A matte halogen-free elastic composite material and its preparation method and application

Abstract

The present invention discloses a matte halogen-free elastic composite material and a preparation method and application thereof. The matte halogen-free elastic composite material is prepared from raw materials including: 10wt% to 50wt% of polyolefin elastomer; 10wt% to 50wt% of EPDM elastomer; 5wt% to 20wt% of styrene elastomer; 1wt% to 5wt% of SEBS‑g‑MAH compatibilizer; 5wt% to 30wt% of filler; and 1wt% to 5wt% of auxiliary agent. The matte halogen-free elastic composite material of the present invention has the properties of good tensile properties, good light and heat aging resistance, high tear strength, scratch resistance, etc., and meets the requirements of matte appearance. The material of the present invention has excellent comprehensive performance, simple preparation process, is worthy of promotion and application, and is suitable for use as an elastomer material for automotive soft accessories.

Description

Technical Field

[0001] The invention relates to the field of polymer technology, and in particular to a matte halogen-free elastic composite material and a preparation method and application thereof. Background Art

[0002] At present, the halogen-free elastomer materials for automotive soft accessories are generally made of TPU, TPE and other materials, with a hardness requirement of 75-85A, and a matte surface. TPU materials have good scratch resistance and elasticity, but poor light and heat aging and hydrolysis resistance, and are prone to aging cracking and powdering. The surface of TPU materials is bright and difficult to meet the matte requirements. TPE materials are a mixture of SEBS, white oil, and polypropylene as the basic components. Although they appear semi-matte, the material has low tensile strength and tear strength, poor scratch resistance, and is also prone to tearing and scratching problems.

[0003] Taking into account the situation of existing materials, improving the performance of elastomeric materials for automotive soft accessories and meeting the technical requirements of good tensile properties, resistance to light and heat aging, high tear strength, scratch resistance and matte surface has become a hot issue in the industry. Summary of the invention

[0004] The present invention aims to solve at least one of the above-mentioned technical problems existing in the prior art and meet the requirements of elastomeric materials for automotive soft accessories. The purpose of the present invention is to provide a matte halogen-free elastic composite material and a preparation method and application thereof. The matte halogen-free elastic composite material has excellent tensile properties, light and heat aging resistance, high tear strength and scratch resistance.

[0005] In order to achieve the above object, the technical solution adopted by the present invention is:

[0006] A matte halogen-free elastic composite material, the raw materials for preparation include:

[0007]

[0008] In some embodiments of the present invention, the matte halogen-free elastic composite material is prepared by raw materials including:

[0009]

[0010]

[0011] In some embodiments of the present invention, the polyolefin elastomer includes at least one of a copolymer of ethylene and propylene, a copolymer of ethylene and hexene, and a copolymer of ethylene and octene.

[0012] In some embodiments of the present invention, the polyolefin elastomer has a melt index of 20 g / 10 min to 40 g / 10 min under the test conditions of 190° C. and 2.16 kg. In the present invention, the polyolefin elastomer is an elastomer material with good fluidity, which can obtain a good appearance effect during the injection molding of automotive soft parts, avoiding the occurrence of water marks, whitening, glue deficiency and the like.

[0013] In some embodiments of the present invention, the EPDM elastomer is a terpolymer of ethylene, propylene and non-conjugated diene, and is a type of ethylene-propylene rubber. In the present invention, the EPDM elastomer has good compatibility with polyolefin elastomers, has excellent oxidation resistance, light and heat aging resistance, and can reduce the hardness of the product.

[0014] In some embodiments of the present invention, the ethylene mass content of the EPDM elastomer is 40% to 70%.

[0015] In some embodiments of the present invention, the styrene elastomer includes at least one of SEBS, SEPS, SIS, SBS, and SOE. In the present invention, the styrene elastomer has good compatibility with polyolefin elastomers and EPDM elastomers, which can improve the elasticity of the product and give the product surface a matte effect.

[0016] In some embodiments of the present invention, the styrene elastomer is SEBS, and the styrene content of the SEBS is 25% to 35%.

[0017] In some embodiments of the present invention, the SEBS-g-MAH compatibilizer includes maleic anhydride grafted SEBS. In the present invention, the SEBS-g-MAH compatibilizer promotes better fusion of styrene elastomers with polyolefin elastomers and EPDM elastomers, thereby improving the tensile properties of the product.

[0018] In some embodiments of the present invention, the grafting rate of the SEBS-g-MAH compatibilizer is 0.5% to 1.5%.

[0019] In some embodiments of the present invention, the filler includes at least one of calcium carbonate, magnesium hydroxide, talc, wollastonite, kaolin, barium sulfate, magnesium oxide, and aluminum oxide.

[0020] In some embodiments of the present invention, the filler includes at least one of calcium carbonate, magnesium hydroxide, and talc.

[0021] In some embodiments of the present invention, the auxiliary agent includes at least one of a lubricant, an antioxidant, a light stabilizer, and a colorant.

[0022] In some embodiments of the present invention, the lubricant includes at least one of silicone masterbatch, fatty acid amide, stearate, erucamide, ethylene bisstearamide, pentaerythritol stearate, and polyethylene wax.

[0023] In some embodiments of the present invention, the antioxidant includes at least one of a hindered phenol antioxidant and a phosphite antioxidant.

[0024] In some embodiments of the present invention, the antioxidant comprises a mixture of a hindered phenol antioxidant and a phosphite antioxidant, such as Antioxidant B215.

[0025] In some embodiments of the present invention, the light stabilizer includes at least one of benzophenone, benzotriazole, salicylate, triazine, acrylonitrile derivatives, and hindered amine light stabilizers.

[0026] In some embodiments of the present invention, the light stabilizer includes at least one of UV-329, UV-531, UV-622, UV-770, UV-944, and V9900.

[0027] In some embodiments of the present invention, the light stabilizer includes a composite light stabilizer composed of UV-531, UV-329 and UV-622 in a mass ratio of 2:2:1.

[0028] In some embodiments of the present invention, the colorant includes at least one of titanium dioxide, carbon black, and toner.

[0029] According to a second aspect of the present invention, a method for preparing the matte halogen-free elastic composite material is provided, comprising the following steps:

[0030] S1: weighing raw materials according to the above composition, mixing, and obtaining a mixed material;

[0031] S2: adding the mixed material into a twin-screw extruder, extruding, and granulating to obtain a matte halogen-free elastic composite material.

[0032] In some embodiments of the present invention, the process conditions of the twin-screw extruder are as follows: the aspect ratio of the twin-screw extruder is (48-56):1; the maximum operating temperature is not higher than 200°C; the main engine speed is 220r / min-360r / min.

[0033] In some embodiments of the present invention, the process conditions of the twin-screw extruder are as follows: the aspect ratio of the twin-screw extruder is 52:1; the operating temperature is 180°C to 200°C; and the main engine speed is 280r / min to 320r / min.

[0034] According to a third aspect of the present invention, a soft automotive accessory is provided, comprising the matte halogen-free elastic composite material.

[0035] In some embodiments of the present invention, the automobile soft accessories include any one of storage box rubber pads, leather decorative rubber bags, wheel air dams, fenders, and foot pads.

[0036] The beneficial effects of the present invention are:

[0037] The matte halogen-free elastic composite material of the present invention has good tensile properties, good light and heat aging resistance, high tear strength, scratch resistance and other properties, and meets the matte surface requirements. The material of the present invention has excellent comprehensive performance and simple preparation process, and is worthy of promotion and application. It is suitable for use as an elastomer material for automotive soft accessories, such as storage box rubber pads, leather grain decorative rubber bags, wheel air dams, fenders, foot pads, etc. It has obvious advantages over the existing TPU and TPE materials. DETAILED DESCRIPTION

[0038] The present invention is further described in detail below by specific examples. Unless otherwise specified, the raw materials, reagents or devices used in the examples and comparative examples can be obtained from conventional commercial sources or can be obtained by prior art methods. Unless otherwise specified, the experiments or test methods are conventional methods in the art.

[0039] Examples and Comparative Examples

[0040] The raw materials used in Inventive Examples 1 to 4 and Comparative Examples 1 to 5 are shown in Table 1.

[0041] Table 1

[0042]

[0043] The formulation components (mass percentage) of Examples 1 to 4 and Comparative Examples 1 to 5 are shown in Table 2.

[0044] Table 2

[0045]

[0046]

[0047] The preparation methods of Examples 1 to 4 and Comparative Examples 1 to 4 in Table 2 are as follows:

[0048] a) Weigh each raw material according to the formula components;

[0049] b) mixing all raw materials uniformly to obtain a mixture;

[0050] c) The mixed material was added to a twin-screw extruder for extrusion and granulation to obtain the materials of Examples 1 to 4 and Comparative Examples 1 to 4.

[0051] Among them, the aspect ratio of the twin-screw extruder is 52:1. The set temperatures of each temperature zone of the twin-screw extruder are: 150℃, 180℃, 200℃, 200℃, 200℃, 200℃, 195℃, 195℃, 190℃, 190℃, 185℃, 180℃. The main engine speed is 300r / min.

[0052] The preparation method of Comparative Example 5 in Table 2 is as follows:

[0053] a) Weigh each raw material according to the formula components;

[0054] b) stirring and mixing SEBS and white oil, and then adding other ingredients to obtain a mixture;

[0055] c) pouring the mixed material into a twin-screw extruder for extrusion and granulation to obtain the material of Example 5.

[0056] Among them, the aspect ratio of the twin-screw extruder is 52:1. The set temperatures of each temperature zone of the twin-screw extruder are: 150℃, 180℃, 200℃, 200℃, 200℃, 200℃, 195℃, 195℃, 190℃, 190℃, 185℃, 180℃. The main engine speed is 300r / min.

[0057] The matte halogen-free elastic composite materials prepared in Examples 1 to 4 can all be used as an elastomeric material for automotive soft accessories, which will be further described in detail below.

[0058] Example 1

[0059] The raw material composition of the matte halogen-free elastic composite material of Example 1 is shown in Table 2. Among them, the polyolefin elastomer is POE8401, and the melt index is 30g / 10min. The EPDM elastomer is EPDM 2060M, and the ethylene content is 49.2%. The styrene elastomer is SEBS 6153. The SEBS-g-MAH compatibilizer is KT-25. The calcium carbonate is JY-2800. The lubricant is BN500. The antioxidant is B215, which is compounded by a hindered phenol antioxidant and a phosphite antioxidant. The light stabilizer is UV-531, UV-329 and UV-622 compounded in a mass ratio of 2:2:1. The colorant is M717.

[0060] Example 2

[0061] The difference between Example 2 and Example 1 is that POE is 22% and EPDM is 40%. In this example, by reducing the POE content and increasing the EPDM content, the hardness of the product can be reduced, which is suitable for the hardness requirements of different models and parts. The mass percentages of other components in this example are shown in Table 2.

[0062] Example 3

[0063] The difference between Example 3 and Example 1 is that POE is 40% and EPDM is 22%. In this example, by increasing the POE content and reducing the EPDM content, the hardness of the product can be increased, which is suitable for the hardness requirements of different models and parts. The mass percentages of other components in this example are shown in Table 2.

[0064] Example 4

[0065] The difference between Example 4 and Example 1 is that POE is 30%, EPDM is 27%, and SEBS is 20%. This example describes the performance and matte condition of the material by increasing the addition amount of SEBS. The mass percentages of other components in this example are shown in Table 2.

[0066] Comparative Example 1

[0067] Comparative Example 1 differs from Example 1 in that no SEBS-g-MAH compatibilizer is added. SEBS is 20%. Comparison is made with the case where no SEBS-g-MAH compatibilizer is added. The mass percentages of other components in this example are shown in Table 2.

[0068] Comparative Example 2

[0069] The difference between Comparative Example 2 and Example 1 is that SEBS is not added, POE is 40%, and EPDM is 37%. Comparison is made when SEBS is not added. The mass percentages of other components in this example are shown in Table 2.

[0070] Comparative Example 3

[0071] The difference between Comparative Example 3 and Example 1 is that EPDM is not added and POE is 62%. The mass percentages of other components in this example are shown in Table 2.

[0072] Comparative Example 4

[0073] Comparative Example 4 differs from Example 1 in that POE, EPDM, SEBS, and SEBS-g-MAH compatibilizer are not added. TPU is 82%. The performance of TPU materials at the same hardness is compared. The mass percentages of other components in this example are shown in Table 2.

[0074] Comparative Example 5

[0075] Comparative Example 5 differs from Example 1 in that POE and EPDM are not added, SEBS is 25%, white oil is 27%, and PP is 25%. The performance of TPE materials at the same hardness is compared. The mass percentages of other components in this example are shown in Table 2.

[0076] Test example

[0077] This test example tests the properties of the elastomeric materials prepared in Examples 1 to 4 and Comparative Examples 1 to 5. The results are shown in Table 3.

[0078] Table 3

[0079]

[0080]

[0081]

[0082] It can be seen from the test results in Table 3 that the matte halogen-free elastic composite material prepared in the embodiment of the present invention has a hardness of 75 to 85A, which can meet the requirements of automotive soft accessories for elastomeric materials, and has good tensile properties, light and heat aging resistance, high tear strength, scratch resistance and other performance requirements, and has a matte surface effect. In Comparative Example 1, the role of SEBS-g-MAH compatibilizer can be seen. In Comparative Example 2, it can be seen that the styrene-based elastomer material has an effect on the apparent matte effect in the formula. In Comparative Example 3, it can be seen that the EPDM elastomer material allows the material to maintain excellent performance at low hardness. In Comparative Examples 4 to 5, TPU and TPE materials cannot meet the relevant performance requirements in the embodiments of the present invention.

[0083] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.

Claims

1. A matte halogen-free elastic composite material, characterized in that: The raw materials for preparation consist of the following components: Polyolefin elastomer 20wt%~40wt%; EPDM elastomer 20wt%~40wt%; Styrene elastomer 10wt%~20wt%; SEBS-g-MAH compatibilizer 3wt%-5wt%; Filler 10wt%~20wt%; Additives: 3wt%~5wt%; The auxiliary agent comprises polyethylene wax, antioxidant B215, UV-531, UV-329 and UV-622 in a mass ratio of 2:2:

1.

2. The matte halogen-free elastic composite material according to claim 1, characterized in that: The polyolefin elastomer has a melt index of 20 g / 10 min to 40 g / 10 min under the test conditions of 190° C. and 2.16 kg.

3. The matte halogen-free elastic composite material according to claim 1 or 2, characterized in that: The polyolefin elastomer includes at least one of a copolymer of ethylene and propylene, a copolymer of ethylene and hexene, and a copolymer of ethylene and octene.

4. The matte halogen-free elastic composite material according to claim 1 or 2, characterized in that: The ethylene mass content of the EPDM elastomer is 40% to 70%.

5. The matte halogen-free elastic composite material according to claim 1 or 2, characterized in that: The styrene elastomer includes at least one of SEBS, SEPS, SIS, SBS and SOE.

6. The matte halogen-free elastic composite material according to claim 1 or 2, characterized in that: The SEBS-g-MAH compatibilizer includes maleic anhydride grafted SEBS.

7. The matte halogen-free elastic composite material according to claim 1 or 2, characterized in that: The filler includes at least one of calcium carbonate, magnesium hydroxide, talc, wollastonite, kaolin, barium sulfate, magnesium oxide, and aluminum oxide.

8. A method for preparing the matte halogen-free elastic composite material according to any one of claims 1 to 7, characterized in that: The following steps are involved: S1: weighing raw materials according to the composition of any one of claims 1 to 7, mixing to obtain a mixed material; S2: adding the mixed material into a twin-screw extruder, extruding, and granulating to obtain a matte halogen-free elastic composite material.

9. An automotive soft accessory, characterized in that: The invention comprises the matte halogen-free elastic composite material as claimed in any one of claims 1 to 7.

10. The automotive soft accessory according to claim 9, characterized in that: The automobile soft accessories include any one of a storage box rubber pad, a leather decorative rubber bag, a wheel air dam, a fender, and a foot pad.

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