DE1941630A1 - Molding compounds based on bitumen and olefin polymers - Google Patents

Description

Our reference: O. Z. 26 JIl Ks / Dh

67OO Ludwigshafen.,. August 13, 1969 molding compounds based on bitumen and olefin polymers

The present invention relates to bitumen molding compositions, Olefin polymers and sulfur.

Molding compositions of bitumen and olefin polymers are known for example from the belgiaäten Patent 675,892. Moldings which are produced from these molding compositions have a number of advantageous properties. However, it is disadvantageous that the surface of these shaped bodies becomes very sticky due to oily components exuding from the bitumen. This phenomenon is particularly troublesome when storing foils or granulates because the molded parts are firmly caked together and are difficult to handle.

Attempts have therefore already been made to prevent the molded parts produced from these molding compositions from sticking together by dusting them with finely powdered release agents, for example talc, chalk, slate or quartz. The use of these release agents is associated with disadvantages because once their effectiveness leaves something to be desired, and above all because molded parts with poorer mechanical properties are obtained from granules that have been dusted with a release agent. In addition, films that have been treated with a release agent can only be unsatisfactorily welded to one another if the release agent is not removed beforehand at the location of the intended weld seam.

The object of the invention was to provide a mixture of substances based on bitumen and ethylene polymers, from which molded parts can be produced which do not stick to one another even after prolonged storage under pressure. The mechanical properties of molded parts made from these mixtures of substances should be at least comparable with the mechanical properties obtained from the known molding compositions made from bitumen and olefin polymers. 109808/2045 286/69 -2-

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It has been found that this object is achieved when preparing mixtures consisting of a) 10 to 90% by weight of bitumen, b) 90 to 10 wt # of Olefinpolymerisates and -.., Where appropriate, - c)% 5 to 50 wt. based on components a) and b), customary additives, the mixtures of substances containing 1 to 10% by weight of sulfur based on components a) and b). Bitumens which, according to DIN 1995, have a penetration of 1 to 200 and a softening point (ring and ball) of 140 to 40 ° C. are suitable for the molding compositions according to the invention. Penetration is understood to be the depth of penetration of a standardized needle in 1/10 mm under the conditions specified in DIN 1995. All commercially available natural and synthetic bitumen types, as well as asphalt and tar, can be used to produce the molding compounds.

For the purposes of the invention, olefin polymers are intended to include the homopolymers of ethylene, propylene, isobutylene and 1-butene. as well as the copolymers of ethylene with propylene and butene-1 are understood. Above all, the copolymers of ethylene with other copolymerizable ethylenically unsaturated compounds are suitable. These copolymers contain at least 50 wt.% Ethylene units. Ethylenically unsaturated compounds copolymerizable with ethylene are acrylic and methacrylic esters, which are derived from alcohols having 1 to 8 carbon atoms, and vinyl carboxylic esters. Particularly noteworthy are the copolymers of ethylene with the n * -, i- or tert-butyl esters of acrylic or methacrylic acid and vinyl acetate. However, it is also possible to produce molding compounds from mixtures of the olefin polymers mentioned, for example from a mixture of ethylene with a copolymer of ethylene and acrylic acid tert-butyl ester. Terpolymers, for example of ethylene, an acrylic ester and acrylic acid, are also suitable for special applications of the molding compositions according to the invention. The terpolymers are obtained, for example in the copolymerization of ethylene with tert-butyl acrylate, if the production conditions for the polymers are chosen so that some of the polymerized aoryl ester units are formed with isobutylene splitting off to form built-in free acid groups

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leads «In this case contain the ethylene polymers 0.1 to 7 mole percent, preferably 0.2 to 5 mole percent, Carboxylic acid groups in polymerized form.

In order to vary the mechanical properties of the molding compositions, it sets the mixtures of a) 10 to 90 wt.% Of bitumen, and b) 90 to 10 wt.% Of a Olefinpolymerisates, based on the two components, optionally 5 to 50 wt.% Of conventional Fillers too, for example slate powder, limestone powder, gypsum, chalk, calcium silicate, talc, asbestos, glass powder, rock wool, slag wool, clay, dolomite powder, rock flour, titanium dioxide or organic fillers such as wood or cork flour.

It is characteristic of the molding compositions according to the invention that they are 1 to 10, preferably 3 to 6% by weight, based on the bitumen and olefin polymer content . Contain sulfur.

To produce the molding compositions according to the invention, the components are in the for the plastics processing known devices mixed. It does not matter in which order the components are be mixed together. For example, the olefin polymer and bitumen are homogenized in a kneader and then set then the sulfur and - if necessary - the usual additives to. However, you can also first use bitumen, and sulfur if necessary Mix the usual additives and the olefin polymer then work into the homogeneous mixture. The molding compositions can be processed in a conventional manner, for example using extruders or injection molding machines and presses are processed into shaped structures.

Surprisingly, molded parts made from these molding compositions do not stick to one another even when stored for a long time under pressure. For example, granules are still free-flowing even after several months of storage. The physical properties of these molding compositions, as Examples 1 and 2 show, with low sulfur contents (3 to 4% by weight ) are similar to those of sulfur-free ones. Compounds comparable. -

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About the sticking together of granulates made of bitumen and olefin polymers To prevent this, the granules are powdered with elemental sulfur. If the granulate is melted, it is obtained a "molding compound, from which molded parts can be produced that are no longer sticky and do not bake together even during storage. . "

If, for example, two foils are welded from these molding compounds, the weld remains unchanged during a tensile test, while the foil tears at another point. The molding compounds are suitable as corrosion protection for any object and used to make elastic r corrosion protection binding for pipelines * They are particularly suitable for the production of roofing sheets that are laminated with glass fiber fabric. They can also be used in finely divided form for the production of coatings according to the fluidized bed and flame spraying process. The molding compositions according to the invention are also used in building construction and civil engineering.

The parts given in the examples are parts by weight.

example 1

In a kneader at 120 ⁰ C the plasticising a copolymer of 82% ethylene and l8% n-butyl acrylate, then sets bitumen, having a softening point of 48 ° C and a penetration of 80 to and the mixture is homogenized. In this mixture, the in Table I under a) to e) are then indicated. given amounts of sulfur evenly distributed. Foils 1 mm thick are then pressed from the resulting homogeneous mixture. After the films have been stored for J days, their tear strength according to DIN 53 455 and their elongation at break are tested. In addition, the tackiness of the film surface is assessed by means of a hand test and the appearance of the film. The results are summarized in Table I below. With a sulfur content of 3 % , the surface of the film produced is no longer sticky. , · ..

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As shown in a comparative example. (see. Table I), are films made from molding compositions consisting of 50 wt. # bitumen having a penetration of 80 and 50% of a copolymer of 82 wt.% ethylene and 18 wt.% n-butyl acrylate, highly tacky.

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Table I.

a)

ο)

Compare example

Copolymer of 82 wt.% Ethylene and l8 wt «# n-butyl acrylate (parts by weight)

49.5

48.5

47.5

50

Bitumen (parts by weight) 49.5. 49

48.5

47.5

45

50

^ s ■■ co

Sulfur powder (parts by weight)

Appearance of the slide

2.0

3.0

black gray-gray black

5.0 10.0

gray gray-black yellow

Film stickiness

Tear strength according to DIN 53 strong weak not ■ not not strong sticky sticky sticky sticky sticky sticky

■ 45

44

Elongation at break

850

900

830

800

840

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Example 2

A granular mixture of equal parts of a distillation bitumen with a penetration of 80 and of a copolymer of 82 wt. # ethylene and 18 wt. # n-Butyl erylate is mixed in a stirring mixer at room temperature mixed with the amounts of sulfur indicated in Table II under a) to d). This mixture is then put in an extruder Melted at 140 C and now 2 thick and 110 cm wide Foils extruded. The results are shown in Table II.

For Comparative Example ^ ₁ ethylene and 18 percent by homogenizing a granular mixture of equal parts of a bitumen having a penetration of 80, and a copolymer of 82 wt.. ^ N-butyl acrylate in an extruder under the conditions indicated above, but without addition of sulfur.

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Table II

a)

b).

c)

Compare example

Copolymer of 82 wt. ^ Ethylene and 18 wt. % N-butyl acrylate (parts by weight)

48.5

48, ο

. 47.5

CD OO O

Bitumen (parts by weight) 49 48.5 48.0 47.5 50 Sulfur (parts by weight) 2 3.0 4.0 5.0 - 100 100.0 100.0 100.0 100 Appearance of the slide Gray-
black Gray Gray Gray black Film stickiness some
sticky not,
sticky not
sticky; not
sticky strong
sticky Tear strength according to DIN 53 ^ 55
along kp / cm2
cross kp / cra ^. 42
43 42
40 40
40 PYYYYY
VDCO 40
39 Elongation at break according to DIN 53 455
longitudinal % ,
across % 920
930 890
870 870
870 870
850 830
840

00

ro Ov

■■ (> ■ cn

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Example 3

At 15O ° C is mixed 48 parts of bitumen of penetration 80 and 4 parts of sulfur and then kneaded into this mixture at temperatures between 130 and 150 ⁰ C 48 parts of high-pressure polyethylene, a having a density of 0.917 g / cnr and a melt index of 1.3 Has. After homogenization, the mass is pressed into films, which are used for insulation in construction. The film looks gray, is not sticky, has an elongation at break of 160 % and, according to DIN 53 455, a tear strength of 4 l kp / cm ² .

Example 4

According to the data of Example 3 48 parts of bitumen of penetration 80% of acrylic acid are mixed, and 4 parts of sulfur, and then with 48 parts of a copolymer of 88 wt. # Ethylene, 8 wt.% Of tertiary butyl acrylate and 4 wt. Homogenized. The mass is pressed into foils that are used as roofing. The foils look gray and are not sticky. The tear strength of the films is (according to DIN 53 455) 58 kp / cm ² , the elongation at break is 57 %

Example 5

$ 8 parts of bitumen of penetration 80 are mixed with 4 parts of sulfur at 170 ° C and then homogenized at 130 to 150 ⁰ C -in a kneader with 48 parts of a copolymer of 82 wt. # Ethylene and 18 wt.% N-butyl acrylate. The molding compound is pressed into films that look gray and are not sticky. The elongation at break of the films is 850 %, the tear strength (according to DIN 53 455) 49 kp / cm ²

Mixing under the same conditions 48 parts of a copolymer of 82 wt.% Ethylene and 18 wt.% N-butyl acrylate in a kneader with 4 parts of sulfur and operates a 48 parts of bitumen of penetration 8.0 in this mass, we obtain a molding material, from which produces films which, according to DIN 53 455, have a tear strength of 48 kp / cm ² , the tear height is 830 %.

The foils are used for insulation in construction.

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Example 6

78 parts of a copolymer of 82 wt.% Ethylene and l8 wt. # N-butyl acrylate are homogenized with l8 parts of bitumen of penetration into a kneader at temperatures between 150 and l40 ° C. 4 parts of sulfur are worked into this mass and the homogeneous mixture is then pressed into 1 mm thick films. The foils are not sticky. The elongation at break of the films is 850 %, the tear strength (according to DIN 55 455) 58 kp / cm. The foils are used for insulation in construction. . ,.-....-

Example 7

According to acc. To Example 6, initially% ethylene and 18 wt mixes l8 parts of a copolymer of 82 wt..% N-butyl acrylate with 78 parts of bitumen and a penetration of 80. then add 4 parts of sulfur. Foils 1 mm thick are pressed from the homogeneous mixture. The foils look gray and are not sticky. The elongation at break of the films is 1000 %, the tear strength (according to DIN 55 455) 41 kp / cm ² . The molding compound is suitable for sheathing pipes and for sealing roofs.

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Claims (1)

- 11 - OZ 2β patent claim Molding compositions consisting of a) Io to 90 wt.% Of bitumen? b) 90 to 10 wt. # of an olefin poly- merisates and - optionally - c) 5 to 50 Gex?,. # customary additives, based on components a) and b), characterized in that the molding compounds, based on components a) and b), 1 to 10 wt. % Sulfur. Badische Anilin- & Soda-Fabrik AG 109808/2045