A PCR thermoplastic elastomer material

Abstract

The application relates to a PCR thermoplastic elastomer material, relates to the technical field of composite materials, and comprises the following components in mass fractions: SEBS 70-80 parts, white oil 60-70 parts, PCR raw material 150-180 parts, surface-treated glass fiber 60-80 parts, UV resistance agent 8-10 parts, antioxidant 8-10 parts, light stabilizer 3-5 parts and heat stabilizer 3-5 parts. The PCR thermoplastic elastomer material is stable in performance, comparable to virgin plastics, strong in processability, suitable for various processing methods such as injection molding and extrusion, can reduce product manufacturing cost, reduce dependence on fossil fuels, and promotes waste plastic recycling.

Description

Technical Field

[0001] This application relates to the field of polymer composite materials technology, and in particular to a PCR thermoplastic elastomer material. Background Technology

[0002] In the field of materials science today, with the increasing demand for high-performance materials from various industries, thermoplastic elastomers, with their unique high elasticity and processability, have been widely used in many fields such as automobiles, electronics, and construction. They not only provide more possibilities for product design, but also effectively reduce production costs and improve production efficiency, and have become one of the indispensable materials in modern industry.

[0003] However, the widespread use of traditional plastic materials has led to severe environmental pollution problems. Ordinary plastics are difficult to degrade and accumulate in the natural environment over long periods, causing significant damage to soil, water sources, and ecosystems. Plastic pollution has become a global environmental challenge. At the same time, the over-exploitation of plastic raw materials also threatens the sustainable supply of resources.

[0004] Post-consumer recycled (PCR) thermoplastic elastomers, as a novel environmentally friendly material, offer significant advantages such as recyclability and pollution reduction. However, they face challenges in terms of aging resistance. Because their raw materials are derived from recycled plastics, their molecular structure changes during repeated use and recycling, leading to decreased resistance to environmental factors. This aging resistance issue makes PCR thermoplastic elastomers prone to discoloration, decreased mechanical properties, and compromised functional stability, ultimately shortening product lifespan and requiring further improvement. Summary of the Invention

[0005] To improve the aging resistance of PCR thermoplastic elastomers, this application provides a PCR thermoplastic elastomer material.

[0006] The PCR thermoplastic elastomer material provided in this application adopts the following technical solution:

[0007] A PCR thermoplastic elastomer material comprising the following components in parts by weight:

[0008] SEBS 70-80 copies

[0009] 60-70 parts white oil

[0010] PCR raw materials 150-180 samples

[0011] Surface treatment with 60-80 parts glass fiber

[0012] 8-10 parts of UV protectant

[0013] 8-10 parts antioxidant

[0014] 3-5 parts light stabilizer

[0015] Heat stabilizer 3-5 parts.

[0016] SEBS possesses excellent elasticity and flexibility. When combined with white oil, it can improve the material's processing performance and initial toughness, providing a foundation for tensile properties. PCR raw materials originate from post-consumer waste and are recycled, making them highly environmentally friendly. This reduces the demand for new plastics, lowers the environmental burden, and significantly reduces energy consumption and carbon emissions, contributing to low-carbon goals. PCR raw materials can form an interpenetrating network structure with SEBS, enhancing intermolecular forces and improving overall strength and tensile properties. Surface-treated glass fibers, with their high strength and high modulus, are uniformly dispersed in the system, acting as a reinforcing skeleton, effectively bearing and transferring stress, and significantly enhancing tensile properties. Antioxidants can capture free radicals and inhibit oxidation chain reactions, while heat stabilizers can prevent the material from decomposing and degrading at high temperatures. Together, they maintain the stability of the material's chemical structure and improve thermal stability. UV stabilizers can absorb ultraviolet energy, light stabilizers can quench excited-state molecules, and antioxidants can further inhibit oxidative aging. These multiple aspects work synergistically to resist environmental factors, improve the material's aging resistance, and enable the material to function stably in various application scenarios.

[0017] The PCR thermoplastic elastomer material obtained after processing has stable properties comparable to virgin plastics. It is highly processable and suitable for various processing methods such as injection molding and extrusion. It can reduce product manufacturing costs, reduce dependence on fossil fuels, promote the recycling and reuse of waste plastics, and meet the policy requirements of many countries that mandate the use of PCR plastics.

[0018] Preferably, the PCR raw materials include PCR PP, PCR PE and PCR PS.

[0019] PCR-PP possesses high rigidity and crystallinity, providing excellent skeletal support for the material, enhancing intermolecular interactions, and enabling better stress transfer under load, thereby improving tensile properties. PCR-PP itself exhibits thermal stability, improving the overall heat resistance of the material. PCR-PE has good flexibility, working synergistically with PCR-PP to enhance tensile properties while improving impact resistance. Its chemical stability also contributes to improved chemical corrosion resistance, thus enhancing aging resistance. PCR-PS has high hardness and strength, further enhancing overall rigidity and optimizing tensile properties. PCR-PS also exhibits good dimensional stability at high temperatures, synergistically improving thermal stability in conjunction with other components. The combined effect of these three components forms a complex and stable internal structure, effectively improving tensile properties, thermal stability, and aging resistance.

[0020] Preferably, the PCR PP is modified with maleic anhydride to obtain modified PCR PP.

[0021] Grafting maleic anhydride onto the PCR PP molecular chain increases the polarity and interaction forces between the molecular chains, making them less prone to slippage under stress and thus enhancing the tensile properties of the material. The modified PCR PP has an optimized molecular structure, an increased thermal decomposition temperature, and greater stability at high temperatures, effectively improving the overall thermal stability of the material. The grafted maleic anhydride structure can hinder the erosion of the molecular chain by external factors such as oxygen and ultraviolet light, reducing aging reactions such as oxidation and photodegradation, thereby improving the aging resistance of the material.

[0022] Preferably, the PCR PE is modified using vinylpyrrolidone and 2-(perfluorohexyl)ethyl methacrylate to obtain modified PCR PE.

[0023] Grafting vinylpyrrolidone onto the PCR PE molecular chain increases the interaction and entanglement between the molecular chains, enabling the material to transfer stress more effectively under load and enhancing the molecular chains' resistance to external force damage, thereby improving the tensile properties of the material. Simultaneously, the grafted structure helps stabilize the molecular chains, inhibiting their movement and degradation at high temperatures, thus improving the material's thermal stability. The fluorinated groups introduced by 2-(perfluorohexyl)ethyl methacrylate possess low surface energy and good chemical stability, forming a protective barrier on the material surface to block the erosion of oxygen, ultraviolet radiation, and chemicals, effectively delaying the aging process and improving aging resistance. The synergistic effect of these two components effectively enhances the tensile properties, thermal stability, and aging resistance of the PCR PE material.

[0024] Preferably, the PCR PS is modified with p-toluenesulfonyl chloride to obtain modified PCR PS.

[0025] The p-toluenesulfonyl group possesses strong electron-withdrawing properties. In modifying PCR PS, it influences the electron cloud distribution of the molecular chain through induction and conjugation effects, increasing the intermolecular interaction forces and making the molecular chains more tightly entangled. When the material is subjected to external stretching, it can more effectively transfer stress, reducing the relative slippage of the molecular chains and thus improving the tensile properties of the material. The p-toluenesulfonyl group also has a large steric hindrance effect, not only protecting key groups on the molecular chain but also affecting the spatial configuration of the molecule, further enhancing the intermolecular interaction and improving the tensile properties of the material. Furthermore, the p-toluenesulfonyl group exhibits good stability. Its introduction optimizes the molecular chain structure of PCR PS, enhancing the rigidity of the molecular chains. Under high-temperature environments, it can inhibit the movement and decomposition of the molecular chains, improving the material's resistance to thermal deformation and degradation, thereby enhancing the overall thermal stability of the material. Finally, the good stability of the p-toluenesulfonyl group can block the damage to the molecular chains caused by external factors such as oxygen and ultraviolet radiation, reducing the probability of oxidation reactions and photodegradation, thus enhancing the aging resistance of the material.

[0026] Preferably, the SEBS is subjected to plasma treatment and modification with γ-methacryloyloxypropyltrimethoxysilane to obtain modified SEBS.

[0027] Plasma treatment introduces a large number of active groups onto the SEBS surface, increasing its surface activity and roughness, and enhancing its interfacial bonding with other components. γ-Methacryloxypropyltrimethoxysilane binds to the active sites on the SEBS surface through chemical bonds, forming a cross-linked network between molecular chains, which strengthens the inter-chain forces. When the material is stretched, it can effectively disperse stress and inhibit the slippage of molecular chains, thereby significantly improving tensile properties. The cross-linked structure restricts the thermal motion of molecular chains, increasing the thermal decomposition temperature of the material and making it more stable at high temperatures. The cross-linked structure and the chemical stability of silane can jointly resist the erosion of environmental factors such as oxygen and ultraviolet rays, slow down the degradation and oxidation of molecular chains, and effectively improve aging resistance.

[0028] Preferably, the modified SEBS is prepared using the following steps:

[0029] SEBS was bombarded with plasma to obtain pre-modified SEBS; the pre-modified SEBS and γ-methacryloxypropyltrimethoxysilane were dispersed in a solvent, a catalyst was added, and the reaction was stirred under water bath conditions. After the reaction was completed, the mixture was filtered, washed, and dried to obtain modified SEBS.

[0030] Preferably, the solvent comprises anhydrous ethanol, and the catalyst comprises dibutyltin dilaurate.

[0031] The modified SEBS prepared according to the above steps has good reactivity and compatibility, and can effectively improve the tensile properties, thermal stability and aging resistance of PCR thermoplastic elastomers.

[0032] Preferably, the raw materials for preparing the surface-treated glass fiber include glass fiber body, tetraethyl orthosilicate and trifluoropropyltrimethoxysilane.

[0033] Glass fiber possesses high strength and high modulus, providing stable support for materials. Its excellent thermal stability inhibits material deformation at high temperatures, while its stable physical structure protects against external erosion, effectively improving the tensile properties, thermal stability, and aging resistance of PCR thermoplastic elastomer materials. The siloxane network formed by the hydrolysis of tetraethyl orthosilicate enhances the interfacial adhesion with glass fiber and the matrix, efficiently transferring stress, delaying heat transfer, inhibiting matrix thermal decomposition, and improving tensile and thermal stability. The low surface energy and chemical stability of the fluorinated groups in trifluoropropyltrimethoxysilane allow it to form a protective film on the material surface, resisting erosion from ultraviolet rays, oxygen, and other substances, delaying aging, and improving the material's aging resistance.

[0034] Preferably, the mass ratio of the glass fiber body, tetraethyl orthosilicate and trifluoropropyltrimethoxysilane is 1:0.5:(0.1-0.3).

[0035] The surface-modified glass fibers prepared according to the above mass ratio have good compatibility and can effectively improve the tensile properties, thermal stability and aging resistance of PCR thermoplastic elastomers.

[0036] Preferably, the PCR thermoplastic elastomer material is prepared using the following steps:

[0037] SEBS and white oil were mixed and heated and stirred to obtain a mixture. PCR raw materials were added to the mixture and heated and stirred. UV stabilizer, antioxidant, light stabilizer and heat stabilizer were added and stirred. Surface-treated glass fiber was added and heated and stirred to obtain a composite material. The composite material was melt-blended, extruded and granulated to obtain a PCR thermoplastic elastomer material.

[0038] The PCR thermoplastic elastomer material prepared according to the above steps has good tensile properties, thermal stability and aging resistance. It can maintain good appearance and performance in various complex environments, meet various application requirements and has a long service life.

[0039] In summary, this application includes at least one of the following beneficial technical effects:

[0040] 1. SEBS possesses excellent elasticity and flexibility. When combined with white oil, it can improve the material's processing performance and initial toughness, providing a foundation for tensile properties. PCR raw materials originate from post-consumer waste and are recycled, making them highly environmentally friendly. This reduces the demand for new plastics, lowers the environmental burden, and significantly reduces energy consumption and carbon emissions, contributing to low-carbon goals. PCR raw materials can form an interpenetrating network structure with SEBS, enhancing intermolecular forces and improving overall strength and tensile properties. Surface-treated glass fibers, with their high strength and high modulus, are uniformly dispersed in the system, acting as a reinforcing skeleton, effectively bearing and transferring stress, and significantly enhancing tensile properties. Antioxidants can capture free radicals and inhibit oxidation chain reactions, while heat stabilizers can prevent the material from decomposing and degrading at high temperatures. Together, they maintain the stability of the material's chemical structure and improve thermal stability. UV stabilizers can absorb ultraviolet energy, light stabilizers can quench excited-state molecules, and antioxidants can further inhibit oxidative aging. These multiple aspects work synergistically to resist environmental factors, improve the material's aging resistance, and enable the material to function stably in various application scenarios.

[0041] 2. Plasma treatment introduces a large number of active groups onto the SEBS surface, increasing its surface activity and roughness, and enhancing its interfacial bonding with other components. γ-Methacryloxypropyltrimethoxysilane binds to the active sites on the SEBS surface through chemical bonds, forming a cross-linked network between molecular chains, which enhances the inter-chain forces. When the material is stretched, it can effectively disperse stress and inhibit the slippage of molecular chains, thereby significantly improving tensile properties. The cross-linked structure restricts the thermal motion of molecular chains, increases the thermal decomposition temperature of the material, and makes it more stable at high temperatures. The cross-linked structure and the chemical stability of silane can jointly resist the erosion of environmental factors such as oxygen and ultraviolet rays, slow down the degradation and oxidation of molecular chains, and effectively improve aging resistance.

[0042] 3. Glass fiber possesses high strength and high modulus, providing stable support for materials. Its good thermal stability inhibits material deformation at high temperatures, while its stable physical structure protects against external erosion, effectively improving the tensile properties, thermal stability, and aging resistance of PCR thermoplastic elastomer materials. The siloxane network formed by the hydrolysis of tetraethyl orthosilicate enhances the interfacial adhesion with glass fiber and the matrix, efficiently transferring stress, delaying heat transfer, inhibiting matrix thermal decomposition, and improving tensile and thermal stability. The fluorinated groups in trifluoropropyltrimethoxysilane have low surface energy and chemical stability, forming a protective film on the material surface that resists erosion from ultraviolet rays, oxygen, and other substances, delaying aging and improving the material's aging resistance. Detailed Implementation

[0043] This application discloses a PCR thermoplastic elastomer material. Unless otherwise specified, all raw materials used in this application are commercially available. The following detailed description, in conjunction with embodiments, further illustrates this application:

[0044] Raw material description: PCR PP is post-consumer recycled polypropylene, maleic anhydride (CAS No.: 108-31-6); PCR PE is post-consumer recycled polyethylene, benzoyl peroxide (CAS No.: 94-36-0), vinylpyrrolidone (CAS No.: 88-12-0), 2-(perfluorohexyl)ethyl methacrylate (CAS No.: 2144-53-8); PCR PS is post-consumer recycled polystyrene, p-toluenesulfonyl chloride (CAS No.: 98-59-9), glass fiber (CAS No.: 65997-17-3), tetraethyl orthosilicate (CAS No.: 78-10-4), trifluoropropyltrimethoxysilane (CAS No.: 429-60-7), white oil (CAS No.: 8012-95-1), UV stabilizer model UV-3638, antioxidant model antioxidant 1010, light stabilizer model LQ-622, heat stabilizer barium stearate (CAS No.: 6865-35-6), SEBS (CAS No.: 91261-65-3), γ-methacryloyloxypropyltrimethoxysilane (CAS No.: 2530-85-0).

[0045] Example 1

[0046] Preparation of modified PCR PP

[0047] 100g of PCR PP and 20g of maleic anhydride were stirred and mixed at 500rpm for 12min, then transferred to a twin-screw extruder and reacted at 200℃ for 2h. The mixture was then extruded and granulated to obtain modified PCR PP.

[0048] Preparation of modified PCR PE

[0049] 100g of PCR PE was dispersed in 500mL of toluene and stirred at 200rpm at 120℃ until completely dissolved to obtain a PCR PE solution. 1g of benzoyl peroxide was added to the PCR PE solution and, after dissolution, 3g of vinylpyrrolidone was added over 20min. After the addition was complete, the mixture was stirred at 200rpm at 120℃ for 1h. 2g of 2-(perfluorohexyl)ethyl methacrylate was added over 20min, and the mixture was stirred at 200rpm at 120℃ for 2h. After the reaction was complete, the mixture was poured into ethanol for precipitation. The precipitate was collected by filtration, washed three times with ethanol, and dried under vacuum at 70℃ to obtain modified PCR PE.

[0050] Preparation of modified PCR PS

[0051] 100g of PCR PS was mixed with 300mL of chloroform, heated to 60℃, and stirred at 200rpm until completely dissolved to obtain the PCR PS solution. 2g of anhydrous aluminum trichloride was added to the PCR PS solution and stirred evenly. 15g of p-toluenesulfonyl chloride was added dropwise over 30min. After the addition was complete, the temperature was raised to 70℃ and stirred at 200rpm for 3h. After the reaction was completed, the reaction solution was poured into a 5% (w / w) dilute hydrochloric acid solution for quenching. The mixture was stirred for 15min, and the organic phase was separated. The organic phase was washed three times with deionized water, dried with anhydrous sodium sulfate for 2h, filtered, and the dried organic phase was rotary evaporated to remove chloroform, yielding the modified PCR PS.

[0052] Preparation of surface-treated glass fibers

[0053] Glass fibers were ultrasonically washed with anhydrous ethanol and dried at 80°C to obtain washed glass fibers. 46.88g of tetraethyl orthosilicate and 9.37g of trifluoropropyltrimethoxysilane were added to a mixed solution of 500mL of anhydrous ethanol and water in a volume ratio of 4:1. 2g of 36% hydrochloric acid was added as a catalyst, and the mixture was stirred at 25°C for 2h to obtain a sol. 93.75g of washed glass fibers were immersed in the sol for 1h. After immersion, the fibers were dried at 60°C for 3h, placed in a muffle furnace, heated to 400°C at a rate of 5°C / min, and calcined for 1h. After cooling, surface-treated glass fibers were obtained.

[0054] Preparation of PCR thermoplastic elastomer materials

[0055] 70g of SEBS and 60g of white oil were mixed and stirred at 120℃ and 800rpm for 30min to obtain a mixture. 150g of PCR raw materials, consisting of modified PCR PP, modified PCR PE, and modified PCR PS in a mass ratio of 1:1:0.5, were added to the mixture. The mixture was stirred at 120℃ and 800rpm for 45min. 8g of UV stabilizer, 8g of antioxidant, 3g of light stabilizer, and 3g of heat stabilizer were added, and the mixture was stirred at 600rpm for 20min. 60g of surface-treated glass fiber was added, and the mixture was stirred at 150℃ and 500rpm for 60min to obtain a composite material. The composite material was melt-blended and extruded into granules using a twin-screw extruder. The extruder temperatures were set as follows: first section 160℃, second section 170℃, third section 180℃, fourth section 185℃, die head 180℃, and screw speed 300rpm to obtain the PCR thermoplastic elastomer material.

[0056] Example 2

[0057] Preparation of modified PCR PP

[0058] 100g of PCR PP and 20g of maleic anhydride were stirred and mixed at 500rpm for 12min, then transferred to a twin-screw extruder and reacted at 200℃ for 2h. The mixture was then extruded and granulated to obtain modified PCR PP.

[0059] Preparation of modified PCR PE

[0060] 100g of PCR PE was dispersed in 500mL of toluene and stirred at 200rpm at 120℃ until completely dissolved to obtain a PCR PE solution. 1g of benzoyl peroxide was added to the PCR PE solution and, after dissolution, 3g of vinylpyrrolidone was added over 20min. After the addition was complete, the mixture was stirred at 200rpm at 120℃ for 1h. 2g of 2-(perfluorohexyl)ethyl methacrylate was added over 20min, and the mixture was stirred at 200rpm at 120℃ for 2h. After the reaction was complete, the mixture was poured into ethanol for precipitation. The precipitate was collected by filtration, washed three times with ethanol, and dried under vacuum at 70℃ to obtain modified PCR PE.

[0061] Preparation of modified PCR PS

[0062] 100g of PCR PS was mixed with 300mL of chloroform, heated to 60℃, and stirred at 200rpm until completely dissolved to obtain the PCR PS solution. 2g of anhydrous aluminum trichloride was added to the PCR PS solution and stirred evenly. 15g of p-toluenesulfonyl chloride was added dropwise over 30min. After the addition was complete, the temperature was raised to 70℃ and stirred at 200rpm for 3h. After the reaction was completed, the reaction solution was poured into a 5% (w / w) dilute hydrochloric acid solution for quenching. The mixture was stirred for 15min, and the organic phase was separated. The organic phase was washed three times with deionized water, dried with anhydrous sodium sulfate for 2h, filtered, and the dried organic phase was rotary evaporated to remove chloroform, yielding the modified PCR PS.

[0063] Preparation of surface-treated glass fibers

[0064] Glass fibers were ultrasonically washed with anhydrous ethanol and dried at 80°C to obtain washed glass fibers. 41.67g of tetraethyl orthosilicate and 25g of trifluoropropyltrimethoxysilane were added to a mixed solution of 500mL of anhydrous ethanol and water in a volume ratio of 4:1. 2g of 36% hydrochloric acid was added as a catalyst, and the mixture was stirred at 25°C for 2h to obtain a sol. 83.33g of washed glass fibers were immersed in the sol for 1h. After immersion, the fibers were dried at 60°C for 3h, placed in a muffle furnace, heated to 400°C at a rate of 5°C / min, and calcined for 1h. After cooling, surface-treated glass fibers were obtained.

[0065] Preparation of PCR thermoplastic elastomer materials

[0066] Mix 80g of SEBS and 70g of white oil, and stir at 120℃ and 800rpm for 30min to obtain a mixture. Add 180g of PCR raw materials to the mixture. The PCR raw materials consist of modified PCR PP, modified PCR PE, and modified PCR PP in a mass ratio of 1:1:0.5. The PS composition was stirred at 120℃ and 800 rpm for 45 minutes. 10g of UV stabilizer, 10g of antioxidant, 5g of light stabilizer, and 5g of heat stabilizer were added, and the mixture was stirred at 600 rpm for 20 minutes. 80g of surface-treated glass fiber was added, and the mixture was stirred at 150℃ and 500 rpm for 60 minutes to obtain a composite material. The composite material was melt-blended and extruded into granules using a twin-screw extruder. The extruder temperatures were set as follows: Section 1 160℃, Section 2 170℃, Section 3 180℃, Section 4 185℃, Die Head 180℃, and Screw Speed ​​300 rpm to obtain a PCR thermoplastic elastomer material.

[0067] Example 3

[0068] Preparation of modified PCR PP

[0069] 100g of PCR PP and 20g of maleic anhydride were stirred and mixed at 500rpm for 12min, then transferred to a twin-screw extruder and reacted at 200℃ for 2h. The mixture was then extruded and granulated to obtain modified PCR PP.

[0070] Preparation of modified PCR PE

[0071] 100g of PCR PE was dispersed in 500mL of toluene and stirred at 200rpm at 120℃ until completely dissolved to obtain a PCR PE solution. 1g of benzoyl peroxide was added to the PCR PE solution and, after dissolution, 3g of vinylpyrrolidone was added over 20min. After the addition was complete, the mixture was stirred at 200rpm at 120℃ for 1h. 2g of 2-(perfluorohexyl)ethyl methacrylate was added over 20min, and the mixture was stirred at 200rpm at 120℃ for 2h. After the reaction was complete, the mixture was poured into ethanol for precipitation. The precipitate was collected by filtration, washed three times with ethanol, and dried under vacuum at 70℃ to obtain modified PCR PE.

[0072] Preparation of modified PCR PS

[0073] 100g of PCR PS was mixed with 300mL of chloroform, heated to 60℃, and stirred at 200rpm until completely dissolved to obtain the PCR PS solution. 2g of anhydrous aluminum trichloride was added to the PCR PS solution and stirred evenly. 15g of p-toluenesulfonyl chloride was added dropwise over 30min. After the addition was complete, the temperature was raised to 70℃ and stirred at 200rpm for 3h. After the reaction was completed, the reaction solution was poured into a 5% (w / w) dilute hydrochloric acid solution for quenching. The mixture was stirred for 15min, and the organic phase was separated. The organic phase was washed three times with deionized water, dried with anhydrous sodium sulfate for 2h, filtered, and the dried organic phase was rotary evaporated to remove chloroform, yielding the modified PCR PS.

[0074] Preparation of surface-treated glass fibers

[0075] Glass fibers were ultrasonically washed with anhydrous ethanol and dried at 80°C to obtain washed glass fibers. 44.12g of tetraethyl orthosilicate and 17.65g of trifluoropropyltrimethoxysilane were added to a mixed solution of 500mL anhydrous ethanol and water in a volume ratio of 4:1. 2g of 36% hydrochloric acid was added as a catalyst, and the mixture was stirred at 25°C for 2h to obtain a sol. 88.23g of washed glass fibers were immersed in the sol for 1h. After immersion, the fibers were dried at 60°C for 3h and placed in a muffle furnace. The temperature was increased to 400°C at a rate of 5°C / min and calcined for 1h. After cooling, surface-treated glass fibers were obtained.

[0076] Preparation of PCR thermoplastic elastomer materials

[0077] 75g of SEBS and 65g of white oil were mixed and stirred at 120℃ and 800rpm for 30min to obtain a mixture. 165g of PCR raw materials, consisting of modified PCR PP, modified PCR PE, and modified PCR PS in a mass ratio of 1:1:0.5, were added to the mixture. The mixture was stirred at 120℃ and 800rpm for 45min. 9g of UV stabilizer, 9g of antioxidant, 4g of light stabilizer, and 4g of heat stabilizer were added, and the mixture was stirred at 600rpm for 20min. 70g of surface-treated glass fiber was added, and the mixture was stirred at 150℃ and 500rpm for 60min to obtain a composite material. The composite material was melt-blended and extruded into granules using a twin-screw extruder. The extruder temperatures were set as follows: first section 160℃, second section 170℃, third section 180℃, fourth section 185℃, die head 180℃, and screw speed 300rpm to obtain the PCR thermoplastic elastomer material.

[0078] Example 4

[0079] Example 4 is based on Example 3. The only difference between Example 4 and Example 3 is that in Example 4, the modified PCRPP is replaced with PCR PP.

[0080] Example 5

[0081] Example 5 is based on Example 3. The only difference between Example 5 and Example 3 is that vinylpyrrolidone is not added when preparing the modified PCR PE in Example 5.

[0082] Example 6

[0083] Example 6 is based on Example 3. The only difference between Example 6 and Example 3 is that in Example 6, the modified PCRPS is replaced with PCR PS.

[0084] Example 7

[0085] Example 7 is based on Example 3. The only difference between Example 7 and Example 3 is that in Example 7, the amount of glass fiber is 96.77g, the amount of tetraethyl orthosilicate is 48.39g, and the amount of trifluoropropyltrimethoxysilane is 4.84g.

[0086] Example 8

[0087] Example 8 is based on Example 3. The only difference between Example 8 and Example 3 is that in Example 8, the amount of glass fiber is 78.95g, the amount of tetraethyl orthosilicate is 39.47g, and the amount of trifluoropropyltrimethoxysilane is 31.58g.

[0088] Preparation Example 1: Preparation of Modified SEBS

[0089] 100g of SEBS was placed in the reaction chamber of a plasma treatment device, evacuated to 5Pa, and argon gas was introduced at a flow rate of 60sccm. The plasma treatment power was set to 120W and the treatment time to 15min to obtain pre-modified SEBS. 100g of pre-modified SEBS and 10g of γ-methacryloyloxypropyltrimethoxysilane were dispersed in 250mL of anhydrous ethanol, and 0.5g of dibutyltin dilaurate was added. The mixture was stirred at 250rpm for 4h in a constant temperature water bath at 65℃. After the reaction was completed, the mixture was filtered and washed with anhydrous ethanol and dried under vacuum at 75℃ to obtain modified SEBS.

[0090] Example 9

[0091] Example 9 is based on Example 3. The only difference between Example 9 and Example 3 is that in Example 9, SEBS is replaced with the modified SEBS prepared in Preparation Example 1.

[0092] Comparative Example 1

[0093] Comparative Example 1 is based on Example 3. The only difference between Comparative Example 1 and Example 3 is that the surface-treated glass fiber is replaced with glass fiber in Comparative Example 1.

[0094] Comparative Example 2

[0095] Comparative Example 2 is based on Example 3. The only difference between Comparative Example 2 and Example 3 is that the PCR raw materials in Comparative Example 2 consist of PCR PP and PCR PE in a mass ratio of 1:1.

[0096] Comparative Example 3

[0097] Comparative Example 3 is based on Example 3. The only difference between Comparative Example 3 and Example 3 is that the PCR raw materials in Comparative Example 3 include only PCR PP.

[0098] Performance testing

[0099] (1) Select GB / T 1040.2-2006 Determination of tensile properties of plastics - Part 2: Test conditions for molded and extruded plastics as the standard, test the tensile strength and elongation at break of the specimens. Prepare three samples for each specimen, take the average value after measurement, and record the results in Table 1.

[0100] (2) Select GB / T 7141-2008 Plastics Thermal Aging Test Method as the standard, treat the sample at 100℃ for 7 days, test the tensile strength of the sample before and after treatment, calculate the strength retention rate, prepare three samples for each sample, take the average value after measurement, and record the results in Table 1.

[0101] (3) Select GB / T 16422.2-2014 Plastics Laboratory Light Source Exposure Test Method Part 2: Xenon Arc Lamp as the standard, use xenon arc lamp for aging treatment for 1000h, test the tensile strength of the sample before and after xenon arc lamp aging treatment, calculate the strength retention rate, prepare three samples for each sample, take the average value after measurement, and record the results in Table 1.

[0102] Table 1. Test results of tensile properties, thermal stability and aging resistance of PCR thermoplastic elastomer materials.

[0103]

[0104]

[0105] As shown in Table 1, the tensile strength of Examples 1-3 is greater than 37.8 MPa, the elongation at break is greater than 216%, the strength retention rate after heat treatment is greater than 87.9%, and the strength retention rate after xenon arc lamp aging is greater than 80.6%. This shows that the PCR thermoplastic elastomer material prepared in this application has good tensile properties, thermal stability and aging resistance.

[0106] As shown in Table 1, the differences between Examples 4, 5, and 6 and Example 3 are only as follows: in Example 4, modified PCR PP was replaced with PCR PP; in Example 5, vinylpyrrolidone was not added when preparing modified PCR PE; and in Example 6, modified PCR PS was replaced with PCR PS. Compared with Example 3, the performance of the materials in Examples 4, 5, and 6 has decreased. This is because if the various PCR materials are not modified, the compatibility between the materials decreases, the intermolecular interaction forces weaken, and the stability decreases, thereby reducing the tensile properties, thermal stability, and aging resistance of the materials.

[0107] As shown in Table 1, the only difference between Examples 7 and 8 and Example 3 is that the mass ratio of glass fiber, tetraethyl orthosilicate, and trifluoropropyltrimethoxysilane in Example 7 is 1:0.5:0.05, while the mass ratio of glass fiber, tetraethyl orthosilicate, and trifluoropropyltrimethoxysilane in Example 8 is 1:0.5:0.4. Compared with Example 3, the performance of Examples 7 and 8 is reduced. This is because the proportion of trifluoropropyltrimethoxysilane added to the surface-treated glass fiber has been changed. Too much or too little trifluoropropyltrimethoxysilane will affect the modification effect and the microstructure of the material surface, thereby affecting the compatibility and dispersibility of the material, and thus the performance of the PCR thermoplastic elastomer material is reduced.

[0108] As shown in Table 1, the only difference between Example 9 and Example 3 is that in Example 9, SEBS was replaced with the modified SEBS prepared in Preparation Example 1. Compared with Example 3, the performance of Example 9 has improved. This is because the modification treatment of SEBS increases the number of active groups on the SEBS surface, enhances the interfacial bonding force between components, and increases the cross-linking structure, thereby improving the tensile properties, thermal stability, and aging resistance.

[0109] As shown in Table 1, the only difference between Comparative Example 1 and Example 3 is that the surface-treated glass fiber was replaced with glass fiber in Comparative Example 1. Compared with Example 3, the performance of Comparative Example 1 is significantly reduced. This is because the glass fiber was not modified, the interfacial bonding force of the glass fiber decreased, the reinforcing effect was weakened, and thus the performance was reduced.

[0110] As shown in Table 1, the only difference between Comparative Examples 2 and 3 and Example 3 is that Comparative Example 2 replaced the PCR raw materials with PCR PP and PCR PE in a mass ratio of 1:1, and Comparative Example 3 replaced the PCR raw materials with PCR PP. Compared with Example 3, the performance of Comparative Examples 2 and 3 is significantly reduced. This is because the components of the PCR raw materials are reduced and no modification treatment is performed, which reduces the synergistic effect between materials, the compatibility and interfacial bonding force, and thus the performance of the materials is affected, and the tensile properties, thermal stability and aging resistance are reduced.

[0111] This specific embodiment is merely an explanation of this application and is not intended to limit it. Based on the above description, those skilled in the art can make various changes and modifications without departing from the technical concept of this application. The technical scope of this application is not limited to the contents of the specification but must be determined according to the scope of the claims.

Claims

1. A PCR thermoplastic elastomer material, characterized in that: The components include the following parts by mass: SEBS 70-80 copies 60-70 parts white oil PCR raw materials 150-180 samples Surface treatment with 60-80 parts glass fiber 8-10 parts of UV protectant 8-10 parts antioxidant 3-5 parts light stabilizer 3-5 parts heat stabilizer; The PCR raw materials include PCR PP, PCR PE, and PCR PS; The PCR PP was modified with maleic anhydride to obtain modified PCR PP; The PCR PE was modified with vinylpyrrolidone and 2-(perfluorohexyl)ethyl methacrylate to obtain modified PCR PE; The PCR PS was modified with p-toluenesulfonyl chloride to obtain modified PCR PS; The SEBS was subjected to plasma treatment and modification with γ-methacryloxypropyltrimethoxysilane to obtain modified SEBS. The modified SEBS was prepared using the following steps: SEBS was bombarded with plasma to obtain pre-modified SEBS; the pre-modified SEBS and γ-methacryloxypropyltrimethoxysilane were dispersed in a solvent, a catalyst was added, and the reaction was stirred under water bath conditions. After the reaction was completed, the mixture was filtered, washed, and dried to obtain modified SEBS. The raw materials for preparing the surface-treated glass fiber include glass fiber body, tetraethyl orthosilicate and trifluoropropyltrimethoxysilane; The mass ratio of the glass fiber body, tetraethyl orthosilicate and trifluoropropyltrimethoxysilane is 1:0.5:(0.1-0.3).

2. The PCR thermoplastic elastomer material according to claim 1, characterized in that: The PCR thermoplastic elastomer material was prepared using the following steps: SEBS and white oil were mixed and heated and stirred to obtain a mixture. PCR raw materials were added to the mixture and heated and stirred. UV stabilizer, antioxidant, light stabilizer and heat stabilizer were added and stirred. Surface-treated glass fiber was added and heated and stirred to obtain a composite material. The composite material was melt-blended, extruded and granulated to obtain a PCR thermoplastic elastomer material.

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