Ultralow-hardness TPV (thermoplastic vulcanizate) material for simulated skin

Abstract

The embodiment of the invention provides an ultralow-hardness TPV material for simulated skin. The ultralow-hardness TPV material is prepared from the following components in parts by weight: 100 parts of EPDM (Ethylene-Propylene-Diene Monomer), 300 to 600 parts of ammonolysis modified diester oil, 50 parts of SEEPS (Styrene Ethylene-Ethylene-Phenylene-Diene Monomer), 0.1 to 0.3 part of cross-linking agent and 0.3 to 1.5 parts of fluorocarbon surfactant. Wherein the ammonolysis modified diester oil is obtained by carrying out ammonolysis on modified disubstituted diester oil through an ammonolysis agent, and the modified disubstituted diester oil is obtained by carrying out transesterification on diester oil and aromatic alcohol. By adding high-content ammonolysis modified diester oil and a fluorocarbon surfactant into a material system, the TPV material has the characteristics of ultralow hardness, high smoothness, high precipitation resistance and the like, so that the TPV material can be completely suitable for simulation skin of an intelligent robot.

Description

Technical Field

[0001] This application relates to the field of polymer materials technology, and in particular to a TPV material for ultra-low hardness simulated skin. Background Technology

[0002] In recent years, with the rapid development of AI and the emergence of various large-scale emotion processing models, intelligent robots have once again become a hot research area, especially in terms of emotion processing, structural optimization, and motion perception, where significant progress has been made. However, current research and development of intelligent robots mainly focuses on internal hardware aspects such as algorithms and structures, while research on simulated skin has not received sufficient attention or further breakthroughs. Silicone and traditional TPE are still used as epidermal materials. When applied, these materials not only differ greatly from human skin in appearance and feel, but also generally suffer from problems such as insufficient smoothness and easy exudation, leading to dust accumulation and severely limiting the further development of human-like intelligent robots. Summary of the Invention

[0003] This application aims to address the technical problems of insufficient smoothness and easy exudation in existing materials used for simulated skin of intelligent robots. It proposes an ultra-low hardness TPV material for simulated skin, which combines ultra-low hardness, high smoothness, and high resistance to exudation. After molding, it can give the product a human skin-like feel and can be used for a long time in various environments.

[0004] To achieve the above objectives, this application adopts the following technical solution: A TPV material for ultra-low hardness simulated skin comprises the following components in parts by weight: 100 copies of EPDM 300-600 parts of ammonolytic modified diester oil SEEPS 50 servings Crosslinking agent 0.1~0.3 parts 0.3 to 1.5 parts of fluorocarbon surfactant.

[0005] Furthermore, the ammonolytic modified diester oil is obtained by ammonolysis of modified disubstituted diester oil with an ammonolytic agent, and the modified disubstituted diester oil is obtained by transesterification reaction of diester oil and aromatic alcohol.

[0006] Furthermore, the ammonolysis agent is a primary amine.

[0007] Furthermore, the preparation process of the ammonolytic modified diester oil is as follows: the modified disubstituted diester oil, ammonolytic agent and catalyst are placed in a reaction vessel for ammonolysis reaction, and after the reaction is completed, the ammonolytic modified diester oil is obtained after washing, drying and purification.

[0008] Furthermore, the catalyst is sodium methoxide or sodium cyanide.

[0009] Furthermore, the crosslinking agent includes a primary crosslinking agent and a secondary crosslinking agent, wherein the primary crosslinking agent is a peroxide, and the secondary crosslinking agent is one of triallyl isocyanate and N,N-m-phenylbismaleimide.

[0010] Furthermore, the peroxide is one of dicumyl peroxide, benzoyl peroxide, or di-tert-butyl peroxide.

[0011] Furthermore, the fluorocarbon surfactant is one of environmentally friendly fluorocarbon surfactants such as short-chain fluorocarbon surfactants, polyether-type fluorocarbon surfactants, and fluorinated tetraoxacarboxylic acid quaternary ammonium salts.

[0012] A method for preparing an ultra-low hardness TPV material for simulated skin, as described above, includes the following steps: Weigh out EPDM, ammonolytic modified diester oil, SEEPS, crosslinking agent and fluorocarbon surfactant by weight; The weighed ammonolytic modified diester oil and EPDM were placed in a high-speed mixer and mixed for 3-5 minutes. Then add the weighed SEEPS and crosslinking agent to the high-speed mixer and continue mixing for 3-5 minutes; Finally, the weighed fluorocarbon surfactant is placed into the high-speed mixer mentioned above and mixed for another 3-5 minutes to obtain a mixture; The desired TPV material can be obtained by extruding and granulating the mixture through a twin-screw extruder.

[0013] Furthermore, the temperatures of each heating zone from the feed port to the die head in the twin-screw extruder are set sequentially as follows: 140℃, 200℃, 200℃, 190℃, 190℃, 180℃, 180℃, 160℃, 160℃, 150℃, 150℃, and the rotation speed is 300~500rpm.

[0014] The beneficial effects of this application are: This application enables TPV materials to simultaneously possess ultra-low hardness, high smoothness, and high resistance to exudation by adding a high content of ammonolytic modified diester oil and fluorocarbon surfactants to the material system, making it fully suitable for use as simulated skin for intelligent robots. Specifically: Ammonolytic modified diester oil possesses both a nonpolar benzene ring structure and a polar and stable amide bond. While ensuring good compatibility with EPDM and preventing precipitation, it also endows the overall material with good hydrolysis resistance, photothermal resistance, and high stability, enabling its TPV products to be used in various environments. Fluorocarbon surfactants, as low surface energy small molecule lubricants, spontaneously migrate to the material surface after injection molding, forming a dense surface layer that provides the parts with a good feel and smoothness. At the same time, the strong hydrogen bonding between the ammonolytic modified diester oil and the small molecule fluorocarbon surfactants greatly avoids the short-term large-scale precipitation of fluorocarbon surfactants and generates a strong cohesive layer near the surface of the parts, ensuring long-term lubrication and smoothness. Detailed Implementation

[0015] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of the embodiments will be described clearly and completely below. Obviously, the described embodiments are only a part of the embodiments of this application, and not all of them. Based on the embodiments in this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application. In the description of this application, the experimental methods, unless otherwise specified, are conventional methods; the reagents and materials, unless otherwise specified, are all commercially available.

[0016] The following disclosure provides many different implementations or examples for carrying out this application. To simplify the disclosure of this application, specific examples of components and arrangements are described below. Of course, these are merely examples and are not intended to limit the scope of this application. Those skilled in the art will recognize the application of other processes and / or the use of other materials.

[0017] Example 1

[0018] The preparation of modified disubstituted diester oil includes the following steps: Weigh each component according to the following weights: 1000g dioctyl adipate, 100g phenylbutanol, 1.5g 98wt.% concentrated sulfuric acid; Weigh out dioctyl adipate, phenylbutanol and concentrated sulfuric acid and place them in a reaction vessel. Heat to 110°C and react for 6 hours to obtain the primary product. After washing away the phenylbutanol and concentrated sulfuric acid from the primary product with sodium carbonate solution, water and fusel oil are removed by rotary evaporation to obtain the modified disubstituted diester oil. The rotary evaporation temperature is 90°C.

[0019] The preparation of modified ammonolysis-modified diester oil includes the following steps: Weigh each component according to the following weights: 1000g modified disubstituted diester oil, 300g 2-methoxyethylamine, and 2.5g sodium methoxide. The modified disubstituted diester oil used is the same as that used in Example 1.

[0020] The modified disubstituted diester oil, 2-methoxyethylamine, and sodium methoxide were placed in a reaction vessel for ammonolysis reaction at a temperature of 180°C for 70 min. After the ammonolysis reaction is completed, the residual ammonolysis agent is washed away with NaHCO3 aqueous solution and the water is dried to obtain the crude product; The crude product was purified by chromatography to obtain ammonolytic modified diester oil.

[0021] The eluent used in the chromatography method is a mixture of petroleum ether and ethyl acetate prepared by mixing them in a volume ratio of 5:1.

[0022] The preparation of TPV material for ultra-low hardness simulated skin includes the following steps: Weigh each component according to the following weights: The composition includes 100g EPDM, 300g ammonolytic modified diester oil, 50g SEEPS, 0.15g dicumyl peroxide, 0.15g triallyl isocyanate, and 0.5g perfluoroalkyl ethanol ammonium phosphate; the EPDM used is commercially available grade KEP902 with an ethylene content of 30%, and the SEEPS used is commercially available grade Kuraray SEPTON. TM 4099, SEEPS with a styrene segment content of 30%; Weigh out the ammonolytic modified diester oil and EPDM and mix them in a high-speed mixer for 3 minutes; Then add the weighed SEEPS, dicumyl peroxide and triallyl isocyanate to the high-speed mixer above and continue mixing for 5 minutes; Finally, the weighed perfluoroalkyl ethanol ammonium phosphate was placed into the high-speed mixer mentioned above and mixed for another 5 minutes to obtain the mixture; The desired TPV material can be obtained by extruding and granulating the mixture through a twin-screw extruder. The temperatures of the heating zones from the feed inlet to the die head in the twin-screw extruder are set sequentially as follows: 140℃, 200℃, 200℃, 190℃, 190℃, 180℃, 180℃, 160℃, 160℃, 150℃, 150℃, with a rotational speed of 350 rpm.

[0023] Example 2

[0024] A method for preparing an ultra-low hardness TPV material for simulated skin includes the following steps: Weigh each component according to the following weights: EPDM 100g, ammoniated modified diester oil 450g, SEEPS 50g, dicumyl peroxide 0.15g, triallyl isocyanate 0.15g, amphoteric perfluorohexylsulfonamide alkyl betaine 1g; wherein, the ammoniated modified diester oil, EPDM and SEEPS used in this example are the same as in Example 1.

[0025] Weigh out the ammonolytic modified diester oil and EPDM and mix them in a high-speed mixer for 3 minutes; Then add the weighed SEEPS, dicumyl peroxide and triallyl isocyanate to the high-speed mixer above and continue mixing for 4 minutes; Finally, the weighed amphoteric perfluorohexylsulfonamide alkyl betaine was placed into the above high-speed mixer and mixed for another 5 minutes to obtain the mixture; The desired TPV material can be obtained by extruding and granulating the mixture through a twin-screw extruder. The temperatures of the heating zones from the feed inlet to the die head in the twin-screw extruder are set sequentially as follows: 140℃, 200℃, 200℃, 190℃, 190℃, 180℃, 180℃, 160℃, 160℃, 150℃, 150℃, with a rotational speed of 350 rpm.

[0026] Example 3

[0027] A method for preparing an ultra-low hardness TPV material for simulated skin includes the following steps: Weigh each component according to the following weights: EPDM 100g, ammoniac-modified diester oil 600g, SEEPS 50g, dicumyl peroxide 0.15g, triallyl isocyanate 0.15g, perfluoropolyether acyl fluoride 1.3g; wherein, the ammoniac-modified diester oil, EPDM and SEEPS used in this example are the same as those in Example 1.

[0028] Weigh out the ammonolytic modified diester oil and EPDM and mix them in a high-speed mixer for 5 minutes; Then add the weighed SEEPS, dicumyl peroxide and triallyl isocyanate to the high-speed mixer above and continue mixing for 4 minutes; Finally, the weighed perfluoropolyether acyl fluoride was placed into the high-speed mixer mentioned above and mixed for another 5 minutes to obtain a mixture; The desired TPV material can be obtained by extruding and granulating the mixture through a twin-screw extruder. The temperatures of the heating zones from the feed inlet to the die head in the twin-screw extruder are set sequentially as follows: 140℃, 200℃, 200℃, 190℃, 190℃, 180℃, 180℃, 160℃, 160℃, 150℃, 150℃, with a rotational speed of 400 rpm.

[0029] Example 4

[0030] A method for preparing an ultra-low hardness TPV material for simulated skin includes the following steps: Weigh each component according to the following weights: EPDM 100g, ammoniac-modified diester oil 450g, SEEPS 50g, benzoyl peroxide 0.1g, triallyl isocyanate 0.15g, perfluorooctyl carboxylic acid quaternary ammonium salt 0.8g; wherein, the ammoniac-modified diester oil, EPDM and SEEPS used in this example are the same as those in Example 1.

[0031] Weigh out the ammonolytic modified diester oil and EPDM and mix them in a high-speed mixer for 5 minutes; Then add the weighed SEEPS, benzoyl peroxide and triallyl isocyanate to the high-speed mixer and continue mixing for 4 minutes. Finally, the weighed perfluorooctyl carboxylic acid quaternary ammonium salt was placed into the high-speed mixer mentioned above and mixed for another 5 minutes to obtain the mixture; The desired TPV material can be obtained by extruding and granulating the mixture through a twin-screw extruder. The temperatures of the heating zones from the feed inlet to the die head in the twin-screw extruder are set sequentially as follows: 140℃, 200℃, 200℃, 190℃, 190℃, 180℃, 180℃, 160℃, 160℃, 150℃, 150℃, with a rotational speed of 400 rpm.

[0032] Comparative Example 1

[0033] A method for preparing TPV material includes the following steps: Weigh each component according to the following weights: EPDM 100g, ammonolytic modified diester oil 450g, SEEPS 50g, dicumyl peroxide 0.15g, triallyl isocyanate 0.15g; Weigh out the ammonolytic modified diester oil and EPDM and mix them in a high-speed mixer for 3 minutes; Then add the weighed SEEPS, dicumyl peroxide and triallyl isocyanate to the high-speed mixer above and continue mixing for 5 minutes to obtain a mixture; The desired TPV material can be obtained by extruding and granulating the mixture through a twin-screw extruder. The temperatures of the heating zones from the feed inlet to the die head in the twin-screw extruder are set sequentially as follows: 140℃, 200℃, 200℃, 190℃, 190℃, 180℃, 180℃, 160℃, 160℃, 150℃, 150℃, with a rotational speed of 350 rpm. The difference between Comparative Example 1 and Example 2 above is that no fluorocarbon surfactant was added.

[0034] Comparative Example 2

[0035] A method for preparing TPV material includes the following steps: Weigh each component according to the following weights: EPDM 100g, mineral oil 450g, SEEPS 50g, dicumyl peroxide 0.15g, triallyl isocyanate 0.15g, amphoteric perfluorohexylsulfonamide alkyl betaine 1g; Place the weighed mineral oil and EPDM in a high-speed mixer and mix for 3 minutes; Then add the weighed SEEPS, dicumyl peroxide and triallyl isocyanate to the high-speed mixer above and continue mixing for 4 minutes; Finally, the weighed amphoteric perfluorohexylsulfonamide alkyl betaine was placed into the above high-speed mixer and mixed for another 5 minutes to obtain the mixture; The desired TPV material can be obtained by extruding and granulating the mixture through a twin-screw extruder. The temperatures of the heating zones from the feed inlet to the die head in the twin-screw extruder are set sequentially as follows: 140℃, 200℃, 200℃, 190℃, 190℃, 180℃, 180℃, 160℃, 160℃, 150℃, 150℃, with a rotational speed of 350 rpm.

[0036] The difference between Comparative Example 2 and Example 2 above is that the ammonolytic modified diester oil is replaced with conventional mineral oil.

[0037] Comparative Example 3

[0038] A method for preparing TPV material includes the following steps: Weigh each component according to the following weights: EPDM 100g, ammonolytic modified diester oil 450g, PP 50g, dicumyl peroxide 0.15g, triallyl isocyanate 0.15g, amphoteric perfluorohexylsulfonamide alkyl betaine 1g; wherein, the ammonolytic modified diester oil used in this example is the same as that in Example 1.

[0039] Weigh out the ammonolytic modified diester oil and EPDM and mix them in a high-speed mixer for 3 minutes; Then add the weighed PP, dicumyl peroxide and triallyl isocyanate to the high-speed mixer above and continue mixing for 4 minutes; Finally, the weighed amphoteric perfluorohexylsulfonamide alkyl betaine was placed into the above high-speed mixer and mixed for another 5 minutes to obtain the mixture; The desired TPV material can be obtained by extruding and granulating the mixture through a twin-screw extruder. The temperatures of the heating zones from the feed inlet to the die head in the twin-screw extruder are set sequentially as follows: 140℃, 200℃, 200℃, 190℃, 190℃, 180℃, 180℃, 160℃, 160℃, 150℃, 150℃, with a rotational speed of 350 rpm.

[0040] The difference between Comparative Example 3 and Example 2 above is that SEEPS is replaced with PP.

[0041] Performance testing

[0042] To verify the performance of the TPV materials obtained in the above embodiments and comparative examples, the hardness, static friction coefficient, slip properties, and long-term oil separation performance of the TPV materials obtained in the above embodiments and comparative examples were tested. The hardness test standard was ISO 48-4, with a 15s reading. The static friction coefficient was tested according to the ISO 8295 standard. Slip properties were evaluated according to the standards in Table 1 below. The long-term oil separation performance test method was as follows: the obtained TPV material was made into a cylindrical test sample with a diameter of Ø29mm*6mm. The test sample was placed on oil-absorbing paper, and a 1kg weight was placed on the test sample. The sample was then placed in a 90℃ oven for 1000 hours. Finally, the weight gain rate of the oil-absorbing paper was tested; a higher weight gain rate indicates poorer oil separation performance. The test results of various performance parameters of the TPV materials obtained in each embodiment and comparative example are shown in Table 2.

[0043] Table 1. Relationship between Smoothness Grade and Evaluation Criteria

[0044] Table 2 Performance test results of TPV materials obtained in each embodiment and comparative example

[0045] As can be seen from the test results of various performances of the TPV materials obtained by the above embodiments and comparative examples, the low-hardness TPV material obtained by the method of the present invention has a low coefficient of friction, high smoothness, good hand feel, and excellent long-term resistance to precipitation.

[0046] In the above embodiments, the descriptions of each embodiment have different focuses. For parts not described in detail in a certain embodiment, please refer to the relevant descriptions in other embodiments.

[0047] The preparation method of an ultra-low hardness simulated skin TPV material provided in the embodiments of this application has been described in detail above. Specific examples have been used to illustrate the principles and implementation methods of this application. The description of the above embodiments is only for the purpose of helping to understand the technical solutions and core ideas of this application. Those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. These modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of this application.

Claims

1. A TPV material for ultra-low hardness simulated skin, characterized in that, The components include the following parts by weight: 100 copies of EPDM 300-600 parts of ammonolytic modified diester oil SEEPS 50 servings Crosslinking agent 0.1~0.3 parts 0.3 to 1.5 parts of fluorocarbon surfactant.

2. The ultra-low hardness TPV material for simulated skin as described in claim 1, characterized in that: The ammonolytic modified diester oil is obtained by ammonolysis of modified disubstituted diester oil with an ammonolytic agent, and the modified disubstituted diester oil is obtained by transesterification reaction of diester oil and aromatic alcohol.

3. The ultra-low hardness TPV material for simulated skin as described in claim 2, characterized in that: The ammonolysis agent is a primary amine.

4. The TPV material for ultra-low hardness simulated skin as described in claim 1, characterized in that: The preparation process of the ammonolysis modified diester oil is as follows: the modified disubstituted diester oil, ammonolysis agent and catalyst are placed in a reaction vessel for ammonolysis reaction. After the reaction is completed, the ammonolysis modified diester oil is obtained after washing, drying and purification.

5. The ultra-low hardness TPV material for simulated skin as described in claim 4, characterized in that: The catalyst is sodium methoxide or sodium cyanide.

6. The TPV material for ultra-low hardness simulated skin as described in claim 1, characterized in that: The crosslinking agent includes a primary crosslinking agent and a secondary crosslinking agent. The primary crosslinking agent is a peroxide, and the secondary crosslinking agent is one of triallyl isocyanate and N,N-m-phenylbismaleimide.

7. The ultra-low hardness TPV material for simulated skin as described in claim 6, characterized in that: The peroxide is one of dicumyl peroxide, benzoyl peroxide, or di-tert-butyl peroxide.

8. The ultra-low hardness TPV material for simulated skin as described in claim 1, characterized in that: The fluorocarbon surfactant is one of short-chain fluorocarbon surfactants, polyether-type fluorocarbon surfactants, or fluorinated tetraoxacarboxylic acid quaternary ammonium salts.

9. A method for preparing an ultra-low hardness simulated skin TPV material as described in any one of claims 1-8, characterized in that, Includes the following steps: Weigh out EPDM, ammonolytic modified diester oil, SEEPS, crosslinking agent and fluorocarbon surfactant by weight; The weighed ammonolytic modified diester oil and EPDM were placed in a high-speed mixer and mixed for 3-5 minutes. Then add the weighed SEEPS and crosslinking agent to the high-speed mixer and continue mixing for 3-5 minutes; Finally, the weighed fluorocarbon surfactant is placed in a high-speed mixer and mixed for another 3-5 minutes to obtain a mixture; The desired TPV material can be obtained by extruding and granulating the mixture through a twin-screw extruder.

10. The method for preparing the ultra-low hardness simulated skin TPV material as described in claim 9, characterized in that, The temperatures of each heating zone from the feed inlet to the die head in the twin-screw extruder are set sequentially as follows: 140℃, 200℃, 200℃, 190℃, 190℃, 180℃, 180℃, 160℃, 160℃, 150℃, 150℃, and the rotation speed is 300~500rpm.

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