Anti-impact anti-cracking polyvinyl chloride decorative film and preparation method thereof

Abstract

This invention relates to the field of decorative films, specifically to an impact-resistant and crack-resistant polyvinyl chloride (PVC) decorative film and its preparation method. It addresses the problems of existing PVC decorative films, such as high brittleness and poor impact resistance, which easily lead to brittle fracture or stress whitening under external impact or bending, affecting aesthetics and causing premature material failure. This preparation method uses modified PVC as the main raw material, significantly increasing the overall toughness of the PVC decorative film, thereby significantly improving its impact resistance. Adding coated tungsten carbide powder further enhances the mechanical properties of the PVC decorative film, providing strong strength support. The combination of these two factors significantly improves the impact resistance of the PVC decorative film under external forces, thus significantly enhancing its crack resistance, durability, and service life.

Description

Technical Field

[0001] This invention relates to the field of decorative films, specifically to an impact-resistant and crack-resistant polyvinyl chloride decorative film and its preparation method. Background Technology

[0002] Polyvinyl chloride (PVC) decorative films are widely used in furniture veneers, integrated wall panels, window and door films, elevator finishes, and automotive interiors due to their low cost, rich colors, and resistance to chemical corrosion. However, current PVC decorative films are brittle and have poor impact resistance. When subjected to external impacts or bending, they are prone to brittle fracture or stress whitening, affecting their appearance and causing premature material failure.

[0003] Therefore, developing an impact-resistant and crack-resistant polyvinyl chloride decorative film 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 an impact-resistant and crack-resistant polyvinyl chloride decorative film and its preparation method, which solves the problems of existing polyvinyl chloride decorative films being brittle and having poor impact resistance. When subjected to external impact or bending, they are prone to brittle fracture or stress whitening, which affects the appearance and causes premature material failure.

[0005] The objective of this invention can be achieved through the following technical solutions: In a first aspect, this application provides an impact-resistant and crack-resistant polyvinyl chloride decorative film, comprising the following components in parts by weight: 100-110 parts modified polyvinyl chloride, 1-9 parts coated tungsten carbide powder, 2-3 parts calcium-zinc composite stabilizer, 0.5-0.7 parts stearic acid, 0.2-0.4 parts oxidized polyethylene wax, 0.1-0.5 parts antioxidant, and 0.2-0.6 parts ultraviolet absorber; The modified polyvinyl chloride is prepared by the following steps: Step a1: Allyl alcohol glycidyl ether, chloroplatinic acid and isopropanol are added to a three-necked flask equipped with a stirrer, thermometer, reflux condenser and gas delivery tube. Nitrogen gas is introduced for protection. The mixture is stirred for 20-30 min at a temperature of 25-30℃ and a stirring rate of 300-400 r / min. Then 1,1,3,3-tetramethyldisiloxane is added and the mixture is heated to 70-75℃ and stirred for 1-3 h. After the reaction is completed, the reaction product is cooled to room temperature and the solvent is removed by rotary evaporation to obtain an epoxy-terminated organosilicon compound. Step a2: Add the terminal epoxy organosilicon compound, diethanolamine, and ethanol to a three-necked flask equipped with a stirrer, thermometer, reflux condenser, and gas delivery tube. Purge with nitrogen for protection and stir the reaction at 25-30℃ and 300-400 r / min for 20-30 min. Then raise the temperature to 70-75℃ and continue stirring for 6-8 h. After the reaction is complete, cool the reaction product to room temperature and then remove the solvent by rotary evaporation to obtain the terminal hydroxyl organosilicon compound. Step a3: Add polyvinyl chloride, hydroxyl-terminated organosilicon compound, and N,N-dimethylformamide to a three-necked flask equipped with a stirrer, thermometer, reflux condenser, and gas delivery tube. Purge with nitrogen for protection and stir at 25-30℃ and 300-400 r / min for 30-50 min. Then raise the temperature to 80-85℃ and continue stirring for 2-4 h. After the reaction is complete, cool the reaction product to room temperature, pour it into a methanol solution, centrifuge, and place the precipitate in a vacuum drying oven at 60-70℃ for 5-6 h to obtain modified polyvinyl chloride.

[0006] In a preferred embodiment of the present invention, the ratio of allyl alcohol glycidyl ether, chloroplatinic acid, isopropanol and 1,1,3,3-tetramethyldisiloxane in step a1 is 20 mmol: 0.3-0.5 g: 100-110 mL: 10 mmol.

[0007] In a preferred embodiment of the present invention, the ratio of the terminal epoxy organosilicon compound, diethanolamine and ethanol in step a2 is 10 mmol: 20 mmol: 60-70 mL.

[0008] In a preferred embodiment of the present invention, the ratio of polyvinyl chloride, hydroxyl-terminated organosilicon compound and N,N-dimethylformamide in step a3 is 10g:0.2-2g:100-110mL.

[0009] In a preferred embodiment of the present invention, the polyvinyl chloride in step a3 is PVC SG-5; and the volume fraction of the methanol solution is 10-15%.

[0010] In a preferred embodiment of the present invention, the coated tungsten carbide powder is prepared by the following steps: Step b1: 4-Bromo-1,8-naphthalenedicarboxylic anhydride, 4-vinylaniline, and ethanol were added to a three-necked flask equipped with a stirrer, thermometer, reflux condenser, and gas delivery tube. Nitrogen gas was introduced for protection, and the mixture was stirred for 10-20 min at a temperature of 25-30℃ and a stirring rate of 300-400 r / min. Then, the mixture was heated to reflux and stirred for 5-7 h. Potassium carbonate, 1-formaldehyde piperazine, and ethylene glycol monomethyl ether were then added and the mixture was stirred for 8-10 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 purified by silica gel column chromatography using a mixed solvent as the eluent to obtain the aldehyde vinylnaphthalene compound. Step b2: Add silane coupling agent KH-550 and acetic acid solution to a three-necked flask equipped with a stirrer, thermometer, reflux condenser and gas delivery tube. Purge with nitrogen for protection and stir for 30-50 min at 25-30℃ and 300-400 r / min. Then adjust the pH to 8-9 with sodium hydroxide solution. Add nano tungsten carbide powder and continue stirring for 20-25 h at 65-70℃. After the reaction is complete, cool the reaction product to room temperature, centrifuge, wash the precipitate 2-3 times with ethanol, and then place it in a vacuum drying oven and dry at 60-70℃ for 5-6 h to obtain aminated tungsten carbide powder. Step b3: Aminated tungsten carbide powder, aldehyde vinylnaphthalene compound, hydrochloric acid solution, N,N-dimethylformamide, and 1,4-dioxane are added to a three-necked flask equipped with a stirrer, thermometer, reflux condenser, and gas delivery tube. Nitrogen gas is introduced for protection. The mixture is stirred and reacted for 20-30 min at a temperature of 25-30℃ and a stirring rate of 300-400 r / min. Then, the temperature is raised to 110-120℃ and the reaction is continued for 4-6 h. After that, the temperature is lowered to 60-70℃ and azobisisobutyronitrile is added, and the reaction is continued for 10-15 h. After the reaction is completed, the reaction product is cooled to room temperature and then centrifuged. The precipitate is washed 2-3 times with ethanol, acetone, and distilled water in sequence. Then, it is placed in a vacuum drying oven and dried for 8-10 h at a temperature of 60-70℃ to obtain coated tungsten carbide powder.

[0011] In a preferred embodiment of the present invention, the ratio of 4-bromo-1,8-naphthalenedicarboxylic anhydride, 4-vinylaniline, ethanol, potassium carbonate, 1-formaldehyde piperazine, and ethylene glycol monomethyl ether in step b1 is 10 mmol: 10 mmol: 50-60 mL: 20-25 mmol: 10 mmol: 30-40 mL.

[0012] In a preferred embodiment of the present invention, the mixed solvent in step b1 is a mixture of petroleum ether and ethyl acetate in a volume ratio of 5-7:1.

[0013] In a preferred embodiment of the present invention, the ratio of the silane coupling agent KH-550, the acetic acid solution, and the nano-tungsten carbide powder in step b2 is 8-10g: 100-110mL: 5g.

[0014] In a preferred embodiment of the present invention, the acetic acid solution in step b2 has a mass fraction of 3-5%; the sodium hydroxide solution has a mass fraction of 10-12%; and the tungsten carbide nanoparticles have an average particle size of 100 nm.

[0015] In a preferred embodiment of the present invention, the ratio of the amount of amino-modified tungsten carbide powder, aldehyde vinyl naphthalene compound, hydrochloric acid solution, N,N-dimethylformamide, 1,4-dioxane and azobisisobutyronitrile in step b3 is 3g:0.5-1.7g:0.5-0.6mL:40-50mL:10-15mL:0.03-0.07g.

[0016] In a preferred embodiment of the present invention, the molar concentration of the hydrochloric acid solution in step b3 is 3-4 mol / L.

[0017] Secondly, this application provides a method for preparing an impact-resistant and crack-resistant polyvinyl chloride decorative film, comprising the following steps: Step 1: Weigh out 100-110 parts of modified polyvinyl chloride, 1-9 parts of coated tungsten carbide powder, 2-3 parts of calcium-zinc composite stabilizer, 0.5-0.7 parts of stearic acid, 0.2-0.4 parts of oxidized polyethylene wax, 0.1-0.5 parts of antioxidant, and 0.2-0.6 parts of ultraviolet absorber according to the following weight proportions, and set aside for later use; Step 2: Add modified polyvinyl chloride, coated tungsten carbide powder, calcium-zinc composite stabilizer, stearic acid, oxidized polyethylene wax, antioxidant, and ultraviolet absorber to a mixer and mix for 10-15 minutes at a temperature of 80-100℃ and a stirring speed of 1000-2000 r / min. Then add it to an extruder and melt-extrude it at a temperature of 160-170℃ and a screw speed of 50-60 r / min. After that, calender it through a calender to obtain a 30μm thick impact-resistant and crack-resistant polyvinyl chloride decorative film.

[0018] In a preferred embodiment of the present invention, the antioxidant is antioxidant 168; the ultraviolet absorber is ultraviolet absorber UV-531.

[0019] The beneficial effects of this invention are: This invention discloses an impact-resistant and crack-resistant polyvinyl chloride (PVC) decorative film and its preparation method. The method involves mixing modified PVC, coated tungsten carbide powder, calcium-zinc composite stabilizer, stearic acid, oxidized polyethylene wax, antioxidant, and ultraviolet absorber, followed by melt extrusion and calendering to obtain the impact-resistant and crack-resistant PVC decorative film. This preparation method uses modified PVC as the main raw material, significantly increasing the overall toughness of the PVC decorative film, thereby significantly improving its impact resistance. The addition of coated tungsten carbide powder greatly enhances the mechanical properties of the PVC decorative film, providing strong strength support. The combination of these two factors significantly improves the impact resistance of the PVC decorative film under external forces, thereby significantly enhancing its crack resistance, durability, and service life.

[0020] In the preparation of polyvinyl chloride decorative film, a modified polyvinyl chloride was first prepared. This was achieved by reacting allyl alcohol glycidyl ether with 1,1,3,3-tetramethyldisiloxane. The alkenyl group on the allyl alcohol glycidyl ether undergoes a hydrosilylation reaction with the Si-H group on the 1,1,3,3-tetramethyldisiloxane, simultaneously introducing epoxy groups to obtain a terminal epoxy-based organosilicon compound. This compound was then reacted with diethanolamine. The epoxy groups on the terminal epoxy-based organosilicon compound react with the secondary amine group on the diethanolamine, forming hydroxyl groups and introducing multiple hydroxyl groups. A hydroxyl-terminated organosilicon compound is obtained by modifying polyvinyl chloride (PVC) with the hydroxyl-terminated organosilicon compound. The hydroxyl groups on the hydroxyl-terminated organosilicon compound react with some chlorine atoms on PVC, thereby incorporating ether bonds, carbon chains, and organosilicon structures into the side chains of PVC, resulting in modified PVC. The molecular structure of this modified PVC contains a large number of ether bonds, carbon chains, and organosilicon structures, which can also connect different PVC molecules to form a buffer network, thereby improving its toughness, impact resistance, and ensuring excellent mechanical properties.

[0021] In the process of preparing polyvinyl chloride decorative film, a coated tungsten carbide powder was also prepared. This was achieved through a reaction between 4-bromo-1,8-naphthalenedicarboxylic anhydride and 4-vinylaniline. The anhydride group on the 4-bromo-1,8-naphthalenedicarboxylic anhydride reacts with the amino group on the 4-vinylaniline, simultaneously introducing an alkenyl group. Furthermore, the bromine atom on the 4-bromo-1,8-naphthalenedicarboxylic anhydride reacts with the secondary amino group on the 1-formaldehyde piperazine, simultaneously introducing an aldehyde group, resulting in an aldehyde-based vinylnaphthalene compound. The nano-tungsten carbide powder was then modified using the silane coupling agent KH-550. The siloxane on the silane coupling agent KH-550 hydrolyzes to form silanols, which are then grafted onto the surface of the nano-tungsten carbide powder particles, simultaneously introducing a large number of amino groups, resulting in aminated tungsten carbide powder. This aminated tungsten carbide powder, along with the aldehyde group... In the reaction of vinyl naphthalene compounds, the amino groups on the aminated tungsten carbide powder react with the aldehyde groups on the aldehyde-based vinyl naphthalene compound to form a Schiff base structure, introducing alkenyl groups. Subsequently, polymerization is carried out to form a polymer coating the surface of the aminated tungsten carbide powder, resulting in coated tungsten carbide powder. This coated tungsten carbide powder, leveraging the excellent mechanical properties of tungsten carbide itself, can significantly enhance PVC decorative films. After modification, it can be well distributed within the PVC decorative film, effectively dispersing and buffering impact forces, preventing the formation of concentrated stress within the PVC decorative film, reducing stress concentration points, thereby significantly enhancing the crack resistance of the PVC decorative film and improving its durability and service life. Detailed Implementation

[0022] 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. Example

[0023] This embodiment describes a method for preparing an impact-resistant and crack-resistant polyvinyl chloride decorative film, comprising the following steps: Step S1: 20 mmol of allyl alcohol glycidyl ether, 0.3 g of chloroplatinic acid and 100 mL of isopropanol were added to a three-necked flask equipped with a stirrer, thermometer, reflux condenser and gas delivery tube. Nitrogen gas was introduced for protection. The mixture was stirred for 20 min at 25 °C and 300 r / min. Then 10 mmol of 1,1,3,3-tetramethyldisiloxane was added and the mixture was heated to 70 °C and stirred for 1 h. After the reaction was completed, the product was cooled to room temperature and the solvent was removed by rotary evaporation to obtain an epoxy-terminated organosilicon compound. Step S2: 10 mmol of terminal epoxy organosilicon compound, 20 mmol of diethanolamine and 60 mL of ethanol were added to a three-necked flask equipped with a stirrer, thermometer, reflux condenser and gas delivery tube. Nitrogen gas was introduced for protection. The mixture was stirred at 25 °C and 300 r / min for 20 min. Then the temperature was raised to 70 °C and the mixture was stirred for 6 h. After the reaction was completed, the reaction product was cooled to room temperature and the solvent was removed by rotary evaporation to obtain the terminal hydroxyl organosilicon compound. Step S3: Add 10g of polyvinyl chloride (PVC) SG-5, 0.2g of hydroxyl-terminated organosilicon compound, and 100mL of N,N-dimethylformamide to a three-necked flask equipped with a stirrer, thermometer, reflux condenser, and gas delivery tube. Purge with nitrogen for protection and stir at 25℃ and 300r / min for 30min. Then, raise the temperature to 80℃ and continue stirring for 2h. After the reaction is complete, cool the reaction product to room temperature and pour it into a 10% methanol solution. Centrifuge the solution and place the precipitate in a vacuum drying oven at 60℃ for 5h to obtain modified polyvinyl chloride. Step S4: 10 mmol of 4-bromo-1,8-naphthalenedicarboxylic anhydride, 10 mmol of 4-vinylaniline, and 50 mL of ethanol were added to a three-necked flask equipped with a stirrer, thermometer, reflux condenser, and gas delivery tube. Nitrogen gas was introduced for protection, and the mixture was stirred at 25 °C and a stirring rate of 300 r / min for 10 min. The mixture was then heated to reflux and stirred for 5 h. After that, 20 mmol of potassium carbonate, 10 mmol of 1-formaldehyde piperazine, and 30 mL of ethylene glycol monomethyl ether were added, and the mixture was stirred for 8 h. After the reaction was completed, the reaction product was cooled to room temperature, and the solvent was removed by rotary evaporation. The product was then purified by silica gel column chromatography using a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 5:1 as the eluent to obtain the aldehyde vinylnaphthalene compound. Step S5: Add 8g of silane coupling agent KH-550 and 100mL of 3% acetic acid solution to a three-necked flask equipped with a stirrer, thermometer, reflux condenser and gas delivery tube. Purge with nitrogen for protection and stir at 25℃ and 300r / min for 30min. Then adjust the pH to 8 with 10% sodium hydroxide solution. Add 5g of tungsten carbide nanoparticles with an average particle size of 100nm and continue stirring at 65℃ for 20h. After the reaction is complete, cool the reaction product to room temperature, centrifuge, wash the precipitate twice with ethanol, and then place it in a vacuum drying oven and dry at 60℃ for 5h to obtain aminated tungsten carbide powder. Step S6: 3g of aminated tungsten carbide powder, 0.5g of aldehyde vinylnaphthalene compound, 0.5mL of 3mol / L hydrochloric acid solution, 40mL of N,N-dimethylformamide, and 10mL of 1,4-dioxane were added to a three-necked flask equipped with a stirrer, thermometer, reflux condenser, and gas delivery tube. Nitrogen gas was introduced for protection, and the mixture was stirred at 25℃ and 300r / min for 20min. The temperature was then raised to 110℃ and the mixture was stirred for 4h. The temperature was then lowered to 60℃ and 0.03g of azobisisobutyronitrile was added, and the mixture was stirred for 10h. After the reaction was completed, the reaction product was cooled to room temperature and centrifuged. The precipitate was washed twice with ethanol, acetone, and distilled water, and then placed in a vacuum drying oven and dried at 60℃ for 8h to obtain coated tungsten carbide powder. Step S7: Weigh out 100 parts by weight of modified polyvinyl chloride, 1 part by weight of coated tungsten carbide powder, 2 parts by weight of calcium-zinc composite stabilizer, 0.5 parts by weight of stearic acid, 0.2 parts by weight of oxidized polyethylene wax, 0.1 parts by weight of antioxidant, and 0.2 parts by weight of ultraviolet absorber, and set aside; the antioxidant is antioxidant 168; the ultraviolet absorber is ultraviolet absorber UV-531; Step S8: Modified polyvinyl chloride, coated tungsten carbide powder, calcium-zinc composite stabilizer, stearic acid, oxidized polyethylene wax, antioxidant and ultraviolet absorber are added to a mixer and stirred for 10 minutes at a temperature of 80℃ and a stirring speed of 1000r / min. Then it is added to an extruder and melt-extruded at a temperature of 160℃ and a screw speed of 50r / min. After that, it is calendered to obtain an impact-resistant and crack-resistant polyvinyl chloride decorative film with a thickness of 30μm. Example

[0024] This embodiment describes a method for preparing an impact-resistant and crack-resistant polyvinyl chloride decorative film, comprising the following steps: Step S1: 20 mmol of allyl alcohol glycidyl ether, 0.4 g of chloroplatinic acid and 105 mL of isopropanol were added to a three-necked flask equipped with a stirrer, thermometer, reflux condenser and gas delivery tube. Nitrogen gas was introduced for protection. The mixture was stirred for 25 min at 28 °C and 350 r / min. Then 10 mmol of 1,1,3,3-tetramethyldisiloxane was added and the mixture was heated to 72 °C and stirred for another 2 h. After the reaction was completed, the product was cooled to room temperature and the solvent was removed by rotary evaporation to obtain an epoxy-terminated organosilicon compound. Step S2: 10 mmol of terminal epoxy organosilicon compound, 20 mmol of diethanolamine and 65 mL of ethanol were added to a three-necked flask equipped with a stirrer, thermometer, reflux condenser and gas delivery tube. Nitrogen gas was introduced for protection. The mixture was stirred at 28 °C and 350 r / min for 25 min. Then the temperature was raised to 72 °C and the mixture was stirred for 7 h. After the reaction was completed, the reaction product was cooled to room temperature and the solvent was removed by rotary evaporation to obtain the terminal hydroxyl organosilicon compound. Step S3: Add 10g of polyvinyl chloride (PVC) SG-5, 1.1g of hydroxyl-terminated organosilicon compound, and 105mL of N,N-dimethylformamide to a three-necked flask equipped with a stirrer, thermometer, reflux condenser, and gas delivery tube. Purge with nitrogen for protection and stir at 28℃ and 350r / min for 40min. Then raise the temperature to 82℃ and continue stirring for 3h. After the reaction is complete, cool the reaction product to room temperature and pour it into a 12% methanol solution. Centrifuge the solution and place the precipitate in a vacuum drying oven at 65℃ for 5.5h to obtain modified polyvinyl chloride. Step S4: 10 mmol of 4-bromo-1,8-naphthalenedicarboxylic anhydride, 10 mmol of 4-vinylaniline, and 55 mL of ethanol were added to a three-necked flask equipped with a stirrer, thermometer, reflux condenser, and gas delivery tube. Nitrogen gas was introduced for protection, and the mixture was stirred at 28 °C and a stirring rate of 350 r / min for 15 min. The mixture was then heated to reflux and stirred for 6 h. 22 mmol of potassium carbonate, 10 mmol of 1-formaldehyde piperazine, and 35 mL of ethylene glycol monomethyl ether were added, and the mixture was stirred for another 9 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 purified by silica gel column chromatography using a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 6:1 as the eluent to obtain the aldehyde vinylnaphthalene compound. Step S5: Add 9g of silane coupling agent KH-550 and 105mL of 4% acetic acid solution to a three-necked flask equipped with a stirrer, thermometer, reflux condenser and gas delivery tube. Purge with nitrogen for protection and stir at 28℃ and 350r / min for 40min. Then adjust the pH to 8.5 with 11% sodium hydroxide solution. Add 5g of tungsten carbide nanoparticles with an average particle size of 100nm and continue stirring at 68℃ for 22h. After the reaction is complete, cool the reaction product to room temperature, centrifuge, wash the precipitate twice with ethanol, and then place it in a vacuum drying oven and dry at 65℃ for 5.5h to obtain aminated tungsten carbide powder. Step S6: 3g of aminated tungsten carbide powder, 1.1g of aldehyde vinylnaphthalene compound, 0.55mL of 3.5mol / L hydrochloric acid solution, 45mL of N,N-dimethylformamide, and 12mL of 1,4-dioxane were added to a three-necked flask equipped with a stirrer, thermometer, reflux condenser, and gas delivery tube. Nitrogen gas was introduced for protection, and the mixture was stirred at 28℃ and 350r / min for 25min. The temperature was then raised to 115℃ and the mixture was stirred for 5h. The temperature was then lowered to 65℃ and 0.05g of azobisisobutyronitrile was added, and the mixture was stirred for 12h. After the reaction was completed, the reaction product was cooled to room temperature and centrifuged. The precipitate was washed twice with ethanol, acetone, and distilled water, and then placed in a vacuum drying oven and dried at 65℃ for 9h to obtain coated tungsten carbide powder. Step S7: Weigh out 105 parts by weight of modified polyvinyl chloride, 5 parts by weight of coated tungsten carbide powder, 2.5 parts by weight of calcium-zinc composite stabilizer, 0.6 parts by weight of stearic acid, 0.3 parts by weight of oxidized polyethylene wax, 0.3 parts by weight of antioxidant, and 0.4 parts by weight of ultraviolet absorber, and set aside; the antioxidant is antioxidant 168; the ultraviolet absorber is ultraviolet absorber UV-531; Step S8: Modified polyvinyl chloride, coated tungsten carbide powder, calcium-zinc composite stabilizer, stearic acid, oxidized polyethylene wax, antioxidant and ultraviolet absorber are added to a mixer and stirred for 12 minutes at a temperature of 90℃ and a stirring speed of 1500r / min. Then it is added to an extruder and melt-extruded at a temperature of 165℃ and a screw speed of 55r / min. After that, it is calendered to obtain an impact-resistant and crack-resistant polyvinyl chloride decorative film with a thickness of 30μm. Example

[0025] This embodiment describes a method for preparing an impact-resistant and crack-resistant polyvinyl chloride decorative film, comprising the following steps: Step S1: 20 mmol of allyl alcohol glycidyl ether, 0.5 g of chloroplatinic acid and 110 mL of isopropanol were added to a three-necked flask equipped with a stirrer, thermometer, reflux condenser and gas delivery tube. Nitrogen gas was introduced for protection. The mixture was stirred at 30 °C and 400 r / min for 30 min. Then 10 mmol of 1,1,3,3-tetramethyldisiloxane was added and the mixture was heated to 75 °C and stirred for another 3 h. After the reaction was completed, the product was cooled to room temperature and the solvent was removed by rotary evaporation to obtain an epoxy-terminated organosilicon compound. Step S2: 10 mmol of terminal epoxy organosilicon compound, 20 mmol of diethanolamine and 70 mL of ethanol were added to a three-necked flask equipped with a stirrer, thermometer, reflux condenser and gas delivery tube. Nitrogen gas was introduced for protection. The mixture was stirred at 30 °C and 400 r / min for 30 min. Then the temperature was raised to 75 °C and the mixture was stirred for 8 h. After the reaction was completed, the reaction product was cooled to room temperature and the solvent was removed by rotary evaporation to obtain the terminal hydroxyl organosilicon compound. Step S3: Add 10g of polyvinyl chloride (PVC) SG-5, 2g of hydroxyl-terminated organosilicon compound, and 110mL of N,N-dimethylformamide to a three-necked flask equipped with a stirrer, thermometer, reflux condenser, and gas delivery tube. Purge with nitrogen for protection and stir at 30℃ and 400r / min for 50min. Then raise the temperature to 85℃ and continue stirring for 4h. After the reaction is complete, cool the reaction product to room temperature and pour it into a 15% methanol solution. Centrifuge the solution and place the precipitate in a vacuum drying oven at 70℃ for 6h to obtain modified polyvinyl chloride. Step S4: 10 mmol of 4-bromo-1,8-naphthalenedicarboxylic anhydride, 10 mmol of 4-vinylaniline, and 60 mL of ethanol were added to a three-necked flask equipped with a stirrer, thermometer, reflux condenser, and gas delivery tube. Nitrogen gas was introduced for protection, and the mixture was stirred at 30 °C and 400 r / min for 20 min. The mixture was then heated to reflux and stirred for 7 h. 25 mmol of potassium carbonate, 10 mmol of 1-formaldehyde piperazine, and 40 mL of ethylene glycol monomethyl ether were added, and the mixture was stirred for another 10 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 purified by silica gel column chromatography using a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 7:1 as the eluent to obtain the aldehyde vinylnaphthalene compound. Step S5: Add 10g of silane coupling agent KH-550 and 110mL of 5% acetic acid solution to a three-necked flask equipped with a stirrer, thermometer, reflux condenser and gas delivery tube. Purge with nitrogen for protection and stir at 30℃ and 400r / min for 50min. Then adjust the pH to 9 with 12% sodium hydroxide solution. Add 5g of tungsten carbide nanoparticles with an average particle size of 100nm and continue stirring at 70℃ for 25h. After the reaction is complete, cool the reaction product to room temperature, centrifuge, wash the precipitate three times with ethanol, and then place it in a vacuum drying oven and dry at 70℃ for 6h to obtain aminated tungsten carbide powder. Step S6: 3g of aminated tungsten carbide powder, 1.7g of aldehyde vinylnaphthalene compound, 0.6mL of hydrochloric acid solution with a molar concentration of 4mol / L, 50mL of N,N-dimethylformamide, and 15mL of 1,4-dioxane were added to a three-necked flask equipped with a stirrer, thermometer, reflux condenser, and gas delivery tube. Nitrogen gas was introduced for protection, and the mixture was stirred at 30℃ and a stirring rate of 400r / min for 30min. Then, the temperature was raised to 120℃ and the mixture was stirred for 6h. After that, the temperature was lowered to 70℃ and 0.07g of azobisisobutyronitrile was added, and the mixture was stirred for 15h. After the reaction was completed, the reaction product was cooled to room temperature and then centrifuged. The precipitate was washed three times with ethanol, acetone, and distilled water, and then placed in a vacuum drying oven and dried at 70℃ for 10h to obtain coated tungsten carbide powder. Step S7: Weigh out 110 parts by weight of modified polyvinyl chloride, 9 parts by weight of coated tungsten carbide powder, 3 parts by weight of calcium-zinc composite stabilizer, 0.7 parts by weight of stearic acid, 0.4 parts by weight of oxidized polyethylene wax, 0.5 parts by weight of antioxidant, and 0.6 parts by weight of ultraviolet absorber, and set aside; the antioxidant is antioxidant 168; the ultraviolet absorber is ultraviolet absorber UV-531; Step S8: Modified polyvinyl chloride, coated tungsten carbide powder, calcium-zinc composite stabilizer, stearic acid, oxidized polyethylene wax, antioxidant and ultraviolet absorber are added to a mixer and stirred for 15 minutes at a temperature of 100℃ and a stirring speed of 2000 r / min. Then, it is added to an extruder and melt-extruded at a temperature of 170℃ and a screw speed of 60 r / min. After that, it is calendered to obtain an impact-resistant and crack-resistant polyvinyl chloride decorative film with a thickness of 30 μm.

[0026] Comparative Example 1: This comparative example illustrates a method for preparing an impact-resistant and crack-resistant polyvinyl chloride decorative film, comprising the following steps: Step S1: Weigh out 110 parts of polyvinyl chloride (PVC) SG-5, 3 parts of calcium-zinc composite stabilizer, 0.7 parts of stearic acid, 0.4 parts of oxidized polyethylene wax, 0.5 parts of antioxidant, and 0.6 parts of ultraviolet absorber according to the following weight proportions, and set aside for later use; the antioxidant is antioxidant 168; the ultraviolet absorber is ultraviolet absorber UV-531. Step S2: Add PVC SG-5, calcium-zinc composite stabilizer, stearic acid, oxidized polyethylene wax, antioxidant, and ultraviolet absorber to a mixer and mix for 15 minutes at 100°C and 2000 r / min. Then add it to an extruder and melt-extrude it at 170°C and 60 r / min. After that, calender it to obtain a 30 μm thick impact-resistant and crack-resistant PVC decorative film.

[0027] Comparative Example 2: This comparative example illustrates a method for preparing an impact-resistant and crack-resistant polyvinyl chloride decorative film, comprising the following steps: Step S1: 20 mmol of allyl alcohol glycidyl ether, 0.5 g of chloroplatinic acid and 110 mL of isopropanol were added to a three-necked flask equipped with a stirrer, thermometer, reflux condenser and gas delivery tube. Nitrogen gas was introduced for protection. The mixture was stirred at 30 °C and 400 r / min for 30 min. Then 10 mmol of 1,1,3,3-tetramethyldisiloxane was added and the mixture was heated to 75 °C and stirred for another 3 h. After the reaction was completed, the product was cooled to room temperature and the solvent was removed by rotary evaporation to obtain an epoxy-terminated organosilicon compound. Step S2: 10 mmol of terminal epoxy organosilicon compound, 20 mmol of diethanolamine and 70 mL of ethanol were added to a three-necked flask equipped with a stirrer, thermometer, reflux condenser and gas delivery tube. Nitrogen gas was introduced for protection. The mixture was stirred at 30 °C and 400 r / min for 30 min. Then the temperature was raised to 75 °C and the mixture was stirred for 8 h. After the reaction was completed, the reaction product was cooled to room temperature and the solvent was removed by rotary evaporation to obtain the terminal hydroxyl organosilicon compound. Step S3: Add 10g of polyvinyl chloride (PVC) SG-5, 2g of hydroxyl-terminated organosilicon compound, and 110mL of N,N-dimethylformamide to a three-necked flask equipped with a stirrer, thermometer, reflux condenser, and gas delivery tube. Purge with nitrogen for protection and stir at 30℃ and 400r / min for 50min. Then raise the temperature to 85℃ and continue stirring for 4h. After the reaction is complete, cool the reaction product to room temperature and pour it into a 15% methanol solution. Centrifuge the solution and place the precipitate in a vacuum drying oven at 70℃ for 6h to obtain modified polyvinyl chloride. Step S4: Weigh out 110 parts of modified polyvinyl chloride, 3 parts of calcium-zinc composite stabilizer, 0.7 parts of stearic acid, 0.4 parts of oxidized polyethylene wax, 0.5 parts of antioxidant, and 0.6 parts of ultraviolet absorber according to the following weight proportions, and set aside for later use; the antioxidant is antioxidant 168; the ultraviolet absorber is ultraviolet absorber UV-531. Step S5: Add modified polyvinyl chloride, calcium-zinc composite stabilizer, stearic acid, oxidized polyethylene wax, antioxidant and ultraviolet absorber to a mixer and mix for 15 minutes at a temperature of 100℃ and a stirring speed of 2000 r / min. Then add it to an extruder and melt extrude it at a temperature of 170℃ and a screw speed of 60 r / min. After that, calender it through a calender to obtain an impact-resistant and crack-resistant polyvinyl chloride decorative film with a thickness of 30 μm.

[0028] Comparative Example 3: This comparative example illustrates a method for preparing an impact-resistant and crack-resistant polyvinyl chloride decorative film, comprising the following steps: Step S1: 20 mmol of allyl alcohol glycidyl ether, 0.5 g of chloroplatinic acid and 110 mL of isopropanol were added to a three-necked flask equipped with a stirrer, thermometer, reflux condenser and gas delivery tube. Nitrogen gas was introduced for protection. The mixture was stirred at 30 °C and 400 r / min for 30 min. Then 10 mmol of 1,1,3,3-tetramethyldisiloxane was added and the mixture was heated to 75 °C and stirred for another 3 h. After the reaction was completed, the product was cooled to room temperature and the solvent was removed by rotary evaporation to obtain an epoxy-terminated organosilicon compound. Step S2: 10 mmol of terminal epoxy organosilicon compound, 20 mmol of diethanolamine and 70 mL of ethanol were added to a three-necked flask equipped with a stirrer, thermometer, reflux condenser and gas delivery tube. Nitrogen gas was introduced for protection. The mixture was stirred at 30 °C and 400 r / min for 30 min. Then the temperature was raised to 75 °C and the mixture was stirred for 8 h. After the reaction was completed, the reaction product was cooled to room temperature and the solvent was removed by rotary evaporation to obtain the terminal hydroxyl organosilicon compound. Step S3: Add 10g of polyvinyl chloride (PVC) SG-5, 2g of hydroxyl-terminated organosilicon compound, and 110mL of N,N-dimethylformamide to a three-necked flask equipped with a stirrer, thermometer, reflux condenser, and gas delivery tube. Purge with nitrogen for protection and stir at 30℃ and 400r / min for 50min. Then raise the temperature to 85℃ and continue stirring for 4h. After the reaction is complete, cool the reaction product to room temperature and pour it into a 15% methanol solution. Centrifuge the solution and place the precipitate in a vacuum drying oven at 70℃ for 6h to obtain modified polyvinyl chloride. Step S4: Weigh out 110 parts by weight of modified polyvinyl chloride, 9 parts by weight of nano-tungsten carbide powder, 3 parts by weight of calcium-zinc composite stabilizer, 0.7 parts by weight of stearic acid, 0.4 parts by weight of oxidized polyethylene wax, 0.5 parts by weight of antioxidant, and 0.6 parts by weight of ultraviolet absorber, and set aside; the average particle size of the nano-tungsten carbide powder is 100 nm; the antioxidant is antioxidant 168; the ultraviolet absorber is ultraviolet absorber UV-531. Step S5: Modified polyvinyl chloride, nano tungsten carbide powder, calcium-zinc composite stabilizer, stearic acid, oxidized polyethylene wax, antioxidant and ultraviolet absorber are added to a mixer and stirred for 15 minutes at a temperature of 100℃ and a stirring speed of 2000 r / min. Then, it is added to an extruder and melt-extruded at a temperature of 170℃ and a screw speed of 60 r / min. After that, it is calendered to obtain an impact-resistant and crack-resistant polyvinyl chloride decorative film with a thickness of 30 μm.

[0029] Performance testing The impact-resistant and crack-resistant polyvinyl chloride decorative films of Examples 1-3 and Comparative Examples 1-3 were tested for impact performance according to GB / T 9639.1-2008, and tensile strength and elongation at break were tested according to GB / T1040.1-2025.

[0030] The test results are shown in the table below:

[0031] 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 modified polyvinyl chloride as the main raw material and adding coated tungsten carbide powder can significantly improve the impact resistance and mechanical properties of polyvinyl chloride decorative film.

[0032] 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.

[0033] 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. An impact resistant, crack resistant polyvinyl chloride decorative film, characterized by, Includes the following components by weight: 100-110 parts modified polyvinyl chloride, 1-9 parts coated tungsten carbide powder, 2-3 parts calcium-zinc composite stabilizer, 0.5-0.7 parts stearic acid, 0.2-0.4 parts oxidized polyethylene wax, 0.1-0.5 parts antioxidant, and 0.2-0.6 parts ultraviolet absorber; The modified polyvinyl chloride is prepared by the following steps: Step a1: Allyl alcohol glycidyl ether, chloroplatinic acid and isopropanol were stirred and reacted, then 1,1,3,3-tetramethyldisiloxane was added and the reaction was continued with stirring. After the reaction was completed, the reaction product was cooled and then rotary evaporated to obtain an epoxy-terminated organosilicon compound. Step a2: The terminal epoxy organosilicon compound, diethanolamine and ethanol are stirred and reacted. After the reaction is completed, the reaction product is cooled and then rotary evaporated to obtain the terminal hydroxyl organosilicon compound. Step a3: Polyvinyl chloride, hydroxyl-terminated organosilicon compound and N,N-dimethylformamide are stirred and reacted. After the reaction is completed, the reaction product is cooled and then poured into a methanol solution. After centrifugation, the precipitate is dried to obtain modified polyvinyl chloride.

2. The impact-resistant, crack-resistant PVC decorative film according to claim 1, characterized in that, The ratio of allyl alcohol glycidyl ether, chloroplatinic acid, isopropanol and 1,1,3,3-tetramethyldisiloxane in step a1 is 20 mmol: 0.3-0.5 g: 100-110 mL: 10 mmol.

3. The impact-resistant, crack-resistant PVC decorative film according to claim 1, wherein, The ratio of the terminal epoxy organosilicon compound, diethanolamine, and ethanol used in step a2 is 10 mmol: 20 mmol: 60-70 mL.

4. The impact-resistant, crack-resistant PVC decorative film according to claim 1, wherein, In step a3, the ratio of polyvinyl chloride, hydroxyl-terminated organosilicon compound, and N,N-dimethylformamide is 10g:0.2-2g:100-110mL; the polyvinyl chloride is PVC SG-5; and the volume fraction of the methanol solution is 10-15%.

5. The impact-resistant, crack-resistant PVC decorative film according to claim 1, wherein, The coated tungsten carbide powder is prepared by the following steps: Step b1: 4-bromo-1,8-naphthalenedicarboxylic anhydride, 4-vinylaniline and ethanol were stirred and reacted. Then potassium carbonate, 1-formaldehyde piperazine and ethylene glycol monomethyl ether were added and the reaction was continued with stirring. After the reaction was completed, the reaction product was cooled, then rotary evaporated, and then purified by silica gel column chromatography to obtain aldehyde vinylnaphthalene compound. Step b2: Stir the reaction of silane coupling agent KH-550 and acetic acid solution, then adjust the pH with sodium hydroxide solution, add nano tungsten carbide powder and continue stirring. After the reaction is completed, cool the reaction product, then centrifuge, wash and dry the precipitate to obtain aminated tungsten carbide powder. Step b3: Aminated tungsten carbide powder, aldehyde vinylnaphthalene compound, hydrochloric acid solution, N,N-dimethylformamide and 1,4-dioxane were stirred and reacted. Then, azobisisobutyronitrile was added and the reaction was continued with stirring. After the reaction was completed, the reaction product was cooled, centrifuged, and the precipitate was washed and dried to obtain coated tungsten carbide powder.

6. The impact resistant, crack resistant, polyvinyl chloride decorative film according to claim 5, wherein, The ratio of 4-bromo-1,8-naphthalenedicarboxylic anhydride, 4-vinylaniline, ethanol, potassium carbonate, 1-formaldehyde piperazine, and ethylene glycol monomethyl ether in step b1 is 10 mmol: 10 mmol: 50-60 mL: 20-25 mmol: 10 mmol: 30-40 mL.

7. The impact resistant, crack resistant, polyvinyl chloride decorative film according to claim 5, wherein In step b2, the ratio of silane coupling agent KH-550, acetic acid solution, and nano-tungsten carbide powder is 8-10g: 100-110mL: 5g; the mass fraction of the acetic acid solution is 3-5%; the mass fraction of the sodium hydroxide solution is 10-12%; and the average particle size of the nano-tungsten carbide powder is 100nm.

8. The impact resistant, crack resistant, polyvinyl chloride decorative film according to claim 5, wherein, The ratio of the amino-modified tungsten carbide powder, aldehyde vinylnaphthalene compound, hydrochloric acid solution, N,N-dimethylformamide, 1,4-dioxane, and azobisisobutyronitrile in step b3 is 3g. 0.5-1.7g; 0.5-0.6mL; 40-50mL; 10-15mL; 0.03-0.07g; the molar concentration of the hydrochloric acid solution is 3-4mol / L.

9. A method of producing the impact-resistant, crack-resistant polyvinyl chloride decorative film according to any one of claims 1 to 8, characterized by, Includes the following steps: Step 1: Weigh out 100-110 parts of modified polyvinyl chloride, 1-9 parts of coated tungsten carbide powder, 2-3 parts of calcium-zinc composite stabilizer, 0.5-0.7 parts of stearic acid, 0.2-0.4 parts of oxidized polyethylene wax, 0.1-0.5 parts of antioxidant, and 0.2-0.6 parts of ultraviolet absorber according to the following weight proportions, and set aside for later use; Step 2: Add modified polyvinyl chloride, coated tungsten carbide powder, calcium-zinc composite stabilizer, stearic acid, oxidized polyethylene wax, antioxidant, and ultraviolet absorber to a mixer and mix for 10-15 minutes at a temperature of 80-100℃ and a stirring speed of 1000-2000 r / min. Then add it to an extruder and melt-extrude it at a temperature of 160-170℃ and a screw speed of 50-60 r / min. After that, calender it through a calender to obtain a 30μm thick impact-resistant and crack-resistant polyvinyl chloride decorative film.

10. The method for preparing an impact-resistant and crack-resistant polyvinyl chloride decorative film according to claim 9, characterized in that, The antioxidant is antioxidant 168; the ultraviolet absorber is ultraviolet absorber UV-531.

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