastomers may be mixed with usual rubber compounding materials such as carbon black.
The A blocks of Holden’s copolymer are blocks of polymerised alkenyl aromatic hydrocarbons, and the B block is a block of polymerised conjugated diene. A method to prepare such a composition wherein the composition has good storage stability is not disclosed by Holden.
U.K. Patent No. 1,143,895 (Nielsen) discloses compositions of bitumen, fillers, carbon black and block copolymers. The block copolymer has an A-B-A configuration where the A blocks are polymerised vinyl-substituted aromatic hydrocarbons, and the B block is an elastomeric block of an alkene, a conjugated diene or a hydrogenated derivative thereof. Nielsen also discloses a process for preparing the composition wherein the carbon black is premixed into a portion of the bitumen, producing a master batch.
The copolymer may then be added to the master batch. Alternatively, the copolymer may be blended into the remaining bitumen to,form a second master batch and then the two master batches combined. Although the properties of the composition disclosed by Nielsen are
PS19004 excellent, a relatively large amount of block copolymer is required to obtain these properties. The copolymer is considerably more expensive than the other components of the composition, so it would be advantageous to gain the improvements in the bitumen properties achieved by the addition of block copolymers with less copolymer necessary. It has also been found that the compatibility of the compositions prepared by the process of Nielsen, as measured by the amount of phase separation during hot storage of the composition, is also deficient.
U.S. Patent No. 3,978,014 (Van Beem et al) discloses a bituminous composition which is said to have excellent storage stability. Van Beem's bituminous composition comprises: 95 to 75% by weight of a bituminous component having an aromaticity exceeding 0.004 X P + 0.280, where P is the n-heptane asphaltene content; 4 to 15% by weight of a block copolymer which is preferably a polystyrene-polyalkadiene-polystyrene block copolymer and 4 to 15% by weight of a thermoplastic polymer, different from the block copolymer, which has a molecular weight above 10,000, a solubility parameter of 7.8 to 8.8, and a crystallinity below 60% at 25°C.
Van Beem does not disclose a process for combining carbon black in the disclosed bitumen-block copolymer mixture.
There has now surprisingly been found a process for preparing bitumen compositions containing carbon black, block copolymers, and bitumen which are capable of exhibiting excellent storage stability, tensile properties and weatherability.
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According to the present invention there is provided a process for preparing a bitumen composition, which process comprises the steps of:
a) blending a carbon black composition 5 comprising carbon black and containing 0 to 10% by weight of bitumen based on the carbon black composition with a block copolymer composition, the block copolymer composition comprising a block copolymer and containing 0 to 10% by weight of bitumen based on the block copolymer composition, the block copolymer being selected from the group consisting of hydrogenated and unhydrogenated block copolymers, the block copolymer, before hydrogenation, comprising at least two blocks A, the blocks A comprising predominantly polymerized monoalkenyl arene monomer units, and at least one block B, the block B comprising predominantly polymerized conjugated diolefin monomer units; and
b) combining the carbon black composition block copolymer blend with a bitumen to form the bitumen composition.
It has been surprisingly found that mixing of the carbon black with the block copolymer before the block copolymer is contacted with the bitumen results in a composition having very acceptable tensile strength, improved compatibility (as measured by hot storage stability) and improved weatherability. Such compositions are, inter alia, particularly suitable for use as roofing compositions.
The bitumens employed in the process of the present invention may have properties which vary widely, depending on the desired-consistency of the finished product. Suitable bitumens may conveniently have softening points in the range from 26°C (80°F) to 105°C (220°F) and preferably from 32°C (90°F) to 49°C
PS19004 (120°F). The bitumen may be a residue from distillation of straight-run crude oil, produced by cracking straight run or cracked residue, blowing a crude oil or residues of crude oil distillation or extracts of crude oils, a bitumen derived from coal tar, propane bitumen, butane bitumen, pentane bitumen or mixtures thereof.
The block copolymers useful in the process of this invention include linear block copolymers, A-B-A block copolymers and radial block copolymers. Radial block polymers are also known as star polymers, and have a plurality of polymeric arms extending from a central coupling agent.
Linear block copolymers which may be utilised in the process of the present invention may be represented by the following general formula:
Αζ-(Β-Α)γ-Βχ wherein:
A is a polymeric block comprising predominantly monoalkenyl aromatic hydrocarbon monomer units;
B is a polymeric block comprising predominantly conjugated dioletin monomer units or the corresponding hydrogenated derivative;
X and Z are, independently, 0 or 1; and
Y is an integer from 1 to 15.
Radial block copolymers which may be utilised in the process of this invention may be represented by the following general formulae:
[3X-(A-3)Y-Az]n-C; and [Bx-(A-B)Y-Az]nl-C-CB’]nI, wherein:
A, Β, X, Y and Z are as previously defined;
n is an integer from 3 to 30;
c is the core of the radial polymer formed with a
L 9 L 0 0 0 dV
PS19004 polyfunctional coupling agent?
B' is a polymeric block comprising predominantly conjugated diolefin units, which B' may be the same or different from B? and n' and n are integers representing the number of each type of arm, wherein (n1 and n) is an integer from 3 to 30.
It is preferred that the A blocks have a number average molecular weight in the range from 5000 to
35,000 each while the block B should each have a number average molecular weight in the range from 20,000 to 300,000. It is more preferred that the A blocks each have a number average molecular weight in the range from 7,500 to 30,000 and each B block has a number average molecular weight in the range from 30,000 to 150,000. It is most preferred that the A blocks each have a number average molecular weight in the range from 10,000 to 20,000, and each B block has a number average molecular weight in the 45,000 to
75,000. Number average molecular weights are preferably measured by gel permeation chromatography with a polystyrene standard.
Blocks A and B may be either homopolymer, random or tapered copolymer blocks as long as each block is predominantly the class of the monomer characterising the block. For example, the block copolymer may contain A blocks which are styrene/alpha-methylstyrene copolymer blocks or styrene/ butadiene random or tapered copolymer blocks as long as the blocks individually predominate in alkenyl arenes. The A blocks are preferably monoalkenyl arene homopolymer blocks. The term ''monoalkenyl arene will be taken . to include those of the benzene series such as styrene and its analogues and homologues including o-methylstyrene, p-methy1styrene, p-tert-butylstyrene,
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1,3-dimethylstyrene, alpha-methylstyrene and other ring alkylated styrenes, particularly ring-methylated styrenes, and other monoalkenyl polycyclic aromatic compounds such as vinyl naphthalene and vinyl anthracene. The preferred monoalkenyl arenes are monovinyl monocyclic arenes such as styrene and alpha-methylstyrene, and sytrene is particularly preferred. Thus the blocks A are preferably predominantly polymerised styrene.
LO By predominantly being the class of the monomer characterising the block, it is meant that more than 75% by weight of the A blocks are vinyl arene monomer units, and more than 75% by weight of the B blocks are conjugated diene monomer units.
The blocks B may comprise homopolymers of conjugated diene monomers, copolymers of two or more conjugated dienes, and copolymers of one or more of the dienes with a vinyl arene as long as the blocks B are predominantly conjugated diene units. The conjugated diene monomers preferably contain from 4 to 8 carbon atoms. Examples of such suitable conjugated diene monomers include: 1,3-butadiene (butadiene),
2-methy1-1,3-butadiene (isoprene),
2, 3-dimethyl-l,3-butadiene, 1,3-pentadiene (piperylene) and 1,3-hexadiene. The blocks B are preferably polymerised butadiene or polymerised isoprene.
Preferably, the block copolymers of conjugated dienes and vinyl arene hydrocarbons which may be utilised include those butadiene derived elastomers which have 1,2-microstructure contents prior to hydrogenation of from about 7 to 100 percent, more preferably 25 to 65 percent, most preferably 35 to 55 percent. The proportion of the copolymer which is alkenyl arene monomer units is in the range from 1 to
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PS19004 percent by weight of the block copolymer, preferably 5 to 50 percent, more preferably 15 to 45 percent by weight, most preferably 20 to 40 percent by weight.
The A blocks, e.g. polystyrene blocks, preferably comprise 5 to 50% by weight of the total block copolymer, more preferably 25 to 35% by weight of the total block copolymer, most preferably 28 to 32% by weight of the total block copolymer.
The block copolymers may be produced by any block polymerisation or copolymerisation procedures including sequential addition of monomer techniques, incremental addition of monomer technique or coupling technique as illustrated in, for example, U.S. Patents
Nos. 3,251,905; 3,390,207; 3,598,887 and 4,219,627.
As is well known in the block copolymer art, tapered copolymer blocks can be incorporated in the multiblock copolymer by copolymerising a mixture of conjugated diene and alkenyl arene monomers utilising the difference in their copolymerisation reactivity rates. Various patents describe the preparation of multiblock copolymers containing tapered copolymer blocks including U.S. Patents Nos. 3,251,905;-3,265,765; 3,639,521 and 4,208,356.
It should be observed that the above-described polymers and copolymers may, if desired, be readily prepared by the methods set forth above. However, since many of these polymers and copolymers are commercially available, it is convenient to employ the commercially available polymer as this serves to reduce the number of processing steps involved in the overall process.
These copolymers ase preferably hydrogenated to increase their thermal stability, high temperature properties, and resistance to oxidation. The
PS19004 hydrogenation of these copolymers may be carried out by a variety of processes including hydrogenation in the presence of such catalysts as Raney nickel, nobel metals such as platinum and palladium and soluble transition metal catalysts. Suitable hydrogenation processes which can be used are ones wherein the diene-containing polymer or copolymer is dissolved in an inert hydrocarbon diluent such as cyclohexane and hydrogenated by reaction with hydrogen in the presence of a soluble hydrogenation catalyst. Such processes are disclosed in U.S. Patents Nos. 3,113,986 and 4,226,952. The copolymers may be hydrogenated in such a manner as to produce hydrogenated copolymers having a residual ethylenic unsaturation content (in the polydiene block) of less than 20 percent, preferably not more than 10 percent, most preferably not more than 5 percent, of their initial ethylenic unsaturation content (prior to hydrogenation).
Particularly suitable block copolymers, prior to hydrogenation, which may be employed for the present purpose include the following species:
Polystyrene-polyisoprene-polystyrene Polystyrene-polybutadiene-polystyrene
The amount of block copolymer useful in the process of the present invention is preferably from 2 to 25 percent by weight based on the amount of bitumen plus block copolymer. The amount of block copolymer is more preferably in the range form 4 to 15 percent. Significantly higher levels of block copolymer can cause the composition to be relatively expensive and also increase the viscosity of the finished composition excessively. Significantly lower levels of bl£>ck copolymer, in general, .will not form polymeric domains within the bituminous composition and therefore will not provide the desired
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PS19004 improvements in the properties of the composition.
The block copolymer must not be combined with a significant portion of bitumen before it is mixed with the carbon black because the benefits of process will not be realised. The amount of bitumen in the block copolymer composition, if present is therefore preferably less than 10% by weight of the block copolymer composition.
The carbon black which is used in the present invention may conveniently have a particle size in the range from 5 to 500 nanometers. Preferred carbon blacks are those of ASTM grades N660, N550, N330,
N110, N220, N761, N762, N601, 5300 and 5301. Most preferred carbon blacks are N-110 (ASTM D-2516) type carbon blacks. An example of this most preferred carbon black is available from Cabot, Boston, Massachusetts, USA, under the trade mark Vulcan 9A32. The weight ratio of the block copolymer to carbon black may conveniently be in the range 0.01:1 to 500:1. Preferably the ratio is 1:1 to 100:1 and most preferably 4:1 to 7:1. The amount of carbon black utilised is most preferably is the range from 2 to 25 percent by weight of the amount of bitumen and carbon black.
Carbon blacks are typically commercially available in pellet form, with particles bound into larger pellets to enhance handling. Commercial binders include naphthenic oils and diblock copolymers of vinyl arenes and conjugated diolefins. The particular binder used is not critical to the practice of the present invention so long as the carbon black composition does not contain more than 10% by weight of bitumen, the percent weight based on the total . carbon black composition. Some minimal amount of bitumen may be contained in the carbon black
PS19004 composition without a detrimental effect on the compatibility and other properties of the composition produced by the process of the present invention, but if a significant amount of bitumen is present in the carbon black before the carbon black is admixed with the block copolymer the advantages of the present invention will not be realised. Preferably, less than 10 percent by weight of the carbon black composition is bitumen, and more preferably, less than 5 percent by weight of the carbon black composition is bitumen. Advantageously, the carbon black composition is essentially free of bitumen and it is preferably in the form of pellets bound by a naphthenic oil binder.
The carbon black composition may conveniently be mixed with the block copolymer in a high shear mixing device. An extruder, Banbury mill, Ferrel continuous mixer, and two roll-mil are referred as the high shear mixing device for the process of this invention. A most preferred carbon black/block copolymer blending device is a high shear milling device, preferably a Banbury mill.
The blending of the block copolymer and the carbon black mixture is preferably performed with the copolymer in a melt phase.
The carbon black mixture-block copolymer composition is then blended with bitumen. This blending is preferably performed using a high shear mixing device capable of mixing the components under a high shear condition. A high shear rotor/stator disintegrator such as a Silverson mixer, is preferred.
The blending of the carbon black mixture - block copolymer composition with the bitumen is preferably performed with the asphalt initial temperature in the range from 150°C to 180°C, with a final blend
Z 9 I· 0 0 0 dV
PS19004 temperature in the range from 180°C to 220°C. At these temperatures, the viscosity of the blend is sufficiently low for mixing, but at higher temperatures, block copolymers could degrade. The residence time of the composition in the mixing device is preferably more than one hour.
Other fillers, for example silica and calcium carbonate, stabilisers, antioxidants, pigments, and solvents are known to be useful in bitumen compositions and can be incorporated in the compositions of this invention in concentrations taught in the art. Polystyrene, functionalised liquid resins and nonfunctionalised liquid resins are also know as advantageous ingredients in bitumen compositions and may be included in the compositions taught herein.
It is believed, although this is an theory which has not been proven, that the process of the present invention results in stable compositions because chemisorbed oxygen/acidic complexes on the carbon black surface provide interfacial support between polymer rich and polymer lean domains within the bitumen composition. The result is that the contacting of block copolymer with the carbon black prior to contact of the block copolymer with bitumen results in a more stable suspension of the polymer lean (asphaltene) phase in the polymer rich phase.
This also results in the block copolymer being more effective in improving the elasticity of the bitumen composition enabling a lower concentration of block copolymer for a similar level of improvement in elasticity tensile strength and other properties. The invention will be further understood from the following illustrative examples, wherein compositions
1,2,6,8 and 10 were prepared in accordance with the
PS19004 invention, whilst compositions 3 to 5,7,9 and 11 were comparative examples.
Example 1
The block copolymer used in this example was a hydrogenated polystyrene-polybutadiene-polystyrene block copolymer with a 30% by weight sytrene content and a number average molecular weight of 103,000 as measured by GPC with a polystyrene standard. The ethylenic unsaturation of the polymer has been reduced to less than 1% of the original ethylenic unsturation by hydrogenation.
Bitumen a had a softening point of 38°C (100°F) and a penetration of 183 dmm. Bitumen b had a softening point of 44°C (112°F) and a penetration of
120 dmm.
The carbon black used in compositions 1 and 2 of this example was obtained from Cabot Corp, of Boston, Mass, and is sold under the trade mark Vulcan 9A32. This carbon black was a SAF type, and was a grade
N-110 (ASTM D-2516). This carbon black was obtained in the form of pellets in which a naphthenic oil was used as a binder. An example of naphthenic oil is available from Shell Oil Company of Houston, Texas under the trade mark Shellflex 371. When additional naphthenic oil was added to the carbon black-block copolymer blends, Shellflex 371 was utilised.
Compositions 1,2 and 3 were prepared containing the components as described in Table 1. Compositions 1 and 2 were prepared by compounding the block copolymer and carbon black in a Banbury mill. The carbon black-block copolymer blend was then combined with the bitumen and mixed in a Silverson high shear mixer for about one hour. In this process, the bitumen was heated to 160°C, then the carbon black-block copolymer mixture was added.
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Composition 3 was a comparative composition prepared by a process taught by Nielsen in U.K. Patent Specification No. 1,143,895. A carbon black of grade N-110 (ASTM D-2516) was blended with bitumen b. The bitumen-carbon black blend was then combined with the naphthenic oil and the block copolymer in a Silverson high shear mixer and mixed for about one hour, beginning at a temperature of about 160°C, and ending at a temperature of 200°C.
Compositions 4 and 5 were comparative examples which did not contain carbon black. Compositions 4 and 5 were prepared by blending the hydrogenated block copolymer into bitumens a and b respectively in a Silverson high shear mixer for about 1 hour at a temperature of about 160°C.
The compatibility of the compositions was measured as the fraction by weight of polymer rich phase (”FPRW) of a sample which had been stored for 5 days at a temperature of 160°C. A FPR of 100% indicates that the composition did not phase separate during this time period. The compositions were stored under a nitrogen blanket during this 5 day period. Table 2 includes the FPR and tensile energy to fail properties of the five compositions. Tensile Energy to Fail was determined according to ASTM test method D412, using size MD'· dies and a crosshead speed of 10/min (25.4 cm/min).
It can be seen from Table 2 that only the compositions prepared according to the process of the present invention had a 100% FPR. This is an extremely important characteristics for bitumen compositions which must be stored before application, such as roofing compositions. Joint compounds, adhesives and paving compositions would also greatly benefit from this improved compatibility. It can also
PS19004 be seen from Table 2 that the Tensile Energy to Break was improved for identical asphalts when the block copolymer was added by the process of this invention.
A similar '’Tensile Energy to Break composition could therefore be prepared using less block copolymer when the present invention is practised. Because the block copolymer is an expensive component of these compositions, this results in a less expensive composition.
TABLE 1 Composition
| Parts by Weight | 2i | 4 | 5 | ||
| 15 Bitumen a | 85 | — | 88 | — | |
| Bitumen b | * «Μ | 85 | 85 | — | 88 |
| Block Copolymer | 12 | 12 | 12 | 12 | 12 |
| Carbon Black | 2. | 3 2.3 | 2.3 | 0 | 0 |
| Naphthenic Oil | 0. | 7 0.7 | 0.7 | 0 | 0 |
| 20 ^Compositions 1 | and 2 | were prepared | by mixing pellets |
of carbon black in which the naphthenic oil was used as a binder with the block copolymers, then combining with the bitumen.
. .
Composition 3 was prepared by blending the asphalt 25 and carbon black first, then combining the asphalt and carbon black blend with the remaining components.
TABLE 2 Composition
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1
FPR %w 100
Tensile Energy 12
| 2 | 3 | 4 | 5 |
| — | “ | ||
| 100 | 60 | 63 | 74 |
| 16 | 13 | 11 | 13 |
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Example 2
This example demonstrates the improvement in retention of tensile strength of the composition produced by the method of this invention over bitumen-block copolymer mixtures which do not contain carbon black.
Three different bitumens were utilised, bitumens c,d and e. These bitumens were all Grade AC-20 asphalts. The block copolymer utilised was identical to the block copolymer of Example 1. The carbon black pellets bound by naphthenic oil were also identical to those used in Example 1.
Compositions 6, 8 and 10 were prepared according to the process of this invention, using the same procedure as was used for compositions 1 and 2. Compositions 7, 9 and 11 did not contain carbon black and were prepared using the same procedure as was used for Compositions 4 and 5.
The six compositions of Example 2 were divided into aliquots and the aliquots were stored at 70°C. Tensile Energy to Failure, in lb-in (x 180 g-cm), was measured initially, and after 500, 1000 and 1500 hours of storage at 70°C. Table 3 lists the contents of Compositions 6 to ll, along with the Tensile Energy to Failure data.
Aliquots of compositions 6 to 11 were also stored at 60°C for five days to measure the storage stability, as described in Example 1. Compositions 6, 8 and 10 each has a 100% FPR after the five day;s whereas Compositions 7, 9 and 11 showed phase separation having FPR's of 48%, 39% and 55% respectively. Compositions 6, 8 and 10, like compositions 1 and 2, could be stored after preparation without requiring remixing before use due to improved storage stability.
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It can be seen from Table 3 that each of the compositions prepared according to the process of this invention maintained an excellent Tensile Energy to Failure over the duration of the aging test. Although one of the examples which did not contain carbon black, Composition 9, also maintained a good Tensile Energy to Failure over the duration of the test, the other two compositions deteriorated rapidly in Tensile Energy to Failure. This indicates that the process of this invention can serve to widen the types of asphalts successfully used with the block copolymers.
TABLE 3 Composition
| Parts by Weight | 6 | 7 | 8 | 9 | 10 | 11 |
| Bitumen c | 85 | 38 | ||||
| d | 35 | 88 | ||||
| e | 85 | 88 | ||||
| Block Copolymer | 12 | 12 | 12 | 12 | 12 | 12 |
| Carbon Black | 2.3 | 0 | 2.3 | 0 | 2.3 | 0 |
| Naphthenic oil | 0.7 | 0 | 0.7 | 0 | 0.7 | 0 |
| Tensile Energy to | Failure | |||||
| Lb-In (x 130 g-cm) (Hrs. of Aging at | 70°C) | |||||
| 0 Hrs. | 10.4 | 10.2 | 14.9 | 18.4 | 14.3 | 12.4 |
| 500 Hrs. | 22.0 | 15.7 | 21.5 | 16.4 | 17.9 | 10.8 |
| 1000 Hrs. | 16.9 | 1.2 | 22.9 | 17.1 | 19.0 | 1.3 |
| 1500 Hrs. | 9.0 | 1.4 | 19.5 | 21.7 | 22.9 | 0.3 |
| FPR % weight | 100 | 43 | 100 | 39 * | 100 | 55 |
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Claims (10)
1. A process for preparing a bitumen composition, which process comprises the steps of:
a) blending a carbon black composition comprising carbon black and containing 0 to 10% by
5 weight of bitumen based on the carbon black composition with a block copolymer composition, the block copolymer composition comprising a block copolymer and containing 0 to 10% by weight of bitumen based on the block copolymer composition, the block 10 copolymer being selected from the group consisting of hydrogenated and unhydrogenated block copolymers, the block copolymer, before hydrogenation, comprising at least two blocks A, the blocks A comprising
15 predominantly polymerised monoalkenyl arene monomer units, and at least one block B, the block B comprising predominantly polymerised conjugated diolefin monomer units; and
b) combining the carbon black composition
20 copolymer blend with a bitumen to form the bitumen composition.
2. A process according to Claim 1 wherein the block copolymer is a linear block copolymer, an ABA linear block copolymer or a radial block copolymer.
3. A process according to Claim 1 or 2 wherein the blocks A are predominantly polymerised styrene.
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4. A process according to any one of Claims 1 to 3 wherein the block B is predominantly polymerised butadiene or polymerised isoprene.
5. A process according to any one of Claims 1 to
5 4 wherein the carbon black is in the form of pellets bound by a naphthenic oil binder.
6. A process according to any one of Claims 1 to
5 wherein the block copolymer is hydrogenated, reducing the ethylenic unsaturation to less than 20%
10 of initial ethylenic unsaturation.
7. A process according to any one of Claims 1 to
6 wherein the weight ratio of block copolymer to carbon black is in the range from 1:1 to 100:1.
8. A process according to any one of Claims 1 to
15 7 wherein the block copolymer utilised is from 2 weight percent to 25 weight percent based on the amount of bitumen plus block copolymer.
9. A process according to Claim 8 wherein the amount of carbon black utilised is from 2 to 25 weight
20 percent based on the amount of bitumen and carbon black.
10. A process according to any one of claims 1 to 9 wherein the bitumen has a softening point in the range from 26°C to 105°C.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/422,194 US5036119A (en) | 1989-10-16 | 1989-10-16 | Process for preparing bituminous composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AP9000214A0 AP9000214A0 (en) | 1990-10-31 |
| AP167A true AP167A (en) | 1992-01-16 |
Family
ID=23673785
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| APAP/P/1990/000214A AP167A (en) | 1989-10-16 | 1990-10-15 | Process for preparing bituminous compositions. |
Country Status (22)
| Country | Link |
|---|---|
| US (1) | US5036119A (en) |
| EP (1) | EP0423875A1 (en) |
| JP (1) | JPH03139567A (en) |
| KR (1) | KR910008086A (en) |
| CN (1) | CN1051048A (en) |
| AP (1) | AP167A (en) |
| AR (1) | AR244285A1 (en) |
| AU (1) | AU633635B2 (en) |
| BR (1) | BR9005167A (en) |
| CA (1) | CA2027692A1 (en) |
| FI (1) | FI905057A0 (en) |
| HU (1) | HU209708B (en) |
| IE (1) | IE903688A1 (en) |
| MA (1) | MA21977A1 (en) |
| MX (1) | MX169290B (en) |
| MY (1) | MY105981A (en) |
| NO (1) | NO177429C (en) |
| NZ (1) | NZ235692A (en) |
| PH (1) | PH26969A (en) |
| PT (1) | PT95592A (en) |
| TR (1) | TR25227A (en) |
| ZA (1) | ZA908226B (en) |
Families Citing this family (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| USH1186H (en) | 1991-03-25 | 1993-05-04 | Self-adhesive water proofing product | |
| GB2255979A (en) * | 1991-05-24 | 1992-11-25 | Shell Int Research | Bituminous roofing composition |
| US5308676A (en) * | 1991-09-20 | 1994-05-03 | Shell Oil Company | Torchable roll roofing membrane |
| US5342866A (en) * | 1992-12-30 | 1994-08-30 | Owens-Corning Fiberglas Technology Inc. | Oxidized asphalt rubber system |
| US5447775A (en) * | 1994-02-23 | 1995-09-05 | Shell Oil Company | Torchable roll roofing composition |
| US5719216A (en) * | 1995-05-22 | 1998-02-17 | Shell Oil Company | Preparation process for polymer-modified bitumen |
| US5773496A (en) * | 1996-05-31 | 1998-06-30 | Koch Industries, Inc. | Polymer enhanced asphalt |
| US6133350A (en) * | 1996-08-13 | 2000-10-17 | Shell Oil Company | Oil free compounds of styrenic block copolymers, amorphous polyolefins, and carbon black |
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- 1990-10-15 IE IE368890A patent/IE903688A1/en unknown
- 1990-10-15 TR TR90/0934A patent/TR25227A/en unknown
- 1990-10-15 MX MX022842A patent/MX169290B/en unknown
- 1990-10-15 FI FI905057A patent/FI905057A0/en not_active Application Discontinuation
- 1990-10-15 AU AU64622/90A patent/AU633635B2/en not_active Ceased
- 1990-10-15 NZ NZ235692A patent/NZ235692A/en unknown
- 1990-10-15 JP JP2276115A patent/JPH03139567A/en active Pending
- 1990-10-15 ZA ZA908226A patent/ZA908226B/en unknown
- 1990-10-15 AP APAP/P/1990/000214A patent/AP167A/en active
- 1990-10-15 HU HU906451A patent/HU209708B/en not_active IP Right Cessation
- 1990-10-15 PT PT95592A patent/PT95592A/en not_active Application Discontinuation
- 1990-10-15 MY MYPI90001785A patent/MY105981A/en unknown
- 1990-10-15 NO NO904453A patent/NO177429C/en unknown
- 1990-10-15 MA MA22246A patent/MA21977A1/en unknown
- 1990-10-15 PH PH41378A patent/PH26969A/en unknown
- 1990-10-15 KR KR1019900016384A patent/KR910008086A/en not_active Application Discontinuation
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Also Published As
| Publication number | Publication date |
|---|---|
| FI905057A0 (en) | 1990-10-15 |
| NO177429C (en) | 1995-09-13 |
| HU209708B (en) | 1994-10-28 |
| AU6462290A (en) | 1991-04-18 |
| IE903688A1 (en) | 1991-04-24 |
| NO904453D0 (en) | 1990-10-15 |
| CA2027692A1 (en) | 1991-04-17 |
| PH26969A (en) | 1992-12-28 |
| CN1051048A (en) | 1991-05-01 |
| EP0423875A1 (en) | 1991-04-24 |
| AU633635B2 (en) | 1993-02-04 |
| NO904453L (en) | 1991-04-17 |
| US5036119A (en) | 1991-07-30 |
| ZA908226B (en) | 1991-08-28 |
| JPH03139567A (en) | 1991-06-13 |
| MY105981A (en) | 1995-02-28 |
| HU906451D0 (en) | 1991-04-29 |
| AP9000214A0 (en) | 1990-10-31 |
| BR9005167A (en) | 1991-09-17 |
| KR910008086A (en) | 1991-05-30 |
| HUT57248A (en) | 1991-11-28 |
| NO177429B (en) | 1995-06-06 |
| AR244285A1 (en) | 1993-10-29 |
| PT95592A (en) | 1991-09-13 |
| TR25227A (en) | 1993-01-01 |
| NZ235692A (en) | 1992-01-29 |
| MX169290B (en) | 1993-06-28 |
| MA21977A1 (en) | 1991-07-01 |
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