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GB2036760A - Bituminous compositions - Google Patents

Bituminous compositions Download PDF

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Publication number
GB2036760A
GB2036760A GB7938595A GB7938595A GB2036760A GB 2036760 A GB2036760 A GB 2036760A GB 7938595 A GB7938595 A GB 7938595A GB 7938595 A GB7938595 A GB 7938595A GB 2036760 A GB2036760 A GB 2036760A
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United Kingdom
Prior art keywords
thermoplastic rubber
parts
weight
bitumen
filler
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Granted
Application number
GB7938595A
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GB2036760B (en
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BP PLC
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BP PLC
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Publication of GB2036760A publication Critical patent/GB2036760A/en
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Publication of GB2036760B publication Critical patent/GB2036760B/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L19/00Compositions of rubbers not provided for in groups C08L7/00 - C08L17/00
    • C08L19/003Precrosslinked rubber; Scrap rubber; Used vulcanised rubber
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • C08K5/17Amines; Quaternary ammonium compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00Compositions of unspecified rubbers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L95/00Compositions of bituminous materials, e.g. asphalt, tar, pitch
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/01Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013Fillers, pigments or reinforcing additives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06Copolymers with styrene

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Civil Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Bituminous compositions having good energy absorbing properties contain bitumen, hardened extract, a thermoplastic rubber, finely divided particles of a non-thermoplastic rubber and a filler, the amount of non- thermoplastic rubber by weight being equal to or greater than the amount of filler by weight. Optionally an antioxidant and/or a long chain hydrocarbyl amine may be present. The compositions can be formed into sheets or slabs using rubber compounding equipment and are suitable for use as safety surfaces, e.g. childrens playgrounds.

Description

SPECIFICATION Bituminous composition This invention relates to a composition containing bitumen and rubber having energy absorbing properties and suitable for use, for example, as a safety surface for childrens playgrounds.
Various compositions containing bitumen and rubber have been proposed with greater or lesser energy adsorbing properties. In particular compositions containing bitumen, a thermoplastic rubber and a non-thermoplastic rubber have been proposed.
The present invention is concerned with compositions having good energy absorbing properties combined with a low compression set and low rebound resilience. The required balance of properties is obtained by a suitable selection of components and their proportions.
According to the present invention, a bituminous composition comprises bitumen, hardened extract, a thermoplastic rubber, finely divided particles of a non-thermoplastic rubber and a filler, the amount of non-thermoplastic rubber by weight being equal to or greater than the amount of filler by weight. Preferably the ratio by weight of non-thermoplastic rubber to filler is in the range 1:1 to 3:1.
Preferred proportions of the components by weight may be: Bitumen + hardened extract: 100 parts (of which bitumen may be 95 to 70 parts and hardened extract may be 5 to 30 parts) Thermoplastic rubber: 5 - 15 parts, particularly 10 - 15 parts Non-thermoplastic rubber: 50 - 150 parts Filler: 50 - 150 parts The compositions may also contain an anti-oxidant in an amount of 1 - 5 parts. Such materials are well known in the rubber industry and include amines, e.g. phenyl -B-naphthylamine, (an example being Nonox D sold by ICI Limited), quinolines, e.g. polymerised 2,2,4-trimethyl-1,2-dihydroquinoline (an example being Flectol H sold by Monsanto Limited) and phosphates, e.g. alkylated aryl phosphites (an example being Polygard HR sold by The Rubber Regenerating Company Limited).
A long chain hydrocarbyl amine (e.g. octadecyl amine) may also be incorporated in an amount of 0.1 - 5 parts by weight to assist the mixing and milling of the composition.
A characteristic of the composition is the relatively high proportion of non-thermoplastic rubber which gives the energy absorbing properties. The hardness may be controlled by the proportions of hardened extract and filler and the hardness is preferably from 28 - 50 on the IRHD scale. At lower hardness value, the compositions tend to be soft and tacky; at higher values they tend to be too stiff and to have reduced energy absorbing properties.
The rebound resilience is preferably 1 5% as measured by a falling weight or pendulum. This compares with figures of > 30% for most rubbers and indicates that the compositions have a high capacity to absorb impact energy.
Another desirable characteristic of the compositions is that they should deform readily under load and recover slowly. Typical recoveries of the distance indented may be of the order of 80 - 90% after 24 hours.
Compression set is the reverse of recovery and is the residual deformation of a test specimen when subjected to compression under defined conditions. Typical compression sets under conditions specified hereafter may be less than 20%.
The bitumen may be derived from petroleum, e.g. the residues from the vacuum distillation of crude oils and may be straight run bitumen, an oxidised bitumen obtained by air blowing an atmospheric or vacuum residue to a suitable penetration, or an asphalt obtained from an atmospheric or vacuum residue by precipitation with a low boiling paraffin hydrocarbon, e.g. propane. The bitumen may have a penetration of from 10 to 450 at 25"C and a softening point (Ring and Ball) of from 25 to 1 500C.
Thermoplastic rubbers are known and any of such known rubbers may be used. They are normally synthetic polymers produced by the block co-polymerisation of a diene, e.g. butadiene and another unsaturated monomer, e.g. styrene. Examples of suitable thermoplastic rubbers are those sold by Phillips Petroleum Company under the Registered Trade Mark "Solprene" and by Shell Chemical Company under the Registered Trade Mark "Cariflex". The thermoplastic rubber may be used in any form but is preferably used as powder or crumb to reduce the time of dissolution in the bitumen.
The non-thermoplastic rubber is used in the form of finely divided particles which may, for example, be finer than 20 mesh BSS. The rubber will normally be vulcanised and may be, for example, a synthetic rubber, e.g. SBR or polybutadiene or natural rubber. It may be oil extended and/or filled and may be a material produced as a by-product in the manufacture of rubber articles, e.g. tyre crumb, which is the buffings produced when smoothing tyre treads. The non-thermoplastic rubber is not believed to blend with the bitumen but to remain as discrete particles which act to stiffen the bitumen but which, at the same time, give resilience to the composition.
Any of the normal fillers for bitumen may be suitable. They may be powdered or fibrous but preferably the former and examples of suitable fillers are powdered limestone, silica, alumina, Portland cement, barytes, pulverised fuel ash, talc, asbestos fibres and glass fibres. The presence of a small amount of talc has been found beneficial during the mixing and the filler content may include 1-7% wt by weight of the composition of talc added at the mixing stage.
The hardened extract may be produced by blowing a petroleum extract with an oxygen containing gas, preferably air, at 250 - 350"C either in the absence or presence of a catalyst, e.g. a Friedel-Crafts metal halide such as ferric chloride. Petroleum extracts are obtained by the solvent extraction of distillate petroleum fractions boiling in the lubricating oil range, i.e. 350 - 600"C and contain a major proportion of aromatic hydrocarbons. The blowing of the extract is believed to cause condensation of the aromatics giving a hardened product with a high proportion as asphaltenes, cyclics and insolubles and a relatively low proportion of saturates.The hardened extract may have a penetration of from 0.1 to 6 at 25"C and softening points (Ring and Ball) of from 60 to 1700C.
The compositions may be produced in the form of a solid crumb by mixing in, e.g. a Z-blade mixer, at 120 1 30"C for 1 - 2 hours. To ensure complete homogeneity ofthe product and to develop its optimum physical properties the crumb is preferably milled to a thick hide. Alternatively, all the components (except the bitumen) may be preblended in a high speed mixer (e.g. a Papenmeir mixer) and then mixed with the bitumen in a Z-blade mixer at 120 - 1300C for 1 - 2 hours. The product as hide or crumb may be used to form a moulded or extruded product. Suitable moulding temperatures are in the range 120 - 1 800C for 3 to 30 minutes under pressures of 0.1 - 1 ton psi.
The compositions may be used as safety surfaces, e.g. on childrens playgrounds, particularly around swings, roundabouts, slides, etc., where children may fall. They may also be used as energy absorbing bumpers for vehicles, as ship's fenders, or as motorway barriers.
Typically the material may be moulded into slabs with dimensions of 60 x 45 x 1.6 centimetres for use as safety paving.
Slabs or continuous sheets may be stuck onto an underlaying surface (e.g. asphalt or concrete) with a suitable adhesive. A hot melt of bitumen (e.g. 200 penetration bitumen) and 3 - 12% of thermoplastic rubber (e.g. Solprene rubber) has been found to be a suitable adhesive.
The invention is illustrated by the following examples.
Example 1 24 g bitumen (200 penetration), 6 g hardened extract (1 50"C softening point), 3.3 g "Solprene" 411 P styrene-butadiene thermoplastic rubber ex Phillips Petroleum, 33.3 g tyre crumb 30 mesh (ex United Reclaim Limited) and 16.7 g "Snowcal" 7ML limestone filler (ex Cement Marketing Company Limited) were charged to the mixing chamber of a Brabender Plastograph type 100 fitted with a roller mixing measuring head type 50. The charge was mixed for one hour at 130 - 150"C at a mixing speed of 60 rpm.
Test specimens of the product were moulded at 140"C for 6 minutes under a pressure of 0.3 tons psi. The following properties were measured:- IRHD hardness 44, and a permanent compression set of 15% 24 hours after being compressed by 26% of the original thickness.
Example 2 101.5 g bitumen (200 penetration), 33.75 g hardened extract (softening point 150"C), 15 g Solprene 411 P thermoplastic rubber, 166.5 g tyre crumb, 125 g Snowcal 7ML limestone filler and 2 g Polygard HR were charged to a 1 litre capacity Winkworth mixer which had been preheated to 130"C. The composition was mixed for lol hours at 130or. The mixing chamber was initially purged with nitrogen and kept under a continuous flow of nitrogen of 50 cc/minute. The product was removed as a black crumb and milled on a Bridges 2 roll mill at ambient temperature for 5 minutes.
A specimen of the product was moulded at 160"C for 5 minutes under 20 tonnes in a 8 inch x 8 inch press.
An IRHD hardness of 50 was measured on the product.
Example 3 Example 2 was repeated using eight times the charge weight in a 5 litre capacity Winkworth mixer with a nitrogen flow rate of 100 cc/minute. The product was milled at 80"C for 5 minutes.
The following tests were carried out on moulded specimens of the materials.
(a) IRHD hardness 43 (b) A Lu. pke Pendulum method was used to measure resilience.
Pendulum weights of 350 g, 1336 g and 2981 g were employed suspended from a height of 2 metres and at an angle of 18 from the vertical. The impacting energies were 0.36, 1.36 and 3.04 Joules respectively.
The results are shown in Table 1 below.
TABLE 1 Rebound Height % Material Thickness Energy Level 1 sot 2nd 3rd 4th 5th mm JOULES Rebound Rebound Rebound Rebound Rebound 0.36 13 2 Too Low to 12.61 0.2 1.36 13.5 2 Measure As Example 3 Accurately 3.04 10.5 1.75 24.8 1.36 14 3 Acommercially 0.36 52 27 15 8 4.5 available bonded tyre 16.810.5 1.36 49 25 14 7.5 4 crumb safety surface 3.04 38.5 18.5 9.5 5 2.5 The Rebound Height, expressed as a percentage of the original drop height is quoted for the 1 st to 5th rebounds. The first rebound is a measure of the resilience of the material and the first rebound results show that the experimental material absorbs more energy than the commercially available bonded tyre crumb product.
The results show that the rebound height drops by a factor of six for each bounce on the experimental material compared with a factor of about 2 for the commercial bonded tyre crumb product. There is some reduction in the apparent resiliences of both materials at the highest impact energy level tested.
(c) The compression set of the material was 7%, 24 hours after being compressed by 26%.
The compression set may be defined as the residual deformation of a test specimen measured at a specified time interval after removal from a suitable compression device in which the specimen has been subjected for a definite time to a compressive deformation under specified conditions.
The compression device used consisted of several stiff flat plates arranged so that they were held parallel to each other by bolts. The space between these plates was adjusted by means of spacers to give a compression of 26%.
Specimens 12 mm thick and 25.4 mm and 25.4 mm square were used in the test. The specimens were compressed in the apparatus in a constant temperature of 23"C for 22 hours and after removal of the specimens the compression set was calculated using the following formula.
Compression set = (to - to) / (to - tS) x 100 to = original thickness.
tf = thickness at time of test (24 hrs) to = thickness of spacer bar.

Claims (9)

1. A bituminous composition having energy absorbing properties, comprising bitumen, hardened extract, a thermoplastic rubber, finely divided particles of a non-thermoplastic rubber and a filler, in which the amount of non-thermoplastic rubber is equal to or greater than the amount of filler by weight.
2. A bituminous composition as claimed in claim 1 wherein the ratio by weight of non-thermoplastic rubber to filler is in the range 1:1 to 3:1.
3. A bituminous composition as claimed in claim 1 or 2 having the following components in parts by weight: Bitumen + hardened extract: 100 parts (of which bitumen is 95 to 70 parts and the hardened extract is 5 to 30 parts) Thermoplastic rubber: 5 - 15 parts Non-thermoplastic rubber: 50 - 150 parts Filler: 50 - 150 parts
4. A bituminous composition as claimed in claim 3 which also contains from 1 - 5 parts by weight of an antioxidant.
5. A bituminous composition as claimed in claim 4 which also contains from 0.1 - 5 parts by weight of a long chain hydrocarbyl amine.
6. A bituminous composition as claimed in any of claims 1 to 5 which has a hardness from 28 - 50 on the IRHD scale and a rebound resilience of nof more than 15%.
7. A bituminous composition as claimed in any of claims 1 to 6 which has a compression set as hereinbefore defined of less than 20%.
8. A composition as claimed in any of the previous claims in which the non-thermoplastic rubber is a tyre crumb.
9. A bituminous composition as hereinbefore described with reference to any one of the Examples 1 to 3.
GB7938595A 1978-11-08 1979-11-07 Bituminous compositions Expired GB2036760B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB7843606 1978-11-08

Publications (2)

Publication Number Publication Date
GB2036760A true GB2036760A (en) 1980-07-02
GB2036760B GB2036760B (en) 1983-04-13

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DE (1) DE2943706A1 (en)
FR (1) FR2440977A1 (en)
GB (1) GB2036760B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015009177A3 (en) * 2013-07-18 2015-03-19 Instytut Inzynierii Materialow Polimerowych I Barwnikow Mixture for the production of vibroinsulation materials to protect railways and roads

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2112399B (en) * 1981-12-10 1985-06-05 British Petroleum Co Plc Particulate mixtures of rubbers and hardened petroleum extracts

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015009177A3 (en) * 2013-07-18 2015-03-19 Instytut Inzynierii Materialow Polimerowych I Barwnikow Mixture for the production of vibroinsulation materials to protect railways and roads

Also Published As

Publication number Publication date
DE2943706A1 (en) 1980-05-22
FR2440977A1 (en) 1980-06-06
GB2036760B (en) 1983-04-13
FR2440977B1 (en) 1984-04-20

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