Colloid of anti-skid layer of electrostatic sand-planting film and manufacturing method of colloid
By coating the surface of modified polystyrene nanospheres with polyaniline and sulfonating them, combined with hydrothermal synthesis of calcium-based MOF, core-shell conductive composite nanospheres are formed. This solves the problem of loosening of the anti-slip layer of electrostatic sand-coated film during high-speed grinding, improves bonding strength and friction, and is suitable for high-value-added fields.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-02-03
- Publication Date
- 2026-03-31
AI Technical Summary
The anti-slip colloid of existing electrostatic sand-coated films is prone to loosening during high-speed polishing, resulting in insufficient bonding stability and friction control, which limits its application in high-value-added fields.
Modified polystyrene nanospheres were used as a carrier. After surface coating with polymerized polyaniline and sulfonation treatment, calcium-based MOF was hydrothermally synthesized to form core-shell conductive composite nanospheres, which served as the reinforcing phase of the colloid. These nanospheres were then crosslinked with polyvinyl alcohol to form an electrostatic sand-coated anti-slip film layer.
It improves the bonding strength and mechanical strength of the colloid, enhances its antistatic and frictional properties, prevents slippage, and meets the application needs of high value-added fields.
Smart Images
Figure CN121759115A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of adhesive technology, specifically the colloid of an electrostatic sand-coated anti-slip film layer and its manufacturing method. Background Technology
[0002] Sponge abrasive, as a highly efficient and environmentally friendly abrasive material, is widely used in the surface treatment and processing of various materials. Currently, the sponge abrasive application industry is in a phase of rapid development, with continuously growing market demand and constantly improving technology. At present, in both domestic and international markets, the demand for roller abrasive belts mainly comes from the automotive, shipbuilding, machinery, aerospace, and electronics manufacturing sectors. These sectors are gradually increasing their demand for roller abrasive belts, and with product upgrades and technological advancements, the quality and performance requirements for roller abrasive belts are also becoming increasingly stringent. In the future, with the development of manufacturing and continuous technological progress, the market demand for roller abrasive belts will continue to grow. At the same time, the quality and performance requirements for abrasive belts will continue to rise, requiring manufacturers to continuously improve their technology and processes to enhance product quality and competitiveness to meet market demands.
[0003] In the application of roller-type abrasive belts, the anti-slip colloid of the electrostatically coated abrasive film is one of the core components ensuring the accuracy, efficiency, and durability of the abrasive belt. The fundamental requirement is to solve the problems of "stability of adhesion between the abrasive belt and the workpiece, friction control, and process compatibility in roller-type abrasive applications." The core of the electrostatically coated abrasive film is that it adheres to the substrate via electrostatic adsorption, with the anti-slip colloid coated on the back of the substrate. If the adhesion between the colloid and the substrate is insufficient, or if the colloid itself has poor flexibility, the substrate is prone to slight deformation under the vibration and tension of high-speed abrasion, leading to loosening of the abrasive layer. These technical bottlenecks have become the core obstacles restricting the penetration of electrostatically coated abrasive films into high-value-added fields such as 3C electronics and automobiles. Summary of the Invention
[0004] The purpose of this invention is to provide a colloid for an electrostatic sand-coated anti-slip film and its manufacturing method. Modified polystyrene nanospheres are used as a carrier to coat polymerized polyaniline on the surface, and then sulfonated to obtain sulfonated conductive composite nanospheres. Using these as a carrier, calcium-based MOFs are synthesized on the surface by hydrothermal synthesis to obtain core-shell conductive composite nanospheres, which serve as the reinforcing phase of the colloid and participate in the crosslinking of the colloid's main component, polyvinyl alcohol.
[0005] The objective of this invention can be achieved through the following technical solutions: The colloid of the electrostatic sand-coated anti-slip film layer and its manufacturing method include the following steps: Step 1: Polystyrene nanospheres are hydrolyzed with γ-aminopropyltriethoxysilane to obtain modified polystyrene nanospheres, which are then used as a carrier to coat the surface with polymerized polyaniline to obtain composite nanospheres.
[0006] Step 2: Modified composite nanospheres are obtained by acetalization of benzaldehyde with the hydroxyl groups on the surface of the composite nanospheres under acid catalysis.
[0007] Step 3: Using fuming sulfuric acid as a strong sulfonating agent, the defect sites on the surface of the composite nanospheres are attacked, and sulfonic acid groups are grafted through an electrophilic substitution reaction to obtain sulfonated conductive composite nanospheres.
[0008] Step 4: Using sulfonated conductive composite nanospheres as a carrier, calcium-based MOFs are synthesized on the surface by hydrothermal synthesis to obtain core-shell conductive composite nanospheres.
[0009] Step 5: The colloid of the electrostatic sand-coated antislip film layer is obtained by cross-linking and curing the hydroxyl groups of polyvinyl alcohol and core-shell conductive composite nanospheres under the action of toluene diisocyanate.
[0010] Furthermore, the specific preparation steps of the modified polystyrene nanospheres are as follows: Polystyrene nanospheres with a particle size of 50-60 μm, anhydrous ethanol, and deionized water were added to a reaction vessel and stirred for 10-20 min at 50-60℃ and 500-600 r / min. Then, γ-aminopropyltriethoxysilane was added, and the pH value was adjusted to 3-4 with hydrochloric acid solution. The reaction was continued to be stirred for 6-7 h. After filtration, the precipitate was washed 2-4 times with deionized water and anhydrous ethanol and dried under vacuum at 60-70℃ for 1-2 h to obtain modified polystyrene nanospheres.
[0011] Furthermore, the ratio of polystyrene nanospheres, anhydrous ethanol, deionized water, and γ-aminopropyltriethoxysilane is 100-120g: 120-140mL: 200-250mL: 100-120mL.
[0012] Furthermore, the specific preparation steps of the composite nanospheres are as follows: Modified polystyrene nanospheres, aniline, and deionized water were added to a reaction vessel and stirred at 20-25℃ and 500-600 r / min for 20-30 min. Then, ammonium persulfate initiator was added, and the mixture was heated to 80-90℃ and stirred for 4-5 h. The mixture was then cooled to 0-4℃ and reacted for 12-14 h. The mixture was filtered, and the filter cake was washed 2-4 times with anhydrous ethanol and deionized water, respectively. The cake was then vacuum dried at 60-70℃ for 1-2 h to obtain composite nanospheres.
[0013] Furthermore, the ratio of modified polystyrene nanospheres, aniline, deionized water, and ammonium persulfate is 100-120g: 15-20mL: 500-600mL: 2-3g.
[0014] Furthermore, the specific preparation steps of the modified composite nanospheres are as follows: The composite nanospheres and dimethyl sulfoxide were added to a reaction vessel and stirred at 20-25℃ and 500-600 r / min for 20-30 min. Then benzaldehyde and p-toluenesulfonic acid were added, and the mixture was heated to 85-90℃ and reacted for 1-2 h. The mixture was filtered, and the precipitate was washed 2-4 times with deionized water and anhydrous ethanol. The precipitate was then dried under vacuum at 60-70℃ for 1-2 h to obtain the modified composite nanospheres.
[0015] Furthermore, the ratio of composite nanospheres, dimethyl sulfoxide, benzaldehyde, and p-toluenesulfonic acid is 80-90g: 500-600mL: 2-3g: 0.15-0.2g.
[0016] Furthermore, the specific preparation steps of the sulfonated conductive composite nanospheres are as follows: Modified composite nanospheres and 50-65% fuming sulfuric acid were added to a polytetrafluoroethylene-lined reactor at a ratio of 70-80g:400-500mL. The mixture was stirred at 20-25℃ and 500-600r / min for 20-30min, heated to 98-100℃, and reacted for another 30-40min. After natural cooling to room temperature, the mixture was filtered, and the product was transferred to a sodium hydroxide solution. The mixture was stirred until a large amount of precipitate was released. The precipitate was filtered, washed 2-4 times with deionized water and anhydrous ethanol, and dried under vacuum at 60-70℃ for 1-2h. The product was then transferred to a muffle furnace and calcined at 500-600℃ for 2-3h under nitrogen protection to obtain sulfonated conductive composite nanospheres.
[0017] Furthermore, the specific preparation steps of the core-shell conductive composite nanospheres are as follows: 2,5-Dihydroxyterephthalic acid and N,N-dimethylformamide were added to a polytetrafluoroethylene reactor and stirred for 30-40 minutes at 20-25°C and 500-600 r / min. The mixture was then heated to 130-140°C and stirred for another 30-40 minutes. Calcium chloride was then added and stirred for 10-12 hours. Sulfonated conductive composite nanospheres were then added and stirred for another 10-12 hours. The mixture was filtered, and the filter cake was washed 2-4 times with N,N-dimethylformamide and dried under vacuum at 60-70°C for 1-2 hours to obtain core-shell conductive composite nanospheres.
[0018] Furthermore, the ratio of 2,5-dihydroxyterephthalic acid, N,N-dimethylformamide, calcium chloride, and sulfonated conductive composite nanospheres is 50-60g: 400-500mL: 30-40g: 60-70g.
[0019] Furthermore, the specific preparation steps of the colloid for the electrostatic sand-coated anti-slip film are as follows: Polyvinyl alcohol, core-shell conductive composite nanospheres and deionized water were added to a reaction vessel and stirred for 20-30 minutes at 20-25℃ and 500-600 r / min. The mixture was then heated to 80-90℃, and toluene diisocyanate, a crosslinking curing agent, was added. The reaction was continued for 2-3 hours to obtain the colloid of the electrostatic sand-coated antislip film layer.
[0020] Furthermore, the ratio of polyvinyl alcohol, core-shell conductive composite nanospheres, deionized water, and toluene diisocyanate is 100-120g: 0.5-0.7g: 900-950mL: 4-6g.
[0021] The beneficial effects of this invention are: 1. The colloid of the electrostatic sand-coated anti-slip film layer of this invention possesses excellent adhesive strength and mechanical strength. This invention uses modified polystyrene nanospheres as a carrier, coating the surface with polymerized polyaniline to obtain composite nanospheres. After sulfonation treatment of the composite nanospheres, sulfonated conductive composite nanospheres are obtained. Using these as a carrier, calcium-based MOFs are synthesized on the surface via hydrothermal synthesis to obtain core-shell conductive composite nanospheres. On the one hand, the formation of the core-shell structure can act as a reinforcing phase to increase the mechanical strength of the colloid; on the other hand, the sulfonic acid groups generated by the sulfonation treatment of the sulfonated conductive composite nanospheres can partially coordinate with calcium ions during the hydrothermal synthesis of MOFs, but their coordination ability is weaker than that of carboxylic acid groups. This coordination competition leads to some calcium ions in the MOF lattice forming unsaturated coordination with sulfonic acid groups, thereby generating coordination vacancy defects. These defects increase the specific surface area and are more conducive to releasing local stress concentrations. 2. Toluene diisocyanate and other crosslinking curing agents react with the hydroxyl groups of polyvinyl alcohol and the hydroxyl groups of the core-shell conductive composite nanospheres to perform chemical crosslinking. At the same time, the core-shell conductive composite nanospheres contain calcium ions, which can also crosslink with polyvinyl alcohol to further increase the strength of the colloid.
[0022] 3. The core-shell conductive composite nanospheres contain polyaniline conductive components, which can increase the antistatic properties of the anti-slip layer of the electrostatic sand-coated film. The core-shell structure of the core-shell conductive composite nanospheres allows the colloid of the anti-slip layer of the electrostatic sand-coated film to disperse stress through sliding when acting as an adhesive. Furthermore, the nanoscale rough structure on the surface of the core-shell structure can increase friction and prevent accidental slippage. Attached Figure Description
[0023] Figure 1 Scanning electron microscope (SEM) images of the core-shell conductive composite nanospheres prepared in Examples 1-3 and Comparative Examples 1-3. Detailed Implementation
[0024] 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.
[0025] Example 1: The colloid of the electrostatic sand-coated anti-slip film and its manufacturing method, comprising the following steps: S1: 100g of polystyrene nanospheres with a particle size of 50μm, 120mL of anhydrous ethanol and 200mL of deionized water were added to a reaction vessel and stirred for 10min at 50℃ and 500r / min. Then, 100mL of γ-aminopropyltriethoxysilane was added, and the pH value was adjusted to 3 with hydrochloric acid solution. The reaction was continued to be stirred for 6h. After filtration, the precipitate was washed twice with deionized water and anhydrous ethanol and dried under vacuum at 60℃ for 1h to obtain modified polystyrene nanospheres.
[0026] Modified polystyrene nanospheres are obtained by combining silanol groups generated from the hydrolysis of γ-aminopropyltriethoxysilane with hydroxyl groups on the surface of polystyrene nanospheres.
[0027] S2: Modified polystyrene nanospheres, 15 mL aniline and 500 mL deionized water were added to a reaction vessel and stirred at 20 °C and 500 r / min for 20 min. Then, 2 g of initiator ammonium persulfate was added, heated to 80 °C, and stirred for 4 h. The mixture was then cooled to 0 °C and reacted for another 12 h. The mixture was filtered, and the filter cake was washed twice with anhydrous ethanol and deionized water, respectively. The cake was then vacuum dried at 60 °C for 1 h to obtain composite nanospheres.
[0028] Modified polystyrene nanospheres serve as the core and provide the reaction substrate. Aniline is dispersed in deionized water, and ammonium persulfate is added as an initiator. The ammonium persulfate decomposes at 80°C to generate free radicals, which initiate the polymerization of aniline molecules and amino groups on the surface of the modified polystyrene nanospheres. The aniline molecules lose electrons and are oxidized to phenylenediamine cationic free radicals, which then form polyaniline chains through head-to-tail connections, resulting in composite nanospheres.
[0029] S3: Add 80g of composite nanospheres and 500mL of dimethyl sulfoxide to a reaction vessel, stir at 20℃ and 500r / min for 20min, then add 2g of benzaldehyde and 0.15g of p-toluenesulfonic acid, heat to 85℃, continue to react for 1h, filter, wash the precipitate twice with deionized water and anhydrous ethanol, and vacuum dry at 60℃ for 1h to obtain modified composite nanospheres.
[0030] S4: 70g of modified composite nanospheres and 400mL of 50% fuming sulfuric acid were added to a polytetrafluoroethylene-lined reactor. The mixture was stirred at 20℃ and 500r / min for 20min, heated to 98℃, and reacted for another 30min. The mixture was then allowed to cool naturally to room temperature. The product was filtered and transferred to a sodium hydroxide solution. The mixture was stirred until a large amount of precipitate was released. The precipitate was filtered and washed twice with deionized water and anhydrous ethanol. The precipitate was then dried under vacuum at 60℃ for 1h to obtain sulfonated conductive composite nanospheres.
[0031] S5: Add 50g of 2,5-dihydroxyterephthalic acid and 400mL of N,N-dimethylformamide to a polytetrafluoroethylene reactor. Stir for 30min at 20℃ and 500r / min, heat to 130℃, and continue stirring for 30min. Then add 30g of calcium chloride and continue stirring for 10h. Add 60g of sulfonated conductive composite nanospheres and continue stirring for 10h. Filter the mixture and wash the filter cake twice with N,N-dimethylformamide. Dry the filter cake under vacuum at 60℃ for 1h to obtain core-shell conductive composite nanospheres.
[0032] S6: Add 100g of polyvinyl alcohol, 0.5g of core-shell conductive composite nanospheres and 900mL of deionized water to a reaction vessel, stir at 20℃ and 500r / min for 20min, heat to 80℃, then add 4g of crosslinking curing agent toluene diisocyanate, and continue the reaction for 2h to obtain the colloid of electrostatic sand-planting film antislip layer.
[0033] Example 2: The colloid of the electrostatic sand-coated anti-slip film layer and its manufacturing method, comprising the following steps: S1: 110g of polystyrene nanospheres with a particle size of 55μm, 130mL of anhydrous ethanol and 225mL of deionized water were added to a reaction vessel and stirred for 15min at 55℃ and 550r / min. Then, 110mL of γ-aminopropyltriethoxysilane was added, and the pH value was adjusted to 3.5 with hydrochloric acid solution. The reaction was continued to be stirred for 6.5h. After filtration, the precipitate was washed three times with deionized water and anhydrous ethanol and dried under vacuum at 65℃ for 1.5h to obtain modified polystyrene nanospheres.
[0034] S2: 110g of modified polystyrene nanospheres, 17.5mL of aniline and 550mL of deionized water were added to a reaction vessel and stirred at 22.5℃ and 550r / min for 25min. Then, 2.5g of initiator ammonium persulfate was added, and the mixture was heated to 85℃ and stirred for 4.5h. The mixture was then cooled to 2℃ and reacted for another 13h. The mixture was filtered, and the filter cake was washed three times with anhydrous ethanol and deionized water, respectively. The cake was then vacuum dried at 65℃ for 1.5h to obtain composite nanospheres.
[0035] S3: Add 85g of composite nanospheres and 550mL of dimethyl sulfoxide to a reaction vessel, stir at 22.5℃ and 550r / min for 25min, then add 2.5g of benzaldehyde and 0.175g of p-toluenesulfonic acid, heat to 87.5℃, and continue the reaction for 1.5h. Filter, wash the precipitate three times with deionized water and anhydrous ethanol, and dry under vacuum at 65℃ for 1.5h to obtain modified composite nanospheres.
[0036] S4: 75g of modified composite nanospheres and 450mL of 57.5% fuming sulfuric acid were added to a polytetrafluoroethylene-lined reactor. The mixture was stirred at 22.5℃ and 550r / min for 25min, heated to 99℃, and reacted for another 35min. The mixture was then allowed to cool naturally to room temperature. The product was filtered and transferred to a sodium hydroxide solution. The mixture was stirred until a large amount of precipitate was released. The precipitate was filtered and washed three times with deionized water and anhydrous ethanol. The precipitate was then dried under vacuum at 65℃ for 1.5h to obtain sulfonated conductive composite nanospheres.
[0037] S5: Add 60g of 2,5-dihydroxyterephthalic acid and 500mL of N,N-dimethylformamide to a polytetrafluoroethylene reactor. Stir for 35min at 22.5℃ and 550r / min, heat to 135℃, and continue stirring for 35min. Then add 35g of calcium chloride and continue stirring for 11h. Next, add 65g of sulfonated conductive composite nanospheres and continue stirring for 11h. Filter the mixture and wash the filter cake three times with N,N-dimethylformamide. Dry the filter cake under vacuum at 65℃ for 1.5h to obtain core-shell conductive composite nanospheres.
[0038] S6: Add 110g of polyvinyl alcohol, 0.6g of core-shell conductive composite nanospheres and 925mL of deionized water to a reaction vessel, stir for 25min at 22.5℃ and 550r / min, heat to 85℃, then add 5g of crosslinking curing agent toluene diisocyanate, and continue the reaction for 2.5h to obtain the colloid of the electrostatic sand-planting film antislip layer.
[0039] Example 3: The colloid of the electrostatic sand-coated anti-slip film layer and its manufacturing method, comprising the following steps: S1: 120g of polystyrene nanospheres with a particle size of 60μm, 140mL of anhydrous ethanol and 250mL of deionized water were added to a reaction vessel and stirred for 20min at 60℃ and 600r / min. Then, 120mL of γ-aminopropyltriethoxysilane was added, and the pH value was adjusted to 4 with hydrochloric acid solution. The reaction was continued to be stirred for 7h. After filtration, the precipitate was washed 4 times with deionized water and anhydrous ethanol and dried under vacuum at 70℃ for 2h to obtain modified polystyrene nanospheres.
[0040] S2: Add 120g of modified polystyrene nanospheres, 20mL of aniline and 600mL of deionized water to a reaction vessel, stir at 25℃ and 600r / min for 30min, then add 3g of initiator ammonium persulfate, heat to 90℃, continue stirring for 5h, cool to 4℃, continue the reaction for 14h, filter, wash the filter cake with anhydrous ethanol and deionized water 4 times respectively, and vacuum dry at 70℃ for 2h to obtain composite nanospheres.
[0041] S3: Add 90g of composite nanospheres and 600mL of dimethyl sulfoxide to a reaction vessel, stir at 25℃ and 600r / min for 30min, then add 3g of benzaldehyde and 0.2g of p-toluenesulfonic acid, heat to 90℃, continue to react for 2h, filter, wash the precipitate 4 times with deionized water and anhydrous ethanol, and vacuum dry at 70℃ for 2h to obtain modified composite nanospheres.
[0042] S4: Add 80g of modified composite nanospheres and 500mL of 65% fuming sulfuric acid to a polytetrafluoroethylene-lined reactor. Stir at 25℃ and 600r / min for 30min, heat to 100℃, continue the reaction for 40min, cool naturally to room temperature, filter, transfer the product to sodium hydroxide solution, stir until a large amount of precipitate is volatilized, filter, wash the precipitate 4 times with deionized water and anhydrous ethanol, and vacuum dry at 70℃ for 2h to obtain sulfonated conductive composite nanospheres.
[0043] S5: Add 70g of 2,5-dihydroxyterephthalic acid and 600mL of N,N-dimethylformamide to a polytetrafluoroethylene reactor. Stir for 40min at 25℃ and 600r / min, heat to 140℃, and continue stirring for 40min. Then add 40g of calcium chloride and continue stirring for 12h. Add 70g of sulfonated conductive composite nanospheres and continue stirring for 12h. Filter the mixture and wash the filter cake four times with N,N-dimethylformamide. Dry the filter cake under vacuum at 70℃ for 2h to obtain core-shell conductive composite nanospheres.
[0044] S6: Add 120g of polyvinyl alcohol, 0.7g of core-shell conductive composite nanospheres and 950mL of deionized water to a reaction vessel, stir at 25℃ and 600r / min for 30min, heat to 90℃, then add 6g of crosslinking curing agent toluene diisocyanate, and continue the reaction for 3h to obtain the colloid of electrostatic sand-planting film antislip layer.
[0045] Comparative Example 1: Based on Example 3, the composite nanospheres in step S3 were replaced with the same mass of raw material polystyrene nanospheres in step S2, while the rest remained unchanged, to obtain a colloid of electrostatic sand-coated film anti-slip layer.
[0046] Comparative Example 2: Based on Example 3, the sulfonated conductive composite nanospheres in step S5 were replaced with the same mass of modified composite nanospheres prepared in step S3, while the rest remained unchanged, to obtain the colloid of the electrostatic sand-coated film anti-slip layer.
[0047] Comparative Example 3: Based on Example 3, the core-shell conductive composite nanospheres in step S6 were replaced with sulfonated conductive composite nanospheres of the same mass prepared in step S4, while the rest remained unchanged, to obtain a colloid of electrostatic sand-coated film anti-slip layer.
[0048] Comparative Example 4: Based on Example 3, the core-shell conductive composite nanospheres in step S6 were replaced with commercially available conductive carbon black.
[0049] 1. Adhesive coatings of 1.5mm thick poplar veneer and electrostatic sand-coated anti-slip film were used to prepare plywood specimens according to GB / T9846-2015 standard, with a total adhesive application rate of 800g / m². 2 The hot pressing temperature is 120℃, the hot pressing time is 15min, and after applying the adhesive, it is left at room temperature for 24h. The bonding strength is tested according to GB / T17657-2022 standard.
[0050] 2. Pour the colloid of the electrostatic sand-coated anti-slip film into a mold, degas under vacuum, cure at 70℃ for 4 hours, and then place at room temperature for 24 hours to make dumbbell-shaped samples. The sample has a rectangular shape of 50mm×10mm in the middle. Test the tensile properties according to the method of GB / T1040.1-2018, with a tensile rate of 50mm / min.
[0051] 3. Volume resistivity test: The test was conducted using the GEST-123 volume resistivity tester from Beijing Guance Precision Instrument Equipment Co., Ltd., in accordance with the standard QJ1523-1988. The test requirements were: sample size 50mm×5mm×0.5mm.
[0052] 4. Friction coefficient test: The test was conducted in accordance with the standard ASTM D1894-2014.
[0053] The performance of the colloids in the electrostatic sand-coated antislip film obtained in Examples 1-3 and Comparative Examples 1-3 was tested, and the results are shown in Table 1: Table 1 project Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Bond strength (MPa) 4.56 4.63 4.70 3.2 3.6 2.0 3.8 Tensile strength (MPa) 52.6 53.4 54.1 43 44 27 46 Elongation at break (%) 85.6 89.5 92.3 74 79 41 86 <![CDATA[Volume resistivity (Ω·cm x 10 -5 )]]> 2.781 2.531 2.364 3.735 3.435 3.715 2.835 coefficient of friction 0.832 0.812 0.795 1.235 1.206 1.591 1.012 As can be seen from Table 1, the colloid of the electrostatic sand-coated antislip film obtained in Examples 1-3 has good bonding strength and mechanical properties.
[0054] In Comparative Example 1, the composite nanospheres were replaced with the same mass of polystyrene nanospheres in step S2, resulting in a loss of antistatic properties. The failure of antistatic properties easily led to dust adsorption.
[0055] In Comparative Example 2, the sulfonated conductive composite nanospheres in step S5 were replaced with the modified composite nanospheres of the same mass prepared in step S3. The sulfonation treatment was not performed, resulting in the lack of sulfonic acid groups on the surface of the polyaniline microspheres, which could not provide nucleation sites for subsequent MOF growth. The sulfonic acid groups can compete with some calcium ions in the MOF lattice for coordination, forming unsaturated coordination, thereby generating coordination vacancy defects. The defects increase the specific surface area and are more conducive to releasing local stress concentration.
[0056] In Comparative Example 3, the core-shell conductive composite nanospheres in step S6 were replaced with sulfonated conductive composite nanospheres of the same mass prepared in step S4. No calcium-based MOF structure was formed, and calcium ions could not be provided, resulting in insufficient crosslinking density. The modified microspheres did not contain calcium-based MOF and could not provide calcium ion crosslinking points. They relied only on toluene diisocyanate and polyvinyl alcohol hydroxyl crosslinking, resulting in a sparse crosslinking network, decreased mechanical strength, and inability to disperse stress through core-shell sliding, increasing the risk of local stress concentration. The lack of MOF nanoscale rough surface significantly reduced the anti-slip properties.
[0057] Comparative Example 4 replaced the core-shell conductive composite nanospheres in step S6 with commercially available conductive carbon black. As shown in the table, after losing the core-shell conductive composite nanospheres, all performance tests showed a significant decrease.
[0058] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principles and spirit of the invention.
Claims
1. A method for manufacturing the colloid of an electrostatically coated sand-film anti-slip layer, characterized in that, Includes the following steps: Step 1: Polystyrene nanospheres are hydrolyzed with γ-aminopropyltriethoxysilane to obtain modified polystyrene nanospheres, which are then used as a carrier to coat the surface with polymerized polyaniline to obtain composite nanospheres. Step 2: Modified composite nanospheres are obtained by acetalization of benzaldehyde with hydroxyl groups on the surface of the composite nanospheres under acid catalysis. Step 3: Using fuming sulfuric acid as a strong sulfonating agent, the defect sites on the surface of the hollow carbon spheres are attacked, and sulfonic acid groups are grafted through an electrophilic substitution reaction to obtain sulfonated conductive composite nanospheres. Step 4: Using sulfonated conductive composite nanospheres as a carrier, calcium-based MOFs are hydrothermally synthesized on the surface to obtain core-shell conductive composite nanospheres; Step 5: The colloid of the electrostatic sand-coated antislip film layer is obtained by cross-linking and curing the hydroxyl groups of polyvinyl alcohol and core-shell conductive composite nanospheres under the action of toluene diisocyanate.
2. The method for manufacturing the colloid of the electrostatic sand-coated anti-slip film layer according to claim 1, characterized in that, The specific preparation steps of the modified polystyrene nanospheres are as follows: Polystyrene nanospheres with a particle size of 50-60 μm, anhydrous ethanol, and deionized water were added to a reaction vessel and stirred for 10-20 min at 50-60℃ and 500-600 r / min. Then, γ-aminopropyltriethoxysilane was added, and the pH value was adjusted to 3-4 with hydrochloric acid solution. The reaction was continued to be stirred for 6-7 h. After filtration, the precipitate was washed 2-4 times with deionized water and anhydrous ethanol and dried under vacuum at 60-70℃ for 1-2 h to obtain modified polystyrene nanospheres. The ratio of polystyrene nanospheres, anhydrous ethanol, deionized water, and γ-aminopropyltriethoxysilane is 100-120g: 120-140mL: 200-250mL: 100-120mL.
3. The method for manufacturing the colloid of the electrostatic sand-coated anti-slip film layer according to claim 1, characterized in that, The specific preparation steps of the composite nanospheres are as follows: Modified polystyrene nanospheres, aniline, and deionized water were added to a reaction vessel and stirred at 20-25℃ and 500-600 r / min for 20-30 min. Then, ammonium persulfate initiator was added, and the mixture was heated to 80-90℃ and stirred for 4-5 h. The mixture was then cooled to 0-4℃ and reacted for 12-14 h. The mixture was filtered, and the filter cake was washed 2-4 times with anhydrous ethanol and deionized water, respectively. The mixture was then vacuum dried to obtain composite nanospheres. The ratio of the modified polystyrene nanospheres, aniline, deionized water and ammonium persulfate is 100-120g: 15-20mL: 500-600mL: 2-3g.
4. The method for manufacturing the colloid of the electrostatic sand-coated anti-slip film layer according to claim 1, characterized in that, The specific preparation steps of the modified composite nanospheres are as follows: The composite nanospheres and dimethyl sulfoxide were added to a reaction vessel and stirred at 20-25℃ and 500-600 r / min for 20-30 min. Then benzaldehyde and p-toluenesulfonic acid were added, and the mixture was heated to 85-90℃ and reacted for 1-2 h. The mixture was filtered, and the precipitate was washed 2-4 times with deionized water and anhydrous ethanol and dried under vacuum to obtain the modified composite nanospheres. The ratio of the composite nanospheres, dimethyl sulfoxide, benzaldehyde, and p-toluenesulfonic acid is 80-90g: 500-600mL: 2-3g: 0.15-0.2g.
5. The method for manufacturing the colloid of the electrostatic sand-coated anti-slip film layer according to claim 1, characterized in that, The specific preparation steps of the sulfonated conductive composite nanospheres are as follows: Modified composite nanospheres and 50-65% fuming sulfuric acid were added to a polytetrafluoroethylene-lined reactor at a ratio of 70-80g:400-500mL. The mixture was stirred at 20-25℃ and 500-600r / min for 20-30min, heated to 98-100℃, and reacted for another 30-40min. After natural cooling to room temperature, the mixture was filtered, and the product was transferred to a sodium hydroxide solution. The mixture was stirred until a large amount of precipitate was released. The precipitate was filtered, washed 2-4 times with deionized water and anhydrous ethanol, and dried under vacuum at 60-70℃ for 1-2h. The product was then transferred to a muffle furnace and calcined at 500-600℃ for 2-3h under nitrogen protection to obtain sulfonated conductive composite nanospheres.
6. The method for manufacturing the colloid of the electrostatic sand-coated anti-slip film layer according to claim 1, characterized in that, The specific preparation steps of the core-shell conductive composite nanospheres are as follows: 2,5-Dihydroxyterephthalic acid and N,N-dimethylformamide were added to a polytetrafluoroethylene reactor and stirred for 30-40 minutes at 20-25°C and 500-600 r / min. The mixture was then heated to 130-140°C and stirred for another 30-40 minutes. Calcium chloride was then added and stirred for 10-12 hours. Sulfonated conductive composite nanospheres were then added and stirred for another 10-12 hours. The mixture was filtered, and the filter cake was washed 2-4 times with N,N-dimethylformamide and dried under vacuum at 60-70°C for 1-2 hours to obtain core-shell conductive composite nanospheres.
7. The method for manufacturing the colloid of the electrostatic sand-coated anti-slip film layer according to claim 6, characterized in that, The ratio of 2,5-dihydroxyterephthalic acid, N,N-dimethylformamide, calcium chloride, and sulfonated conductive composite nanospheres is 50-60g: 400-500mL: 30-40g: 60-70g.
8. The method for manufacturing the colloid of the electrostatic sand-coated anti-slip film layer according to claim 1, characterized in that, The specific preparation steps of the colloid for the electrostatic sand-coated anti-slip film layer are as follows: Polyvinyl alcohol, core-shell conductive composite nanospheres and deionized water were added to a reaction vessel and stirred for 20-30 minutes at 20-25℃ and 500-600 r / min. The mixture was then heated to 80-90℃, and toluene diisocyanate, a crosslinking curing agent, was added. The reaction was continued for 2-3 hours to obtain the colloid of the electrostatic sand-coated antislip film layer.
9. The method for manufacturing the colloid of the electrostatic sand-coated anti-slip film layer according to claim 8, characterized in that, The ratio of polyvinyl alcohol, core-shell conductive composite nanospheres, deionized water and toluene diisocyanate is 100-120g: 0.5-0.7g: 900-950mL: 4-6g.
10. The colloid of the electrostatic sand-coated anti-slip film layer, characterized in that, It is prepared by the manufacturing method described in any one of claims 1-9.