Thermoplastic Elastomer and Its Preparation Method and Application

Abstract

The present application relates to a thermoplastic elastomer, which comprises the following components by mass parts: 40 to 70 parts of styrene-butadiene-styrene block copolymer, 15 to 50 parts of butadiene maleic anhydride copolymer, 5 to 10 parts of compatibilizer, 5 to 10 parts of terpene resin, and 0.05 to 0.2 parts of antioxidant. The above thermoplastic elastomer has a relatively high static and dynamic friction coefficient and has good anti-slip performance, and is very suitable for preparing anti-slip materials.

Description

Technical Field

[0001] The present application relates to the technical field of polymer functional materials, and in particular to a thermoplastic elastomer and a preparation method and application thereof. Background Art

[0002] At present, most of the common anti-slip materials on the market are made of traditional rubber and its modified materials, and are mainly used in tires, shoes and sports industrial products, with good anti-slip or anti-slip properties. However, high-performance rubber with high elasticity and high strength needs to go through plasticizing, mixing, calendering and vulcanization to obtain. The preparation process from raw rubber to rubber products is very complicated, and the production process has problems such as high cost, high energy consumption, high pollution, low efficiency, difficulty in recycling, and difficulty in large-scale use.

[0003] Thermoplastic elastomer is a polymer material that has the characteristics of both vulcanized rubber and thermoplastic plastics. Thermoplastic elastomer can show the high elasticity of vulcanized rubber at room temperature, and can be easily processed and formed like thermoplastic plastics at high temperature. Due to the special properties of thermoplastic elastomer, thermoplastic elastomer is also called "third generation rubber". Since it does not require vulcanization and the molding process is simple, compared with traditional vulcanized rubber, the industrial production process of thermoplastic elastomer is shortened by 1 / 4, energy consumption is saved by 25% to 40%, and efficiency is increased by 10 to 20 times, which can be regarded as another technological revolution in the rubber industry. In addition, thermoplastic elastomer can be processed and recycled many times, which can save the petroleum resources needed for synthesizing polymer materials and reduce environmental pollution. In general, thermoplastic elastomer is a new material with great application value.

[0004] However, the coefficient of static and dynamic friction of thermoplastic elastomer materials is very low when encountering water, surfactant solutions or on ice, and its anti-slip performance is difficult to reach the performance level of traditional rubber materials. Therefore, when using thermoplastic elastomer as a raw material to prepare products with anti-slip performance, it is more necessary to rely on the structure of the product to improve the anti-slip performance of the product. However, many application scenarios cannot achieve the anti-slip effect by relying solely on the structure, resulting in the application of thermoplastic elastomers in scenarios with anti-slip requirements. How to improve its anti-slip performance is a major challenge in improving the performance of thermoplastic elastomer materials, and the market prospects of this material are also very broad. Summary of the invention

[0005] Based on this, it is necessary to provide a thermoplastic elastomer and a preparation method and application thereof that can improve the anti-slip performance of the material.

[0006] An embodiment of the present application provides a thermoplastic elastomer, which comprises the following components by weight:

[0007]

[0008] In one embodiment, the viscosity of the styrene-butadiene-styrene block copolymer in a toluene solution at 23 °C and 25% is ≥ 500 Pa·s;

[0009] The content of butadiene in the styrene-butadiene-styrene block copolymer is ≥ 50%.

[0010] In one embodiment, the content of maleic anhydride in the butadiene-maleic anhydride copolymer is ≥ 8%;

[0011] The number average molecular weight of the butadiene-maleic anhydride copolymer is ≤ 10,000.

[0012] In one embodiment, the compatibilizer includes one or more of styrene-maleic anhydride copolymer, ethylene-methyl acrylate copolymer, and ethylene-n-butyl acrylate copolymer.

[0013] In one embodiment, the softening point of the terpene resin is ≤ 120 °C.

[0014] In one embodiment, the antioxidant includes one or more of tris(2,4-di-tert-butylphenyl) phosphite, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], and n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate.

[0015] One embodiment of the present application also provides a method for preparing a thermoplastic elastomer as described in any of the above embodiments, including the following steps:

[0016] First, mix the styrene-butadiene-styrene block copolymer and the butadiene-maleic anhydride copolymer, and let it stand to obtain a first mixture;

[0017] Then, mix the first mixture with the compatibilizer, the terpene resin, and the antioxidant to obtain a second mixture;

[0018] Extrude and pelletize the second mixture.

[0019] In one embodiment, the standing time is ≥ 168 hours.

[0020] In one embodiment, extrusion is carried out using a twin-screw extruder, the extrusion temperature is 180 °C to 200 °C, and the rotation speed is 150 r / min to 300 r / min;

[0021] The length-diameter ratio of the twin-screw extruder is 24:1 to 36:1.

[0022] One embodiment of the present application also provides the application of the thermoplastic elastomer as described in any of the above embodiments in the preparation of anti-slip materials.

[0023] The above-mentioned thermoplastic elastomer is composed of styrene-butadiene-styrene block copolymer, butadiene maleic anhydride copolymer, compatibilizer, terpene resin and antioxidant in specific mass parts. It has relatively high dynamic and static friction coefficients and good anti-slip performance, and is very suitable for preparing anti-slip materials. Detailed implementation manners

[0024] To facilitate the understanding of the present application, the present application will be more comprehensively described below in conjunction with embodiments. The present application can be implemented in many different forms and is not limited to the embodiments described in the present application. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure content of the present application more thorough and comprehensive.

[0025] Unless otherwise defined, all technical and scientific terms used in the present application have the same meaning as commonly understood by those skilled in the technical field to which the present application belongs. The terms used in the specification of the present application are only for the purpose of describing specific embodiments and are not intended to limit the present application. The term "and / or" used in the present application includes any and all combinations of one or more of the related listed items.

[0026] In the present application, among the technically characterized described in an open-ended manner, there are included closed technical solutions composed of the listed features, as well as open technical solutions including the listed features.

[0027] In the present application, terms such as "multiple", "diverse", "multiple times", "pluralistic", etc., unless otherwise specified, refer to a quantity greater than 2 or equal to 2. For example, "one or more" means one or greater than or equal to two.

[0028] In the present application, "preferred", "better", "more preferable", "preferably" are only for describing embodiments or examples with better effects, and it should be understood that they do not constitute a limitation on the protection scope of the present invention.

[0029] In the present application, "further", "even further", "especially", etc. are used for descriptive purposes and indicate differences in content, but should not be construed as a limitation on the protection scope of the present invention.

[0030] In the present application, "optionally", "optional", "optional" mean that it can be either present or absent, that is, it refers to any one of the two parallel options of "present" or "absent". If "optional" appears multiple times in a technical solution, unless otherwise specified and there are no contradictions or mutual restrictions, each "optional" is independent of each other.

[0031] Except as otherwise indicated in the operating examples or otherwise stated, all numbers used in the specification and claims to represent the amounts of ingredients, physical and chemical properties, etc. are understood to be adjusted by the term "about" in all cases. For example, therefore, unless otherwise stated, the numerical parameters listed in the above specification and the appended claims are approximate values, and those skilled in the art can appropriately change these approximate values to obtain the desired characteristics by using the teachings disclosed herein. The use of numerical ranges expressed by endpoints includes all numbers within the range and any ranges within that range. For example, 1 to 5 includes 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4, and 5, and so on.

[0032] The temperature parameters in this application, unless otherwise specified, allow both constant temperature treatment and fluctuations within a certain temperature range. It should be understood that the constant temperature treatment allows the temperature to fluctuate within the accuracy range controlled by the instrument. Fluctuations within ranges such as ±5°C, ±4°C, ±3°C, ±2°C, and ±1°C are allowed.

[0033] An embodiment of the present application provides a thermoplastic elastomer, which, by mass parts, comprises the following components:

[0034]

[0035] The styrene-butadiene-styrene block copolymer (abbreviated as SBS) has a large surface friction coefficient, good low-temperature performance, and good resilience.

[0036] In one of the embodiments, the viscosity of the styrene-butadiene-styrene block copolymer in a toluene solution at 23°C and 25% is ≥500 Pa·s. Further, the content of butadiene in the styrene-butadiene-styrene block copolymer is ≥50%. The styrene-butadiene-styrene block copolymer within this range has suitable low-temperature performance, resilience, and a large surface friction coefficient. Preferably, the styrene-butadiene-styrene block copolymer (SBS) is selected from at least one of SBS3546 and SBS3501 of Lee Chang Yung.

[0037] The butadiene maleic anhydride copolymer can lower the glass transition temperature (Tg) of the styrene-butadiene-styrene block copolymer (SBS), can also reduce the hardness of the material and increase the fluidity of the material, which is beneficial to improving the processing performance of the material. Further, the butadiene maleic anhydride copolymer itself has an anti-wet and anti-slip effect, and adding the butadiene maleic anhydride copolymer to the material can further increase the dynamic and static friction coefficients of the thermoplastic elastomer.

[0038] In one embodiment, the content of maleic anhydride in the butadiene maleic anhydride copolymer is ≥ 8%. Further, the number average molecular weight (Mn) of the butadiene maleic anhydride copolymer is ≤ 10,000. The blending of the butadiene maleic anhydride copolymer within this condition with SBS can significantly improve the anti-slip performance of the thermoplastic elastomer. Preferably, the butadiene maleic anhydride copolymer is selected from at least one of Ricon 130MA8 and Ricon130MA13 of CRAY VALIEY.

[0039] The compatibilizer can improve the compatibility between SBS and the butadiene maleic anhydride copolymer, thereby overall improving the wear resistance of the thermoplastic elastomer. In one embodiment, the compatibilizer includes one or more of styrene maleic anhydride copolymer, ethylene methyl acrylate copolymer (abbreviation: EMA), and ethylene-n-butyl acrylate copolymer (abbreviation: EBA). Preferably, the compatibilizer is selected from styrene maleic anhydride copolymer, and further preferably, from XIBOND X250. Preferably, the compatibilizer is selected from ethylene methyl acrylate copolymer (EMA), and further preferably, from 1125AC of DuPont.

[0040] The inventors found that in the traditional process for preparing thermoplastic elastomers, the commonly used resin is C5 or C9 resin. However, the polarity of C5 and C9 resins is very weak, and their compatibility with hydrogenated styrene-butadiene block copolymer (abbreviation: SEBS) is very good. But when C5 or C9 resin is used in the SBS system, the compatibility significantly deteriorates, which has an adverse effect on the wear resistance, anti-slip, weather resistance and other properties of the thermoplastic elastomer. Therefore, the resin selected by the inventors is terpene resin. The terpene resin itself has polarity and better compatibility with SBS with higher polarity than SEBS, which can improve the cohesion and weather resistance of the SBS system. The compatibility between the terpene resin and SBS and the butadiene maleic anhydride copolymer is enhanced, making the thermoplastic elastomer more wear-resistant.

[0041] In one embodiment, the softening point of the terpene resin is ≤ 120 °C. When the softening point of the terpene resin is within this range, it is beneficial to further improve the compatibility with SBS and the butadiene maleic anhydride copolymer. Preferably, the terpene resin is selected from LHTB1100 of Maoming Luhua.

[0042] The antioxidant is beneficial to prevent the thermoplastic elastomer from oxidizing and deteriorating. In one embodiment, the antioxidant includes one or more of tris(2,4-di-tert-butylphenyl) phosphite, pentaerythritol tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], and n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate. Preferably, the antioxidant is selected from one or more of antioxidant 168, antioxidant 1010, and antioxidant 1076 of BASF.

[0043] One embodiment of the present application further provides a method for preparing a thermoplastic elastomer as described in any of the above embodiments, comprising the following steps:

[0044] First, mix the styrene-butadiene-styrene block copolymer and the butadiene maleic anhydride copolymer, and let it stand still to obtain a first mixture;

[0045] Then, mix the first mixture with a compatibilizer, a terpene resin, and an antioxidant to obtain a second mixture;

[0046] Extrude and granulate the second mixture.

[0047] Further, the standing time is ≥168 hours.

[0048] In one embodiment, during the process of obtaining the first mixture, in the mixing step, the mixing efficiency is improved by stirring. Further, the stirring is carried out in a horizontal mixer, the stirring rate is 20 r / min to 40 r / min, and the stirring time is 5 min to 10 min.

[0049] In one embodiment, during the process of obtaining the second mixture, in the mixing step, the mixing efficiency is improved by stirring. Further, the stirring is carried out in a horizontal mixer, the stirring rate is 40 r / min to 60 r / min, and the stirring time is 10 min to 15 min.

[0050] In one embodiment, a twin-screw extruder is used for extrusion, the extrusion temperature is 180°C to 200°C, and the rotation speed is 150 r / min to 300 r / min. Further, the length-diameter ratio of the twin-screw extruder is 24:1 to 36:1.

[0051] In one embodiment, homogenization is further included after the steps of extrusion and granulation.

[0052] The preparation method of the thermoplastic elastomer provided by one embodiment of the present application has a simple process flow, low requirements for equipment, and is suitable for large-scale industrial production.

[0053] Further, through reasonable proportioning of each component, the prepared thermoplastic elastomer has a high dynamic and static friction coefficient, very good wear resistance and anti-slip performance. Especially, the addition of the butadiene maleic anhydride copolymer during the preparation process greatly enhances the anti-slip performance of the thermoplastic elastomer material. Moreover, the prepared thermoplastic elastomer also has excellent properties such as good elasticity, high transparency, good demolding effect, high tensile strength, and high elongation at break. Adding an antioxidant externally during the preparation process further improves the anti-caking performance of the thermoplastic elastomer material. The thermoplastic elastomer material provided by the present application does not contain toxic auxiliaries and free phthalates, so it also has the advantages of long-term use and recyclability.

[0054] An embodiment of the present application also provides the application of the thermoplastic elastomer in any of the above embodiments in the preparation of anti-slip materials. Further, the anti-slip materials can be, for example but not limited to, tires, shoe materials, and other sports industrial products, etc.

[0055] The thermoplastic elastomer material provided by the present application has high static and dynamic friction coefficients in different medium application scenarios such as water, ice cubes, and 50% surfactant, and has excellent wear resistance, and is suitable for use in wet, ice surfaces or environments with anti-slip requirements containing surfactants. The above thermoplastic elastomer meets the environmental protection requirements of ROHS, REACH, and EN71-3 tested by a third-party testing institution.

[0056] The following further elaborates on the thermoplastic elastomer of the present application, its preparation method, and application in combination with specific examples and comparative examples. It can be understood that in specific examples, unless otherwise specified, all raw materials can be obtained from ordinary commercial sources.

[0057] Among them, the main parameters of the sources of some raw materials are shown in Table 1 below.

[0058] Table 1 Main parameters of some raw materials

[0059]

[0060]

[0061] The parts in the following examples are parts by mass.

[0062] Example 1

[0063] After uniformly stirring 30 parts of SBS 3501, 10 parts of SBS 3546, and 50 parts of butadiene maleic anhydride copolymer Ricon130MA8, let it stand for more than 168 hours, and stir for 5 minutes at room temperature under the condition of a rotation speed of 20 r / min to obtain a first mixture;

[0064] Mix the first mixture with 5 parts of compatibilizer styrene maleic anhydride copolymer, 5 parts of terpene resin, and 0.05 part of antioxidant (a mixed antioxidant formed by mixing 168 and 1076 by a mass ratio of 1:1), and stir at room temperature under the condition of a rotation speed of 40 r / min for 10 minutes to obtain a second mixture;

[0065] Place the second mixture in a twin-screw extruder with a temperature of 190 °C, a rotation speed of 150 r / min, and a length-to-diameter ratio of 24:1 for extrusion and granulation to obtain a thermoplastic elastomer material.

[0066] Example 2

[0067] After uniformly stirring 30 parts of SBS 3501, 10 parts of SBS 3546 and 45 parts of butadiene maleic anhydride copolymer Ricon130MA8, let it stand for more than 168 hours, and stir for 10 min at room temperature with a rotation speed of 40 r / min to obtain the first mixture;

[0068] Mix the first mixture with 10 parts of compatibilizer styrene maleic anhydride copolymer, 5 parts of terpene resin, and 0.05 part of antioxidant (a mixed antioxidant formed by mixing 168 and 1076 in a mass ratio of 1:1), and stir at room temperature with a rotation speed of 40 r / min for 15 min to obtain the second mixture;

[0069] Place the second mixture in a twin-screw extruder with a temperature of 190 °C, a rotation speed of 150 r / min, and a length-diameter ratio of 24:1 for extrusion and pelletization to obtain a thermoplastic elastomer material.

[0070] Example 3

[0071] After uniformly stirring 25 parts of SBS 3501, 20 parts of SBS 3546 and 45 parts of butadiene maleic anhydride copolymer Ricon130MA8, let it stand for more than 168 hours, and stir for 10 min at room temperature with a rotation speed of 40 r / min to obtain the first mixture;

[0072] Mix the first mixture with 5 parts of compatibilizer EMA, 5 parts of terpene resin, and 0.2 part of antioxidant (a mixed antioxidant formed by mixing 168 and 1076 in a mass ratio of 1:1), and stir at room temperature with a rotation speed of 60 r / min for 15 min to obtain the second mixture;

[0073] Place the second mixture in a twin-screw extruder with a temperature of 190 °C, a rotation speed of 300 r / min, and a length-diameter ratio of 36:1 for extrusion and pelletization to obtain a thermoplastic elastomer material.

[0074] Example 4

[0075] After uniformly stirring 20 parts of SBS 3501, 30 parts of SBS 3546 and 35 parts of butadiene maleic anhydride copolymer Ricon130MA8, let it stand for more than 168 hours, and stir for 10 min at room temperature with a rotation speed of 40 r / min to obtain the first mixture;

[0076] Mix the first mixture with 5 parts of compatibilizer EMA, 10 parts of terpene resin, and 0.2 part of antioxidant (a mixed antioxidant formed by mixing 168 and 1076 in a mass ratio of 1:1), and stir at room temperature with a rotation speed of 60 r / min for 15 min to obtain the second mixture;

[0077] The second mixture is extruded and pelletized in a twin-screw extruder at a temperature of 190 °C, a rotation speed of 300 r / min, and a length-diameter ratio of 36:1 to obtain a thermoplastic elastomer material.

[0078] Example 5

[0079] 10 parts of SBS 3501, 60 parts of SBS 3546, and 15 parts of butadiene maleic anhydride copolymer Ricon130MA13 are stirred evenly and then left standing for more than 168 hours, and stirred for 10 min at room temperature under the condition of a rotation speed of 40 r / min to obtain a first mixture;

[0080] The first mixture is mixed with 5 parts of compatibilizer EMA, 5 parts of terpene resin, and 0.05 part of antioxidant (a mixed antioxidant formed by mixing 168 and 1076 in a mass ratio of 1:1) and stirred for 15 min at room temperature under the condition of a rotation speed of 60 r / min to obtain a second mixture;

[0081] The second mixture is extruded and pelletized in a twin-screw extruder at a temperature of 190 °C, a rotation speed of 300 r / min, and a length-diameter ratio of 36:1 to obtain a thermoplastic elastomer material.

[0082] Comparative Example 1

[0083] 30 parts of SBS 3501, 10 parts of SBS 3546, and 50 parts of naphthenic oil KN4006 are stirred evenly and then left standing for more than 168 hours, and stirred for 5 min at room temperature under the condition of a rotation speed of 20 r / min to obtain a first mixture;

[0084] The first mixture is mixed with 5 parts of compatibilizer styrene maleic anhydride copolymer, 5 parts of terpene resin, and 0.05 part of antioxidant (a mixed antioxidant formed by mixing 168 and 1076 in a mass ratio of 1:1) and stirred for 10 min at room temperature under the condition of a rotation speed of 40 r / min to obtain a second mixture;

[0085] The second mixture is extruded and pelletized in a twin-screw extruder at a temperature of 190 °C, a rotation speed of 150 r / min, and a length-diameter ratio of 24:1 to obtain a thermoplastic elastomer material.

[0086] Comparative Example 2

[0087] 40 parts of solution-polymerized styrene-butadiene rubber 2605 and 50 parts of naphthenic oil KN4006 are stirred evenly and then left standing for more than 168 hours, and stirred for 5 min at room temperature under the condition of a rotation speed of 20 r / min to obtain a first mixture;

[0088] The first mixture is stirred with 5 parts of compatibilizer styrene maleic anhydride copolymer, 5 parts of terpene resin, and 0.05 part of antioxidant (a mixed antioxidant formed by mixing 168 and 1076 in a mass ratio of 1:1) at room temperature and a rotation speed of 40 r / min for 10 min to obtain a second mixture;

[0089] The second mixture is extruded and pelletized in a twin-screw extruder with a temperature of 190 °C, a rotation speed of 150 r / min, and a length-to-diameter ratio of 24:1 to obtain a thermoplastic elastomer material.

[0090] Comparative Example 3

[0091] 20 parts of SBS 3501, 30 parts of SBS 3546, and 35 parts of butadiene maleic anhydride copolymer Ricon130MA8 are stirred evenly and then left standing for more than 168 hours, and stirred at room temperature and a rotation speed of 40 r / min for 10 min to obtain a first mixture;

[0092] The first mixture is stirred with 5 parts of compatibilizer EMA, 10 parts of C9 resin, and 0.2 part of antioxidant (a mixed antioxidant formed by mixing 168 and 1076 in a mass ratio of 1:1) at room temperature and a rotation speed of 60 r / min for 15 min to obtain a second mixture;

[0093] The second mixture is extruded and pelletized in a twin-screw extruder with a temperature of 190 °C, a rotation speed of 300 r / min, and a length-to-diameter ratio of 36:1 to obtain a thermoplastic elastomer material.

[0094] Comparative Example 4

[0095] 25 parts of SBS 3501 and 65 parts of butadiene maleic anhydride copolymer Ricon 130MA8 are stirred evenly and then left standing for more than 168 hours, and stirred at room temperature and a rotation speed of 40 r / min for 10 min to obtain a first mixture;

[0096] The first mixture is stirred with 5 parts of compatibilizer X250, 5 parts of terpene resin, and 0.2 part of antioxidant (a mixed antioxidant formed by mixing 168 and 1076 in a mass ratio of 1:1) at room temperature and a rotation speed of 60 r / min for 15 min to obtain a second mixture;

[0097] The second mixture is extruded and pelletized in a twin-screw extruder with a temperature of 190 °C, a rotation speed of 300 r / min, and a length-to-diameter ratio of 36:1 to obtain a thermoplastic elastomer material.

[0098] The preparation raw material details of the insulating materials in Examples 1 to 5 and Comparative Examples 1 to 4 are as shown in Table 2 below.

[0099] Table 2 Preparation raw material details of insulating materials

[0100]

[0101]

[0102] The performance of the thermoplastic elastomers prepared in Examples 1 to 5 and Comparative Examples 1 to 4 was tested, and the test results are shown in Table 3 below.

[0103] Among them, the dynamic and static friction coefficient tests were carried out in accordance with the test standard of ASTM D1894 COF, and the contacting media were water (the weight was made of metal and the material surface was coated with pure water), ice (the weight was replaced with an ice block of the same weight and cross-sectional area as the weight), and 50% surfactant solution (the weight was made of metal and the material surface was coated with 50% surfactant solution, and the surfactant was a commercially available hand sanitizer). The method for the exudation test was to test a 3-mm sample plate under a pressure of 5 kg at 60 °C for 12 h.

[0104] Table 3 Performance test results of thermoplastic elastomers

[0105]

[0106]

[0107] The thermoplastic elastomers prepared in Examples 1 to 5 have relatively high dynamic and static friction coefficients and good wear resistance and anti-slip performance.

[0108] Compared with Example 1, in Comparative Example 1, the butadiene maleic anhydride copolymer was replaced with naphthenic oil KN4006, and the dynamic and static friction coefficients decreased significantly. The anti-slip performance of the thermoplastic elastomer prepared in Comparative Example 1 was poor.

[0109] Compared with Example 1, in Comparative Example 2, SBS was replaced with solution-polymerized styrene-butadiene rubber 2605, and the butadiene maleic anhydride copolymer was replaced with naphthenic oil KN4006. The base material obtained by using solution-polymerized styrene-butadiene rubber 2605 filled with oil and adding resin could not obtain an injection molding material without vulcanization.

[0110] Compared with Example 4, in Comparative Example 3, the terpene resin was replaced with a common C9 resin on the market. Compared with the terpene resin, the compatibility of the C9 resin with SBS was poor. Therefore, the dynamic and static friction coefficients of the thermoplastic elastomer prepared in Comparative Example 3 were lower, and the anti-slip performance was poor.

[0111] Compared with Example 1, in Comparative Example 4, the content of the butadiene maleic anhydride copolymer was too high. Although it could increase the dynamic and static friction coefficients, the DIN abrasion increased sharply, and exudation occurred during the exudation test.

[0112] The thermoplastic elastomers prepared in Examples 1 to 5 meet the environmental protection requirements of ROHS, REACH, and EN71-3 as tested by a third-party testing agency.

[0113] The technical features of the above embodiments can be combined arbitrarily. For the sake of brevity of description, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, it should be considered as the scope recorded in this specification.

[0114] The above embodiments only represent several embodiments of the present application, and their descriptions are relatively specific and detailed. However, it should not be construed as a limitation on the scope of the invention patent application. It should be noted that for those of ordinary skill in the art, without departing from the inventive concept of the present application, several modifications and improvements can still be made, and these all belong to the protection scope of the present application. Therefore, the protection scope of the patent of the present application shall be subject to the appended claims.

Claims

1. A thermoplastic elastomer, characterized in that, By mass parts, it consists of the following components: The butadiene maleic anhydride copolymer is selected from at least one of Ricon 130MA8 and Ricon 130MA13 of CRAY VALIEY; the viscosity of the styrene-butadiene-styrene block copolymer in a toluene solution at 23°C and 25% is ≥500 Pa·s; the content of butadiene in the styrene-butadiene-styrene block copolymer is ≥50%.

2. The thermoplastic elastomer according to claim 1, wherein The compatibilizer includes one or more of styrene maleic anhydride copolymer, ethylene methyl acrylate copolymer, and ethylene-n-butyl acrylate copolymer.

3. The thermoplastic elastomer according to claim 1, wherein The softening point of the terpene resin is ≤120°C.

4. The thermoplastic elastomer according to any one of claims 1 to 3, characterized in that The antioxidant includes one or more of tris(2,4-di-tert-butylphenyl) phosphite, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], and n-octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate.

5. A method for preparing a thermoplastic elastomer according to any one of claims 1 to 4, characterized in that, It includes the following steps: First, mix the styrene-butadiene-styrene block copolymer and the butadiene maleic anhydride copolymer, and let it stand to obtain a first mixture; Then, mix the first mixture with the compatibilizer, the terpene resin, and the antioxidant to obtain a second mixture; Extrude and pelletize the second mixture.

6. The preparation method of the thermoplastic elastomer according to claim 5, wherein, The standing time is ≥168 hours.

7. The preparation method of the thermoplastic elastomer according to claim 5, characterized in that, Use a twin-screw extruder for extrusion, the extrusion temperature is 180°C to 200°C, and the rotation speed is 150 r / min to 300 r / min; The length-diameter ratio of the twin-screw extruder is 24:1 to 36:

1.

8. Use of the thermoplastic elastomer according to any one of claims 1 to 4 in the preparation of a non-slip material.

Images