Thermoplastic Elastomer Composition Comprising An Elastomer, A Non-Elastomeric Polyolefin, And A Polyolefin Block Copolymer-Based Thermoplastic Elastomer

Abstract

A thermoplastic elastomer composition of an elastomer, a non-elastomeric polyolefin and a thermoplastic elastomer based on polyolefin block copolymers are disclosed. Furthermore, the invention also relates to the use of a mixture of an elastomer and a cross-linking agent for the elastomer for producing a thermoplastic elastomer composition. A further subject of the invention is the use of a mixture of a non-elastomeric polyolefin and a thermoplastic elastomer based on polyolefin block copolymers for producing a thermoplastic elastomer composition. In addition, the invention relates to the use of a thermoplastic elastomer composition for producing a composite material with a polyolefin, in particular polypropylene. The invention also relates to a process for producing a thermoplastic elastomer composition as well as a composite material (article) made of the thermoplastic elastomer composition with a polyolefin.

Claims

1. A thermoplastic elastomer composition comprising: an elastomer, a non-elastomeric polyolefin, and a thermoplastic elastomer based on polyolefin block copolymers (TPO), wherein the elastomer includes a first elastomer selected from the group consisting of ethylene-vinyl acetate copolymer, nitrile butadiene rubber, hydrogenated nitrile butadiene rubber, butyl rubber, natural rubber, isoprene rubber, acrylate rubber, ethylene acrylate rubber, silicone rubber, styrene butadiene rubber, chloroprene rubber, bromobutyl rubber, epichlorohydrin rubber, and epoxidized natural rubber, or a mixture thereof, and wherein the first elastomer is cross-linked or non-cross-linked.

2. The thermoplastic elastomer composition according to claim 1, wherein the first elastomer is cross-linked.

3. The thermoplastic elastomer composition according to claim 1, wherein the mixture of non-elastomeric polyolefin and TPO represents a matrix into which the elastomer is incorporated.

4. The thermoplastic elastomer composition according to claim 1, wherein the TPO is a block copolymer which contains at least two different alkylene units.

5. The thermoplastic elastomer composition according to claim 1, wherein the non-elastomeric polyolefin is a polypropylene.

6. The thermoplastic elastomer composition according to claim 1, wherein a weight ratio of elastomer to non-elastomeric polyolefin lies in a range of from 100:15 to 100:60.

7. The thermoplastic elastomer composition according to claim 1, wherein the weight ratio of elastomer to TPO lies in the range of from 100:5 to 100:45.

8. A mixture of an elastomer and a cross-linking agent for the elastomer for producing the thermoplastic elastomer composition according to claim 1.

9. A mixture of a non-elastomeric polyolefin and a TPO for producing the thermoplastic elastomer composition according to claim 1.

10. The thermoplastic elastomer composition according to claim 1 for producing a composite material with a polyolefin.

11. An article produced from the thermoplastic elastomer according to claim 1 and a polyolefin.

12. The thermoplastic elastomer composition according to claim 1 for producing components or shaped bodies in automobile interiors or in the engine space of vehicles, for producing industrial devices, industrial tools, bathroom fittings, domestic appliances, consumer electronics devices, sporting goods, medical consumables and devices, containers for sanitary products and cosmetics, and sealing materials.

13. A process for producing the thermoplastic elastomer composition according to claim 1, comprising: mixing the elastomer, the non-elastomeric polyolefin and the TPO.

14. The process according to claim 13, wherein in a first step the first elastomer is pre-treated and in a second step the mixture of non-elastomeric polyolefin and TPO is added.

15. The process according to claim 14, wherein in the first step the first elastomer is softened by a temperature effect and mixed with a cross-linking agent.

16. The process according to claim 14, wherein before the second step the mixture of non-elastomeric polyolefin and TPO is produced in an extruder, an internal mixer or a kneader.

17. The thermoplastic elastomer composition according to claim 5, wherein the polypropylene is hPP.

18. The process according to claim 15, wherein the first elastomer is softened at a temperature in the range of from 50° C. to 120° C. and mixed with a cross-linking agent.

19. The process according to claim 15, wherein the first elastomer is softened at a temperature in the range of from 80° C. to 110° C. and mixed with a cross-linking agent.

20. The process according to claim 16, wherein before the second step the mixture of non-elastomeric polyolefin and TPO is produced in a twin-screw extruder.

Description

EXAMPLES

[0144] Methods of Determination and Definitions:

[0145] Determination of the density takes place according to DIN EN ISO 1183-1.

[0146] Determination of the Shore hardness takes place according to DIN EN ISO 868 and DIN ISO 7619-1.

[0147] By “tensile strength” is meant the maximum mechanical tensile stress which a material withstands before it breaks/tears. In the tensile test it is calculated from the maximum tensile force relative to the original cross section of the (standardized) sample and indicated in N/mm.sup.2.

[0148] The elongation at break is a material characteristic which indicates the permanent lengthening in the case of the break, relative to the initial measurement length. In material testing, elongation at break is one of many parameters and characterizes the deformation capability of a material. It is the permanent change in length ΔL relative to the initial measurement length L.sub.0 of a sample in the tensile test after breaking. This change in length is indicated in %.

[0149] The compression set is a measure of how (thermoplastic) elastomers behave in the case of long-lasting, constant compression and subsequent decompression. According to DIN ISO 815 the compression set (CS) is measured at constant strain. This represents the deformation component of the test material. Many test methods for elastomers, such as e.g. tensile strength, characterize the quality and nature of the material. On the other hand, the CS is an important factor which has to be taken into account before use of a material for a specific purpose. Permanent deformation, the compression set (CS) is an important parameter, particularly for the use of seals and shims made of elastomers. In order to determine this parameter a cylindrical test piece is compressed by e.g. 25% and stored thus for a certain time at a specific temperature. The temperature and the medium (usually air, but also oils and other industrial fluids) for the compression test depend on the material to be tested, its intended purpose and the test setup (e.g. 24 h at 150° C.). 30 minutes after decompression the height is again measured at room temperature and the permanent deformation ascertained therefrom. A compression set of 0% means that the test piece has again completely reached its original thickness; a CS of 100% indicates that the test piece has been completely deformed during the test and shows no resetting. The calculation is carried out according to the following formula: CS (%)=(L.sub.0-L.sub.2)/(L.sub.0-L.sub.1)×100%, wherein:

[0150] CS=compression set in %

[0151] L.sub.0=height of the test piece before testing

[0152] L.sub.1=height of the test piece during testing (spacer)

[0153] L.sub.2=height of the test piece after testing.

[0154] In addition, the force in MPa according to DIN ISO 34-1, which is required to stretch the thermoplastic elastomer by 100%, 200% or 300%, was measured. Here a test piece—as defined in the named standard—is taken and stretched by the length indicated while measuring the force required.

[0155] Determination of the tear propagation resistance takes place according to DIN 53504/ISO 37.

[0156] The abrasion of the thermoplastic elastomer compositions is measured, by rubbing a 6 mm high cylinder with a diameter of 16 mm over 40 m of 60-grit sandpaper with a contact pressure of 10 N.

[0157] The adhesion of the thermoplastic elastomer compositions on polypropylene (type: Moplen® HP501L; manufacturer: Basell Polyolefins) is determined according to VDI2019.

Embodiment Examples

[0158] Table 1 indicates the abbreviations used for the components used in the examples:

TABLE-US-00001 TABLE 1 Component Raw material A Elastomer (rubber) B Non-elastomeric polyolefin C Thermoplastic elastomer based on polyolefin block copolymers D Cross-linking agent E Co-crosslinker F Plasticizer G Stabilizer, auxiliary material and dye H Filler

Examples 1 and 2

Production of Compositions of Thermoplastic Elastomers Based on EVM and NBR According to the Invention

[0159] According to the above-named production variant 3, a thermoplastic elastomer composition is produced with the constituents shown in Tables 2 and 3. A twin-screw extruder is used for blending the components used. The measured mechanical values are indicated in Table 4. Tables 5 to 7 indicate the mechanical values after treatment in various media.

TABLE-US-00002 TABLE 2 Compositions Raw material Component Example 1 Example 2 Elastomer (NBR) A1 100 Elastomer (EVM) A2 100 Non-elastomeric polyolefin B 20 16.7 TPO C 10 8.3 Cross-linker (10 wt. - % D 11 13.5 peroxide) Co-crosslinker E 6 6 Plasticizer F 25 25 Stabilization, auxiliary G materials and colour: Additive 1 0.46 0.4 Additive 2 0.24 0.24 Additive 3 0.24 0.25 Additive 4 0.2 0.2 Additive 5 0.1 Additive 6 1 Additive 7 1 Additive 8 1 Additive 9 3 3 Additive 10 1.5 3 Additive 11 0.3 0.4 Filler H 4 4

TABLE-US-00003 TABLE 3 Raw materials used Raw material Component Manufacturer Type Elastomer (NBR) A1 Lanxess Perbunan 3446 F Elastomer (EVM) A2 Lanxess EVM 600 Non-elastomeric polyolefin B Lyondell Basell Moplen HP500 N TPO C Lyondell Basell Hifax CA 10A Cross-linking agent D Pergan Peroxan HXY1OPSVP796 Co-crosslinker E Kettlitz PerTAC-GR Plasticizer F Safic Alkan Edenol T810T Stabilization, auxiliary G materials and colour: Additive 1 BASF Tinuvin 326 Additive 2 BASF Chimasorb 944 FDL Additive 3 BASF Tinuvin 622 SF Additive 4 BASF Irganox 1330 Additive 5 BASF Irganox 3052 FF Additive 6 Nordmann, Rassmann Quantox-45 Additive 7 Lanxess Vulkazon AFS-LG Additive 8 Rhein Chemie Antililux 654 Additive 9 Rhein Chemie Rhenogran PCD-50 EVA Additive 10 Lanxess Vulkanox HS LG Additive 11 BASF Irgafos 168 Fillers H Bayer ZnO Aktiv

TABLE-US-00004 TABLE 4 Mechanical values Value Unit Example 1 Example 2 Density g/cm.sup.3 1.015 1.056 Hardness ShA 73 59 Tensile strength N/mm.sup.2 5.8 7.0 Elongation at break % 353 332 100% MPa 3.0 2.5 200% MPa 3.9 4.3 300% MPa 5.1 6.4 Tear propagation resistance N/mm.sup.2 20 15.3 Compression set at 25° C./22 h % 32.0 31.0 Compression set at 700° C./22 h % 34.0 31.0 Compression set at 100° C./22 h % 39.5 30.5 Compression set at 120° C./22 h % 49.5 35.5 Compression set at 140° C./22 h % 67.0 52.0 Compression set at 150° C./22 h % 76.0 59.5 Adhesion on PP N/mm.sup.2 6 6 Abrasion mm.sup.3 422 317 The values for density, hardness, tensile strength, elongation at break, expansion (100%, 200%, 300%) and tear propagation resistance are recorded at room temperature.

TABLE-US-00005 TABLE 5 Measured Treatment Example Example value period Medium Temperature 1 2 Density Δ% Start value IRM 901 100° C. 0.0 0.0 1 week −3.5 2.2 3 weeks −0.2 3.6 Weight Δ% Start value 0.0 0.0 1 week −0.8 −4.6 3 weeks −1.7 −5.2 Volume Δ% Start value 0.0 0.0 1 week −4.3 −2.5 3 weeks −1.9 −1.8 Hardness Start value 73 60 (ShA) 1 week 76 60 3 weeks 73 59 Tensile Start value 6.6 6.8 strength 1 week 5.1 5.5 (N/mm.sup.2) 3 weeks 4.1 4.9 Elongation Start value 414 366 at break (%) 1 week 287 278 3 weeks 151 250 100 Start value 3.1 2.3 (MPa) 1 week 3.3 2.4 3 weeks 3.6 2.4 200% Start value 3.9 3.9 (MPa) 1 week 4.3 4.2 3 weeks 0.0 4.2 300% Start value 4.9 5.8 (MPa) 1 week 0.0 0.0 3 weeks 0.0 0.0

TABLE-US-00006 TABLE 6 Measured Treatment Example Example value period Medium Temperature 1 2 Density Δ% Start value Diesel RT 0.0 0.0 1 week 10.5 44.9 3 weeks 6.5 40.4 Weight Δ% Start value 0.0 0.0 1 week −2.6 −10.1 3 weeks −2.3 −9.7 Volume Δ% Start value 0.0 0.0 1 week 7.6 30.3 3 weeks 4.1 26.7 Hardness (ShA) Start value 73 60 1 week 65 41 3 weeks 68 42 Tensile strength Start value 6.6 6.8 (N/mm.sup.2) 1 week 4.6 2.6 3 weeks 5.0 2.7 Elongation at Start value 414 366 break (%) 1 week 341 191 3 weeks 347 192 100% (MPa) Start value 3.1 2.3 1 week 2.3 1.5 3 weeks 2.6 1.5 200% (MPa) Start value 3.9 3.9 1 week 3.2 0.0 3 weeks 3.4 0.0 300% (MPa) Start value 4.9 5.8 1 week 4.2 0.0 3 weeks 4.4 0.0

TABLE-US-00007 TABLE 7 Measured Treatment Example Example value period Medium Temperature 1 2 Density Δ% Start value Air 100° C. 0.0 0.0 1 week −1.5 3.0 3 weeks −1.5 3.5 6 weeks −2.0 3.6 Weight Δ% Start value 0.0 0.0 1 week 0.6 −3.4 3 weeks 0.5 −3.7 6 weeks 0.7 −4.1 Volume Δ% Start value 0.0 0.0 1 week −0.9 −0.4 3 weeks −1.0 −0.4 6 weeks −1.3 −0.6 Hardness (ShA) Start value 73 60 1 week 76 63 3 weeks 76 61 6 weeks 78 63 Tensile strength Start value 6.6 6.8 (N/mm.sup.2) 1 week 6.4 6.6 3 weeks 5.9 6.6 6 weeks 5.9 6.7 Elongation at Start value 414 366 break (%) 1 week 333 315 3 weeks 291 330 6 weeks 230 317

TABLE-US-00008 TABLE 8 Measured Treatment Example Example value period Medium Temperature 1 2 100% (MPa) Start value Air 100° C. 3.1 2.3 1 week 3.5 2.6 3 weeks 3.5 2.5 6 weeks 4.0 2.7 200% (MPa) Start value 3.9 3.9 1 week 4.6 4.6 3 weeks 4.7 4.3 6 weeks 5.5 4.6 300% (MPa) Start value 4.9 5.8 1 week 6.0 6.5 3 weeks 0.0 6.2 6 weeks 0.0 6.6

Examples 3 to 6

Production of Compositions of Thermoplastic Elastomers Based on SBR and NR According to the Invention

[0160] According to the above-named production variant 3, a thermoplastic elastomer composition is produced with the constituents shown in Tables 9 and 10. A twin-screw extruder is used for blending the components used.

[0161] Both TPEs based on SBR and TPEs based on NR result in homogeneous mixtures with good adhesion properties on polypropylene. As examples of this, the measured mechanical values and the values for the adhesion on polypropylene for TPEs based on SBR are indicated in Table 11.

TABLE-US-00009 TABLE 9 Raw material Component Example 3 Example 4 Example 5 Example 6 Elastomer (SBR) A1 100 100 Elastomer (NR) A2 100 100 Non-elastomeric polyolefin B 26.7 26.7 26.7 26.7 TPO C 13.3 13.3 13.3 13.3 Cross-linker D 10 10 10 10 Plasticizer F 40 40 40 40 Stabilization, auxiliary materials G and colour: Additive 1 0.3 0.3 0.3 0.3 Additive 2 0.1 0.1 0.1 0.1 Additive 3 0.32 0.32 0.32 0.32 Additive 4 0.1 0.1 0.1 0.1 Additive 5 8 8 Filler H 4 4 4 4

TABLE-US-00010 TABLE 10 Raw materials used Raw material Component Manufacturer Type Elastomer (SBR) A1 synthos Kralex SBR 1502 Elastomer (NR) A2 Weber & Schaer Natural Rubber SIR 20 Non-elastomeric polyolefin B Lyondell Basell Moplen HP500 N TPO C Lyondell Basell Hifax CA 10A Cross-linking agent (phenolic D SI Group SP 1045H resin) Plasticizer (white oil) F Shell Shell Ondina 941 Stabilization, auxiliary materials G and colour: Additive 1 BASF Tinuvin 326 Additive 2 BASF Chimasorb 944 FDL Additive 3 BASF Irganox 1330 Additive 4 BASF Irgafos 168 Additive 5 Rhenogran Zheolite 70 Rhein Chemie Additives Fillers H Bayer ZnO Aktiv

TABLE-US-00011 TABLE 11 Mechanical values Value Unit Example 3 Example 4 Density g/cm.sup.3 0.927 0.94 Hardness ShA 64 64 Tensile strength N/mm.sup.2 4 4.1 Elongation at break % 209 206 100% MPa 2.5 2.7 200% MPa 4.0 4.1 Tear propagation resistance N/mm.sup.2 13.3 16.3 Compression set at 700° C./22 h % 26.5 25.0 Compression set at 1000° C./22 h % 33.3 30.5 Compression set at 1200° C./22 h % 46.0 47.0 Adhesion on PP N/mm.sup.2 4.5 4.7 The values for density, hardness, tensile strength, elongation at break, expansion (100%, 200%) and tear propagation resistance are recorded at room temperature.