DE2320655A1 - RUBBER-LIKE POLYMERS COMPOSITION - Google Patents

Description

Patent attorney Dipl.-Phys. Gerhard Liedl 8 Munich 22 Steinsdorfstr. 21-22 Tel. 29 84

B 6070

MARUZEN PETROCHEMICAL Co., Ltd. No. 25-10, Hacchoborl 2-chome, Chuo-ku, TOKYO / Japan

Rubber-like polymeric composition

The invention relates to a rubber-like polymeric composition from a 1: 1 alternating copolymer of propylene and butadiene.

The production of 1: 1 alternating copolymer from propylene and butadiene is known, but there are still insufficient studies on the properties of this alternating Mlschpoly-

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merlsates before. There have already been compositions made up of 1: 1 alternating copolymer of propylene and butadiene and the preparation of these compositions are described (Japanese Patent applications 110 393/70 and 110 394/70). With the compositions described there, vulcanized products with high Resistance, high durability against abrasion, lower Heat deformability, a low value in terms of permanent

Settlement, good weathering properties and low temperature dependencies getting produced. However, no detailed studies have been carried out on the microstructure of the butadiene units of the 1: 1 alternating copolymer of propylene and butadiene and the resulting physical properties. With regard to the microstructure of the butadiene units in the known No restrictions were imposed on copolymers. The above Properties of the vulcanized products, which are composed of 1: 1 alternating copolymers of propylene and butadiene were achieved regardless of the microstructure of the butadiene units.

It has now been found that the microstructure of the butadiene units In a 1: 1 alternating copolymer of propylene and butadiene Is the control factor for determining the liquidity or low viscosity of the product.

The object of the invention is therefore to provide a copolymer of the type mentioned to show that a good thin liquid having.

This object is achieved according to the invention in that at least 80% of the butadiene units are bound in trana-1,4-conguratlon.

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The invention is based on the assumption that in order to achieve a good thin liquid of the mixed polymer, the configuration or the microstructure the butadiene units must be highly specific. The elastic polymeric compositions obtained according to the invention have a good thin liquid and are therefore suitable for use as a raw material for vulcanized rubber. The compositions according to the invention show extremely good molding properties, in particular then, if molding processes of the type of spray volcanic treatment, Extrusion vulcanization and blow vulcanization can be carried out. The compositions according to the invention are particularly suitable for injection vulcanization and extrusion vulcanization.

In a preferred embodiment of the invention, there are more than 90% of the butadiene units bound in the trans-1,4 configuration. It. it has been found that under these conditions the rubber-like compositions with a 1: 1 alternating copolymer not only has the properties described above, i.e. high resistance, high resistance to abrasion, low heat deformability, low value for permanent settlement, good Weathering properties and low temperature dependencies, but also has excellent molding properties.

To make a rubber composition into a desired shape To form vulcanization, is it not beneficial to use chemical reactions, such as a tell catfish scorching the composition the vulcanization stage. In order to achieve this during the injection molding process, for example, the injection temperature must and the injection pressure can be kept as low as possible. The injection tent should be as short as possible, i.e. it is desired, the sample only for as short a tent as possible on one

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keep high temperature. From an economic point of view

From a point of view, low injection pressures result in low ones There are costs for the system and from a short injection tent an increased efficiency of the system. So far, however, the Vulcanization after the injection molding process with rubber has a higher injection pressure and a longer injection time than with thermoplastic Plastics is necessary. It has therefore not yet been Proven to be economical, the vulcanization of rubber by an injection molding process instead of vulcanization using of pressure to perform. It is therefore the vulcanization with the application of pressure, especially in tire production, used in most use cases.

The following table is an example of the relationship between the Injection tent and the injection pressure required for the injection molding of different rubber compositions are necessary. These compositions contain SRF carbon black 40 phr and approximately equal Mooney viscosities ML-. (100 ° C). The spray nozzle has a diameter of 2 mm and an injection volume of 60 ecm with an injection cylinder temperature from 93 C to ("Injection Molding of Elastomers", Ed. by W. S. Penn, Elsevler Publishing Company, Amsterdam, p. 156, Flg. 12. 4).

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Butyl rubber Injection
pressure
²¹ 2
(kg / cm) i Injection
pressure
²⁸
(kg / cm) Table 1 Injection tent E imprltz-
pressure
⁴⁹ 2
(kg / cm) Injection
pressure
⁵⁶ 2
(kg / cm) Injection
pressure
63
(kg / cm) I.
I. Injection
pressure
⁷⁷ 2
(kg / cm) Polyisoprene 30th 17th Injection
pressure
42 2
(kg / cm) 10. 8th 6th 6.4 Chlorobutyl 20th 6th 12th 3 3 3 2.8 Natural rubber 15th E inject-j
pressure
³⁵ 2
(kg / cm) 3 6th 5 4.5 3.6 IO
O SBB - 13th 8th 21 18th 15th 10 co
co Polychloroprene
¹ - 4th 30th 3 2.5 2.4 2.2 ■ <] - 11 5 4th 3 2.6 2
I. O 60 7th GO 20th 30th
i

N> O CD

The table shows that the rubber compositions having the same Mooney Volumes ML. (100 ° C), depending on the type of the rubber occur differently. The injection speed of polyisoprene, for example, shows a strong

2 speed of the injection pressure within the pressure range of 21 kg / cm

2 2

and 35 kg / cm. There is only above the injection pressure of 35 kg / cm a very low dependence of the injection speed on the EInsp scratch print.

On the other hand, shows the injection speed of

Natural rubber, for example, has a clear dependence on the injection pressure

2 2

over the entire injection pressure range from 35 kg / cm to 63 kg / cm The injection speeds themselves differentiate Depending on the type of rubber used. Of the The reason for this is that the Mooney Vlskosltät ML (100 ° C) at a low shear rate and the spray swirls was measured at a high shear rate. Independent of shear rates is a good one for economical products Desired flow. The thin liquid at a low shear rate affects the efficiency and quality of one Molding process while the thin liquid evolves at a high Shear rate affects efficiency and quality an injection process, extrusion process and calendering. Solution polymerized SBR shows lower flux at high shear rate than oily SBH, however it does better flow than oily SBR at a low shear rate.

In Table 2 is the relationship between the injection tent and the injection pressure, which is used in the injection molding of natural

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Rubber and butyl rubber compositions comprising SRP 40 Phr carbon black and various Mooney ML (100 C) viscosity are required. The spray nozzle has a diameter of 2 mm and an injection volume of 60 ecm with an injection cylinder temperature of 93 ° C (Ibid., P. 158, Fig. 12. 7).

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Tabel

Natural rubber (Mooney 79)

Natural rubber (Mooney 35)

Butyl rubber (Mooney 94)

Butyl rubber (Mooney 76)

Injection tent

Injection Injection Injection pressure pressure 21 ₂ 28 ₂ 35 (kg / cm) (kg / cm) (kg / cm)

Injection- Injection- Injection- 'Injection- Injection-

49 ₂ 56 ■: 63. ₂ ; 77 ₂

(kg / cm) (kg / cm) (kg / cm) (kg / cm) (kg / cm)

70

35

20th

40

pressure

pressure

pressure

pressure

pressure

2.3

7.5

11

3.7

6.7

6.2

7.3

2.7

, 5.4

2.4

CO K)

CD CD

cn

This table shows that in the case of Guniml varieties of the same type, the spray temperature is shorter if the Mooney viscosity ML ₁ (100 ° C.) is lowered. Accordingly, it is therefore desirable, at least in the case of rubber compositions of the same type, _{to keep the Mooney viscosity ML 4} (100 ° C.) low in order to obtain a good flow of the rubber composition during the molding process.

In general, however, the Mooney viscosity depends on ML. (100 C) of the rubber depends on its molecular weight and the Mooney viscosity becomes lower, the lower the molecular weight of the rubber and vice versa. If the average molecular weight of rubber is lowered below a certain limit or threshold value, the physical properties of the vulcanized product decrease also below the values required for practical use. Economically unsuitable products then result. Everyone Rubber, therefore, has had the lowest molecular weight value for its practical use.

The 1: 1 alternating copolymer of propylene and butadiene according to the invention, which has a highly specific microstructure of the butadiene units, with more than 80% of the butadiene units in the copolymer being bound in trans-1,4-conguration and rubber-like compositions, Which copolymers and at least one additive containing a vulcanizer had been investigated and the following was found: Alternating copolymers of propylene and butadiene with approximately the same average molecular weights, which were more than 80%, preferably more than 90%, trans-1,4-configuration ButadIen units have a significantly lower Mooney viscosity ML ₁₊ . (100 ° C) than those which have less than 80% trans-1,4-koaflguratlons content. the

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critical values or the threshold values of the average molecular weights for the vulcanized products, which have a tensile strength of

ο
200 kg / cm are usually between 40,000 and 60.

for those copolymers which have a content of more than 80% Contains trans-1,4-conguration butadlene. The average Molecular weights for those copolymers which have a content contain more than 90% trans-1,4-conguration butadiene between 40,000 and 50,000. In contrast, in order to obtain a vulcanized product which has the same tensile strength, the Average molecular weight between 60,000 and 70,000 for such copolymers, their content of trans-1,4-configuration Is less than 80%. Of course, these values also depend on the vulcanization conditions. It was found that at least with Compositions consisting of 1: 1 alternating copolymers of propylene and butadiene with average molecular weight below 70,000 to 80,000 were produced, lower molecular weights for the rubber raw material, which is an alternating copolymer of propylene and butadiene with more than 80% trans-1,4 configuration for a vulcanization product that has the same tensile strength is sufficient as those substances which have less than 80% trans-1,4-conguratlon.

It has been found that for a Vulkanlslerprodukt. Which should have the same tensile strength, the Mooney Vlskosltät ML ₁ . (100 ° C) of a rubber raw material which has more than 80% trans-1,4-conguratlon-butadlene inlays is lower than those which have less than 80% of this structure. In addition, the injection speed measurement on the Koka-shlkl flow tester (available from Shlmazu Selsakusho, Japan) shows higher injection speeds for the former material than for the second material. In addition, the formed products of the former material have a smoother surface, a lower one

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Mill contraction and lower tool thresholds than the latter Material.

There were comparative measurements with respect to the Mooney viscosity ML. . (100 C) and the thin liquid using a Koka-shikl flow tester on a number of known rubber stocks and it has been observed that the compositions according to the invention are better Mooney viscosities and extrusion speeds than that conventional rubbers.

The compositions according to the invention contain a 1: 1 alternating copolymer of propylene and butadiene, the microstructure of the butadiene units in the copolymer being highly specific and more than 80 % of the butadiene units in the copolymer being bound in a trans-1,4 configuration as an unconditional component. The composition according to the invention further contains a vulcanizer as an ingredient. In addition, the compositions according to the invention may, if necessary, contain other known additives which are used in the manufacture of molded products by mold vulcanization of rubber. These are, for example, Vulkanlsatlonsbesch Abblger, Vulkanlsatlons-Ko-accelerators such as metal oxides and fatty acids, activators, dispersants, vulcanization retardants, reinforcing agents such as carbon black, carbon, activated calcium carbonate, talc and organic reinforcing agents, inorganic fillers, organic fillers, plasticizers such as vegetable oil softeners and , Plastic fillers, adhesives, peptizers, coloring agents, reinforcing agents, foaming agents, lubricants and textiles for rubber such as Cotton, reinforced silk, nylon, vinyl, polyester, polypropylene, fibrous material made of steel, glass, carbon, boron and the like. The vulcanizers that are used are known as such and, for example, sulfur,

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organic peroxides and sulfur-containing compounds are used. The quantities of the additives that are used are in the area of known quantities.

The process for preparing the 1: 1 alternating copolymer of propylene and butadiene, which has more than 80 % trans-1,4 configuration of the butadiene unit, is carried out as described in detail, for example, in Japanese Patent Publication No. 9,413 / 72 and Japanese Patent Specification 23 670/72 (German Offenlegungsschrift 20 20 168 and 20 23 405).

Since the compositions according to the invention have excellent molding properties which are comparable with the known compositions can not be achieved, the compositions according to the invention are preferably used when composite objects with intricate structures, which tie and metal, plastic and Holzte the like should be produced. An injection molding process or an extrusion molding process can be used here, with the rubber products are reinforced by piping in which the compositions according to the invention in three-dimensional network constructions, which are formed by the pasers, injected or injected.

The following examples show preferred embodiments of the compositions according to derErflndurtg as well as the advantages achieved with these will. The quantities given are parts by weight. The examples are intended to explain the invention.

example 1

A rubber composition containing the following ingredients was made by a conventional method using rollers

309 tfÄ 77076 Λ

of 15 cm made as raw material. The raw material contained a 1: 1 alternating Copolymer of propylene and butadiene with one

0 °

Mooney viscosity ML _{1 + 4} (100 ° C.) of 14, an average molecular weight of 78,900 and the microstructure of the butadiene units was 99 % trans-1,4-configuration.

1: 1 alternating copolymer of propylene

Butadiene 100 parts zinc oxide lTell Sterarin door ITell CZ (N-Cyclohexylbenzothiazolesulfonam Id) Part 1 Antioxidants (phenyl-ß-naphthylamine) Part 1 sulfur I ₁ 5 parts HAP carbon black 50 parts

The values for the grinding contraction are shown in Table 3:

Table 3

after 1 mn. after 1 hr after 2 hr after 3 hr Calender rolling direction (%) 15.3 19. 0 19. 3 19.3 Perpendicular to the calendar
rolling direction (%) -β. 8th -8.3 - 8.3 - 8.3

The Oummlzueammeneätze were from conventional Polycls-Butadlene and conventional SBR with the same compositions as those in im Examples described above except that the alternating

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The copolymer according to the invention has been replaced by poly-cls-butadiene and SBR. The mill contraction values measured on these samples are shown in Tables 4 and 5;

Table 4

Poly-cls-butadlene after 1 MLn. after 1 hr ¹ after 2hr after 3 hr 20.0 24. 0 25th 3 25.3 Calender rolling direction% -7.3 -10. 7th - 11. 0 -11.3 ^! Perpendicular to the calender
whale breeding (%)

Table 5 SBR

■ · Calender rolling direction {%) after 1 min. after 1 hr after 2 hr after 3 hr Perpendicular to the calender
rolling direction (%) ' 21.3 27.0 27.3. 28. 0 ■■ - 7.3 ι
- 9.3 - 9.3 - 9.0

The tables show that the composition according to the invention is lower Has contraction values and a better stability or durability with respect to of dimensions than the compositions in which poly-ciy-butadlene and SBR has been used 1st.

The 1: 1 alternating copolymer composition of propylene and

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Butadiene, which was described above, was pressed for 30 minutes at 140 ° C, so that a vulcanized product with a tensile strength

2
strength of 245 kg / cm, an elongation of 420%, a

Elasticity of 66 % (measured with a Dunlop Tripsometer) and a permanent settlement of 7.4% resulted.

Example 2

A rubber composition with the ingredients described above was prepared under similar conditions as in Example 1 using 15 cm rolls of rubber raw material as in Example 1.

1: 1 alternating copolymer of

Propylene and butadiene 100 parts

Zinc oxide 1 part

Stearic acid 1 part

CZ (N-Cyclohexylbenzothlazolsulfonamtd 1 part

Antioxidants (phenyl- ß> - naphthylamine) 1 part

Sulfur 2 parts

HAF Büß 70 parts

Aromatic oil 37.5 parts

This composition had a Mooney viscosity ML. (100 ° C.) and the values for the grinding contraction are given in Table 6 below.

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Table 6

after 1 min. after 1 hr after 2 hr after 3 hr Calender roll direction. (%). 5. 3. 7.0 7.0 7.0 Right to the calender
rolling direction (%) -3.8 - 3.8 -4.2 - 4.2

It turns out that the sample has a low value for the grinding contraction and has excellent dimensional stability.

This composition was then closed at 140 ° C. for 25 minutes

processed a vulcanized product, this product being a tensile

strength of 196 kg / cm, an elongation of 560%, an elasticity of 58 %, a heat deformability of 17 C, as measured by ASTM D-623, and a permanent settlement of 9.6%.

Example 3

The Mooney viscosity ML ₁ - (100 ° C.) was measured at various temperatures on the following compositions. It was the composition of Example 1, a composition which consists of conventional natural rubber with a Mooney Vlskosltät ML (100 C)

1 + 4

from 87 to a composition consisting of conventional polyisoprene with a Mooney viscosity ML _1. (100 ° C.) of 49 to a composition consisting of conventional polybutadiene with a Mooney viscosity ML

(100 C) of 33 and a composition consisting of conventional

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SBR having a Mooney viscosity ML _{1 + 4} (IOO ⁰ C) of 45, each composition having the same structure as the composition in Example 1 and was prepared in the same catfish in Example 1 and Example 2. FIG. The results are shown in Table 7. All of the rubber compositions of this example had sufficient vulcanization properties for practical use. The compositions according to the invention made good rubber stocks due to their low Mooney viscosities.

Table 7

Mooney viscosity ML 100 ° C 120 ° C 140 ° C 8O ⁰ C 43 30th 24 Composition of Example 1 59 25th 19th 15th Composition of example 2 36 68 56 51 Composition of natural rubber
with ML ₁ . (100 ° C) 87
1 + 4 86 70 60 57 Composition of polyisoprene
with ML ₁ . (100 ° C) 49
1 + 4 84 85 74 67 Composition of the polybutadiene
with ML _{1 + 4} (100 ° C) 33 94 72 56 48 Composition of the SBR with
KM (100 ° C) 45 97

The table shows that the compositions according to Examples 1 and 2 have extremely low Mooney viscosities ML ₁ over the entire temperature range shown in the table. (100 ° C).

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Example 4

Compositions of Sl extended SBR and oil extended polybutadiene with compositions given below under the same conditions as described in Example 1, prepared.

oil-extended rubber 137. 5 parts zinc oxide 5 It Stearic acid 1 Il sulfur 2 Il Antioxidants
amln) (Phenyl-ß-naphthyl- 1 Il HAF carbon black 70 It

C Z (N-eyciohßxyibenzothlazolsulfenamid)

The Mooney ML Vlskosität (IQO ⁰ C) of the composition, which was prepared from the oil-extended SBR ₉ was 39 and that of the composition which was prepared from the oil-extended polybutadiene, was 42nd

The extrusion diapers of the composition of Example 2 and the above-described compositions in this

Examples were then using a Koka-shlkl flow tester at different

2 2

low temperatures (pressure: 70 kg / cm or 50 kg / cm, Nozzle diameter:! Mm, DU nozzle length: 1mm, tool preheating time: 15 minutes, sample preparation tent: 2 minutes). The results are in the shown in Table 8 below.

These compositions resulted in rubber materials during vulcanization, which had sufficient properties for practical use.

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Table 8

Mooney
Vlskosltät Pressure extruded volume 7.47 120 ° C 140 ° C ^ ^{/ cm} 80 ° d ioo ° c 2.49 13.50 nd ⁺ composition
of example 2 25th 70 2.94 4.98 5.10 7.24 Composition.
of example 2 25th 50 1.05 3.74 8.28 L2.94 oil-expanded SBR
composition 39 70 2.30 4.35 5.36 oil expanded poly
butadiene together
settlement 42 70 1.98

+) The speed was too great for the measurement.

As a result, the composition of Example 2 was higher Has thinness than the two types of conventional, oil-extended synthetic rubbers of the present example.

Example 5

The composition of Example 1, an SBB composition with a Mooney viscosity ML ₁ . (100 C) of 64 and a conventional polybutadlene composition with a Mooney viscosity ML ₁ . (100 ° C) of 63 were examined, each composition having the same structure as described in Example 1. The results are compiled in Table 9 below. The pressure applied was 70 kg / cm.

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Table 9

I Mooney Viscosity 'Extruded Volume J

ML,. (100 ° C)! Z ö ~ j ö ~~ * ö '

1 + 4 ^v 80 C 100 Cl 120 C ¹ 140 C

Composition of Example 1

SBR composition

Polybutadiene
! composition

j 63

0. 75! 1. 57
; 0. 30 0. 54

2. 88 j 4. 46

. 99 1. 36

0. 31 0. 36 '0. 52

0.48

The table shows that the composition of Example 1 is higher Has thin liquid than the two types of conventional synthetic Rubber grades, although the compositions of this example are substantially equivalent and each composition when vulcanized has sufficient properties for practical use.

Example 6

A rubber composition with the same composition as them Is described in Example 1, was prepared in the conventional manner, 15 cm rolls were used as raw material. The raw material was a 1: 1 alternating copolymer of propylene and butadiene with a Mooney viscosity ML 100 C) of 8, one Average molecular weight of 41,000, with the microstructure being the 98% of butadiene units had a trans-1,4 configuration. the Mooney viscosity ML. (100 C) the composition was 26. Die Composition was pressed for 23 minutes at 150 G, resulting in

, 2

a vulcanized product with a tensile strength of 202 kg / cm, an elongation of 380% and an elasticity of 55%.

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Example 7

A rubber composition having the same composition as that described in Example 1 was prepared by a conventional method using 15 cm bolts. A 1: 1 alternating copolymer of propylene and butadiene with a Mooney Vtskosltät ML (100 ° C) of 21, a stretching molecular weight of 62,000 and with 69.9% trans-1,4-, to 24, served as Bohmaterlal. 4% cls-1,4 and 5.7% 1,2-conguration of the butadiene units. The Mooney viscosity ML (100 ° C) of this composition was 46. The composition was pressed for 40 minutes at 150 ⁰ C to produce a vulcanized product having a tensile strength of 206 kg / cm, an elongation of 370% and an elasticity 63% yielded. The comparison between Examples 6 and 7 shows that a higher molecular weight for an alternating copolymer of propylene and butadiene with less regularity with regard to the microstructure of the butadiene units is necessary than for an alternating copolymer with a high specific microstructure of the butadiene units, for example with one more as 80% tgen tans-1,4-conguratlon. The composition of the present example thus has a higher Mooney viscosity ML- . (100 ⁰ C) as the composition in Example 6.

Example 8

An alternating copolymer of propylene and butadiene with 78.8% trane-1,4-, 16.2% cle-1,4- and 5.0% 1,2-configuration of the butadiene units and with a stretching molecular weight of 71. 000 had a Mooney Vlskoeltät ML _{1 + 4} (100 ° C) of 44. The rubber composition with the same composition as in Example 1

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described, which was produced from the alternating copolymer just described, had a Mooney Vlskositäfc ML ₁ . (100 ° C) of 60. This composition was pressed for 20 minutes at 15O ⁰ C, eo that a vulcanized product resulted having a tensile strength of 239 kg / cm, an elongation of 410% and an elasticity of 63%. On the other hand, a copolymer of propylene and butadiene with 96% trans-1,4-, 2% cls-1,4- and 2% 1,2-configuration of the butadiene units and with the glelehea average molecular weight, i. 71,000, a Mooney Viscose ML ₁ . (100 ° C) of 16. It follows that copolymers of the same molecular weight, which are made from an alternating copolymer, which has a low regularity with respect to the microstructure of the butadiene units, a higher Mooney Vlskosltät than a composition, which from an alternating copolymer with a high specific microstructure of the butadiene units, for example with a trans-1,4 conguration of more than 80%.

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Claims (6)

Claims 1. Rubber-like polymeric composition with a 1: 1 alternating Copolymer of propylene and butadiene, characterized in that 80% and more of the butadiene units are bound in a trans-1,4-configuration are. 2. rubber-like polymeric composition according to claim 1, characterized characterized in that more than 90% of the butadiene units are in trans-1,4-conguration are bound. 3. rubber-like polymeric composition according to claim 1 or 2, characterized in that a Vulkanisieret is included as a component 1st. 4. Use of a rubber-like polymeric composition according to any one of claims 1 to 3, as a starting mate rial in a vulcanization proceed after an injection. 5. Use of a rubber-like polymeric composition according to any one of claims 1 to 3, as a starting material in a vulcanization in the manner of an extrusion process. 6. Use of a rubber-like polymeric composition according to any one of claims 1 to 3, for an article with high elasticity, high abrasion resistance, low heat deformation, low permanent settlement, good properties at low temperatures, smooth surface and more precise shape retention. 309847/0764