DK142176B - UNDER THE PREPARATION CONDITIONS AGAINST MIXING STABLE MIXTURES OF ATACTIC POLYOLEFINES AND THE BITUM AND PROCEDURE FOR THEIR PREPARATION - Google Patents

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(11) PUBLICATION NOTICE 142176 DENMARK <= '> ΐη..α · o us l 95/00' (21) Application No 5167/77 (22) Filed on 12 July. 1977 (24) Race day 12 Jul. 1977 (44) The application presented and the 1 ndial of presentation published on ·> · 1 DIRECTORATE FOR, „. u _ ..

PATENT AND TRADEMARKET SYSTEM »°> 2631361, DE

(71) VEBA CHEMISTRY ACTIVITIES, 4660 Gelsenkirchen-Buer, Pawiker = "Strasse 50, DE.

(72) Inventor! Helmut Kehr, Moellenweg 25 and 4270 Dors ten, DE: Heinrich Leppek, Leins tras se 16, 4660 Gelsenkirchen-Buer, DE: Helmut Haus®

Tcnecht, Kreuzstrasse 10, 4270 Borsten, DE: Walter Taeuber, Eeldmark * street 25, 4559 Lippramsdorf, DE.

(74) Plenipotentiary in the proceedings:

International Patent Bureau._ (54) Under the processing conditions against blending stable mixtures of atactic polyolefins and bitumen as well as process for their preparation.

In many areas of application, it is desirable to change the property image of the tested building material bitumen to meet the increasing demands - usually in terms of the aging resistance and the temperature range of the plasticity. The addition of polymers belongs to the state of the art. Of particular importance are the atactic polyolefins, especially because, unlike crystalline polyolefins, e.g. polyolefin regenerate, easily and without technical hassle mixes with bitumen. Atactic polyolefins are to be understood as the majority soluble polymers of propylene and higher homologs thereof and copolymers with α-olefins, as obtained by polymerization of the monomers by catalysts of Ziegler-Natta type. The properties of these polymers can be varied within a wide range by the polymerization conditions, by mixing the polymers with each other and similar confectionary measures. The ring and ball softening points for the commercially available products are between 70 ° C and 160 ° C, the melt viscosity, usually measured at 170 ° C to 190 ° C, between 500 mPa. s and sometimes 100,000 mPa. p. Typical representatives have the following characteristics:

Atactic polypropylene (homopolymer)

1. A B C D

2. 6% 0 11% 5%

3. 153 ° C 114 ° C 156 ° C 156 ° C

4. 8000 mPa. s 480 mPa. s 3500 mPa. s 120,000 mPa. s 5. 22 1/10 mm 42 1/10 mm 15 1/10 mm 25 1/10 mm 1. - Product 2. = n-heptane insoluble part 3. = Softening point, ring and ball

4. = Melt viscosity at 190 ° C

5. = Penetration

Atactic polybutene-1 (homopolymer)

Ethereal soluble part 0

Softening point, ring and ball 112 ° C

Melt viscosity at 190 ° C 10000 mPa. p

Penetration 40 1/10 mm

Atactic butene-1-propene copolymer

Ethereal soluble part 15%

Softening point, ring and ball 89 ° C

Melt viscosity at 190 ° C 5000 mPa. p

Penetration 18 1/10 mm

Mixtures of atactic polyolefins with bitumen serve e.g. as a binder for road construction, for joint pouring masses, sealants, adhesives and as coverings for roofing and sealing paths.

Of technical interest are currently mixtures with an atactic polyolefin content of 3 to 50% by weight. For road construction, over 3 142176 weighing mixtures with 5-15% by weight are used for speech, and roofing and sealing paths are mixtures with 30 to 50% by weight for speech. Mixtures having an atactic polyolefin content of more than 5 and less than 40% by weight have the disadvantage that they tend to blend in the liquid-liquid state for extended periods of time and so as to enrich the upper layers with the atactic polyolefin. Such mixtures must be kept homogeneous by pumping or stirring. However, these possibilities are only present in the few processing plants and transport vehicles or the like. Thus, there is a considerable need for mixtures of bitumen and atactic polyolefins which have no tendency to blend under the processing conditions.

U.S. Patent No. 3,336,252 discloses a process for the rapid mixing of bitumen with polyolefins, wherein the latter may contain 5-30% by weight of a finely divided mineral filler whose grain size should be between 0.01 and 90 µm. No specific information is provided on the specific surface of these fillers and they are used to obtain a faster mixing of bitumen and polyolefins. Since the mixtures prepared according to this US patent are immediately cooled and formed or granulated after their preparation, there is no danger of mixing in these, so the fillers have not been selected taking into account their possible stabilizing effect.

So far, no methods have been proposed to prevent the mixing of atactic polyolefins and bitumen. DOS No. 2,363,733 merely indicates that the blending tendency for bitumen and polyolefin waste mixtures is reduced by a proportion of color pigments or finely divided mineral contaminants with a grain size below 0.5 mm (e.g., sand, fertilizer residues). Polyolefin waste means films, bottles, etc., whose raw material has a melt index between 0.1 g / 10 min. and 10 g / 10 min. However, if mixtures of 10% atactic polypropylene and 90% bitumen B 80 are added to the molten limestone flour with a grain size of maximum 0.5 mm, the mixing tendency is not reduced, but on the contrary it is increased. A mixture of 30% by weight of atactic polypropylene and 70% by weight of bitumen B 80 is quickly blended by the addition of limestone flour with a grain size of maximum 0.5 mm, whereby the filler sinks to the bottom and the atactic polypropylene is enriched at the surface. An addition of color pigment such as soot, commercially available under the name "Printex 60", to the mixture of atactic polypropylene and bitumen B 80 does not reduce the mixing tendency either. The reason why completely different conditions are observed in the case of atactic polyolefin and in the case of regenerate polyolefins according to DOS No. 2,363,733 must surely be sought in the different nature of the polymers. Regenerated polyolefins are defined in DOS No. 2,363,733 high molecular weight products. From the melt index data (page 5), mokelyl weights of 70,000 to 200,000 for polyethylene and 200,000 to 700,000 for polypropylene can be added. On the other hand, the atactic polyolefins present in the bitumen mixtures have on average molecular weights of only 30,000 to 60,000. Thus, due to the different molecular weights, very different conditions must be expected.

DOS No. 2,363,733 further states that the mixing tendency of regeneate polyolefin, even when it contains fillers and / or pigments, is in practice even excessive and must be improved by the addition of suppressive aids.

In contrast, it has now been found that stable mixtures of certain atactic polyolefins and bitumen can be prepared even without suppression aids when the atactic polyolefin contains certain fillers.

The invention relates, under the processing conditions, to blend stable mixtures, for use especially as coating material / of 95 to 50 wt.% Distilled bitumen and 5 to 50 wt.% Atactic polyolefins containing filler, which mixtures are characterized in that the atactic polyolefins have a average molecular weight of 30,000 to 60,000 and contains 5 to 25% by weight, calculated in relation to the mixture of filler and polyolefins, fillers with a specific BET surface of at least 1 m / g.

The invention further relates to a process for preparing such a mixture in which the filler-containing polyolefins are heated in bitumen, which process is characterized by using filler-containing atactic polyolefins using the atactic polyolefins having an average molecular weight of 30,000 to 60,000 and containing 5 to 25% by weight, calculated relative to the mixture of fillers and polyolefins, fillers with a specific BET surface of at least 1 m / g, and that the atactic polyolefins containing filler are preferably introduced in the form of a granule or chips.

It is particularly advantageous to introduce the filler-containing polyolefin in the form of a granule or as chips, as this requires substantially less energy and requires no special plant, as would be the case if the atactic polyolefin was added in the form of a melt. , as is done according to the aforementioned US-PS 3336252.

The amount of mineral fillers must in principle be measured such that the density of the filler containing atactic polyolefin and the bitumen used are close to each other. As the atactic polyolefin at levels greater than 5% by weight in the bitumen is predominantly in the form of finely dispersed droplets, the size of the filler particles must not exceed the maximum droplet size. This is located at approx.

30 microns. Therefore, the fillers used in the composition of the invention must have a particle size corresponding to a specific BET surface of at least 1 m / g. Fillers with smaller surfaces are unsuitable. The filler must be sufficiently dispersed in the atactic polyolefin, taking particular care to dissolve filler agglomerates suggesting larger particle sizes. Fillers which fulfill the above conditions are e.g. by wet grinding and grading, Champagne chalk, fine-milled crystalline calcite filler, technically pure zinc oxide (ISO type I), worked up, furthermore e.g. magnesium carbonate, magnesium oxide, soot and fine limestone. Not suitable are coarser limestone flour or iron oxide.

The former fillers have specific surfaces of 3.5 m / g 2 or 8 to 9 m / g, while the latter fillers have specific surfaces of 0.05 m / g or 0.6 m / g.

It is believed that the atactic polyolefin completely envelops the filler particles, so that after the admixture in the bitumen, polyolefin droplets are present whose density due to a "heavy core" has approached the density of the surrounding bitumen to such an extent that a blend is absent.

If soot is used as a filler, another mechanism appears to be due to a very high specific surface.

The following table further explains the invention. The fillers were admixed in the atactic polyolefins in a Meili elm at 120 DEG-1700C. The filler-containing polyolefin was stirred into the hot bitumen in small pieces. The mixture was homogeneous after approx. 20 minutes. To test the mixing trend, the mixture was left to itself without stirring for 3 hours at 180 ° C in a nitrogen atmosphere. Then the softening points ring and sphere were determined in different layers. The mixture was considered stable if the difference was only found to be within the analytical accuracy.

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