Runway materials, their preparation methods and applications

Abstract

This invention belongs to the field of runway material technology, specifically relating to a runway material comprising star-shaped SEBS, hydrogenated S-(B / S)-S, rubber filler oil, inorganic filler, plastic, and antioxidant; the chemical formula of the star-shaped SEBS is B. n Y; where B is a hydrogenated styrene-butadiene block polymer arm or a hydrogenated styrene-butadiene-styrene block polymer arm; Y is a coupling agent residue; n is 3 or 4; the hydrogenated S-(B / S)-S is a hydrogenated triblock polymer, wherein the first and third blocks are styrene blocks, and the middle block is a random copolymer block of butadiene and styrene. This invention has found that, based on the synergistic effect of the aforementioned star-shaped SEBS and hydrogenated S-(B / S)-S, the compatibility performance of inorganic fillers can be improved, thus improving the performance of the runway. This material has good compatibility and encapsulation with thermoplastics and inorganic fillers, good anti-skid properties, and good processability at low oil filler ratios, giving the runway good mechanical properties and weather resistance.

Description

Technical fields:

[0001] This invention relates to the field of track material technology, specifically to an environmentally friendly sports track material. Background technology:

[0002] With the development of the national economy and the improvement of people's living standards, people have higher and higher requirements for the environmental protection of sports venues when exercising. They require venues to be odorless and non-toxic. The country advocates national fitness and people's enthusiasm for sports and fitness is increasing. The country is building more and more sports venues. In addition to considering the quality and environmental protection of running tracks, the country also attaches great importance to how to recycle and reuse these running track materials in the future. The country requires that venue materials be recycled and reused as much as possible.

[0003] Currently, the mainstream materials on the market are prefabricated running tracks made of thermosetting rubbers such as SBR or EPDM, and permeable running tracks made of SBR or EPDM granules bonded and cured with polyurethane adhesive. This material requires vulcanization, which is complex, generates waste, produces strong odors during processing, and requires significant equipment investment, space, and personnel. Even after installation, the tracks continue to release toxic gases, seriously endangering the health of exercisers.

[0004] Hydrogenated styrene-based elastomer SEBS exhibits excellent rubber resilience at room temperature and resin fluidity at high temperatures. It can be directly processed and molded without vulcanization, simplifying the processing. Scrap materials can be recycled, and waste materials can be reused, reducing production costs and being environmentally friendly. SEBS has good solubility and filler compatibility, improving the processing performance of blends and extending their service temperature range, ensuring good elasticity in running tracks during both winter and summer use. Furthermore, SEBS filler compounds exhibit excellent resistance to outdoor sun exposure. Therefore, SEBS is a preferred material for sports running tracks.

[0005] Patent CN109082063A uses SEBS to produce elastic filler granules for running tracks. During paving, polyurethane adhesives are still used to bond the granules. However, polyurethane adhesives contain diisocyanate monomers, volatile solvents, and various catalysts (containing heavy metals such as lead, mercury, and tin), which are harmful substances and emit an odor. Patent CN106009714A's SEBS running track material formulation has a high content of thermoplastics, resulting in high material hardness that affects the impact absorption performance of the product. The addition of crosslinking agents affects the processing performance of the product, and unstable process control can lead to defective products and the emission of an irritating odor.

[0006] When processing and producing sports running tracks using hydrogenated styrene elastomer SEBS, a small amount of filler oil must be added to ensure that the SEBS blend has good aging resistance and mechanical properties, while a large amount of inorganic filler is added to reduce the cost of the material. Summary of the Invention:

[0007] The purpose of this invention is to provide a track material that, while reducing the amount of rubber filler oil used, effectively improves the compatibility of fillers and enhances track performance.

[0008] The second objective of this invention is to provide a method for preparing the aforementioned runway material.

[0009] The third objective of this invention is to provide an application of the aforementioned track material in sports running tracks, which can improve the shock absorption effect of sports running track materials, prevent athletes' joints from being vibrated, and reduce athletes' exercise wear and tear.

[0010] A running track material comprising star-shaped SEBS, hydrogenated S-(B / S)-S, rubber filler oil, inorganic filler, plastic, and antioxidant (also referred to as an antioxidant in this invention);

[0011] The chemical formula of the star-shaped SEBS is B. n Y; where B is a hydrogenated styrene-butadiene block polymer arm or a hydrogenated styrene-butadiene-styrene block polymer arm; Y is a coupling agent residue; n is 3 or 4;

[0012] The hydrogenated S-(B / S)-S is a hydrogenated triblock polymer, wherein the first and third blocks are styrene blocks, and the middle block is a random copolymer block of butadiene and styrene.

[0013] To address the issue of incompatible inorganic fillers and polymers in running track materials, excessive rubber filler oil is often added to improve compatibility. However, this leads to a series of adverse effects. This invention innovatively discovers that the synergistic effect of star-shaped SEBS and hydrogenated S-(B / S)-S can unexpectedly improve the compatibility of inorganic fillers and enhance running track performance. This material exhibits good compatibility and encapsulation with thermoplastics and inorganic fillers, excellent wet grip, and good processability at low oil filling ratios, resulting in running track products with superior mechanical properties and weather resistance. Furthermore, it significantly improves the impact absorption performance of the running track, reducing sports injuries.

[0014] In this invention, the star-shaped SEBS is preferably a coupling polymer with 3 arms and 4 arms; of course, it is permissible to also contain a small amount of polymer with 1 arm and 2 arms.

[0015] Preferably, the star-shaped SEBS can be prepared using existing methods, for example, by using a star-shaped polymer formed from SiCl4 and polymer arms, followed by hydrogenation using a titanocene catalytic system.

[0016] Preferably, the polymer arms of the star-shaped SEBS are triblock polymers of SBS.

[0017] Preferably, in the star-shaped SEBS, Y is Si and n is 4.

[0018] Preferably, the star-shaped SEBS has a number average molecular weight of 150,000-300,000 and a styrene mass percentage of 25-40%.

[0019] Preferably, the star-shaped SEBS is at least one of SEBSYH-604 and SEBSYH-602.

[0020] Preferably, the hydrogenated S-(B / S)-S has a number-average molecular weight of 50,000-100,000, a styrene mass percentage of 30-50%, and a styrene mass percentage of 5-30% in the second block. In this invention, the hydrogenation methods can all be implemented using existing equipment and methods. For example, a titanocene catalytic system can be used for hydrogenation.

[0021] Preferably, the hydrogenated S-(B / S)-S is at least one of SEBSYH-511 and SEBSYH-512.

[0022] The rubber filler oil is a naphthenic rubber oil or a paraffinic rubber oil.

[0023] Preferably, the inorganic filler is one or more of calcium carbonate, kaolin, and talc.

[0024] Preferably, the thermoplastic is one or two of polypropylene (homopolymer polypropylene or copolymer polypropylene), polyethylene, and polystyrene.

[0025] The antioxidant (also referred to as an antioxidant in this invention) is any one or a mixture of β-(4-hydroxy-3,5-di-tert-butylphenyl)propionate (antioxidant 1076), tris(2,4-di-tert-butylphenyl) phosphite (antioxidant 168), pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (antioxidant 1010), bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite (antioxidant TH-24), and dilauryl thiodipropionate (antioxidant DLTP).

[0026] Preferably, the weight parts of each component in the runway material are as follows:

[0027]

[0028] The present invention has found that the ratio of the star-shaped SEBS to hydrogenated S-(B / S)-S is greater than or equal to 1, which helps to further improve the performance of the runway while reducing the amount of filler oil.

[0029] Further optimization yields a star-shaped SEBS: hydrogenated S-(B / S)-S weight ratio of 1 to 2.5:1; more preferably 1.5 to 2.5:1. Studies have found that at this preferred ratio, runway performance, particularly shock absorption, can be unexpectedly improved.

[0030] Preferably, the weight parts of each component in the runway material are as follows:

[0031]

[0032] Further preferably, the weight parts of each component in the runway material are as follows:

[0033]

[0034] Preferably, the runway material further includes an additive, which is a silicone masterbatch.

[0035] Preferably, the amount of the auxiliary agent is less than or equal to 2 parts by weight, more preferably 0.3 to 1.5 parts; and more preferably 0.3 to 0.5 parts.

[0036] Preferably, the runway material also selectively includes UV stabilizers and pigments.

[0037] Preferably, the UV stabilizer is any one or a mixture of 2-hydroxy-4-n-octyloxybenzophenone (UV531), (2-hydroxy-4-methoxyphenyl)phenyl ketone (UV9), 2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole (UV326), and hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate (UV2908), with UV531 being preferred. More preferably, the UV stabilizer is present in a fraction of 0.5 parts by weight; more preferably, 0.1-0.5 parts.

[0038] Preferably, the pigment is an inorganic pigment. The preferred pigment has a weight of less than or equal to 5 parts, more preferably 3 to 5 parts.

[0039] The present invention also provides a method for preparing the aforementioned runway material, wherein the components are mixed and extruded using a twin-screw extruder.

[0040] The preparation method of this invention, based on the synergistic effect of the components, can improve processability and the encapsulation effect of inorganic fillers. In addition, the preparation method is simple, does not require vulcanization, and the scraps can be recycled. It is safe and environmentally friendly, and can take into account the performance of sports tracks while being conducive to processing and production. The sports tracks made have excellent performance, excellent shock absorption, and are resistant to wet slipping and have a wide operating temperature range.

[0041] Preferred preparation method: includes the following steps:

[0042] [1] Weigh the above raw materials according to the specified quantities.

[0043] [2] Mixing: Allow the hydrogenated S-(B / S)-S and star-shaped SEBS mixture to fully absorb the rubber filler oil, and then add it to the mixer along with the other components and mix evenly.

[0044] [3] Extrusion: The material is melted and mixed at high temperature in a twin-screw extruder with forced feeding, and then extruded into sheets by a single screw.

[0045] [4] Press molding: After the sheet extruded by the single screw exits the die head, it is directly fed into the double roller for extrusion. One side is pressed into a uniform pattern, and the other side is pressed into a uniformly distributed hollow shape to make a prefabricated sports track roll material.

[0046] In the extrusion step, the temperatures of each section of the twin-screw extruder, starting from the feed port, are 180-185℃, 190-200℃, and 190-200℃ respectively, with the die temperature at 170-190℃. For the single-screw extruder, the temperatures of each section, starting from the feed port, are 130-150℃, 150-170℃, 170-190℃ respectively, with the die temperature at 150-170℃.

[0047] The present invention also provides an application of the aforementioned track material, which is used to prepare sports tracks, thereby increasing the shock absorption effect of the track material, effectively reducing the probability of athlete injury and improving athletes' training and competition performance.

[0048] The beneficial effects of this patent are:

[0049] The runway material described in this invention, based on the synergy of hydrogenated S-(B / S)-S, star-shaped SEBS, and other components, can improve the compatibility of plastics and inorganic fillers, eliminating the need for compatibilizers, reducing the melt viscosity of the molten blend, and facilitating processing; in addition, it also helps improve the shock absorption and strength of the runway, making the various indicators of the runway superior to the corresponding standards.

[0050] In addition, the track material described in this invention is odorless and non-toxic during preparation and processing, and has good anti-slip properties, excellent shock absorption effect and aging resistance. It can be recycled and reused after its service life. Detailed implementation method:

[0051] Unless otherwise stated, in the following implementations and comparative examples, the linear SEBS used was SEBSYH-503 (with a polybutadiene block as the median block) provided by Baling Branch of China Petroleum & Chemical Corporation. The star-shaped SEBS used was SEBSYH-602 (with an SB diblock polymer arm) and SEBSYH-604 (with an SBS triblock polymer arm) provided by Baling Branch of China Petroleum & Chemical Corporation. The hydrogenated S-(B / S)-S used was SEBSYH-511 (with a B / S copolymer block as the median block) provided by Baling Branch of China Petroleum & Chemical Corporation.

[0052] The antioxidant is antioxidant 1076;

[0053] The additive is silicone masterbatch;

[0054] Copolymer polypropylene (Sinopec Yanshan Petrochemical Copolymer PP1647)

[0055] Example 1

[0056] 12 parts by weight of triblock-coupled star-shaped SEBSYH-6041; 8 parts by weight of hydrogenated S-(B / S)-S(SEBSYH-511); 20 parts by weight of paraffinic white oil; 4 parts by weight of copolymerized polypropylene; 56 parts by weight of heavy calcium carbonate; 0.4 parts by weight of antioxidant; 0.5 parts by weight of additives. Mix evenly, granulate, and perform performance tests.

[0057] Example 2

[0058] 10 parts by weight of triblock-coupled star-shaped SEBSYH-604; 10 parts by weight of hydrogenated S-(B / S)-S(SEBSYH-511); 20 parts by weight of paraffinic white oil; 4 parts by weight of copolymerized polypropylene; 56 parts by weight of heavy calcium carbonate; 0.4 parts by weight of antioxidant; 0.5 parts by weight of additives. Mix thoroughly, granulate, and perform performance tests.

[0059] Example 3

[0060] Triblock-coupled star-shaped SEBSYH-60414 parts by weight; hydrogenated S-(B / S)-S(SEBSYH-511)6 parts by weight; paraffinic white oil20 parts by weight; copolymerized polypropylene4 parts by weight; heavy calcium carbonate56 parts by weight; antioxidant0.4 parts by weight; additives0.5 parts by weight. Mix evenly and granulate, then perform performance tests.

[0061] Example 4

[0062] Triblock coupling star-shaped SEBSYH-6048 parts by weight; hydrogenated S-(B / S)-S(SEBSYH-511) 12 parts by weight; paraffinic white oil 20 parts by weight; copolymerized polypropylene 4 parts by weight; heavy calcium carbonate 56 parts by weight; antioxidant 0.4 parts by weight; additives 0.5 parts by weight. Mix evenly, granulate, and perform performance tests.

[0063] Comparative Example 1

[0064] Weigh out 20 parts by weight of linear SEBSYH-503; 20 parts by weight of paraffinic white oil; 4 parts by weight of copolymer polypropylene; 56 parts by weight of heavy calcium carbonate; 0.4 parts by weight of antioxidant; and 0.5 parts by weight of additives. Mix the above raw materials evenly in a high-speed mixer and granulate. The mixing temperature is 10-50°C, and the mixing time is 5-15 minutes.

[0065] Comparative Example 2

[0066] Two-block coupled star-shaped SEBS YH-60220 parts by weight; paraffinic white oil 20 parts by weight; copolymer polypropylene 4 parts by weight; heavy calcium carbonate 56 parts by weight; antioxidant 0.4 parts by weight; additives 0.5 parts by weight. Mix evenly and granulate, then perform performance tests.

[0067] Comparative Example 3

[0068] Triblock coupling star-shaped SEBSYH-604 20 parts by weight; paraffinic white oil 20 parts by weight; copolymer polypropylene 4 parts by weight; heavy calcium carbonate 56 parts by weight; antioxidant 0.4 parts by weight; additives 0.5 parts by weight. Mix evenly and granulate, then perform performance tests.

[0069] Comparative Example 4

[0070] 20 parts by weight of hydrogenated S-(B / S)-S(SEBSYH-511); 20 parts by weight of paraffinic white oil; 4 parts by weight of copolymerized polypropylene; 56 parts by weight of heavy calcium carbonate; 0.4 parts by weight of antioxidant; 0.5 parts by weight of additives. Mix evenly and granulate, then perform performance tests.

[0071] Table 1. Results of physical property tests

[0072]

[0073] Note: Melt flow index (MFR) is the melt flow index at 190℃ with a load of 5 kg. The national standard for shock absorption is 35-50%.

[0074] The above test results show that SEBS sports track material without SEBSYH-511 has poor processing performance and cannot be processed. It has good resilience but poor shock absorption performance and cannot meet the impact absorption standards. When the ratio of hydrogenated S-(B / S)-S(SEBSYH-511) to SEBSYH-604 is between 1:2.5 and 1:1, the material has good mechanical properties and processing performance, good shock absorption performance and good impact absorption performance. When used to make prefabricated SEBS sports tracks, it has good performance and low cost, good processing performance, and the product is truly green and safe, and can be recycled after its service life.

Claims

1. A runway material, characterized in that, It contains star-shaped SEBS, hydrogenated S-(B / S)-S, rubber filler oil, inorganic filler, plastics and antioxidants; The chemical formula of the star-shaped SEBS is B. n Y; where B is a hydrogenated styrene-butadiene block polymer arm or a hydrogenated styrene-butadiene-styrene block polymer arm; Y is a coupling agent residue; n is 3 or 4; The hydrogenated S-(B / S)-S is a hydrogenated triblock polymer, wherein the first and third blocks are styrene blocks, and the middle block is a random copolymer block of butadiene and styrene. The weight parts of each component in the aforementioned runway material are as follows: Star-shaped SEBS 10-14 portions Hydrogenated S-(B / S)-S 6-10 parts 15-20 parts of rubber filler oil 3-5 portions of plastic 50-60 parts of inorganic filler Anti-aging agent 0.3-0.5 parts; The star-shaped SEBS is at least one of SEBSYH-604 and SEBSYH-602; The hydrogenated S-(B / S)-S is at least one of SEBSYH-511 and SEBSYH-512.

2. The runway material as described in claim 1, characterized in that, The rubber filler oil is a naphthenic rubber oil or a paraffinic rubber oil.

3. The track material as described in claim 1, characterized in that, The inorganic filler is one or more of calcium carbonate, kaolin, and talc.

4. The runway material as described in claim 1, characterized in that, The plastic is one or two of polypropylene, polyethylene, and polystyrene.

5. The runway material as described in claim 1, characterized in that, The antioxidant is any one or a mixture of β-(4-hydroxy-3,5-di-tert-butylphenyl)propionate (antioxidant 1076), tris(2,4-di-tert-butylphenyl) phosphite (antioxidant 168), pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (antioxidant 1010), bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite (antioxidant TH-24), and dilauryl thiodipropionate (antioxidant DLTP).

6. The runway material as described in claim 1, characterized in that, The weight parts of each component in the aforementioned runway material are as follows: Star-shaped SEBS 10-14 portions Hydrogenated S-(B / S)-S 6-8 parts 15-20 parts of rubber filler oil 3-5 parts plastic; 50-60 parts of inorganic filler The amount of antioxidant is 0.3-0.5 parts.

7. The runway material as described in claim 1, characterized in that, It also contains additives. The additive is a silicone masterbatch; The additive is less than or equal to 2 parts by weight.

8. The runway material according to any one of claims 1 to 7, characterized in that, It also contains UV protectants and pigments; The UV stabilizer is any one or a mixture of 2-hydroxy-4-n-octyloxybenzophenone, (2-hydroxy-4-methoxyphenyl)phenyl ketone, 2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, and n-hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate. The amount of the UV-protective agent is less than or equal to 0.5 parts. The pigment is an inorganic pigment; the amount of pigment used is less than or equal to 3-5 parts.

9. A method for preparing a runway material according to any one of claims 1 to 8, characterized in that, The components are mixed and extruded using a twin-screw extruder.

10. An application of the runway material according to any one of claims 1 to 8, characterized in that, It was used to prepare sports running tracks.

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