Thermoplastic elastomer composite material, method for preparing same, and use thereof

Abstract

The present application relates to a kind of thermoplastic elastomer composite material and its preparation method and application, belong to the composition technical field of polymer compound.The thermoplastic elastomer composite material of the present application includes the following components by weight fraction:styrene thermoplastic elastomer 15~45 parts, ethylene-octene elastomer 1~5 parts, aliphatic C5 petroleum resin 5~30 parts, rubber plasticizer 13~35 parts.The thermoplastic elastomer composite material has good mechanical properties and excellent adsorption performance.

Description

Technical Field

[0001] This invention relates to the field of polymer composition technology, and more particularly to a thermoplastic elastomer composite material, its preparation method, and its application. Background Technology

[0002] Thermoplastic styrene elastomers (TPEs) are widely used in the automotive, toy, medical, and consumer goods industries due to their excellent mechanical properties, thermal stability, soft touch, low odor and emission, and safety and non-toxicity. Taking suction cups as an example, their materials mainly include rubber, silicone, TPE, and soft PVC. Rubber has a long processing cycle and a strong odor; silicone scraps are difficult to recycle; soft PVC has a strong odor, may contain toxic plasticizers, and incinerating waste releases toxic substances. TPE is not only environmentally friendly and non-toxic, but it can also be quickly processed and molded, and the resulting scraps can be repeatedly recycled, giving it a significant advantage over other suction cup materials. However, suction cups made of TPE have poor load-bearing capacity and are prone to detaching from ceramic tile surfaces under prolonged weight. Summary of the Invention

[0003] The purpose of this invention is to overcome the shortcomings of the prior art and provide a thermoplastic elastomer composite material, its preparation method, and its application.

[0004] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0005] In a first aspect, the present invention provides a thermoplastic elastomer composite material, comprising, by weight, the following components: 15-45 parts of styrene thermoplastic elastomer, 1-5 parts of ethylene-octene elastomer, 5-30 parts of aliphatic C5 petroleum resin, and 13-35 parts of rubber plasticizer.

[0006] This invention combines ethylene-octene elastomer with aliphatic C5 petroleum resin and styrene thermoplastic elastomer. Utilizing the self-adhesive properties of the ethylene-octene elastomer and its good compatibility with the styrene thermoplastic elastomer, the adsorption force of the thermoplastic elastomer composite material on ceramic tiles is enhanced. Simultaneously, the degree of entanglement between molecular chains in the thermoplastic elastomer composite material is increased to prevent external air from entering the suction cup and causing vacuum failure, thereby improving the long-term adsorption performance of the thermoplastic elastomer composite material. The addition of a specific petroleum resin gives the molecular chain segments in the thermoplastic elastomer composite material good flexibility, which not only enhances the seal to block air and improve the long-term adsorption performance of the high-thermoplastic elastomer composite material, but also endows the thermoplastic elastomer composite material with good mechanical properties.

[0007] As a preferred embodiment of the thermoplastic elastomer composite material of the present invention, the thermoplastic elastomer composite material comprises the following components in parts by weight: 25-35 parts of styrene thermoplastic elastomer, 2-4 parts of ethylene-octene elastomer, 10-25 parts of aliphatic C5 petroleum resin, and 20-30 parts of rubber plasticizer.

[0008] In a preferred embodiment of the thermoplastic elastomer composite material of the present invention, the weight-average molecular weight of the styrene thermoplastic elastomer is ≥50,000. Studies have found that when the weight-average molecular weight of the styrene thermoplastic elastomer is greater than or equal to 50,000, it not only better reduces intermolecular gaps to prevent air molecules from entering the suction cup and causing vacuum failure, but also reduces surface shrinkage marks during injection molding. The weight-average molecular weight of the styrene thermoplastic elastomer can be measured using gel permeation chromatography (GPC).

[0009] In a preferred embodiment of the thermoplastic elastomer composite material of the present invention, the weight-average molecular weight of the styrene thermoplastic elastomer is 70,000 to 230,000.

[0010] As a preferred embodiment of the thermoplastic elastomer composite material of the present invention, the styrene thermoplastic elastomer includes at least one of SEBS, SBS, and SEEPS; wherein, SEBS refers to styrene-ethylene-butene-styrene copolymer, SBS refers to styrene-butadiene copolymer, and SEEPS refers to styrene-poly(ethylene / ethylene / propylene)-styrene copolymer.

[0011] As a preferred embodiment of the thermoplastic elastomer composite material of the present invention, the ethylene-octene elastomer adopts the ISO 1133-1-2022 standard, and the melt mass flow rate at 190°C and 2.16 kg is 0.1 to 5 g / 10 min, preferably 0.5 to 1.5 g / 10 min.

[0012] In a preferred embodiment of the thermoplastic elastomer composite material of the present invention, the aliphatic C5 petroleum resin has a softening point of 90–110°C and a number-average molecular weight of 500–1500. Optionally, the softening point of the aliphatic C5 petroleum resin is specifically 95°C, 100°C, or 105°C.

[0013] As a preferred embodiment of the thermoplastic elastomer composite material of the present invention, the thermoplastic elastomer composite material further includes 0.1 to 0.5 parts by weight of antioxidant.

[0014] Optionally, the antioxidant may be at least one of 2,6-di-tert-butyl-4-methylphenol, pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, tris(2,4-di-tert-butylphenyl)phosphite, and antioxidant 412S.

[0015] In a preferred embodiment of the thermoplastic elastomer composite material of the present invention, the rubber plasticizer includes at least one of silicone oil, paraffin oil, cycloalkane oil, and aromatic hydrocarbon oil.

[0016] Secondly, the present invention provides a method for preparing the above-mentioned thermoplastic elastomer composite material, comprising the following steps: mixing each component evenly and then melting and extruding to obtain the thermoplastic elastomer composite material.

[0017] Optionally, the above preparation method can be carried out by melt extrusion using a twin-screw extruder, wherein the length-to-diameter ratio of the twin-screw extruder is ≥40:1; the rotational speed of the twin-screw extruder is 150-400 rpm; the total feed rate of the weighing scale is 80-300 kg / h; and the temperature of the twin-screw extruder is 140-230℃.

[0018] Thirdly, the present invention provides the application of the above-mentioned thermoplastic elastomer composite material in the preparation of suction cups.

[0019] Fourthly, the present invention provides a suction cup, which is mainly made of the above-mentioned thermoplastic elastomer composite material.

[0020] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0021] This invention combines ethylene-octene elastomer with aliphatic C5 petroleum resin and styrene thermoplastic elastomer. Utilizing the self-adhesive properties of the ethylene-octene elastomer and its good compatibility with the styrene thermoplastic elastomer, the adsorption force of the thermoplastic elastomer composite material on ceramic tiles is enhanced. Simultaneously, the degree of entanglement between molecular chains in the thermoplastic elastomer composite material is increased to prevent external air from entering the suction cup and causing vacuum failure, thereby improving the long-term adsorption performance of the thermoplastic elastomer composite material. The addition of a specific petroleum resin gives the molecular chain segments in the thermoplastic elastomer composite material good flexibility, which not only enhances the seal to block air and improve the long-term adsorption performance of the high-thermoplastic elastomer composite material, but also endows the thermoplastic elastomer composite material with good mechanical properties. Detailed Implementation

[0022] To better illustrate the purpose, technical solution, and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments.

[0023] Unless otherwise specified, all other materials, reagents, etc. used in the examples and comparative examples are commercially available.

[0024] 1. Raw materials and reagents

[0025] Styrene thermoplastic elastomer 1:

[0026] Styrene-ethylene-butene-styrene copolymer (SEBS), with a weight-average molecular weight of 220,000, is manufactured by Lee Chang Yung Co., Ltd. in Taiwan, China, and its brand name is Globalprene 9551.

[0027] Styrene thermoplastic elastomer 2:

[0028] Styrene-ethylene-butene-styrene copolymer (SEBS), with a weight average molecular weight of 90,000, is manufactured by Lee Chang Yung Co., Ltd. in Taiwan, China, and its brand name is Globalprene 9550.

[0029] Styrene thermoplastic elastomer 3:

[0030] Styrene-butadiene copolymer (SBS), weight average molecular weight 70,000, manufactured by Lee Chang Yung Co., Ltd. in Taiwan, China, brand name Globalprene 3546;

[0031] Ethylene-octene elastomer 1, with a melt mass flow rate of 1 g / 10 min, is manufactured by Dow and its brand name is Engage8842;

[0032] Ethylene-octene elastomer 2, with a melt mass flow rate of 1 g / 10 min, is manufactured by Dow and its brand name is Engage 8100;

[0033] Ethylene-propylene elastomer, melt flow rate of 1.2 g / 10 min, manufactured by ExxonMobil, brand name Vistamaxx 3020;

[0034] Copolymer polypropylene, manufactured by Lee Chang Yung, Taiwan, China, brand name Globalene ST611M;

[0035] Linear low-density polyethylene, manufactured by Zhou Petrochemical, grade DFDA-7042;

[0036] Petroleum resin 1: Aliphatic C5 petroleum resin, softening point 100℃, number average molecular weight 1180, manufacturer Eastman, USA, brand name Piccotac 1100;

[0037] Petroleum resin 2: Aliphatic C5 petroleum resin, softening point 100℃, number average molecular weight 600, manufacturer Eastman, USA, brand name Regalite R 1100;

[0038] Petroleum resin 3: Aromatic C9 petroleum resin, softening point 141℃, number average molecular weight 1690, manufactured by Eastman, USA, brand name Kristalex 5140;

[0039] Rubber plasticizer 1: Paraffin oil, kinematic viscosity at 40℃ is 90 mm. 2 / s, manufactured by Formosa Plastics, grade 500N;

[0040] Rubber plasticizer 2: Paraffin oil, kinematic viscosity at 40℃ is 30 mm. 2 / s, manufactured by Formosa Plastics, grade 150N;

[0041] Rubber plasticizer 3: naphthenic oil, kinematic viscosity at 40℃ is 45 mm. 2 / s, manufactured in Karamay, brand name KN4006;

[0042] The antioxidant is a compound of Irganox 1010 and Irgafos 168 in a mass ratio of 1:1. Both Irganox 1010 and Irgafos 168 were purchased from BASF.

[0043] 2. Preparation method of the thermoplastic elastomer composite material of the present invention

[0044] According to the formula, the components are mixed evenly and then added to a twin-screw extruder for melt extrusion to obtain a thermoplastic elastomer composite material; wherein, the melt extrusion temperature is 140-230℃ and the screw speed of the twin-screw extruder is 150-400 rpm.

[0045] Table 1 shows the weight parts of each component in the thermoplastic elastomer composite materials of Examples 1-11.

[0046]

[0047]

[0048] Table 2 shows the weight parts of each component in the thermoplastic elastomer composites of Comparative Examples 1–5.

[0049] Styrene thermoplastic elastomer 1 30 30 30 30 30 Ethylene-octene elastomer 1 / / / 3 / Ethylene-propylene elastomer 3 / / / / Copolymer polypropylene / 3 / / / Linear low-density polyethylene / / 3 / / Petroleum resin 1 18 18 18 / 18 Petroleum resin 3 / / / 18 / Rubber plasticizer 1 24 24 24 24 24 antioxidants 0.2 0.2 0.2 0.2 0.2

[0050] 3. Performance Testing

[0051] 1) Shore hardness: The thermoplastic elastomer composite material is injection molded into square plates with length, width and height of 100mm×100mm×2mm at 180℃. After being placed at room temperature for 24h, three square plates are stacked to form a sample with a thickness of 6mm. The hardness of the sample is measured using a Shore A hardness tester.

[0052] 2) Tensile strength: Tested according to ISO 37-2017 standard, with a sample size of Type 1A and a tensile rate of 500 mm / min.

[0053] 3) Adsorption performance: Thermoplastic elastomer composite material is injection molded into a hanging suction cup (suction cup diameter is 65mm), and then the hanging suction cup is adsorbed on the surface of the tile and a weight of 3kg is suspended. After 30 days, observe whether the hanging suction cup fails to vacuum and falls off. If it does not fall off, measure the sliding distance of the hanging suction cup on the surface of the tile. The shorter the sliding distance, the better the adsorption performance of the suction cup.

[0054] Table 3 shows the properties of the thermoplastic elastomer composite materials in each example and comparative example.

[0055]

[0056] According to the data in Table 3, the Shore hardness of the thermoplastic elastomer composites in Examples 1-11 is ≤42, the tensile strength is ≥4.2MPa, and they did not fall off after 30 days of suction cup suspension testing with a slippage distance ≤10mm, indicating that the thermoplastic elastomer composites of the present invention have both good mechanical properties and excellent adsorption properties. Based on Comparative Examples 1-3 and Comparative Example 5, it can be found that combining other resins or elastomers besides ethylene-octene elastomers with styrene thermoplastic elastomers can improve the tensile strength of the thermoplastic elastomer composites, giving them better mechanical properties, but cannot improve their adsorption properties. Furthermore, according to Comparative Example 4, using aromatic C9 petroleum resin instead of aliphatic C5 petroleum resin in combination with styrene thermoplastic elastomers and ethylene-octene elastomers is difficult to effectively improve the adsorption properties of the thermoplastic elastomer composites.

[0057] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A thermoplastic elastomer composite material, characterized in that, By weight, it includes the following components: 15-45 parts of styrene thermoplastic elastomer, 1-5 parts of ethylene-octene elastomer, 5-30 parts of aliphatic C5 petroleum resin, and 13-35 parts of rubber plasticizer. The ethylene-octene elastomer conforms to ISO 1133-1-2022 standard, and its melt mass flow rate at 190℃ and 2.16 kg is 0.1~5 g / 10 min. The aliphatic C5 petroleum resin has a softening point of 90~110℃ and a number-average molecular weight of 600~1500.

2. The thermoplastic elastomer composite material as described in claim 1, characterized in that, The thermoplastic elastomer composite material comprises the following components in parts by weight: 25-35 parts of styrene thermoplastic elastomer, 2-4 parts of ethylene-octene elastomer, 10-25 parts of aliphatic C5 petroleum resin, and 20-30 parts of rubber plasticizer.

3. The thermoplastic elastomer composite material as described in claim 1, characterized in that, The weight-average molecular weight of the styrene thermoplastic elastomer is ≥50,000.

4. The thermoplastic elastomer composite material as described in claim 3, characterized in that, The weight-average molecular weight of the styrene thermoplastic elastomer is 70,000 to 230,000.

5. The thermoplastic elastomer composite material as described in claim 1, characterized in that, The styrene thermoplastic elastomer includes at least one of SEBS, SBS, and SEEPS.

6. The thermoplastic elastomer composite material as described in claim 1, characterized in that, The thermoplastic elastomer composite material also includes 0.1 to 0.5 parts by weight of antioxidant; And / or, the rubber plasticizer includes at least one of silicone oil, paraffin oil, naphthenic oil, and aromatic oil.

7. A method for preparing the thermoplastic elastomer composite material according to any one of claims 1 to 6, characterized in that, The process includes the following steps: after mixing the components evenly, the mixture is melt-extruded to obtain a thermoplastic elastomer composite material.

8. The application of the thermoplastic elastomer composite material according to any one of claims 1 to 6 in the preparation of suction cups.

9. A suction cup, characterized in that, It is mainly made of the thermoplastic elastomer composite material as described in any one of claims 1 to 6.

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