DE2844101C2 - Bituminous mass and its uses - Google Patents

Description

The invention relates to compositions containing bitumen and rubber and their use for production of foamed products, which can be used, for example, in the construction and automotive industries as well as carpet backing and suitable for packaging or insulation purposes.

Compositions containing bitumen and thermoplastic rubber are already known, but they have the disadvantage of being sticky and of little dimensional stability. The invention has the task based on masses with reduced stickiness and increased stiffness without impairing the impact resilience to make available, which also have good flexibility at low temperatures and good impact strength in comparison to the known masses.

The solution to this problem are the bituminous masses according to the preamble of claim 1 and the characteristics of the characterizing part of this claim. The further refinement of the bituminous Masses according to the invention is the subject of the subsequent subclaims.

The amounts of the constituents of the masses can thus be in the following ranges (in parts by weight) lie:

Ratio of bitumen to extract:
100 to 50 parts by weight of bitumen to 0 to 50 parts by weight of extract. The quantities of the other components, based on 100 parts of bitumen and extract or bitumen only if no extract is available, can be in the following ranges:

Thermoplastic rubber 2 to 30 parts

Non-thermoplastic

Rubber 5 to 150 parts

Filler Ibis 150 parts

Propellant Ibis 10 parts

Foam stabilizer 1 to 10 parts

The following proportions of the components in parts by weight are particularly preferred:

Weight ratio of bitumen to extract:
100 to 66 parts of bitumen to 0 to 34 parts of extract.

Preferably the extract is present in an amount of 10 to 30 parts per 100 parts of bitumen. The quantities of the other components, based on 100 parts of bitumen and extract or just bitumen, if there is no extract, it can be in the following ranges:

Thermoplastic rubber
Non-thermoplastic
rubber
filler
Propellant
Foam stabilizer

5 to 15 parts

25 to 50 parts

1 was called SQ TajIj;

2 to 5 parts
2 to 5 parts

The bitumen can be made from petroleum, e.g. B. from the residues of vacuum distillation of crude oils. Straight-run bitumen, one by blowing a residue from atmospheric distillation or

Vacuum distillation up to suitable penetration oxidized bitumen or an asphalt that consists of a residue atmospheric distillation or vacuum distillation by precipitation with a low-boiling paraffin hydrocarbon, z. B. propane has been obtained. The bitumen can have a penetration of 10 to 450 25 ° C and a softening point (ring and ball) of 25 ° to 150-C.

Thermoplastic rubbers are known. All of these known rubbers can be used. Normally synthetic polymers are used, the block copolymerization of a Services, e.g. B. butadiene, and another unsaturated monomer, e.g. B. styrene can be produced.

Bitumen and thermoplastic rubbers are compatible and form a homogeneous mixture when they be mixed at an elevated temperature of, for example, 180 ° to 220 ° C. The thermoplastic rubber can be used in any form but is preferably used as a powder or crumb, to shorten the dissolution time in the bitumen. Mixing with the bitumen takes place in the above named temperature.

The non-thermoplastic rubber is used in the form of fine particles, for example, smaller than 0.78 mm. The rubber is usually vulcanized and can be, for example, a synthetic rubber, z. B. styrene-butadiene rubber or polybutadiene, or natural rubber. It can be stretched with oil and / or filled and a material that is a by-product in the manufacture of rubber items accrues, e.g. B. Tire abrasion, which is formed when the treads of pneumatic tires are smoothed. It is believed, that the non-thermoplastic rubber does not mix with the bitumen, but in the form of remains discrete or separate particles that cause stiffening of the bitumen, but the mass at the same time give shock elasticity. The non-thermoplastic rubber particles can with the bitumen mixed simultaneously with the thermoplastic rubber or subsequently and at the same temperature are, however, preferably at lower temperatures, e.g. B. 100 ° to 150 ° C, mixed

If a filler is used, all normal fillers for bitumen are suitable. They can be powdered or fibrous, but the former are preferably used. Examples of suitable fillers are limestone powder, silicon dioxide, aluminum oxide, portland cement, barytes, pulverized fuel ash, Talc, asbestos fibers and glass fibers. In particular, materials with advantageous soundproofing properties can be used by using heavy fillers, for example finely divided calcium carbonate (e.g. limestone), barium sulfate (e.g. barytes) or their mixtures, aluminum oxide or light fillers, z. B. pulverized fuel ash, either alone or in mixtures.

For the production of a flexible elastic foam, e.g. for carpet backing layers, it is advisable to use only a small proportion of the

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The extract used according to the invention can be produced by blowing a petroleum extract with a oxygen-containing gas, preferably air at 250 ° C to 350 ° C in the absence or presence of a catalyst, for example a Friedel-Crafts metal halide such as ferric chloride. Petroleum extracts are obtained by solvent extraction of in the lubricating oil range, i. H. passing over at 350 ° to 600 ° C Produced petroleum distillate fractions and contain a larger proportion of aromatic hydrocarbons. It is believed that condensation of the aromatics is caused by blowing the extract, with a Hardened product with a high proportion of asphaltenes, cyclic hydrocarbons and insolubles Substances and a relatively low proportion of saturated hydrocarbons are formed. This Extract can have a peneiration of 0.1 to 6 at 25 ° C and softening points (ring and ball) of 60 ° to Have 170 °.

The propellant can be added at any convenient stage in the preparation of the compositions. The most diverse Heat-sensitive chemical blowing agents are used in the plastics and rubber fields known, however, a propellant is expediently chosen, which is inactive at a temperature at which the mass is mixed and only at a higher temperature, preferably at 100 ° to 200 ° C, is active Some examples such blowing agents are azobisdibutyronitrile, ammonium chloride, inorganic hydrates, the water Release as steam at 140 ° to 200 ° C, and organic acids with carbonates (either intentionally added or present as a filler) react with the release of CO2 (e.g. sebacic acid, oxalic acid or stearic acid). Commercially available propellants can be suitably used. As examples these blowing agents are in particular azodicarbonamide, benzenesulfonhydrazide and ρ, ρ-oxybisbenzenesulfonhydrazide to call.

Surfactants, which act as foam stabilizers, can also be added to the compositions. Nonionic blowing agents, in particular blowing agents with high foaming power, are preferred.
These foam stabilizers can be added in an amount of 0 to 10 parts by weight per 100 parts by weight of bitumen, and are preferably used in an amount of 2 to 5 parts. They are normally incorporated into the mixture at temperatures from 100 ° to 130 ° C.

The masses can by calendering to form foamed materials, for example sheets or Membranes. The plates or membranes expediently have a thickness of 1 to 6 mm. The foamed material can be used as an insulating material and as a sound-absorbing material, for example in motor vehicles and buildings are used.

The masses can either be foamed as such or applied to a carpet or other textile fabric. You can calendering between heated rollers or under Ver u / ρηΗιιησ vnn 7iicat7Ctr »fFpn u / ia Ritumpn

Ρ / λ1ι / γ »Κ1λ-

for the production of curable semi-rigid foamed materials, e.g. for packaging purposes, higher filler concentrations can be used to advantage.

The filler can be used in any convenient bitumen Added stage of production and mixed in, for example, at 100 ° to 120 ° C.

roprene latex can be attached to the carpet or fabric. The masses can be heated in a Shape that is attached to the carpet or fabric is converted into a foamed material will. The mold can be heated to 130 ° to 200 ° C. It turned out to be particularly useful one Temperature difference between the top and the

Adjust the bottom of the mold. The temperature difference can be 5 ° to 60 ⁰ C, the higher temperature of 130 ° to 200 ⁰ C on the free side of the plate or membrane and not on the side that is attached to the carpet or fabric, if the plate is in attached in this way. The plate or membrane can be placed on the bottom or on top of the mold and foamed upwards or downwards as appropriate. The cooler side can, if desired, be cooled by blowing cooling air. The increase in volume as a result of foaming can be 30 to 200% and is preferably 30 to 60%. It has been found possible to achieve volume increases of this magnitude by heating for a period of 5 to 60 minutes. After the selected time, the temperature is reduced to ambient temperature as quickly as possible

The masses can be used as such to form plates or membranes, that are not applied to carpets or fabrics. For example, can the masses are heated from above, for example by a series of infrared heaters. The surface can be cooled by blowing cooling air over the underside of the plate or membrane.

The masses can also contain small amounts of other additives, for example to improve the Contains low temperature properties. For example, 0 to 50 parts of aromatic petroleum extracts can per 100 parts of bitumen are used. Other oils and Plasticizers, for example naphthenic or paraffinic oil, chlorinated hydrocarbons, / alkyl phosphates, for example trichloroalkyl phosphates, ester plasticizers, for example phthalates, adipates, Azelates, triaryl phosphates, epoxidized oils and polymeric plasticizers can also be used in small proportions be used.

These plasticizers are preferably used in amounts of not more than 30 parts by weight per 100 parts by weight Bitumen mixed in.

The invention is illustrated by the following examples.

example 1

88 parts of bitumen having a penetration of 200 were mixed with a laboratory-Paddelschnellrührers 12 parts of a styrene / butadiene Radialteleblockmischpolymerisats 2 hours at 180 ⁰ C using. The temperature of the mixture was lowered to 16O ⁰ C, followed by a mixture of 25 parts of ground tire abrasion (particle size 0.5 mm) and 2.5 parts was stirred in a nonionic surface active agent as foam stabilizer 30 minutes in the mixture. The temperature was lowered to 130 ° C, whereupon 2 parts of benzenesulfonhydrazide were added and mixed for an additional 10 minutes. The hot bituminous mass thus formed was poured onto silicone-treated, non-adhesive paper and allowed to cool.

A mold a size of 114 χ 76 χ 12.7 mm (Vo-

liimpn 119nm ^ u / iirHp with Hpr Mnccp halh σρΓίϊΠί iinH shear, resilient foam that had expanded by an average of 64%. The material was flexible and could be pressed and then reassumed its shape. It had little residual tack

Example 2

By mixing the bitumen with a penetration of 200 with the styrene / butadiene radial teleblock copolymer for 90 minutes at 180 ° using a high-speed laboratory paddle stirrer, 650 g of a bituminous mass of the composition mentioned in Example 1 were produced. the blowing agent and the foam stabilizer are mixed for 60 minutes at a temperature of 100 ^° C. using a double-arm kneader

400 g of the composition prepared in this manner were then foamed in a press under a pressure of 498.2 kN at a temperature of the plates of 140 ⁰ C. for 8 minutes The foamed material formed in this way had a bulk density of 0.596 g / cm ³ and the following Characteristics:

1) Impact strength of more than 2 J at -20 ⁰ C, tested in a ball drop test in which a steel ball with a diameter of 19 mm was dropped onto the material.

2) Rebound elasticity 8%, determined using the Lüpke pendulum method BS 903, part A8.

3) Compression hardness 0.1 MNm- ² at 50% compression. The measurement was carried out with an Instron tensile testing machine on a square sample with an edge length of 25 mm.

4) The maximum vibration value Q at 500 Hz was 1! Λ The φ value is given by the expression

^v ~ tan ό

with the vibration damping capacity tan r) 'in Relationship brought.

The test was carried out by gluing a sample of the material with a vibrating leaf spring was that in an upright position at one end in a heavy, rigid construction that was surrounded by background vibrations was isolated, firmly clamped and vibrated by a solenoid operated by a deflection oscillator. Measurements were made over the range of 0 to 200 Hz at ambient temperature.

Example 3

3000 g of bitumen with a penetration of 200 and 409 g of styrene / butadiene radial teleblock copolymer were used with a laboratory high-speed paddle stirrer for 2 hours at a temperature in the range from 160 ° to ! ROT apmisrht 9ΟΟα Rpifpnnhriph 400 a KaIk-

between the heated plates of a press for 5 minutes under contact pressure with the lower plate at 160 ⁰ C and the upper plate at 100 ⁰ C. To completely foam the mass, a further 30 minutes were allowed to pass while the mold was held under a pressure of 199.28 kN.
The material thus formed was a elastisteinfüller, 8 g ρ, ρ-oxy-bis-benzenesulfonhydrazide as blowing agent and 10 g of nonionic surfactant Sohaumstabilisator were added to the mixture for one hour at 100 ⁰ C in a double-arm kneader with a capacity of 1 liter of mixed .

400 g of the bituminous mass thus formed were placed in a press and at a temperature of

140 ° C heated for 3 minutes under a pressure of the plates of 0 and 5 minutes under a pressure of 498.2 kN and then quickly cooled to room temperature. The foamed material thereby formed was a square one Plate that was 25 χ 25 cm in size and 6 mm thick.

The material had a density of 0.778 g / cm ³ and represented a high-quality foam. It had an impact strength of more than 2 J at -20 ⁰ C and a rebound resilience of 3% as measured by the Lupke pendulum method BS 903 Part A8 . The compressive strength of a laminated square sample with an edge length of 25 mm and a thickness of 20 mm was 0.61 MNm- ² , measured with an Instron tensile tester at 50% compression.

The materia! had a maximum <? - value of! 0.1, measured according to the method described in Example 2.

B e i s ρ i e I 4

34 g bitumen with a penetration of 200, 10 g of a hardened extract with a softening point (ring and ball) of 90 ° C., 6 g of a styrene / butadiene radial teleblock mixed polymer, 1.3 g of a nonionic surface-active agent serving as a foam stabilizer, 25 g limestone as a filler, 12.5 g tire wear and 1 g of serving as a heat-sensitive chemical blowing agent p, p-oxy-bis-benzoIsulfonhydrazid one hour at 8O ⁰ C were mixed in a Brabender plastograph which was measuring head provided with a Walzenmisch- and, mixed at a mixing speed of 60 rpm.

In a press held 53 g of the bituminous composition thus formed under a pressure of 199.28 kN for 30 minutes at 140 ⁰ C, with a foamed material was formed. The foamed material had a size of 10 cm × 10 cm and a thickness of 8 mm. It consisted of a very fine foam that had no residual stickiness on the surface. The foam had a density of 0.595 g / cm ³ . The average expansion due to the foaming was 63%. The foamed material had a return elasticity of 5%, measured according to the Lüpke Pendelmeihode BS963, Part A8.

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Claims (1)

Patent claims: I. Bituminous mass containing a bitumen and a thermoplastic rubber, thereby characterized in that it also comprises a finely divided non-thermoplastic rubber and a contains heat sensitive chemical blowing agent Z Bituminous mass according to Claim 1, characterized in that the non-thermoplastic Rubber has a particle size of less than 0.78 mm. 3. Bituminous composition according to claim 1 or 2, characterized in that the non-thermoplastic Rubber consists of the abrasion that occurs when smoothing tire treads 4. Bituminous composition according to claim 1 to 3, characterized in that the heat-sensitive chemical blowing agent is only effective at a temperature in the range of 100 ° to 200 ° C 5. Bituminous composition according to claim 1 to 4, characterized in that it also contains an extract which has been obtained by blowing a petroleum extract containing aromatic hydrocarbons with an oxygen-containing gas at 250 ^c C to 350 ^c C. 6. Bituminous composition according to claim 5, characterized in that the extract has a penetration of 0.1 to 6.0 at 25 ° C and a softening point (ring and ball) of 60 ⁰ C to 170 ⁰ C. 7. Bituminous composition according to claim 5 or 6, characterized in that it contains 50 to 100 parts by weight Contains bitumen to 0 to 50 parts by weight of extract. 8. Bituminous composition according to claim 5 to 7, characterized in that it is the thermoplastic Rubber in an amount of 2 to 30 parts by weight per 100 parts by weight of bitumen and extract or, if the extract is not present, contains bitumen per 100 parts by weight. 9. Bituminous composition according to claim 5 to 8, characterized in that it is the non-thermoplastic Rubber in an amount of 5 to 150 parts by weight per 100 parts by weight of bitumen and extract or, if the extract is not present, contains bitumen per 100 parts by weight. 10. Bituminous composition according to claim 1 to 9, characterized in that it is finely divided calcium carbonate or contains barium sulfate or a mixture of calcium carbonate and barium sulfate as filler. II. Bituminous mass according to claim 5 to 10, characterized characterized in that they contain the filler in an amount of 1 to 150 parts by weight per 100 parts by weight Bitumen and extract or, if the extract is not present, bitumen per 100 parts by weight. 12. Bituminous composition according to claim 1 to 11, characterized characterized in that they contain the thickening agent in an amount of 1 to 10 parts by weight per 100 parts by weight of bitumen and extract or, if the extract is not present, per 100 parts by weight of biturns contains. 13. Bituminous composition according to claim 1 to 12, characterized characterized in that they contain a foam stabilizer in an amount of 1 to 10 parts by weight per 100 Parts by weight of bitumen and extract, or if the extract is not present, per 100 parts by weight of bitumen contains. 14. Use of the bituminous mass according to claim 1 to 13 for the production of foamed Products.