A high temperature creep resistant polypropylene composition and its preparation method and application

Abstract

The present invention discloses a high temperature creep resistant polypropylene composition and its preparation method and application. The high temperature creep resistant polypropylene composition comprises the following components calculated by weight: 70 to 92 parts of polypropylene resin; 5 to 20 parts of branched linear low density polyethylene resin; 3 to 10 parts of ultra-high molecular weight polypropylene resin; the branched linear low density polyethylene resin is obtained by irradiation treatment of linear low density polyethylene resin, the M1 / M2 of the branched linear low density polyethylene resin is not less than 10:1, and the M2 is 3 to 45 g / 10 min. By adding a small amount of branched linear low density polyethylene resin and ultra-high molecular weight polypropylene resin to the polypropylene resin system, the "bridging" effect is utilized to form a super entangled structure so that the polypropylene composition has good high temperature creep resistance, and the components are compatible with each other and have good flow properties.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, and more specifically to a high-temperature creep-resistant polypropylene composition and a preparation method and application thereof. Background Art

[0002] Polypropylene materials have the advantages of low density, acid and alkali resistance and low price. They are widely used in various industries. The application of polypropylene in the automotive industry is gradually increasing. The auxiliary water tank material of traditional fuel vehicles is polypropylene material. Some material specifications are selected as pure polypropylene composite specifications, and some material specifications are selected as PP plus glass fiber reinforced polypropylene composite materials. Regardless of the technical direction, polypropylene is relatively weak in creep resistance at high temperatures. Therefore, in the design of automobile auxiliary water tanks and other parts, thicker part wall thickness is required to resist the risk of weak high temperature creep resistance.

[0003] In the prior art, there are two main ways to improve the high temperature creep resistance of polypropylene composite materials. One is to add aspect ratio fillers or nucleating agents to increase physical bonding points; the other is to achieve micro-crosslinking or molecular chain shuttling. However, both methods are limited by polypropylene resins and cannot improve the high temperature creep resistance under high fluidity, which affects the processing performance of polypropylene materials. Therefore, there is a need in the art to develop a high temperature creep resistant polypropylene composition with good fluidity. Summary of the invention

[0004] The purpose of the present invention is to provide a high temperature creep resistant polypropylene composition in order to overcome the defects in the above-mentioned prior art. The polypropylene composition has good high temperature creep resistance and good fluidity.

[0005] Another object of the present invention is to provide a method for preparing the high temperature creep resistant polypropylene composition.

[0006] Another object of the present invention is to provide application of the high temperature creep resistant polypropylene composition in automobiles.

[0007] In order to achieve the above object, the present invention adopts the following technical solutions:

[0008] A high temperature creep resistant polypropylene composition comprises the following components calculated in parts by weight:

[0009] Polypropylene resin 70-92 parts;

[0010] 5-20 parts of branched linear low-density polyethylene resin;

[0011] 3-10 parts of ultra-high molecular weight polypropylene resin;

[0012] The branched linear low-density polyethylene resin M1 / M2 is not less than 10:1; M1 is the melt flow rate of the branched linear low-density polyethylene resin at 190°C and 10kg load; M2 is the melt flow rate of the branched linear low-density polyethylene resin at 190°C and 2.16kg load; and M2 is 3-45g / 10min.

[0013] The invention provides a high-temperature creep resistant polypropylene composition. The high-temperature creep resistant polypropylene composition is prepared by adding a small amount of branched linear low-density polyethylene resin and ultra-high molecular weight polypropylene resin into polypropylene resin. Through a "bridging" effect, the bonding force between the ultra-high molecular weight polypropylene resin and the polypropylene resin and its own high-temperature creep resistance are utilized, and the high-temperature creep resistance of the branched linear low-density polyethylene resin is integrated to form a super entangled structure, so that the polypropylene composition has good high-temperature creep resistance. The ultra-high molecular weight polypropylene plays the role of "entanglement bond" between the polypropylene resin and the branched linear low-density polyethylene resin. When the branched linear low-density polyethylene resin M1 / M2 is within a specific range, as M1 / M2 increases, it indicates that the branched linear low-density polyethylene resin has more long branches, the branched linear low-density polyethylene resin has more branches, and the branched physical points are more, so that the polypropylene composition can obtain better high-temperature creep resistance. At the same time, due to the addition of a small amount of branched linear low-density polyethylene resin, the fluidity of the composition will not be significantly reduced, and the composition has good high-temperature creep resistance.

[0014] Specifically, the M2 is 3 to 45 g / 10 min, for example, it can be 5, 7, 10, 12, 15, 18, 20, 22, 25, 28, 30, 32, 35, 38, 40 or 42 g / 10 min, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the said range.

[0015] Specifically, the mass parts of the polypropylene resin are 70 to 92 parts, for example, 72 parts, 75 parts, 77 parts, 80 parts, 82 parts, 85 parts, 88 parts or 90 parts, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0016] The mass parts of the branched linear low-density polyethylene resin are 5 to 20 parts, for example, 7 parts, 10 parts, 12 parts, 15 parts or 18 parts, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the said range.

[0017] The mass parts of the ultra-high molecular weight polypropylene resin are 3 to 10 parts, for example, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts or 9 parts, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0018] Furthermore, the high temperature creep resistant polypropylene composition comprises the following components calculated in parts by weight:

[0019]

[0020] Furthermore, the M2 is 10 to 25 g / 10 min.

[0021] It should be noted that the melt flow rate described in the present invention is measured in accordance with ISO 1133-2011.

[0022] It should be noted that the content of polypropylene resin in the polypropylene composition of the present invention is not less than 65wt%.

[0023] Those skilled in the art should understand that the weight average molecular weight of the ultra-high molecular weight polypropylene resin in the present invention is not less than 100w.

[0024] In a specific embodiment, the weight average molecular weight of the ultra-high molecular weight polypropylene resin is 100w to 150w.

[0025] The weight average molecular weight of the polypropylene resin in the present invention is 10w to 35w.

[0026] The present invention also protects a branched linear low-density polyethylene resin, characterized in that M1 / M2 of the branched linear low-density polyethylene resin is not less than 10:1; M1 is the melt flow rate of the branched linear low-density polyethylene resin at 190°C and 10kg load; M2 is the melt flow rate of the branched linear low-density polyethylene resin at 190°C and 2.16kg load; the M2 is 3 to 45g / 10min; further, the M2 is 10 to 25g / 10min.

[0027] Furthermore, the preparation method of the branched linear low-density polyethylene resin is as follows:

[0028] The linear low-density polyethylene was irradiated with 60Co gamma rays under vacuum conditions.

[0029] Furthermore, the irradiation dose is 5 to 8 kgy, and the irradiation time is 20 to 28 hours.

[0030] In a specific embodiment, the preparation method is as follows:

[0031] All linear low-density polyethylenes were compression molded into 1 mm thick flat sheets using a hydraulic press at 170-190°C, 1-5 minutes, and a maximum pressure of 10 MPa. They were then cooled at room temperature and placed in a Pyrex tube connected to a vacuum glass line and placed under high vacuum for 20-28 hours. The samples were then sealed in the same heat-resistant glass tube. The irradiation of the samples was performed at room temperature using 50-70Co source gamma ray irradiation.

[0032] Specifically, the radiation dose is measured by a red organic glass dosimeter. After irradiation, the sample is annealed at 130-150° C. for 1.5-2.5 hours, and the sample is crushed to obtain branched linear low-density polyethylene.

[0033] Furthermore, the M1 / M2 of the branched linear low-density polyethylene resin is (13-20):1.

[0034] Furthermore, the melt flow rate of the polypropylene resin at 230° C. and 2.16 kg is 3.0 to 35.0 g / 10 min.

[0035] Furthermore, the polypropylene resin is a homopolymer polypropylene resin or a copolymer polypropylene resin.

[0036] Furthermore, the ultra-high molecular weight polypropylene resin is a homopolymer ultra-high molecular weight polypropylene resin or a copolymer ultra-high molecular weight polypropylene resin.

[0037] Furthermore, the ultra-high molecular weight polypropylene resin has a melt flow rate of 0.1 to 15 g / 10 min at 230° C. and a load of 2.16 kg.

[0038] Specifically, the melt flow rate of the ultra-high molecular weight polypropylene resin at 230° C. and 2.16 kg load is 0.1 to 15 g / 10 min, for example but not limited to 0.2, 0.3, 0.5, 0.8, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, 10.0, 10.5, 11.0, 11.5, 12.0, 12.5, 13.0, 13.5, 14.0, 14.5 g / 10 min, and specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the said range.

[0039] Furthermore, the antioxidant may be a commonly used antioxidant, including hindered phenol antioxidants, phosphite antioxidants, diphenylamine antioxidants, copper salt antioxidants or thioether antioxidants.

[0040] Specifically, the hindered phenol antioxidant is one or more of N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxyphenylpropionamide (Irganox 1098), pentaerythritol tetrakis[1093,5-di-tert-butyl-4-hydroxyphenyl)propionate (Irganox 1010), triethylene glycol bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate (Iragnox 259), β-(4-hydroxy-3,5-di-tert-butylphenyl) propionate n-octadecyl (Iragno 1076) or spiroethylene glycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] (ADK AO-80).

[0041] The phosphite antioxidant is one or more of 2,4-di-tert-butylphenol (Irganox 168), bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol phosphite (PEP-36) or 627A.

[0042] It should be noted that the polypropylene composition of the present invention may further include one or more of a lubricant, a colorant, an anti-ultraviolet agent or a filler without impairing the effects of the present invention.

[0043] The method for preparing the high temperature creep resistant polypropylene composition of the present invention comprises the following steps:

[0044] The polypropylene resin, the branched linear low-density polyethylene resin, the ultra-high molecular weight polypropylene resin and the antioxidant are mixed and added into an extruder, and granulated by melt extrusion to obtain a high-temperature creep-resistant polypropylene composition.

[0045] Furthermore, the mixing rotation speed is 300-400 rpm.

[0046] Furthermore, the mixing time is 120 to 240 seconds.

[0047] Furthermore, the melting temperature is 200-220°C.

[0048] The present invention protects the use of the high temperature creep resistant polypropylene composition in automobiles, for example, in the preparation of cold air outlet pipes, water chambers or cooling fan materials in automobiles.

[0049] Compared with the prior art, the present invention has the following beneficial effects:

[0050] The invention provides a high-temperature creep resistant polypropylene composition. The high-temperature creep resistant polypropylene composition is prepared by adding a small amount of branched linear low-density polyethylene resin and ultra-high molecular weight polypropylene resin into a polypropylene resin system, and a super-entangled structure is formed through a "bridging" effect, so that the polypropylene composition has good high-temperature creep resistance. At the same time, due to the small amount of branched linear low-density polyethylene resin, the fluidity of the polypropylene composition will not be significantly reduced, and the melt flow rate is not less than 10g / 10min, so the composition has good processing performance, and the creep rupture time is not less than 200h. DETAILED DESCRIPTION

[0051] The present invention is further described below in conjunction with specific embodiments, but the embodiments do not limit the present invention in any form. Unless otherwise specified, the raw materials and reagents used in the embodiments of the present invention are conventionally purchased raw materials and reagents.

[0052] The raw materials used in the embodiments and comparative examples of the present invention are:

[0053] Polypropylene resin:

[0054] Polypropylene resin 1: 230°C, melt flow rate at 2.16 kg is 12.0 g / 10 min, weight average molecular weight is 24w, PP HP500N, CNOOC Shell Petrochemical Co., Ltd.;

[0055] Polypropylene resin 2: 230°C, melt flow rate at 2.16 kg is 26.0 g / 10 min, weight average molecular weight is 19w, PPH-Y26 (ZHONGKE), Zhongke (Guangdong) Refining and Chemical Co., Ltd.;

[0056] Branched linear low density polyethylene resin:

[0057] Linear low-density polyethylene resin 1: 190°C, melt flow rate at 2.16 kg is 20.0 g / 10 min, LLDPE-7144, Maoming Petrochemical;

[0058] Linear low-density polyethylene resin 2: 190°C, melt flow rate at 2.16 kg is 50.0 g / 10 min, TJZS-2650, Tianjin Petrochemical;

[0059] The branched linear low-density polyethylene resin used in the present invention is prepared by the following method:

[0060] All linear low-density polyethylenes were compression molded into 1 mm thick flat sheets using a hydraulic press at 180 °C, 2 minutes, and a maximum pressure of 10 MPa. They were subsequently cooled at room temperature and placed in a Pyrex tube connected to a vacuum glass line and placed under high vacuum for 24 hours. The samples were then sealed in the same heat-resistant glass tube. Irradiation of the samples was performed at room temperature using 60Co source gamma ray irradiation.

[0061] Specifically, the radiation dose was measured by a red organic glass dosimeter. After irradiation, the sample was annealed at 140°C for 2 hours, and the sample was crushed to obtain branched linear low-density polyethylene.

[0062] Branched linear low-density polyethylene resin 1: linear low-density polyethylene resin 1 was used as raw material for treatment, and after treatment, M1 / M2 was 13:1; the melt flow rate of branched linear low-density polyethylene resin 1 at 190°C and 10kg load was 205g / 10min (M1); the melt flow rate of branched linear low-density polyethylene resin 1 at 190°C and 2.16kg load was 15.7g / 10min (M2), the irradiation dose was 5kgy, and the irradiation time was 24h;

[0063] Branched linear low-density polyethylene resin 2: linear low-density polyethylene resin 2 was used as raw material for treatment, and the M1 / M2 after treatment was 17:1; the melt flow rate of branched linear low-density polyethylene resin 2 at 190°C and 10kg load was 682g / 10min (M1); the melt flow rate of branched linear low-density polyethylene resin 2 at 190°C and 2.16kg load was 40.11g / 10min (M2), the irradiation dose was 8kgy, and the irradiation time was 24h;

[0064] Branched linear low-density polyethylene resin 3: linear low-density polyethylene resin 1 is used as raw material for treatment, and the M1 / M2 after treatment is 20:1; the melt flow rate of branched linear low-density polyethylene resin 3 at 190°C and 10kg load is 300g / 10min (M1); the melt flow rate of branched linear low-density polyethylene resin 3 at 190°C and 2.16kg load is 15g / 10min (M2), the irradiation dose is 10kgy, and the irradiation time is 24h;

[0065] Branched linear low-density polyethylene resin 4: linear low-density polyethylene resin 1 was used as raw material for treatment, and the M1 / M2 after treatment was 12:1; the melt flow rate of branched linear low-density polyethylene resin 4 at 190°C and 10kg load was 192g / 10min (M1); the melt flow rate of branched linear low-density polyethylene resin 4 at 190°C and 2.16kg load was 16g / 10min (M2), the irradiation dose was 4kgy, and the irradiation time was 24h;

[0066] Ultra-high molecular weight polypropylene resin: BA202E, weight average molecular weight 102w, Borealis;

[0067] Antioxidants:

[0068] Antioxidant 1010, Tianjin Lianlong; the parallel tests of Examples 1 to 11 and Comparative Examples 1 to 3 all adopted the same antioxidant.

[0069] Examples 1 to 11 and Comparative Examples 1 to 3

[0070] According to the formulations in Tables 1 to 3, a high temperature creep resistant polypropylene composition was prepared according to the following preparation method:

[0071] Polypropylene resin, branched linear low-density polyethylene resin, ultra-high molecular weight polypropylene resin and antioxidant are placed in a premix and stirred at a speed of 350 rpm / min for 180 seconds, and then added to a twin-screw extruder for melt blending and extrusion granulation to obtain a high-temperature creep-resistant polypropylene composition; the feeding section temperature is 180°C, the melting temperature is 210°C, the screw aspect ratio is 48:1, and the screw speed of the twin-screw extruder is 400 rpm.

[0072] Table 1 Amount of each component in the high temperature creep resistant polypropylene composition in Examples 1 to 7 (parts by weight)

[0073]

[0074]

[0075] Table 2 Amount of each component in the high temperature creep resistant polypropylene composition in Examples 8 to 11 (parts by weight)

[0076]

[0077] Table 3 Amount of each component in the high temperature creep resistant polypropylene composition in Comparative Examples 1 to 3 (parts by weight)

[0078] Components Comparative Example 1 Comparative Example 2 Comparative Example 3 Polypropylene resin 1 77 77 77 Linear low density polyethylene resin 1 15 - - Branched Linear Low Density Polyethylene Resin 1 - 15 - Ultra high molecular weight polypropylene resin 8 - 8 Antioxidants 0.6 0.6 0.6

[0079] Performance Testing

[0080] 1. Test methods

[0081] The high temperature creep resistant polypropylene composition prepared above was subjected to performance tests:

[0082] (1) Melt flow rate test: The high temperature creep resistant polypropylene composition prepared above was tested according to standard ISO1133-2011, wherein the test conditions were 230°C / 2.16kg;

[0083] (2) High temperature creep resistance test: The high temperature creep resistant polypropylene composition prepared above was injection molded to obtain ISO mechanical 1A tensile specimens. The injection molding conditions were injection temperature of 200°C throughout the entire range, injection pressure of 70% throughout the entire range, holding pressure of 70% throughout the entire range, holding time of 15 seconds, and cooling time of 8 seconds. Injection mold: ISO mechanical 1A bending specimens.

[0084] Step 1: Use ISO mechanics 1A tensile specimen to test the static tensile strength at 80°C; Step 2: Calculate 80% of the static tensile strength at 80°C as the tensile creep set load; Step 3: Set the temperature of the environmental chamber to 80°C and place the specimen in the creep environmental chamber for 4 hours; Step 4: Fix the tensile specimen on the clamp and start the tensile creep experiment after the force is reset to zero; Step 5: Observe the rupture time of the equipment, conduct the experiment until the specimen breaks, and record the creep rupture time.

[0085] 2. Test Results The test results of the high temperature creep resistant polypropylene composition prepared by the above method are shown in Table 4.

[0086] Table 4 Performance test results of various embodiments and comparative examples

[0087] Test items Melt flow rate (g / 10min) Creep rupture time (h) Example 1 13.2 282 Example 2 35.2 257 Example 3 11.2 301 Example 4 14.5 265 Example 5 12.5 325 Example 6 23.2 209 Example 7 10.5 295 Example 8 15.1 257 Example 9 12.4 301 Example 10 10.1 388 Embodiment 11 30.2 200 Comparative Example 1 20.5 55 Comparative Example 2 13.5 65 Comparative Example 3 10.3 26

[0088] It can be seen from Table 4 that the high-temperature creep-resistant polypropylene compositions prepared in various embodiments of the present invention have good high-temperature creep resistance and good melt flow rate, specifically: the creep rupture time is not less than 200 hours; the melt flow rate at 230°C and 2.16kg is not less than 10g / 10min, and has good processing performance and can complete injection molding well.

[0089] It can be seen from Examples 1 and 3 to 4 that as the M1 / M2 in the branched linear low-density polyethylene resin increases, the comprehensive performance of the obtained polypropylene composition is better. This is because within this range, the branched linear low-density polyethylene resin contains more long branches and more entanglement physical points. When M1 / M2 is (13 to 20): 1, it can have higher high-temperature creep resistance while satisfying better fluidity, and the creep rupture time is not less than 280 hours.

[0090] In Example 2, due to the high fluidity of the branched linear low-density polyethylene resin, its creep resistance is reduced.

[0091] It can be seen from Examples 1, 5 and 6 that as the amount of branched linear low-density polyethylene resin increases, the melt flow rate of the obtained polypropylene composition gradually decreases, and the high-temperature creep performance gradually increases. When the amount of branched linear low-density polyethylene resin is 12 to 15 parts, the comprehensive performance of the obtained polypropylene composition is better.

[0092] It can be seen from Examples 1, 8 and 9 that with the increase in the amount of ultra-high molecular weight polypropylene resin, the melt flow rate of the obtained polypropylene composition gradually decreases, but the high temperature creep resistance gradually improves. When the amount of ultra-high molecular weight polypropylene resin is 5 to 8 parts, the comprehensive performance of the obtained polypropylene composition is better.

[0093] By comparing Example 7 and Comparative Example 1, it can be seen that when a linear low-density polyethylene resin is used instead of a branched linear low-density polyethylene resin, the high-temperature creep performance of the obtained polypropylene composition is significantly reduced. This is because ordinary linear low-density polyethylene has a straight chain structure without long branches and cannot synergize with the ultra-high molecular weight polypropylene resin to produce a "bridging" effect, resulting in poor high-temperature creep resistance.

[0094] By comparing Example 7 and Comparative Example 2, it can be seen that if the ultra-high molecular weight polypropylene resin is not added, even if the branched linear low-density polyethylene resin is added, the high-temperature creep resistance of the obtained polypropylene composition is still poor, and the creep rupture time is only 65 hours, which is significantly reduced compared with Example 7.

[0095] Comparison of Example 7 and Comparative Example 3 shows that if the branched linear low-density polyethylene resin is not added, the flow rate and high-temperature creep properties of the polypropylene composition obtained are poor even if the ultra-high molecular weight polypropylene resin is added.

[0096] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the embodiments here. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the claims of the present invention.

Claims

1. A polypropylene composition, characterized in that The composition comprises the following components calculated by weight: Polypropylene resin 70-92 parts; 5-20 parts of branched linear low-density polyethylene resin; 3-10 parts of ultra-high molecular weight polypropylene resin; The branched linear low-density polyethylene resin M1 / M2 is not less than 10:1; M1 is the melt flow rate of the branched linear low-density polyethylene resin at 190°C and 10kg load; M2 is the melt flow rate of the branched linear low-density polyethylene resin at 190°C and 2.16kg load; and M2 is 3-45g / 10min.

2. The polypropylene composition according to claim 1, characterized in that The composition comprises the following components calculated by weight:

3. The polypropylene composition according to claim 1 or 2, characterized in that: The preparation method of the branched linear low-density polyethylene resin is as follows: The linear low-density polyethylene was irradiated with 60Co gamma rays under vacuum conditions.

4. The polypropylene composition according to claim 3, characterized in that: The irradiation dosage is 5 to 8 kgy, and the irradiation time is 20 to 28 hours.

5. The polypropylene composition according to claim 1 or 2, characterized in that: The melt flow rate of the polypropylene resin at 230° C. and 2.16 kg is 3.0 to 35.0 g / 10 min.

6. The polypropylene composition according to claim 1 or 2, characterized in that: The polypropylene resin is a homopolymer polypropylene resin or a copolymer polypropylene resin.

7. The polypropylene composition according to claim 1 or 2, characterized in that: The branched linear low-density polyethylene resin M1 / M2 is (13-20):

1.

8. A branched linear low-density polyethylene resin, characterized in that The M1 / M2 of the branched linear low-density polyethylene resin is not less than 10:1; M1 is the melt flow rate of the branched linear low-density polyethylene resin at 190°C and 10kg load; M2 is the melt flow rate of the branched linear low-density polyethylene resin at 190°C and 2.16kg load; and M2 is 3 to 45g / 10min.

9. The method for preparing the polypropylene composition according to any one of claims 1 to 7, characterized in that: The steps include: The polypropylene resin, the branched linear low-density polyethylene resin, the ultra-high molecular weight polypropylene resin and the antioxidant are mixed and added into an extruder, and granulated by melt extrusion to obtain a high-temperature creep-resistant polypropylene composition.

10. Use of the polypropylene composition according to any one of claims 1 to 7 in automobiles.

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