PCR (Polymerase Chain Reaction) thermoplastic elastomer material

Abstract

The invention relates to a PCR thermoplastic elastomer material, and relates to the technical field of composite materials, the PCR thermoplastic elastomer material comprises the following components by mass: 70-80 parts of SEBS, 60-70 parts of white oil, 150-180 parts of a PCR raw material, 60-80 parts of surface treated glass fiber, 8-10 parts of an anti-UV agent, 8-10 parts of an antioxidant, 3-5 parts of a light stabilizer, and 3-5 parts of a heat stabilizer. The PCR thermoplastic elastomer material disclosed by the invention is stable in performance, comparable with raw plastic, high in machinability and suitable for various processing methods such as injection molding and extrusion, the product manufacturing cost can be reduced, dependence on fossil fuel is reduced, and recycling and reusing of waste plastic are promoted.

Description

Technical Field

[0001] This application relates to the technical field of polymer composite materials, and particularly to a PCR thermoplastic elastomer material. Background Art

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

[0003] However, the extensive use of traditional plastic materials has brought serious environmental pollution problems. Ordinary plastics are difficult to degrade and accumulate in the natural environment for a long time, causing great damage to the soil, water sources, and ecosystems. Plastic pollution has become a global environmental problem. At the same time, the overexploitation of plastic raw materials also poses a threat to the sustainable supply of resources.

[0004] As a new type of environmentally friendly material, PCR (post-consumer recycled) thermoplastic elastomers have significant advantages such as recycling and pollution reduction, but they face challenges in terms of aging resistance. Since their raw materials are derived from recycled plastics, during multiple uses and recycling processes, the molecular structure changes, resulting in poor tolerance of the material to environmental factors. The problem of aging resistance makes PCR thermoplastic elastomers prone to problems such as appearance discoloration, mechanical property decline, and functional stability impairment, thus shortening the product life, so it needs to be improved. Summary of the Invention

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

[0006] The PCR thermoplastic elastomer material provided by this application adopts the following technical solutions: A PCR thermoplastic elastomer material, comprising the following components in parts by mass: 70 - 80 parts of SEBS 60 - 70 parts of white oil 150 - 180 parts of PCR raw material 60 - 80 parts of surface-treated glass fiber 8 - 10 parts of UV-resistant agent 8 - 10 parts of antioxidant 3 - 5 parts of light stabilizer 3 - 5 parts of heat stabilizer.

[0007] SEBS has good elasticity and flexibility. When combined with white oil, it can improve the processing performance and initial toughness of the material, providing a basis for tensile performance. PCR raw materials are derived from post-consumer waste, which is recycled and reused, and is highly environmentally friendly. It not only reduces the demand for new plastics and reduces environmental burden, but also greatly reduces energy consumption and carbon emissions, helping to achieve low-carbon goals. PCR raw materials can form an interpenetrating network structure with SEBS, enhance the intermolecular force, and improve the overall strength and tensile performance. Surface-treated glass fiber, with its high strength and high modulus characteristics, is evenly dispersed in the system, plays a role in strengthening the skeleton, effectively bears and transmits stress, and greatly enhances tensile performance. Antioxidants can capture free radicals and inhibit oxidation chain reactions. Thermal stabilizers can prevent the decomposition and degradation of materials at high temperatures. Together, they maintain the stability of the chemical structure of the material and improve thermal stability. Anti-UV agents can absorb ultraviolet energy, light stabilizers can quench excited molecules, and antioxidants can further inhibit oxidative aging. They work together to resist erosion by environmental factors in many aspects, improve the aging resistance of the material, and enable the material to function stably in a variety of application scenarios. The PCR thermoplastic elastomer material obtained after processing has stable performance, comparable to virgin plastic, strong processability, and is suitable for various processing methods such as injection molding and extrusion. It can reduce product manufacturing costs, reduce dependence on fossil fuels, and promote the recycling and reuse of waste plastics. It meets the policy requirements of many countries to mandatory use of PCR plastics.

[0008] Preferably, the PCR raw materials include PCR PP, PCR PE and PCR PS.

[0009] PCR PP has high rigidity and crystallinity, which can provide good skeleton support for the material, enhance the interaction between molecules, and enable the material to better transfer stress when subjected to force, thereby improving the tensile properties; PCR PP itself has thermal stability, which can improve the overall heat resistance of the material; PCR PE has good flexibility, and synergizes with PCR PP to enhance the tensile properties of the material while improving the impact resistance of the material, and its chemical properties are stable, which helps to improve the material's resistance to chemical corrosion, thereby improving its aging resistance; PCR PS has high hardness and high strength, which can further enhance the overall rigidity of the material and optimize the tensile properties of the material, and PCR PS has good dimensional stability at high temperatures, which can cooperate with other components to improve the thermal stability of the material; the three work together to form a complex and stable structure inside the material, thereby effectively improving the tensile properties, thermal stability and aging resistance.

[0010] Preferably, the PCR PP is modified using maleic anhydride to obtain modified PCR PP.

[0011] Maleic anhydride is grafted onto the molecular chain of PCR PP, increasing the polarity and intermolecular force between molecular chains, making it difficult for molecular chains to slip when stressed, thus enhancing the tensile properties of the material; the molecular structure of the modified PCR PP is optimized, and the thermal decomposition temperature is increased, making it more stable in high-temperature environments, effectively improving the overall thermal stability of the material; the grafted maleic anhydride structure can hinder the erosion of molecular chains by external factors such as oxygen and ultraviolet rays, reducing the occurrence of aging reactions such as oxidation and photodegradation, and thus enhancing the aging resistance of the material.

[0012] Preferably, the PCR PE is modified with vinylpyrrolidone and 2-(perfluorohexyl)ethyl methacrylate to obtain modified PCR PE.

[0013] Vinylpyrrolidone is grafted onto the molecular chain of PCR PE, increasing the intermolecular interaction and entanglement degree between molecular chains, enabling the material to transfer stress more effectively when stressed, enhancing the ability of molecular chains to resist external force damage, and thus improving the tensile properties of the material; at the same time, the grafted structure helps to stabilize the molecular chain, inhibits the movement and degradation of the molecular chain at high temperatures, and improves the thermal stability of the material; the fluorine-containing group introduced by 2-(perfluorohexyl)ethyl methacrylate has a low surface energy and good chemical stability, and can form a protective barrier on the material surface to block the erosion of oxygen, ultraviolet rays and chemical substances, effectively delaying the aging process of the material and enhancing the aging resistance; the synergistic effect of the two can effectively improve the tensile properties, thermal stability and aging resistance of the PCR PE material.

[0014] Preferably, the PCR PS is modified with p-toluenesulfonyl chloride to obtain modified PCR PS.

[0015] The p-toluenesulfonyl group has strong electron-withdrawing properties. When modifying PCR PS, it affects the electron cloud distribution of the molecular chain through inductive effect and conjugate effect, increasing the intermolecular force between molecular chains, making the entanglement between molecular chains tighter. When the material is stretched by external force, it can transfer stress more effectively, reducing the relative sliding of molecular chains, thus enhancing the tensile properties of the material; the p-toluenesulfonyl group has a large steric hindrance effect, which can not only protect the key groups on the molecular chain, but also affect the spatial configuration of the molecule, further enhancing the intermolecular interaction and improving the tensile properties of the material; the p-toluenesulfonyl group has good stability. After introduction, it optimizes the molecular chain structure of PCR PS, enhances the rigidity of the molecular chain, and can inhibit the movement and decomposition of the molecular chain in high-temperature environments, improving the ability of the material to resist thermal deformation and thermal degradation, thus enhancing the overall thermal stability of the material; the p-toluenesulfonyl group has good stability, which can block the damage of external factors such as oxygen and ultraviolet rays to the molecular chain, reducing the occurrence probability of oxidation reaction and photodegradation, and thus enhancing the aging resistance of the material.

[0016] Preferably, the SEBS is subjected to plasma treatment and modification with γ-methacryloxypropyltrimethoxysilane to obtain modified SEBS.

[0017] Plasma treatment introduces a large number of active groups on the surface of SEBS, increasing its surface activity and roughness, and enhancing the interfacial bonding force with other components; γ-methacryloxypropyltrimethoxysilane binds to the surface active sites of SEBS through chemical bonds, forming a crosslinked network between molecular chains, enhancing the intermolecular force. When the material is stretched, it can effectively disperse stress and inhibit the slippage of molecular chains, thus greatly improving the tensile performance; the crosslinked structure restricts the thermal movement of molecular chains, increases the thermal decomposition temperature of the material, making it more stable at high temperatures; the crosslinked 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 the aging resistance.

[0018] Preferably, the modified SEBS is prepared by the following steps: The SEBS is bombarded with plasma to obtain preliminarily modified SEBS; the preliminarily modified SEBS and γ-methacryloxypropyltrimethoxysilane are dispersed in a solvent, a catalyst is added, and the mixture is stirred and reacted under a water bath condition. After the reaction is completed, it is filtered, washed, and dried to obtain modified SEBS.

[0019] Preferably, the solvent includes anhydrous ethanol, and the catalyst includes dibutyltin dilaurate.

[0020] The modified SEBS prepared according to the above steps has good reactivity and compatibility, and can effectively improve the tensile performance, thermal stability and aging resistance of the PCR thermoplastic elastomer.

[0021] Preferably, the raw materials for preparing the surface-treated glass fiber include a glass fiber body, tetraethyl orthosilicate and 3-trifluoropropyltrimethoxysilane.

[0022] Glass fiber has high strength and high modulus, which can provide stable support for the material. It has good thermal stability, can inhibit the deformation of the material at high temperatures, and has a stable physical structure, which can block the erosion of external factors, effectively improving the tensile performance, thermal stability and aging resistance of the PCR thermoplastic elastomer material; the siloxane network formed by the hydrolysis of tetraethyl orthosilicate enhances the interfacial adhesion with the glass fiber and the matrix, efficiently transfers stress, delays heat transfer, inhibits the thermal decomposition of the matrix, and improves the tensile performance and thermal stability; the fluorine-containing group in 3-trifluoropropyltrimethoxysilane has a low surface energy and good chemical stability, forming a protective film on the material surface, which can resist the erosion of substances such as ultraviolet rays and oxygen, delay aging, and improve the aging resistance of the material.

[0023] Preferably, the mass ratio of the glass fiber body, tetraethyl orthosilicate, and 3,3,3-trifluoropropyltrimethoxysilane is 1:0.5:(0.1 - 0.3).

[0024] The surface-modified glass fiber prepared according to the above mass ratio has good compatibility and can effectively improve the tensile properties, thermal stability, and aging resistance of the PCR thermoplastic elastomer.

[0025] Preferably, the PCR thermoplastic elastomer material is prepared by the following steps: Mix SEBS and white oil, heat and stir to obtain a mixture; add the PCR raw materials to the mixture, heat and stir, then add an anti-UV agent, an antioxidant, a light stabilizer, and a heat stabilizer, stir, add the surface-treated glass fiber, heat and stir to mix, obtain a composite material, and perform melt blending and extrusion granulation on the composite material to obtain the PCR thermoplastic elastomer material.

[0026] The PCR thermoplastic elastomer material prepared according to the above steps has good tensile properties, thermal stability, and aging resistance, can maintain good appearance and performance in various complex environments, meet various application requirements, and has a long service life.

[0027] In summary, the present application includes at least one of the following beneficial technical effects: 1. SEBS has good elasticity and flexibility. When combined with white oil, it can improve the processing performance and initial toughness of the material, providing a basis for tensile properties; the PCR raw materials are derived from post-consumer waste and are recycled, with strong environmental protection. It not only reduces the demand for new plastics, reduces the environmental burden, but also significantly reduces energy consumption and carbon emissions, contributing to the low-carbon goal; the PCR raw materials can form an interpenetrating network structure with SEBS, enhancing the intermolecular force and improving the overall strength and tensile properties; the surface-treated glass fiber, with its high strength and high modulus characteristics, is evenly dispersed in the system, acting as a reinforcing framework, effectively bearing and transmitting stress, and significantly enhancing the tensile properties; the antioxidant can capture free radicals and inhibit the oxidation chain reaction, and the heat stabilizer can prevent the decomposition and degradation of the material at high temperatures. Their combined action maintains the chemical structure stability of the material and improves the thermal stability; the anti-UV agent can absorb the energy of ultraviolet rays, the light stabilizer can quench the excited-state molecules, and the antioxidant can further inhibit oxidative aging. They work together in multiple aspects to resist the erosion of environmental factors and improve the aging resistance of the material, enabling the material to stably play its role in a variety of application scenarios.

[0028] 2. Plasma treatment introduces a large number of active groups on the SEBS surface, increasing its surface activity and roughness, and enhancing the interfacial bonding force 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, enhancing the intermolecular force. When the material is stretched, it can effectively disperse stress and inhibit the slippage of molecular chains, thus greatly improving the tensile performance; the cross-linked structure restricts the thermal movement 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 the aging resistance performance.

[0029] 3. Glass fiber has high strength and high modulus, which can provide stable support for the material. It has good thermal stability, can inhibit the deformation of the material at high temperatures, and at the same time has a stable physical structure, which can block the erosion of external factors, effectively improving the tensile performance, thermal stability and aging resistance performance of the PCR thermoplastic elastomer material; the siloxane network formed by the hydrolysis of tetraethyl orthosilicate enhances the interfacial adhesion with glass fiber and the matrix, efficiently transfers stress, delays heat transfer, inhibits the thermal decomposition of the matrix, and improves the tensile performance and thermal stability; the fluorine-containing group in 3,3,3-trifluoropropyltrimethoxysilane has low surface energy and chemical stability, forming a protective film on the material surface, which can resist the erosion of substances such as ultraviolet rays and oxygen, delay aging, and improve the aging resistance performance of the material. Detailed implementation mode

[0030] The embodiment of the present application discloses a PCR thermoplastic elastomer material. The raw materials used in the present application can be obtained from commercially available raw materials except as otherwise specified. The following further details the present application in conjunction with embodiments: 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), vinyl pyrrolidone (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), 3,3,3-trifluoropropyltrimethoxysilane (CAS No.: 429-60-7), white oil (CAS No.: 8012-95-1), the anti-UV agent model is UV-3638, the antioxidant model is antioxidant 1010, the light stabilizer model is LQ-622, the heat stabilizer is barium stearate (CAS No.: 6865-35-6), SEBS (CAS No.: 91261-65-3), γ-methacryloxypropyltrimethoxysilane (CAS No.: 2530-85-0).

[0031] Example 1 Preparation of modified PCR PP Mix 100 g of PCR PP and 20 g of maleic anhydride with a stirring speed of 500 rpm for 12 min, transfer it into a twin-screw extruder, react at 200 °C for 2 h, extrude and pelletize to obtain modified PCR PP.

[0032] Preparation of modified PCR PE Disperse 100 g of PCR PE into 500 mL of toluene, stir at a stirring speed of 200 rpm at 120 °C until completely dissolved to obtain a PCR PE solution; add 1 g of benzoyl peroxide to the PCR PE solution, after dissolution, add 3 g of vinyl pyrrolidone within 20 min, after dropping, stir and react at 200 rpm at 120 °C for 1 h, add 2 g of 2-(perfluorohexyl)ethyl methacrylate within 20 min, stir and react at 200 rpm at 120 °C for 2 h, after the reaction is completed, pour it into ethanol for precipitation, filter and collect the precipitate, wash it 3 times with ethanol, and dry it in vacuum at 70 °C to obtain modified PCR PE.

[0033] Preparation of modified PCR PS Mix 100 g of PCR PS and 300 mL of chloroform, heat up to 60 °C, stir at a speed of 200 rpm, and after complete dissolution, obtain a PCR PS solution; add 2 g of anhydrous aluminum trichloride to the PCR PS solution, stir evenly, and dropwise add 15 g of p-toluenesulfonyl chloride within 30 min. After the addition is complete, heat up to 70 °C and stir and react at a speed of 200 rpm for 3 h. After the reaction is completed, pour the reaction solution into a 5% mass fraction dilute hydrochloric acid solution for quenching, stir for 15 min, separate the organic phase, wash the organic phase with deionized water 3 times, add anhydrous sodium sulfate for drying for 2 h, filter, and rotary evaporate the dried organic phase to remove chloroform to obtain modified PCR PS.

[0034] Prepare surface-treated glass fiber Ultrasonically wash the glass fiber with absolute ethanol and dry it at 80 °C to obtain the washed glass fiber; add 46.88 g of tetraethyl orthosilicate and 9.37 g of trifluoropropyltrimethoxysilane to a mixed solution of 500 mL of absolute ethanol and water with a volume ratio of 4:1, add 2 g of 36% hydrochloric acid as a catalyst, and stir at 25 °C for 2 h to obtain a sol; immerse 93.75 g of the washed glass fiber in the sol for 1 h, take it out, dry it at 60 °C for 3 h, put it into a muffle furnace, heat it up to 400 °C at a speed of 5 °C / min, calcine for 1 h, and after cooling, obtain surface-treated glass fiber.

[0035] Prepare PCR thermoplastic elastomer material Mix 70 g of SEBS and 60 g of white oil, stir at a stirring speed of 800 rpm at 120 °C for 30 min to obtain a mixture; add 150 g of PCR raw materials to the mixture. The PCR raw materials are composed of modified PCR PP, modified PCR PE, and modified PCR PS with a mass ratio of 1:1:0.5. Stir at a stirring speed of 800 rpm at 120 °C for 45 min, add 8 g of UV absorber, 8 g of antioxidant, 3 g of light stabilizer, and 3 g of heat stabilizer, stir at a speed of 600 rpm for 20 min, add 60 g of surface-treated glass fiber, and stir and mix at a stirring speed of 500 rpm at 150 °C for 60 min to obtain a composite material. Extrude and pelletize the composite material through a twin-screw extruder. The temperature settings of each section of the extruder are: the first section is 160 °C, the second section is 170 °C, the third section is 180 °C, the fourth section is 185 °C, the die head is 180 °C, and the screw speed is 300 rpm to obtain the PCR thermoplastic elastomer material.

[0036] Example 2 Prepare modified PCR PP 100 g of PCR PP and 20 g of maleic anhydride were stirred and mixed at a speed of 500 rpm for 12 min, then transferred into a twin-screw extruder and reacted at 200 °C for 2 h, and then extruded and pelletized to obtain modified PCR PP.

[0037] Preparation of modified PCR PE 100 g of PCR PE was dispersed in 500 mL of toluene and stirred at a speed of 200 rpm at 120 °C until completely dissolved to obtain a PCR PE solution; 1 g of benzoyl peroxide was added to the PCR PE solution. After dissolution, 3 g of vinyl pyrrolidone was added within 20 min. After the addition was completed, the mixture was stirred and reacted at a speed of 200 rpm at 120 °C for 1 h. Then, 2 g of 2-(perfluorohexyl)ethyl methacrylate was added within 20 min, and the mixture was stirred and reacted at a speed of 200 rpm at 120 °C for 2 h. After the reaction was completed, it was poured into ethanol for precipitation, and the precipitate was collected by filtration, washed 3 times with ethanol, and dried in vacuo at 70 °C to obtain modified PCR PE.

[0038] Preparation of modified PCR PS 100 g of PCR PS and 300 mL of chloroform were mixed, heated to 60 °C, and stirred at a speed of 200 rpm. After complete dissolution, a PCR PS solution was obtained; 2 g of anhydrous aluminum trichloride was added to the PCR PS solution. After stirring evenly, 15 g of p-toluenesulfonyl chloride was added dropwise within 30 min. After the addition was completed, the temperature was raised to 70 °C and stirred and reacted at a speed of 200 rpm for 3 h. After the reaction was completed, the reaction solution was poured into a 5% (mass fraction) dilute hydrochloric acid solution for quenching, stirred for 15 min, and the organic phase was separated. The organic phase was washed 3 times with deionized water, dried with anhydrous sodium sulfate for 2 h, filtered, and the dried organic phase was rotary evaporated to remove chloroform to obtain modified PCR PS.

[0039] Preparation of surface-treated glass fiber The glass fiber was ultrasonically washed with absolute ethanol and dried at 80 °C to obtain the washed glass fiber; 41.67 g of tetraethyl orthosilicate and 25 g of 3-trifluoropropyltrimethoxysilane were added to a mixed solution of 500 mL of absolute ethanol and water with a volume ratio of 4:1, and 2 g of 36% hydrochloric acid was added as a catalyst and stirred at 25 °C for 2 h to obtain a sol; 83.33 g of the washed glass fiber was immersed in the sol for 1 h, taken out, dried at 60 °C for 3 h, placed in a muffle furnace, heated to 400 °C at a rate of 5 °C / min, calcined for 1 h, and after cooling, surface-treated glass fiber was obtained.

[0040] Preparation of PCR thermoplastic elastomer material Mix 80 g of SEBS and 70 g of white oil, and stir at 120 °C with a stirring speed of 800 rpm for 30 min to obtain a mixture; add 180 g of PCR raw materials to the mixture. The PCR raw materials are composed of modified PCR PP, modified PCR PE, and modified PCR PS with a mass ratio of 1:1:0.5. Stir at 120 °C with a stirring speed of 800 rpm for 45 min, add 10 g of UV inhibitor, 10 g of antioxidant, 5 g of light stabilizer, and 5 g of heat stabilizer, stir at a speed of 600 rpm for 20 min, add 80 g of surface-treated glass fiber, and stir and mix at 150 °C with a stirring speed of 500 rpm for 60 min to obtain a composite material. Extrude and pelletize the composite material through a twin-screw extruder. The temperature of each section of the extruder is set as follows: the first section is 160 °C, the second section is 170 °C, the third section is 180 °C, the fourth section is 185 °C, the die head is 180 °C, and the screw speed is 300 rpm to obtain the PCR thermoplastic elastomer material.

[0041] Example 3 Prepare modified PCR PP Mix 100 g of PCR PP and 20 g of maleic anhydride at a speed of 500 rpm for 12 min, transfer to a twin-screw extruder, react at 200 °C for 2 h, extrude and pelletize to obtain modified PCR PP.

[0042] Prepare modified PCR PE Disperse 100 g of PCR PE into 500 mL of toluene, stir at 120 °C with a stirring speed of 200 rpm until completely dissolved to obtain a PCR PE solution; add 1 g of benzoyl peroxide to the PCR PE solution. After dissolution, add 3 g of vinyl pyrrolidone within 20 min. After the addition is complete, stir and react at 120 °C with a stirring speed of 200 rpm for 1 h. Add 2 g of 2-(perfluorohexyl)ethyl methacrylate within 20 min, and stir and react at 120 °C with a speed of 200 rpm for 2 h. After the reaction is completed, pour it into ethanol for precipitation, filter and collect the precipitate, wash it 3 times with ethanol, and dry it in vacuum at 70 °C to obtain modified PCR PE.

[0043] Prepare modified PCR PS Mix 100 g of PCR PS and 300 mL of chloroform, heat up to 60 °C, stir at a speed of 200 rpm. After complete dissolution, a PCR PS solution is obtained; add 2 g of anhydrous aluminum trichloride to the PCR PS solution, stir evenly, and then add 15 g of p-toluenesulfonyl chloride dropwise within 30 min. After the addition is complete, heat up to 70 °C and stir for reaction at a speed of 200 rpm for 3 h. After the reaction is completed, pour the reaction solution into a 5% dilute hydrochloric acid solution for quenching, stir for 15 min, separate the organic phase, wash the organic phase with deionized water 3 times, add anhydrous sodium sulfate for drying for 2 h, filter, and rotary evaporate the dried organic phase to remove chloroform to obtain modified PCR PS.

[0044] Preparation of surface-treated glass fiber Ultrasonically wash the glass fiber with anhydrous ethanol and dry it at 80 °C to obtain the washed glass fiber; add 44.12 g of tetraethyl orthosilicate and 17.65 g of trifluoropropyltrimethoxysilane to a mixed solution of 500 mL of anhydrous ethanol and water with a volume ratio of 4:1, add 2 g of 36% hydrochloric acid as a catalyst, and stir at 25 °C for 2 h to obtain a sol; immerse 88.23 g of the washed glass fiber in the sol for 1 h, take it out, dry it at 60 °C for 3 h, put it into a muffle furnace, heat it up to 400 °C at a speed of 5 °C / min, calcine for 1 h, and after cooling, obtain the surface-treated glass fiber.

[0045] Preparation of PCR thermoplastic elastomer material Mix 75 g of SEBS and 65 g of white oil, stir at a stirring speed of 800 rpm at 120 °C for 30 min to obtain a mixture; add 165 g of the PCR raw materials to the mixture. The PCR raw materials are composed of modified PCR PP, modified PCR PE, and modified PCR PS with a mass ratio of 1:1:0.5. Stir at a stirring speed of 800 rpm at 120 °C for 45 min, add 9 g of UV absorber, 9 g of antioxidant, 4 g of light stabilizer, and 4 g of heat stabilizer, stir at a speed of 600 rpm for 20 min, add 70 g of surface-treated glass fiber, and stir and mix at a stirring speed of 500 rpm at 150 °C for 60 min to obtain a composite material. Extrude and pelletize the composite material through a twin-screw extruder. The temperature settings of each section of the extruder are: the first section is 160 °C, the second section is 170 °C, the third section is 180 °C, the fourth section is 185 °C, the die head is 180 °C, and the screw speed is 300 rpm to obtain the PCR thermoplastic elastomer material.

[0046] Example 4 Example 4 is based on Example 3. The difference between Example 4 and Example 3 is only that in Example 4, modified PCR PP is replaced with PCR PP.

[0047] Example 5 Example 5 is based on Example 3. The only difference between Example 5 and Example 3 is that vinyl pyrrolidone is not added when preparing the modified PCR PE in Example 5.

[0048] Example 6 Example 6 is based on Example 3. The only difference between Example 6 and Example 3 is that the modified PCR PS is replaced by PCR PS in Example 6.

[0049] Example 7 Example 7 is based on Example 3. The only difference between Example 7 and Example 3 is that the amount of glass fiber used in Example 7 is 96.77 g, the amount of tetraethyl orthosilicate used is 48.39 g, and the amount of 3-trifluoropropyltrimethoxysilane used is 4.84 g.

[0050] Example 8 Example 8 is based on Example 3. The only difference between Example 8 and Example 3 is that the amount of glass fiber used in Example 8 is 78.95 g, the amount of tetraethyl orthosilicate used is 39.47 g, and the amount of 3-trifluoropropyltrimethoxysilane used is 31.58 g.

[0051] Preparation Example 1 Preparation of Modified SEBS Place 100 g of SEBS in the reaction chamber of the plasma treatment equipment, evacuate to 5 Pa, introduce argon, the gas flow rate is 60 sccm, set the plasma treatment power to 120 W, and the treatment time to 15 min to obtain preliminarily modified SEBS; disperse 100 g of preliminarily modified SEBS and 10 g of γ-methacryloxypropyltrimethoxysilane into 250 mL of absolute ethanol, add 0.5 g of dibutyltin dilaurate, and stir and react at a speed of 250 rpm in a constant temperature water bath at 65 °C for 4 h. After the reaction, filter and wash with absolute ethanol, and dry in vacuum at 75 °C to obtain modified SEBS.

[0052] Example 9 Example 9 is based on Example 3. The only difference between Example 9 and Example 3 is that SEBS is replaced by the modified SEBS prepared in Preparation Example 1 in Example 9.

[0053] Comparative Example 1 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 by glass fiber in Comparative Example 1.

[0054] Comparative Example 2 Comparative Example 2 is based on Example 3. The only difference between Comparative Example 2 and Example 3 is that the PCR raw material in Comparative Example 2 consists of PCR PP and PCR PE with a mass ratio of 1:1.

[0055] Comparative Example 3 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 only include PCR PP.

[0056] Performance detection test (1) Select "GB / T 1040.2-2006 Plastics - Determination of tensile properties - Part 2: Test conditions for moulded and extruded plastics" as the standard to test the tensile strength and elongation at break of the specimens. Prepare three samples for each specimen, and take the average value after measurement. The results are recorded in Table 1.

[0057] (2) Select "GB / T 7141-2008 Plastics - Methods of heat aging test" as the standard. Treat the specimens at 100 °C for 7 days, test the tensile strength of the specimens before and after treatment, and calculate the strength retention rate. Prepare three samples for each specimen, and take the average value after measurement. The results are recorded in Table 1.

[0058] (3) Select "GB / T 16422.2-2014 Plastics - Methods of exposure to laboratory light sources - Part 2: Xenon-arc lamps" as the standard. Use xenon-arc lamp aging treatment for 1000 h, test the tensile strength of the specimens before and after xenon-arc lamp aging treatment, and calculate the strength retention rate. Prepare three samples for each specimen, and take the average value after measurement. The results are recorded in Table 1.

[0059] Table 1 Detection results of tensile properties, thermal stability and aging resistance of PCR thermoplastic elastomer materials As can be seen from 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%. Thus, it can be seen that the PCR thermoplastic elastomer material prepared in this application has good tensile properties, thermal stability and aging resistance.

[0060] As can be seen from Table 1, the only differences between Examples 4, 5, 6 and Example 3 are as follows: in Example 4, the modified PCR PP is replaced with PCR PP; in Example 5, vinyl pyrrolidone is not added when preparing the modified PCR PE; in Example 6, the modified PCR PS is replaced with PCR PS. Compared with Example 3, the performance of the materials in Examples 4, 5, 6 has decreased; this is because if the various PCR materials are not modified, the compatibility between the materials decreases, the intermolecular interaction force weakens, the stability decreases, and thus the tensile properties, thermal stability and aging resistance of the materials decrease.

[0061] As can be seen from Table 1, the differences between Example 7, Example 8 and Example 3 are only as follows: in Example 7, the mass ratio of glass fiber, tetraethyl orthosilicate and 3,3,3-trifluoropropyltrimethoxysilane is 1:0.5:0.05; in Example 8, the mass ratio of glass fiber, tetraethyl orthosilicate and 3,3,3-trifluoropropyltrimethoxysilane is 1:0.5:0.4. Compared with Example 3, the performance of Example 7 and Example 8 has decreased. This is because the addition ratio of 3,3,3-trifluoropropyltrimethoxysilane in the surface-treated glass fiber is changed. Too much or too little 3,3,3-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 has decreased.

[0062] As can be seen from Table 1, the difference between Example 9 and Example 3 is only that in Example 9, SEBS is replaced by the modified SEBS prepared in Preparation Example 1. Compared with Example 3, the performance of Example 9 has increased. This is because the SEBS is modified, the number of surface active groups of SEBS increases, the interfacial binding force between components is enhanced, and the crosslinked structure increases, so the tensile performance, thermal stability performance and aging resistance performance have all increased.

[0063] As can be seen from Table 1, the difference between Comparative Example 1 and Example 3 is only that in Comparative Example 1, the surface-treated glass fiber is replaced by glass fiber. Compared with Example 3, the performance of Comparative Example 1 has decreased significantly. This is because the glass fiber is not modified, the interfacial binding force of the glass fiber decreases, and the reinforcing effect weakens, so the performance has decreased.

[0064] As can be seen from Table 1, the differences between Comparative Example 2, Comparative Example 3 and Example 3 are only as follows: in Comparative Example 2, the PCR raw material is replaced by PCR PP and PCR PE with a mass ratio of 1:1; in Comparative Example 3, the PCR raw material is replaced by PCR PP. Compared with Example 3, the performance of Comparative Example 2 and Comparative Example 3 has decreased significantly. This is because the components of the PCR raw material are reduced and no modification treatment is carried out, the synergistic effect between materials decreases, the compatibility and interfacial binding force decrease, so the performance of the material is affected, and the tensile performance, thermal stability performance and aging resistance performance decrease.

[0065] This specific embodiment is only an explanation of the present application, and it does not limit the present application. Through the above description, relevant staff can make various changes and modifications completely within the scope without deviating from the technical idea of this application. The technical scope of this application is not limited to the content in the specification, and its technical scope must be determined according to the scope of the claims.

Claims

1. A PCR thermoplastic elastomer material, characterized in that: The composition includes the following components in parts by weight: SEBS 70-80 parts 60-70 parts of white oil PCR raw materials 150-180 copies Surface treated glass fiber 60-80 parts 8-10 parts of anti-UV agent 8-10 parts of antioxidant Light stabilizer 3-5 parts 3-5 parts of heat stabilizer.

2. A PCR thermoplastic elastomer material according to claim 1, characterized in that: The PCR raw materials include PCR PP, PCR PE and PCR PS.

3. A PCR thermoplastic elastomer material according to claim 2, characterized in that: The PCR PP is modified by using maleic anhydride to obtain modified PCR PP.

4. A PCR thermoplastic elastomer material according to claim 3, characterized in that: The PCR PE is modified by using vinyl pyrrolidone and 2-(perfluorohexyl)ethyl methacrylate to obtain modified PCR PE.

5. A PCR thermoplastic elastomer material according to claim 4, characterized in that: The PCR PS is modified by using p-toluenesulfonyl chloride to obtain modified PCR PS.

6. The PCR thermoplastic elastomer material according to claim 1, characterized in that: The SEBS is subjected to plasma treatment and modification treatment with γ-methacryloxypropyltrimethoxysilane to obtain modified SEBS.

7. A PCR thermoplastic elastomer material according to claim 6, characterized in that: The modified SEBS is prepared by the following steps: SEBS is subjected to plasma bombardment to obtain preliminary modified SEBS; the preliminary modified SEBS and γ-methacryloxypropyltrimethoxysilane are dispersed in a solvent, a catalyst is added, and the mixture is stirred and reacted in a water bath. After the reaction is completed, the mixture is filtered, washed, and dried to obtain the modified SEBS.

8. The PCR thermoplastic elastomer material according to claim 1, characterized in that: The raw materials for preparing the surface-treated glass fiber include glass fiber body, tetraethyl orthosilicate and trifluoropropyltrimethoxysilane.

9. The PCR thermoplastic elastomer material according to claim 8, characterized in that: The mass ratio of the glass fiber body, tetraethyl orthosilicate and trifluoropropyltrimethoxysilane is 1:0.5:(0.1-0.3).

10. A PCR thermoplastic elastomer material according to any one of claims 1 to 9, characterized in that: The PCR thermoplastic elastomer material is prepared by the following steps: The SEBS and white oil are mixed, heated and stirred to obtain a mixture; the PCR raw materials are added to the mixture, heated and stirred, and then an anti-UV agent, an antioxidant, a light stabilizer and a heat stabilizer are added, and after stirring, surface-treated glass fiber is added, heated and stirred to obtain a composite material, and the composite material is melt-blended, extruded and granulated to obtain a PCR thermoplastic elastomer material.

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