Thermoplastic elastomer composite material as well as preparation method and application thereof

Abstract

The invention relates to a thermoplastic elastomer composite material as well as a preparation method and application thereof, and belongs to the technical field of compositions of high-molecular compounds. The thermoplastic elastomer composite material disclosed by the invention is prepared from the following components in parts by weight: 15 to 45 parts of styrene thermoplastic elastomer, 1 to 5 parts of ethylene-octylene elastomer, 5 to 30 parts of aliphatic C5 petroleum resin and 13 to 35 parts of rubber plasticizer. The thermoplastic elastomer composite material has good mechanical properties and excellent adsorption performance.

Description

Technical Field

[0001] The present invention relates to the technical field of compositions of polymer compounds, and particularly relates to a thermoplastic elastomer composite material, a preparation method thereof, and an application thereof. Background Art

[0002] Thermoplastic styrene elastomers (TPE) are widely used in the fields of automobiles, toys, medical care, daily consumer goods, etc. due to their good mechanical properties, thermal stability, soft touch, low odor and low emission, safety and non-toxicity. Taking suction cups as an example, their materials mainly include rubber, silica gel, TPE, soft PVC, etc. Among them, rubber has a long processing cycle and a strong odor; the waste of silica gel is difficult to recycle; soft PVC has a strong odor, may contain toxic plasticizers, and the burning treatment of waste products will release toxic substances; TPE is not only environmentally friendly and non-toxic, but also can be quickly processed and formed, and the generated waste can be recycled repeatedly, which has obvious advantages compared with other suction cup materials. However, the load-bearing capacity of suction cups made of TPE is poor, and they are prone to fall off during long-term load-bearing on the tile surface. Summary of the Invention

[0003] The purpose of the present invention is to overcome the deficiencies of the prior art and provide a thermoplastic elastomer composite material, a preparation method thereof, and an application thereof.

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

[0005] In the first aspect, the present invention provides a thermoplastic elastomer composite material, which comprises the following components in parts by weight: 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] The present invention combines ethylene-octene elastomer with aliphatic C5 petroleum resin, and is combined with styrene thermoplastic elastomer. By using the self-adhesion of ethylene-octene elastomer and its good compatibility with styrene thermoplastic elastomer, the adsorption force of the thermoplastic elastomer composite material on the tile is enhanced, and at the same time, the entanglement degree between the 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 can make the molecular chain segments in the thermoplastic elastomer composite material have good flexibility, which can not only enhance the seal to block air and improve the long-term adsorption performance of the thermoplastic elastomer composite material, but also endow the thermoplastic elastomer composite material with good mechanical properties.

[0007] As a preferred embodiment of the thermoplastic elastomer composite of the present invention, the thermoplastic elastomer composite 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] As a preferred embodiment of the thermoplastic elastomer composite of the present invention, the weight-average molecular weight of the styrene thermoplastic elastomer ≥50000. It has been found that when the weight-average molecular weight of the styrene thermoplastic elastomer is greater than or equal to 50000, it can not only better reduce the molecular gap to avoid air molecules entering the suction cup and causing vacuum failure, but also reduce the surface shrinkage marks generated during the injection molding of the product. The weight-average molecular weight of the styrene thermoplastic elastomer can be measured by gel permeation chromatography (GPC).

[0009] As a preferred embodiment of the thermoplastic elastomer composite of the present invention, the weight-average molecular weight of the styrene thermoplastic elastomer is 70000-230000.

[0010] As a preferred embodiment of the thermoplastic elastomer composite of the present invention, the styrene thermoplastic elastomer comprises 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 of the present invention, the ethylene-octene elastomer has a melt mass flow rate of 0.1-5 g / 10 min, preferably 0.5-1.5 g / 10 min, at 190 °C and 2.16 kg according to the ISO 1133-1-2022 standard.

[0012] As a preferred embodiment of the thermoplastic elastomer composite of the present invention, the softening point of the aliphatic C5 petroleum resin is 90-110 °C, and the number-average molecular weight is 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 of the present invention, the components of the thermoplastic elastomer composite further include 0.1-0.5 parts by weight of antioxidant.

[0014] Optionally, the antioxidant may specifically be at least one of 2,6 - di - tert - butyl - 4 - methylphenol, pentaerythritol tetrakis(3 - (3,5 - di - tert - butyl - 4 - hydroxyphenyl)propionate), octadecyl 3 - (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] As 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, naphthenic oil, and aromatic oil.

[0016] In a second aspect, the present invention provides a method for preparing the above - mentioned thermoplastic elastomer composite material, comprising the following steps: mixing the components evenly and then melt - extruding to obtain the thermoplastic elastomer composite material.

[0017] Optionally, a twin - screw extruder can be used for melt - extrusion in the above - mentioned preparation method. The length - to - diameter ratio of the twin - screw extruder is ≥40:1; the rotation speed of the twin - screw extruder is 150 - 400 revolutions per minute, the total feeding of the metering scale is 80 - 300 kg / h; and the temperature of the twin - screw extruder is 140 - 230 °C.

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

[0019] In a fourth aspect, 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] The present invention combines ethylene - octene elastomer with aliphatic C5 petroleum resin and is paired with styrene thermoplastic elastomer. By utilizing the self - adhesiveness of ethylene - octene elastomer and its good compatibility with styrene thermoplastic elastomer, the adsorption force of the thermoplastic elastomer composite material on tiles is enhanced, and at the same time, the entanglement degree 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 can make the molecular chain segments in the thermoplastic elastomer composite material have good flexibility, which can not only enhance the seal to block air and improve the long - term adsorption performance of the thermoplastic elastomer composite material, but also endow the thermoplastic elastomer composite material with good mechanical properties. Specific Embodiments

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

[0023] For other materials, reagents, etc. used in the examples and comparative examples, unless otherwise specified, they can all be obtained through commercial channels.

[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, manufactured by Formosa Plastics Corporation, Taiwan, China, and the grade is Globalprene 9551;

[0027] Styrene thermoplastic elastomer 2:

[0028] Styrene-ethylene-butene-styrene copolymer (SEBS), with a weight-average molecular weight of 90,000, manufactured by Formosa Plastics Corporation, Taiwan, China, and the grade is Globalprene 9550;

[0029] Styrene thermoplastic elastomer 3:

[0030] Styrene-butadiene copolymer (SBS), with a weight-average molecular weight of 70,000, manufactured by Formosa Plastics Corporation, Taiwan, China, and the grade is Globalprene 3546;

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

[0032] Ethylene-octene elastomer 2, with a melt mass flow rate of 1 g / 10 min, manufactured by Dow, and the grade is Engage8100;

[0033] Ethylene-propylene elastomer, with a melt mass flow rate of 1.2 g / 10 min, manufactured by ExxonMobil, and the grade is Vistamaxx 3020;

[0034] Random copolymer polypropylene, manufactured by Formosa Plastics Corporation, Taiwan, China, and the grade is Globalene ST611M;

[0035] Linear low density polyethylene, manufactured by Sinopec, and the grade is DFDA-7042;

[0036] Petroleum resin 1: Aliphatic C5 petroleum resin, with a softening point of 100 °C and a number-average molecular weight of 1180, manufactured by Eastman Chemical Company, USA, and the grade is Piccotac 1100;

[0037] Petroleum Resin 2: Aliphatic C5 petroleum resin, softening point is 100 °C, number average molecular weight is 600, manufacturer is Eastman of the United States, grade is Regalite R 1100;

[0038] Petroleum Resin 3: Aromatic C9 petroleum resin, softening point is 141 °C, number average molecular weight is 1690, manufacturer is Eastman of the United States, grade is Kristalex 5140;

[0039] Rubber Plasticizer 1: Paraffin oil, kinematic viscosity at 40 °C is 90 mm 2 / s, manufacturer is Formosa Plastics, grade is 500N;

[0040] Rubber Plasticizer 2: Paraffin oil, kinematic viscosity at 40 °C is 30 mm 2 / s, manufacturer is Formosa Plastics, grade is 150N;

[0041] Rubber Plasticizer 3: Naphthenic oil, kinematic viscosity at 40 °C is 45 mm 2 / s, manufacturer is Karamay, grade is KN4006;

[0042] The antioxidant is compounded by Irganox 1010 and Irgafos 168 at a mass ratio of 1:1. Both Irganox 1010 and Irgafos 168 are purchased from BASF.

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

[0044] According to the formula, each component is mixed evenly and then added into a twin-screw extruder for melt extrusion to obtain the thermoplastic elastomer composite material; wherein, the temperature of melt extrusion is 140 - 230 °C, and the screw speed of the twin-screw extruder is 150 - 400 revolutions per minute.

[0045] Table 1 Weight parts of each component of the thermoplastic elastomer composite material in Examples 1 - 11

[0046]

[0047]

[0048] Table 2 Weight parts of each component of the thermoplastic elastomer composite material in Comparative Examples 1 - 5

[0049] Comparative Example 1 2 3 4 5 Styrene Thermoplastic Elastomer 1 30 30 30 30 30 Ethylene-Octene Elastomer 1 / / / 3 / Ethylene-Propylene Elastomer 3 / / / / Copolymerized 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 Antioxidant 0.2 0.2 0.2 0.2 0.2

[0050] 3. Performance testing

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

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

[0053] 3) Adsorption performance: The thermoplastic elastomer composite material was injection molded into a hanging suction cup (suction cup diameter: 65 mm). Then the hanging suction cup was adsorbed on the surface of the ceramic tile and a weight of 3 kg was hung. After 30 days, observe whether the hanging suction cup fails to maintain vacuum and drops; if it does not drop, measure the slip distance of the hanging suction cup on the surface of the ceramic tile. The shorter the slip distance, the better the adsorption performance of the suction cup.

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

[0055]

[0056] According to the data in Table 3, it can be seen that the Shore hardness of the thermoplastic elastomer composite materials in Examples 1-11 is ≤ 42, the tensile strength is ≥ 4.2 MPa, and at the same time, none of them dropped after 30 days of the suction cup hanging test and the slip distance is ≤ 10 mm, indicating that the thermoplastic elastomer composite materials of the present invention have both good mechanical properties and excellent adsorption performance. From Comparative Examples 1-3 and Comparative Example 5, it can be found that when other resins or elastomers except ethylene-octene elastomer are combined with styrene thermoplastic elastomer, although the tensile strength of the thermoplastic elastomer composite material can be improved and it has good mechanical properties, its adsorption performance cannot be improved; and further from Comparative Example 4, it can be found that when aromatic C9 petroleum resin is used to replace aliphatic C5 petroleum resin and combined with styrene thermoplastic elastomer and ethylene-octene elastomer, it is difficult to effectively improve the adsorption performance of the thermoplastic elastomer composite material.

[0057] Finally, it should be noted that the above examples are only used to illustrate the technical solutions of the present invention rather than to limit the protection scope of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that the technical solutions of the present invention can be modified or equivalently replaced 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: The composition comprises the following components by weight: 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.

2. The thermoplastic elastomer composite material according to 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 according to claim 1, characterized in that The weight average molecular weight of the styrene thermoplastic elastomer is ≥50,000.

4. The thermoplastic elastomer composite material according to 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 according to claim 1, characterized in that The styrene thermoplastic elastomer includes at least one of SEBS, SBS and SEEPS.

6. The thermoplastic elastomer composite material according to claim 1, characterized in that The ethylene-octene elastomer adopts 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; And / or, the aliphatic C5 petroleum resin has a softening point of 90-110° C. and a number average molecular weight of 500-1500.

7. The thermoplastic elastomer composite material according to claim 1, characterized in that The components of the thermoplastic elastomer composite material also include 0.1 to 0.5 parts by weight of an antioxidant; And / or, the rubber plasticizer includes at least one of silicone oil, paraffin oil, cycloalkane oil, and aromatic hydrocarbon oil.

8. The method for preparing the thermoplastic elastomer composite material according to any one of claims 1 to 7, characterized in that: The method comprises the following steps: mixing the components uniformly and then melting and extruding the components to obtain a thermoplastic elastomer composite material.

9. Use of the thermoplastic elastomer composite material according to any one of claims 1 to 7 in the preparation of a suction cup.

10. A suction cup, characterized in that: The thermoplastic elastomer composite material is mainly made of any one of claims 1 to 7.

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