High-performance modified PVC transparent hard sheet and preparation method thereof

Abstract

The application relates to the field of PVC transparent hard sheets, in particular to a high-performance modified PVC transparent hard sheet and a preparation method thereof, and aims to solve the problems that the existing PVC transparent hard sheet has insufficient impact resistance and low mechanical performance, and is limited in application in some occasions with high material performance requirements; the PVC transparent hard sheet takes long-chain branched polyvinyl chloride as a main raw material; the long-chain structure of the long-chain branched modified polyvinyl chloride can improve the flexibility of molecular chains, so that the PVC transparent hard sheet is not easy to break when subjected to external force, can bear greater impact load, the anti-impact core-shell particles added into the PVC transparent hard sheet have good compatibility with the matrix, can simultaneously provide excellent rigidity and impact resistance, realize excellent comprehensive performance, and can meet the use requirements under different conditions, so that the PVC transparent hard sheet has excellent application prospects in multiple fields. Moreover, the preparation method has simple process and low cost, and is easy to realize industrialized production.

Description

Technical Field

[0001] This invention relates to the field of PVC transparent rigid sheets, and more specifically to a high-performance modified PVC transparent rigid sheet and its preparation method. Background Technology

[0002] Polyvinyl chloride (PVC) is a commonly used general-purpose plastic with advantages such as low cost, good processability, and chemical resistance, leading to its widespread application in numerous fields. Among these, PVC transparent rigid sheets, due to their high transparency, lightweight, and ease of processing, are frequently used in food packaging, stationery, and electronic product packaging. However, ordinary PVC transparent rigid sheets have some significant drawbacks, such as poor toughness, insufficient impact resistance, and relatively low mechanical properties, which limit their application in situations requiring higher material performance.

[0003] Therefore, developing a high-performance modified PVC transparent rigid sheet and its preparation method is of great practical significance. Summary of the Invention

[0004] In order to overcome the above-mentioned technical problems, the purpose of this invention is to provide a high-performance modified PVC transparent rigid sheet and its preparation method, which solves the problems that the existing PVC transparent rigid sheet has insufficient impact resistance and low mechanical properties, which limits its application in some occasions with high material performance requirements.

[0005] The objective of this invention can be achieved through the following technical solutions:

[0006] A high-performance modified PVC transparent rigid sheet comprises the following components in parts by weight:

[0007] The composition includes 60-70 parts of long-linked branched polyvinyl chloride, 7-19 parts of impact-resistant core-shell particles, 0.8-1.6 parts of lubricant, 0.3-0.5 parts of antioxidant, 0.1-0.3 parts of ultraviolet absorber, and 0.1-0.3 parts of light stabilizer.

[0008] The long-linked branched polyvinyl chloride is prepared by the following steps:

[0009] Step a1: Add sodium ethoxide and anhydrous ethanol to a three-necked flask equipped with a stirrer and thermometer. Stir the reaction at 25-30℃ and 200-300 r / min for 10-20 min. Then add 1-eicosethiol and continue stirring for 10-20 min. Then raise the temperature to 75-80℃ and continue stirring for 10-15 h. After the reaction is complete, cool the reaction product to room temperature, then remove the solvent by rotary evaporation. Then wash with petroleum ether 3-5 times. Then place it in a vacuum drying oven and dry at 50-55℃ for 2-3 h to obtain long-chain sodium thiolate.

[0010] Step a2: Add polyvinyl chloride resin and anhydrous tetrahydrofuran to a three-necked flask equipped with a stirrer, thermometer, and gas delivery tube. Purge with nitrogen for protection and stir at 25-30℃ and 200-300 r / min for 30-50 min. Then add long-chain sodium thiolate and continue stirring at 60-65℃ for 10-12 h. After the reaction is complete, cool the reaction product to room temperature and remove the solvent by rotary evaporation. Then wash with anhydrous ethanol and distilled water 3-5 times in sequence. Then place in a vacuum drying oven and dry at 50-55℃ for 5-6 h to obtain long-chain branched polyvinyl chloride.

[0011] As a further aspect of the present invention: the ratio of sodium ethoxide, anhydrous ethanol and 1-eicosethiol used in step a1 is 10 mmol: 50-60 mL: 10 mmol.

[0012] As a further aspect of the present invention: the ratio of polyvinyl chloride resin, anhydrous tetrahydrofuran and long-chain sodium thiolate in step a2 is 10g: 100-110mL: 0.5-5.5g.

[0013] As a further aspect of the present invention: the polyvinyl chloride resin in step a2 is PVC SG-8.

[0014] As a further aspect of the present invention: the impact-resistant core-shell particles are prepared by the following steps:

[0015] Step b1: Add nano-alumina, basalt fiber, hydrochloric acid solution, anhydrous ethanol, and deionized water to a three-necked flask equipped with a stirrer, thermometer, and gas delivery tube. Sonicate the mixture for 20-30 minutes at an ultrasonic frequency of 40-50 kHz. Then, purge with nitrogen and stir for 3-5 minutes at a temperature of 25-30℃ and a stirring rate of 200-300 r / min. Next, add silane coupling agent KH-570 and continue stirring at a temperature of 70-75℃ for 6-8 hours. After the reaction is complete, cool the reaction product to room temperature, centrifuge, wash the precipitate 3-5 times with distilled water, and then place it in a vacuum drying oven and dry it at a temperature of 60-65℃ for 3-4 hours to obtain the modified reinforcing agent.

[0016] Step b2: Add the modified reinforcing agent and anhydrous ethanol to a three-necked flask equipped with a stirrer and thermometer. Sonicate the mixture at an ultrasonic frequency of 40-50 kHz for 20-30 min. Then add methyl methacrylate, styrene, and butyl acrylate and stir the mixture at a temperature of 25-30℃ and a stirring rate of 200-300 r / min for 20-30 min. Next, add benzoyl peroxide and stir the mixture at a temperature of 50-55℃ for 20-30 min. Then, stir the mixture at a temperature of 80-85℃ for 6-8 h. After the reaction is complete, cool the reaction product to room temperature, centrifuge it, wash the precipitate 3-5 times with distilled water, and then place it in a vacuum drying oven and dry it at a temperature of 50-55℃ for 3-4 h to obtain impact-resistant core-shell particles.

[0017] As a further aspect of the present invention: the ratio of the amount of nano-alumina, basalt fiber, hydrochloric acid solution, anhydrous ethanol, deionized water and silane coupling agent KH-570 in step b1 is 10g: 1.3-4.1g: 8-10mL: 90-100mL: 10-15mL: 1.2-4.6g.

[0018] As a further aspect of the present invention: the average particle size of the nano-alumina in step b1 is 100 nm; the average length of the basalt fiber is 12 mm and the average diameter is 15 μm; the mass fraction of the hydrochloric acid solution is 15-20%.

[0019] As a further embodiment of the present invention: the ratio of the modified reinforcing agent, anhydrous ethanol, methyl methacrylate, styrene, butyl acrylate and benzoyl peroxide used in step b2 is 10g: 100-110mL: 2-4g: 1-2g: 0.8-1.4g: 0.2-0.4g.

[0020] As a further aspect of the present invention: a method for preparing a high-performance modified PVC transparent rigid sheet, comprising the following steps:

[0021] Step 1: Weigh out 60-70 parts by weight of long-linked branched polyvinyl chloride, 7-19 parts by weight of impact-resistant core-shell particles, 0.8-1.6 parts by weight of lubricant, 0.3-0.5 parts by weight of antioxidant, 0.1-0.3 parts by weight of ultraviolet absorber and 0.1-0.3 parts by weight of light stabilizer, and set aside.

[0022] Step 2: Add long-linked branched PVC, impact-resistant core-shell particles, lubricant, antioxidant, UV absorber, and light stabilizer to a mixer and mix for 20-30 minutes at a temperature of 25-30℃ and a stirring speed of 1000-1200 r / min. Then, add the mixture to a twin-screw extruder and melt-extrude it at a speed of 80-100 r / min and five temperature zones of 190℃, 195℃, 200℃, 205℃, and 210℃ respectively. After cooling and granulation, high-performance modified PVC granules are obtained.

[0023] Step 3: Add the high-performance modified PVC granules into the calender and calender them at a temperature of 165-175℃ to obtain high-performance modified PVC transparent rigid sheets.

[0024] As a further aspect of the present invention, the lubricant is calcium stearate.

[0025] As a further aspect of the present invention: the antioxidant is antioxidant 1024.

[0026] As a further aspect of the present invention: the ultraviolet absorber is ultraviolet absorber UV-234.

[0027] As a further aspect of the present invention: the light stabilizer is light stabilizer TH-944.

[0028] The beneficial effects of this invention are:

[0029] This invention discloses a high-performance modified PVC transparent rigid sheet and its preparation method. The method involves mixing long-chain branched PVC, impact-resistant core-shell particles, lubricant, antioxidant, UV absorber, and light stabilizer, followed by melt extrusion, cooling, and granulation to obtain high-performance modified PVC granules. These granules are then calendered to obtain the high-performance modified PVC transparent rigid sheet. This PVC transparent rigid sheet uses long-chain branched PVC as the main raw material. The long carbon chain structure in the long-chain branched PVC improves the flexibility of the molecular chain, making the PVC transparent rigid sheet less prone to breakage under external force and able to withstand greater impact loads. The addition of impact-resistant core-shell particles ensures good compatibility with the matrix and provides excellent rigidity and impact resistance, achieving excellent comprehensive performance. This meets the application requirements under various conditions and demonstrates excellent application prospects in multiple fields. Furthermore, the preparation method is simple, low-cost, and easily scalable for industrial production.

[0030] In the preparation of high-performance modified PVC transparent rigid sheets, a long-chain branched PVC was first prepared. This was achieved by reacting sodium ethoxide with 1-eicosenothiol to convert the thiol groups into sodium thiolate groups, yielding long-chain sodium thiolate. Subsequently, the long-chain sodium thiolate was used to modify the PVC resin. The sodium thiolate reacted with the chlorine atoms on the PVC resin molecular chain, thus branching long carbon atoms onto the PVC resin molecular chain, resulting in long-chain branched PVC. The PVC molecular chain exhibits high rigidity and strong intermolecular forces, which enhances the material's resistance to stress and damage. When subjected to external forces, the molecular chains are difficult to slide and deform, making them prone to brittle fracture. After long carbon chain branching modification, a large number of long carbon chains with excellent flexibility are introduced. The introduction of long carbon chains increases the distance between PVC molecular chains and reduces the interaction force between them. When subjected to impact, the long carbon chains can absorb some energy through their own deformation, reducing stress concentration and preventing rapid crack propagation. This allows PVC to withstand greater external forces without being damaged, thereby improving its flexibility and impact resistance.

[0031] In the process of preparing high-performance modified PVC transparent rigid sheets, an impact-resistant core-shell particle was also prepared. Nano-alumina and basalt fibers were treated with the silane coupling agent KH-570. After hydrolysis, the silane coupling agent KH-570 was grafted onto the surface of the nano-alumina and basalt fibers, simultaneously introducing alkenyl groups to obtain a modifier. Subsequently, the modifier was copolymerized with methyl methacrylate, styrene, and butyl acrylate under the initiation of benzoyl peroxide, forming a polymer shell that encapsulates the nano-alumina and basalt fibers, resulting in the impact-resistant core-shell particle. Alumina is a ceramic material with high hardness, exhibiting excellent wear resistance and compressive strength. Basalt fibers possess… The high strength and high modulus characteristics, combined with the synergistic effect of both, provide high strength and high modulus reinforcement at the microscale. When the PVC transparent rigid sheet is subjected to external impact, it can withstand greater stress and prevent further crack propagation, thereby improving the impact strength and tensile strength of the PVC transparent rigid sheet. The presence of the polymer shell allows the nano-alumina and basalt fibers to form a good interfacial bond with the matrix, thus effectively transferring stress. At the same time, the polymer shell has good flexibility. When the PVC transparent rigid sheet is impacted, the polymer shell deforms first and absorbs some energy through its own flexibility, further improving the mechanical properties of the PVC transparent rigid sheet. Detailed Implementation

[0032] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0033] Example 1:

[0034] This embodiment describes a method for preparing a high-performance modified PVC transparent rigid sheet, comprising the following steps:

[0035] Step S1: Add 10 mmol sodium ethoxide and 50 mL anhydrous ethanol to a three-necked flask equipped with a stirrer and thermometer. Stir the reaction at 25 °C and 200 r / min for 10 min. Then add 10 mmol 1-eicosethiol and continue stirring for 10 min. Then raise the temperature to 75 °C and continue stirring for 10 h. After the reaction is complete, cool the reaction product to room temperature, then remove the solvent by rotary evaporation. Then wash three times with petroleum ether and place in a vacuum drying oven to dry at 50 °C for 2 h to obtain long-chain sodium thiolate.

[0036] Step S2: Add 10g of polyvinyl chloride resin PVC SG-8 and 100mL of anhydrous tetrahydrofuran to a three-necked flask equipped with a stirrer, thermometer and gas delivery tube. Purge with nitrogen for protection and stir at 25℃ and 200r / min for 30min. Then add 0.5g of long-chain sodium thiolate and heat to 60℃ and continue stirring for 10h. After the reaction is complete, cool the reaction product to room temperature and then remove the solvent by rotary evaporation. Then wash with anhydrous ethanol and distilled water three times in sequence. Then place it in a vacuum drying oven and dry at 50℃ for 5h to obtain long-chain branched polyvinyl chloride.

[0037] Step S3: 10g of nano-alumina with an average particle size of 100nm, 1.3g of basalt fiber with an average length of 12mm and an average diameter of 15μm, 8mL of 15% hydrochloric acid solution, 90mL of anhydrous ethanol and 10mL of deionized water were added to a three-necked flask equipped with a stirrer, thermometer and gas delivery tube. The mixture was ultrasonically treated at a frequency of 40kHz for 20min. Then, nitrogen gas was introduced for protection and the mixture was stirred at a temperature of 25℃ and a stirring rate of 200r / min for 3min. Then, 1.2g of silane coupling agent KH-570 was added and the mixture was heated to 70℃ and stirred for 6h. After the reaction was completed, the reaction product was cooled to room temperature and then centrifuged. The precipitate was washed three times with distilled water and then placed in a vacuum drying oven and dried at a temperature of 60℃ for 3h to obtain the modified reinforcing agent.

[0038] Step S4: Add 10g of the modifier and 100mL of anhydrous ethanol to a three-necked flask equipped with a stirrer and a thermometer. Sonicate the mixture for 20min at a frequency of 40kHz. Then add 2g of methyl methacrylate, 1g of styrene, and 0.8g of butyl acrylate. Stir the mixture at 25℃ and 200r / min for 20min. Then add 0.2g of benzoyl peroxide and stir the mixture at 50℃ for 20min. Then stir the mixture at 80℃ for 6h. After the reaction is complete, cool the product to room temperature, centrifuge it, wash the precipitate three times with distilled water, and then place it in a vacuum drying oven and dry it at 50℃ for 3h to obtain impact-resistant core-shell particles.

[0039] Step S5: Weigh out 60 parts by weight of long-linked branched polyvinyl chloride, 7 parts by weight of impact-resistant core-shell particles, 0.8 parts by weight of lubricant, 0.3 parts by weight of antioxidant, 0.1 parts by weight of ultraviolet absorber, and 0.1 parts by weight of light stabilizer, and set aside; the lubricant is calcium stearate; the antioxidant is antioxidant 1024; the ultraviolet absorber is ultraviolet absorber UV-234; and the light stabilizer is light stabilizer TH-944.

[0040] Step S6: Add long-linked branched polyvinyl chloride, impact-resistant core-shell particles, lubricant, antioxidant, ultraviolet absorber and light stabilizer to a mixer and mix for 20 minutes at a temperature of 25°C and a stirring rate of 1000 r / min. Then add it to a twin-screw extruder and melt extrude it at a speed of 80 r / min and five temperature zones of 190°C, 195°C, 200°C, 205°C and 210°C respectively. After cooling and granulation, high-performance modified PVC granules are obtained.

[0041] Step S7: Add high-performance modified PVC granules into a calender and calender them at a temperature of 165℃ to obtain high-performance modified PVC transparent rigid sheets.

[0042] Example 2:

[0043] This embodiment describes a method for preparing a high-performance modified PVC transparent rigid sheet, comprising the following steps:

[0044] Step S1: 10 mmol sodium ethoxide and 55 mL anhydrous ethanol were added to a three-necked flask equipped with a stirrer and a thermometer. The mixture was stirred for 15 min at 28 °C and a stirring rate of 250 r / min. Then, 10 mmol 1-eicosethiol was added and the mixture was stirred for another 15 min. The mixture was then heated to 78 °C and stirred for another 12 h. After the reaction was completed, the product was cooled to room temperature and the solvent was removed by rotary evaporation. The product was then washed four times with petroleum ether and placed in a vacuum drying oven at 52 °C for 2.5 h to obtain long-chain sodium thiolate.

[0045] Step S2: 10g of polyvinyl chloride resin PVC SG-8 and 105mL of anhydrous tetrahydrofuran were added to a three-necked flask equipped with a stirrer, thermometer and gas delivery tube. Nitrogen gas was introduced for protection. The mixture was stirred at 28℃ and 250r / min for 40min. Then, 3g of long-chain sodium thiolate was added and the mixture was heated to 62℃ and stirred for 11h. After the reaction was completed, the reaction product was cooled to room temperature. The solvent was then removed by rotary evaporation. The product was then washed four times with anhydrous ethanol and distilled water. Finally, it was placed in a vacuum drying oven and dried at 52℃ for 5.5h to obtain long-chain branched polyvinyl chloride.

[0046] Step S3: 10g of nano-alumina with an average particle size of 100nm, 2.7g of basalt fiber with an average length of 12mm and an average diameter of 15μm, 9mL of 18% hydrochloric acid solution, 95mL of anhydrous ethanol and 12mL of deionized water were added to a three-necked flask equipped with a stirrer, thermometer and gas delivery tube. The mixture was ultrasonically treated at a frequency of 45kHz for 25min. Then, nitrogen gas was introduced for protection and the mixture was stirred at a temperature of 28℃ and a stirring rate of 250r / min for 4min. Then, 2.9g of silane coupling agent KH-570 was added and the mixture was heated to 72℃ and stirred for 7h. After the reaction was completed, the reaction product was cooled to room temperature and then centrifuged. The precipitate was washed four times with distilled water and then placed in a vacuum drying oven and dried at a temperature of 62℃ for 3.5h to obtain the modified reinforcing agent.

[0047] Step S4: Add 10g of the modifier and 105mL of anhydrous ethanol to a three-necked flask equipped with a stirrer and thermometer. Sonicate the mixture at 45kHz for 25min. Then add 3g of methyl methacrylate, 1.5g of styrene, and 1.1g of butyl acrylate. Stir the mixture at 28℃ and 250r / min for 25min. Then add 0.3g of benzoyl peroxide and stir the mixture at 52℃ for 25min. Then stir the mixture at 82℃ for 7h. After the reaction is complete, cool the product to room temperature, centrifuge it, wash the precipitate four times with distilled water, and then place it in a vacuum drying oven and dry it at 52℃ for 3.5h to obtain impact-resistant core-shell particles.

[0048] Step S5: Weigh out 65 parts by weight of long-linked branched polyvinyl chloride, 13 parts by weight of impact-resistant core-shell particles, 1.2 parts by weight of lubricant, 0.4 parts by weight of antioxidant, 0.2 parts by weight of ultraviolet absorber, and 0.2 parts by weight of light stabilizer, and set aside; the lubricant is calcium stearate; the antioxidant is antioxidant 1024; the ultraviolet absorber is ultraviolet absorber UV-234; and the light stabilizer is light stabilizer TH-944.

[0049] Step S6: Add long-linked branched polyvinyl chloride, impact-resistant core-shell particles, lubricant, antioxidant, ultraviolet absorber and light stabilizer to a mixer and mix for 25 minutes at a temperature of 28°C and a stirring rate of 1100 r / min. Then add it to a twin-screw extruder and melt extrude it at a speed of 90 r / min and five temperature zones of 190°C, 195°C, 200°C, 205°C and 210°C respectively. After cooling and granulation, high-performance modified PVC granules are obtained.

[0050] Step S7: Add high-performance modified PVC granules into a calender and calender them at a temperature of 170°C to obtain high-performance modified PVC transparent rigid sheets.

[0051] Example 3:

[0052] This embodiment describes a method for preparing a high-performance modified PVC transparent rigid sheet, comprising the following steps:

[0053] Step S1: 10 mmol sodium ethoxide and 60 mL anhydrous ethanol were added to a three-necked flask equipped with a stirrer and a thermometer. The mixture was stirred at 30 °C and 300 r / min for 20 min. Then, 10 mmol 1-eicosethiol was added and the mixture was stirred for another 20 min. The mixture was then heated to 80 °C and stirred for another 15 h. After the reaction was completed, the product was cooled to room temperature and the solvent was removed by rotary evaporation. The product was then washed five times with petroleum ether and placed in a vacuum drying oven at 55 °C for 3 h to obtain long-chain sodium thiolate.

[0054] Step S2: Add 10g of polyvinyl chloride resin PVC SG-8 and 110mL of anhydrous tetrahydrofuran to a three-necked flask equipped with a stirrer, thermometer and gas delivery tube. Purge with nitrogen for protection and stir at 30℃ and 300r / min for 50min. Then add 5.5g of long-chain sodium thiolate and continue stirring at 65℃ for 12h. After the reaction is complete, cool the reaction product to room temperature and remove the solvent by rotary evaporation. Then wash with anhydrous ethanol and distilled water five times in sequence. Then place in a vacuum drying oven and dry at 55℃ for 6h to obtain long-chain branched polyvinyl chloride.

[0055] Step S3: 10g of nano-alumina with an average particle size of 100nm, 4.1g of basalt fiber with an average length of 12mm and an average diameter of 15μm, 10mL of 20% hydrochloric acid solution, 100mL of anhydrous ethanol and 15mL of deionized water were added to a three-necked flask equipped with a stirrer, thermometer and gas delivery tube. The mixture was ultrasonically treated at a frequency of 50kHz for 30min. Then, nitrogen gas was introduced for protection and the mixture was stirred at a temperature of 30℃ and a stirring rate of 300r / min for 5min. Then, 4.6g of silane coupling agent KH-570 was added and the mixture was heated to 75℃ and stirred for 8h. After the reaction was completed, the reaction product was cooled to room temperature and then centrifuged. The precipitate was washed 5 times with distilled water and then placed in a vacuum drying oven and dried at a temperature of 65℃ for 4h to obtain the modified reinforcing agent.

[0056] Step S4: Add 10g of the modifier and 110mL of anhydrous ethanol to a three-necked flask equipped with a stirrer and thermometer. Sonicate the mixture at 50kHz for 30min. Then add 4g of methyl methacrylate, 2g of styrene, and 1.4g of butyl acrylate. Stir the mixture at 30℃ and 300r / min for 30min. Then add 0.4g of benzoyl peroxide and stir the mixture at 55℃ for 30min. Then stir the mixture at 85℃ for 8h. After the reaction is complete, cool the product to room temperature, centrifuge it, wash the precipitate five times with distilled water, and then place it in a vacuum drying oven and dry it at 55℃ for 4h to obtain impact-resistant core-shell particles.

[0057] Step S5: Weigh out 70 parts by weight of long-linked branched polyvinyl chloride, 19 parts by weight of impact-resistant core-shell particles, 1.6 parts by weight of lubricant, 0.5 parts by weight of antioxidant, 0.3 parts by weight of ultraviolet absorber, and 0.3 parts by weight of light stabilizer, and set aside; the lubricant is calcium stearate; the antioxidant is antioxidant 1024; the ultraviolet absorber is ultraviolet absorber UV-234; and the light stabilizer is light stabilizer TH-944.

[0058] Step S6: Add long-linked branched PVC, impact-resistant core-shell particles, lubricant, antioxidant, UV absorber and light stabilizer to a mixer and mix for 30 minutes at a temperature of 30℃ and a stirring rate of 1200 r / min. Then add it to a twin-screw extruder and melt extrude it at a speed of 100 r / min and five temperature zones of 190℃, 195℃, 200℃, 205℃ and 210℃ respectively. After cooling and granulation, high-performance modified PVC granules are obtained.

[0059] Step S7: Add the high-performance modified PVC granules into the calender and calender them at a temperature of 175°C to obtain a high-performance modified PVC transparent rigid sheet.

[0060] Comparative Example 1:

[0061] This comparative example illustrates a method for preparing a high-performance modified PVC transparent rigid sheet, comprising the following steps:

[0062] Step S1: Weigh out 70 parts by weight of polyvinyl chloride resin PVC SG-870, lubricant 1.6 parts, antioxidant 0.5 parts, ultraviolet absorber 0.3 parts, and light stabilizer 0.3 parts, and set aside; the lubricant is calcium stearate; the antioxidant is antioxidant 1024; the ultraviolet absorber is ultraviolet absorber UV-234; and the light stabilizer is light stabilizer TH-944.

[0063] Step S2: Add polyvinyl chloride resin PVC SG-8, lubricant, antioxidant, ultraviolet absorber and light stabilizer to a mixer and mix for 30 minutes at a temperature of 30℃ and a stirring speed of 1200 r / min. Then add it to a twin-screw extruder and melt extrude it at a speed of 100 r / min and five temperature zones of 190℃, 195℃, 200℃, 205℃ and 210℃ respectively. After cooling and granulation, high-performance modified PVC granules are obtained.

[0064] Step S3: Add high-performance modified PVC granules into a calender and calender them at a temperature of 175°C to obtain high-performance modified PVC transparent rigid sheets.

[0065] Comparative Example 2:

[0066] This comparative example illustrates a method for preparing a high-performance modified PVC transparent rigid sheet, comprising the following steps:

[0067] Step S1: 10 mmol sodium ethoxide and 60 mL anhydrous ethanol were added to a three-necked flask equipped with a stirrer and a thermometer. The mixture was stirred at 30 °C and 300 r / min for 20 min. Then, 10 mmol 1-eicosethiol was added and the mixture was stirred for another 20 min. The mixture was then heated to 80 °C and stirred for another 15 h. After the reaction was completed, the product was cooled to room temperature and the solvent was removed by rotary evaporation. The product was then washed five times with petroleum ether and placed in a vacuum drying oven at 55 °C for 3 h to obtain long-chain sodium thiolate.

[0068] Step S2: Add 10g of polyvinyl chloride resin PVC SG-8 and 110mL of anhydrous tetrahydrofuran to a three-necked flask equipped with a stirrer, thermometer and gas delivery tube. Purge with nitrogen for protection and stir at 30℃ and 300r / min for 50min. Then add 5.5g of long-chain sodium thiolate and continue stirring at 65℃ for 12h. After the reaction is complete, cool the reaction product to room temperature and remove the solvent by rotary evaporation. Then wash with anhydrous ethanol and distilled water five times in sequence. Then place in a vacuum drying oven and dry at 55℃ for 6h to obtain long-chain branched polyvinyl chloride.

[0069] Step S3: Weigh out 70 parts by weight of long-linked polyvinyl chloride, 1.6 parts by weight of lubricant, 0.5 parts by weight of antioxidant, 0.3 parts by weight of ultraviolet absorber, and 0.3 parts by weight of light stabilizer, and set aside; the lubricant is calcium stearate; the antioxidant is antioxidant 1024; the ultraviolet absorber is ultraviolet absorber UV-234; and the light stabilizer is light stabilizer TH-944.

[0070] Step S4: Add long-linked branched polyvinyl chloride, lubricant, antioxidant, ultraviolet absorber and light stabilizer to a mixer and mix for 30 minutes at a temperature of 30℃ and a stirring rate of 1200 r / min. Then add it to a twin-screw extruder and melt extrude it at a speed of 100 r / min and five temperature zones of 190℃, 195℃, 200℃, 205℃ and 210℃ respectively. After cooling and granulation, high-performance modified PVC granules are obtained.

[0071] Step S5: Add high-performance modified PVC granules into a calender and calender them at a temperature of 175℃ to obtain high-performance modified PVC transparent rigid sheets.

[0072] Comparative Example 3:

[0073] This comparative example illustrates a method for preparing a high-performance modified PVC transparent rigid sheet, comprising the following steps:

[0074] Step S1: 10g of nano-alumina with an average particle size of 100nm, 4.1g of basalt fiber with an average length of 12mm and an average diameter of 15μm, 10mL of 20% hydrochloric acid solution, 100mL of anhydrous ethanol and 15mL of deionized water were added to a three-necked flask equipped with a stirrer, thermometer and gas delivery tube. The mixture was ultrasonically treated at a frequency of 50kHz for 30min. Then, nitrogen gas was introduced for protection and the mixture was stirred at a temperature of 30℃ and a stirring rate of 300r / min for 5min. Then, 4.6g of silane coupling agent KH-570 was added and the mixture was heated to 75℃ and stirred for 8h. After the reaction was completed, the reaction product was cooled to room temperature and then centrifuged. The precipitate was washed 5 times with distilled water and then placed in a vacuum drying oven and dried at a temperature of 65℃ for 4h to obtain the modified reinforcing agent.

[0075] Step S2: Add 10g of modified reinforcing agent and 110mL of anhydrous ethanol to a three-necked flask equipped with a stirrer and thermometer. Sonicate the mixture for 30min at an ultrasonic frequency of 50kHz. Then add 4g of methyl methacrylate, 2g of styrene and 1.4g of butyl acrylate and stir for 30min at a temperature of 30℃ and a stirring rate of 300r / min. Then add 0.4g of benzoyl peroxide and stir for 30min at a temperature of 55℃. Then stir for 8h at a temperature of 85℃. After the reaction is complete, cool the reaction product to room temperature, centrifuge, wash the precipitate 5 times with distilled water, and then place it in a vacuum drying oven and dry at a temperature of 55℃ for 4h to obtain impact-resistant core-shell particles.

[0076] Step S3: Weigh out 70 parts by weight of long-linked branched polyvinyl chloride (PVC) SG-870, 19 parts by weight of impact-resistant core-shell particles, 1.6 parts by weight of lubricant, 0.5 parts by weight of antioxidant, 0.3 parts by weight of ultraviolet absorber, and 0.3 parts by weight of light stabilizer, and set aside. The lubricant is calcium stearate; the antioxidant is antioxidant 1024; the ultraviolet absorber is ultraviolet absorber UV-234; and the light stabilizer is light stabilizer TH-944.

[0077] Step S4: Add long-linked branched polyvinyl chloride (PVC) SG-8, impact-resistant core-shell particles, lubricant, antioxidant, UV absorber, and light stabilizer to a mixer and mix for 30 minutes at a temperature of 30°C and a stirring rate of 1200 r / min. Then, add the mixture to a twin-screw extruder and melt-extrude it at a speed of 100 r / min and five temperature zones of 190°C, 195°C, 200°C, 205°C, and 210°C, respectively. After cooling and granulation, high-performance modified PVC granules are obtained.

[0078] Step S5: Add high-performance modified PVC granules into a calender and calender them at a temperature of 175℃ to obtain high-performance modified PVC transparent rigid sheets.

[0079] The high-performance modified PVC transparent rigid sheets of Examples 1-3 and Comparative Examples 1-3 were tested for impact strength according to GB / T1043.1-2008 and tensile strength according to GB / T 1040.1-2018. The test results are shown in the table below:

[0080] sample Impact strength, kJ·m Tensile strength, MPa Example 1 22.1 43.7 Example 2 24.5 45.5 Example 3 27.0 47.4 Comparative Example 1 4.8 27.9 Comparative Example 2 13.9 32.7 Comparative Example 3 18.5 38.6

[0081] Referring to the data in the table above, and based on the comparison between Examples 1-3 and Comparative Examples 1-3, it can be seen that using long-linked branched polyvinyl chloride and adding impact-resistant core-shell particles can significantly improve the impact performance and tensile strength of high-performance modified PVC transparent rigid sheets, resulting in high-performance modified PVC transparent rigid sheets with excellent mechanical properties.

[0082] In the description of this specification, references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0083] The above description is merely an example and illustration of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described or use similar methods to replace them, as long as they do not deviate from the invention or exceed the scope defined in this application, they should all fall within the protection scope of the present invention.

Claims

1. A high-performance modified PVC transparent rigid sheet, characterized in that, Includes the following components by weight: The composition includes 60-70 parts of long-linked branched polyvinyl chloride, 7-19 parts of impact-resistant core-shell particles, 0.8-1.6 parts of calcium stearate, 0.3-0.5 parts of antioxidant 1024, 0.1-0.3 parts of ultraviolet absorber UV-234, and 0.1-0.3 parts of light stabilizer TH-944. The long-linked branched polyvinyl chloride is prepared by the following steps: Step a1: Sodium ethoxide and anhydrous ethanol are stirred and reacted, then 1-eicosenethiol is added and the reaction is continued with stirring. After the reaction is completed, the reaction product is cooled, then evaporated by rotary evaporation, and then washed and dried to obtain long-chain sodium thiolate. The ratio of sodium ethoxide, anhydrous ethanol and 1-eicosenethiol in step a1 is 10 mmol: 50-60 mL: 10 mmol. Step a2: Polyvinyl chloride resin and anhydrous tetrahydrofuran are stirred and reacted, then long-chain thiols sodium is added and the reaction is continued. After the reaction is completed, the reaction product is cooled, then evaporated by rotary evaporation, then washed and dried to obtain long-chain branched polyvinyl chloride; the ratio of polyvinyl chloride resin, anhydrous tetrahydrofuran and long-chain thiols sodium in step a2 is 10g:100-110mL:0.5-5.5g; The impact-resistant core-shell particles are prepared by the following steps: Step b1: Nano-alumina, basalt fiber, hydrochloric acid solution, anhydrous ethanol, and deionized water are ultrasonically treated, and then silane coupling agent KH-570 is added and stirred for reaction. After the reaction is completed, the reaction product is cooled, centrifuged, and the precipitate is washed and dried to obtain the modified reinforcing agent. The ratio of nano-alumina, basalt fiber, hydrochloric acid solution, anhydrous ethanol, deionized water, and silane coupling agent KH-570 in step b1 is 10g:1.3-4.1g:8-10mL:90-100mL:10-15mL:1.2-4.6g. Step b2: The modifier and anhydrous ethanol are ultrasonically treated, then methyl methacrylate, styrene and butyl acrylate are added and stirred to react. Then benzoyl peroxide is added and the reaction is continued to be stirred. After the reaction is completed, the reaction product is cooled, then centrifuged, and the precipitate is washed and dried to obtain impact-resistant core-shell particles. The ratio of the modifier, anhydrous ethanol, methyl methacrylate, styrene, butyl acrylate and benzoyl peroxide in step b2 is 10g:100-110mL:2-4g:1-2g:0.8-1.4g:0.2-0.4g.

2. The high-performance modified PVC transparent rigid sheet according to claim 1, characterized in that, The polyvinyl chloride resin is PVC SG-8.

3. The high-performance modified PVC transparent rigid sheet according to claim 1, characterized in that, The nano-alumina has an average particle size of 100 nm; the basalt fibers have an average length of 12 mm and an average diameter of 15 μm; and the hydrochloric acid solution has a mass fraction of 15-20%.

4. A method for preparing a high-performance modified PVC transparent rigid sheet, characterized in that, The method for preparing the high-performance modified PVC transparent rigid sheet as described in any one of claims 1-3 includes the following steps: Step 1: Weigh out 60-70 parts by weight of long-linked branched polyvinyl chloride, 7-19 parts by weight of impact-resistant core-shell particles, 0.8-1.6 parts by weight of calcium stearate, 0.3-0.5 parts by weight of antioxidant 1024, 0.1-0.3 parts by weight of ultraviolet absorber UV-234, and 0.1-0.3 parts by weight of light stabilizer TH-944, and set aside. Step 2: Add long-linked branched PVC, impact-resistant core-shell particles, calcium stearate, antioxidant 1024, UV absorber UV-234, and light stabilizer TH-944 to a mixer and mix for 20-30 minutes at a temperature of 25-30℃ and a stirring speed of 1000-1200 r / min. Then add the mixture to a twin-screw extruder and melt extrude it at a speed of 80-100 r / min and five temperature zones of 190℃, 195℃, 200℃, 205℃, and 210℃ respectively. After cooling and granulation, high-performance modified PVC granules are obtained. Step 3: Add the high-performance modified PVC granules into the calender and calender them at a temperature of 165-175℃ to obtain high-performance modified PVC transparent rigid sheets.