Thermoplastic Elastomer Composition Comprising An Elastomer And A Non-Elastomeric Polyolefin Functionalized With An Anhydride Of An Organic Carboxylic Acid

Abstract

A thermoplastic elastomer composition of an elastomer and a non-elastomeric polyolefin which is functionalized with an anhydride of an organic carboxylic acid is 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 non-elastomeric polyolefin which is functionalized with an anhydride of an organic carboxylic acid for producing a thermoplastic elastomer composition. In addition, the invention relates to the use of a thermoplastic elastomer composition for producing an article/composite material with a polyamide. The invention also relates to a process for producing a thermoplastic elastomer composition as well as a composite material made of the thermoplastic elastomer composition with a polyamide.

Claims

1. A thermoplastic elastomer composition comprising: an elastomer, and a thermoplast, wherein the thermoplast is a non-elastomeric polyolefin which is functionalized with an anhydride of an organic carboxylic acid, wherein the elastomer 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 elastomer is cross-linked or non-cross-linked.

2. The thermoplastic elastomer composition according to claim 1, wherein the first elastomer is selected from the group consisting of ethylene-vinyl acetate copolymer and nitrile butadiene rubber, or a mixture thereof.

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

4. The thermoplastic elastomer composition according to claim 1, wherein the organic carboxylic acid is an organic dicarboxylic acid.

5. The thermoplastic elastomer composition according to claim 1, wherein a weight ratio of elastomer to thermoplast lies in a range of from 100:15 to 100:60.

6. The thermoplastic elastomer composition according to claim 1, further comprising: a thermoplastic elastomer based on polyolefin block copolymers (TPO), wherein the TPO can be functionalized with an anhydride of an organic carboxylic acid.

7. A method of preparing a mixture of the elastomer and a cross-linking agent for the elastomer for producing a thermoplastic elastomer composition according to claim 1, the method comprising: mixing the elastomer and the cross-linking agent.

8. A non-elastomeric polyolefin which is functionalized with an anhydride of an organic carboxylic acid for producing a thermoplastic elastomer composition according to claim 1.

9. A thermoplastic elastomer composition according to claim 1 for producing a composite material with a polyamide.

10. An article which comprises a thermoplastic elastomer composition according to claim 1 and a polyamide.

11. A 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.

12. A process for producing a thermoplastic elastomer composition according to claim 1, the process comprising: mixing the elastomer with the thermoplast.

13. The process according to claim 12, wherein the elastomer is mixed with the thermoplast in an extruder, an internal mixer or a kneader.

14. The process according to claim 12, further comprising: masticating the elastomer in a first step together with a cross-linking agent before the elastomer is mixed with the thermoplast.

15. The process according to claim 14, wherein the first step is carried out in a temperature range of from 50° C. to 120° C.

16. The thermoplastic elastomer composition according to claim 4, wherein the organic dicarboxylic acid is an organic 1,2-dicarboxylic acid.

17. The thermoplastic elastomer composition according to claim 4, wherein the organic dicarboxylic acid is succinic acid.

18. The thermoplastic elastomer composition according to claim 6, wherein the organic dicarboxylic acid is succinic acid.

19. The process according to claim 13, wherein the elastomer is mixed with the thermoplast in a twin-screw extruder.

Description

EXAMPLES

[0167] Methods of Determination and Definitions:

[0168] Determination of the density takes place according to DIN EN ISO 1183-1.

[0169] Determination of the Shore hardness takes place according to DIN EN ISO 868 and DIN ISO 7619-1.

[0170] 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.

[0171] 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 %.

[0172] 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:

[0173] CS=compression set in %

[0174] L.sub.0=height of the test piece before testing

[0175] L.sub.1=height of the test piece during testing (spacer)

[0176] L.sub.2=height of the test piece after testing.

[0177] 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.

[0178] Determination of the tear propagation resistance takes place according to DIN 53504/ISO 37.

[0179] 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.

[0180] The adhesion of the thermoplastic elastomer compositions on PA6 is determined according to VDI2019: The PA6 used is one with the product name Frianyl B3V2 NC1102.

[0181] In order to determine the media resistance, S2 test rods or platelets of the thermoplastic elastomer compositions according to the invention are stirred in the media indicated in Tables 5 to 8 at the temperatures indicated for the time indicated. The test rods are used for the mechanical measurements and the platelets for determining the density etc.

[0182] After storage in the media indicated, the change in volume, change in density and change in weight are measured. Furthermore, the tensile strength, the elongation at break and the force which is required to stretch the thermoplastic elastomer by 100%, 200% or 300% are measured once again.

[0183] Hot air ageing is carried out at 120° C. and the results achieved are shown in Table 9.

Embodiment Examples

[0184] 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 Polypropylene, functionalized with an anhydride of an organic carboxylic acid C Thermoplastic elastomer based on polyolefin and/or g-TPO D Cross-linking agent E Co-crosslinker F Plasticizer G Stabilizer, auxiliary material and dye H Filler

Examples 1 and 2: Production of Thermoplastic Elastomer Compositions According to the Invention

[0185] According to the above-named production variant 3, thermoplastic elastomer compositions are 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 A1 100 Elastomer A2 100 Non-elastomeric polyolefin B 19 26.7 (functionalized) TPO C 6.5 8.3 Cross-linker (10 wt.-% peroxide) D 11 13.5 Co-crosslinker E 6 6 Plasticizer F 20 25 Stabilization, auxiliary materials G and colour: Additive 1 0.3 0.3 Additive 2 0.1 0.09 Additive 3 0.35 Additive 4 0.1 0.09 Additive 5 0.3 Filler H 4 4

TABLE-US-00003 TABLE 3 Raw materials used Raw material Component Manufacturer Type Elastomer A1 Lanxess Perbunan 3446 F Elastomer A2 Lanxess EVM 600 Non-elastomeric B BYK Scona Tppp polyolefin 2112 GA (functionalized) TPO C Lyondell Basel Hifax CA 10A Cross-linking agent D Pergan Peroxan HXY10PSVP796 Co-crosslinker E Kettlitz PerTAC-GR Plasticizer F Safic Alkan Edenol T810T Stabilization, G auxiliary materials and colour: Additive 1 BASF Tinuvin 326 Additive 2 BASF Chimasorb 944 FDL Additive 3 BASF Tinuvin 622 SF Additive 4 BASF Irgafos 168 Additive 5 BASF Irganox 1330 Fillers H Bayer ZnO Aktiv

TABLE-US-00004 TABLE 4 Mechanical values Value Unit Example 1 Example 2 Density g/cm.sup.3 1.021 1.044 Hardness ShA 70 70 Tensile strength N/mm.sup.2 6.3 7.7 Elongation at break % 268 295 100% MPa 3.2 3.8 200% MPa 4.8 5.8 300% MPa — 7.8 Tear propagation resistance N/mm.sup.2 20.6 17.9 Compression set at 25° C./22 h % 30.0 24.0 Compression set at 70° C./22 h % 30.5 26.0 Compression set at 100° C./22 h % 35.0 29.0 Compression set at 120° C./22 h % 38.0 36.0 Compression set at 140° C./22 h % 57.0 57.0 Compression set at 150° C./22 h % 64.5 67.5 Adhesion on PA6 N/mm.sup.2 5.0 2.7 Abrasion mm.sup.3 502 359 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 value period Medium Temperature Example 1 Example 2 Density Δ% Start value IRM 100° C. 0 0 1 week 901 −5.5 0.4 3 weeks −6.2 1.7 Weight Δ% Start value 0 0 1 week −6.5 −0.8 3 weeks −0.2 −1.7 Volume Δ% Start value 0 0 1 week −6.5 −0.8 3 weeks −6.4 0 Hardness Start value 71 74 (ShA) 1 week 75 74 3 weeks 76 73 Tensile Start value 6.6 7.5 strength 1 week 6.8 7 (N/mm.sup.2) 3 weeks 6.1 6.7 Elongation at Start value 299 305 break (%) 1 week 241 263 3 weeks 174 257 100% (MPa) Start value 3.2 3.6 1 week 3.8 3.7 3 weeks 4.3 3.6 200% (MPa) Start value 4.7 5.5 1 week 5.7 5.8 3 weeks 0 5.7 300% (MPa) Start value 7 7.4 1 week 0 0 3 weeks 0 0

TABLE-US-00006 TABLE 6 Measured Treatment value period Medium Temperature Example 1 Example 2 Density Δ% Start value Diesel RT 0 0 1 week 11.9 37.9 3 weeks 5.8 33.9 Weight Δ% Start value 0 0 1 week −6.2 −2.5 3 weeks −2.2 −5.8 Volume Δ% Start value 0 0 1 week 9.1 29.4 3 weeks 3.5 26.1 Hardness Start value 71 74 (ShA) 1 week 64 56 3 weeks 67 57 Tensile Start value 6.6 7.5 strength 1 week 4.3 3.4 (N/mm.sup.2) 3 weeks 5.2 3.6 Elongation at Start value 299 305 break (%) 1 week 230 171 3 weeks 263 180 100% (MPa) Start value 3.2 3.6 1 week 2.5 2.3 3 weeks 2.7 2.4 200% (MPa) Start value 4.7 5.5 1 week 3.9 0 3 weeks 4.1 0 300% (MPa) Start value 7 7.4 1 week 0 0 3 weeks 0 0

TABLE-US-00007 TABLE 7 Measured Treatment value period Medium Temperature Example 1 Example 2 Density Δ% Start value Air 100° C. 0 0 1 week −0.7 −0.1 3 weeks −0.6 0.5 6 weeks −1.5 1 Weight Δ% Start value 0 0 1 week 0.4 0 3 weeks 0.5 −0.4 6 weeks 1.3 −1.2 Volume Δ% Start value 0 0 1 week −0.3 −0.1 3 weeks −0.1 0.2 6 weeks −0.2 −0.2 Hardness Start value 71 74 (ShA) 1 week 72 75 3 weeks 72 74 6 weeks 77 75 Tensile Start value 6.6 7.5 strength 1 week 6.5 7.8 (N/mm.sup.2) 3 weeks 6 7.1 6 weeks 6.1 7.1 Elongation at Start value 299 305 break (%) 1 week 238 291 3 weeks 184 277 6 weeks 117 254

TABLE-US-00008 TABLE 8 Measured Treatment value period Medium Temperature Example 1 Example 2 100% (MPa) Start value Air 100° C. 3.2 3.6 1 week 3.6 4 3 weeks 3.9 3.7 6 weeks 5.5 4 200% (MPa) Start value 4.7 5.5 1 week 5.6 6.1 3 weeks 0 5.7 6 weeks 0 6.1 300% (MPa) Start value 7 7.4 1 week 0 0 3 weeks 0 0 6 weeks 0 0

Examples 3 to 6: Production of Compositions of Thermoplastic Elastomers Based on SBR and NR According to the Invention

[0186] 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.

[0187] Both TPEs based on SBR and TPEs based on NR result in homogeneous mixtures. For this and for the adhesion on polyamide, the measured mechanical values and the adhesion values for TPEs based on SBR are indicated in Table 11 by way of example.

TABLE-US-00009 TABLE 9 Compositions 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 36.7 45.4 26.7 33 (functionalized with MAH) TPO (functionalized with MAH) C1 18.3 13.3 TPO (not functionalized) C2 9.6 7 Cross-linking agent (peroxide) D 12 12 12 12 Co-crosslinker E 6 6 6 6 Plasticizer (white oil) 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 Filler H 4 4 4 4

TABLE-US-00010 TABLE 10 Raw materials used Raw material Component Manufacturer Type Elastomer (SBR) A1 Synthesis Kralex SBR 1502 Elastomer (NR) A2 Natural Rubber SIR 20 Non-elastomeric polyolefin B BYK Additives & Scona TPPP 2112 GA Instruments TPO (functionalized) C1 BYK Additives & BYK LP-T 23401 Instruments TPO (not functionalized) C2 Lyondell Basell Hifax CA 10A Cross-linking agent (peroxide) D Pergan Peroxan HXY 10 PS Co-crosslinker E Kettlitz PerTAC-GR 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 Fillers H Bayer ZnO Aktiv

TABLE-US-00011 TABLE 11 Mechanical values Value Unit Example 3 Example 4 Density g/cm.sup.3 0.96 0.96 Hardness ShA 80 80 Tensile strength N/mm.sup.2 5.5 5.4 Elongation at break % 204 170 100% MPa 4.2 4.5 Tear propagation resistance N/mm.sup.2 17.3 15.9 Compression set at 70° C./22 h % 30 32 Compression set at 100° C./22 h % 34 33 Compression set at 120° C./22 h % 48 53 Adhesion on PP N/mm.sup.2 0.7 1 The values for density, hardness, tensile strength, elongation at break, expansion (100%) and tear propagation resistance are recorded at room temperature.