Acid-resistant and corrosion-resistant PVC (polyvinyl chloride) film and preparation method thereof

Abstract

The invention relates to the technical field of PVC films, in particular to an acid-resistant and corrosion-resistant PVC film and a preparation method thereof.The acid-resistant and corrosion-resistant PVC film has the advantages that boron nitride modified graphene oxide and double-layer coated modified aluminum pigment are introduced, so that acid resistance and corrosion resistance of the PVC film can be remarkably improved, corrosion of acidic substances and corrosive environments can be effectively resisted, and the service life of the PVC film is prolonged; wherein the boron nitride modified graphene oxide combines the advantages of boron nitride and graphene oxide, boron nitride has good chemical stability and thermal stability, graphene oxide has excellent mechanical properties and electrical conductivity, and boron nitride and graphene oxide are effectively combined through chemical modification; the composite material with excellent acid resistance, corrosion resistance and mechanical properties is formed; according to the double-layer coated modified aluminum pigment, the silicon dioxide coated aluminum pigment is subjected to double-layer coating through aluminum oxide, a double-layer protection structure is formed, direct contact between the aluminum pigment and the external environment can be effectively isolated, and therefore the stability and corrosion resistance of the aluminum pigment are improved.

Description

Technical Field

[0001] The present invention relates to the technical field of PVC films, and in particular to an acid-resistant and corrosion-resistant PVC film and a preparation method thereof. Background Art

[0002] With the development of society and the improvement of people's living standards, the uses of outdoor PVC products are becoming more and more extensive, such as outdoor decoration, outdoor leisure, outdoor sports, outdoor entertainment, etc. Due to the influence of different outdoor environmental factors, the rainwater in some places is highly acidic, and the salt spray corrosion in the coastal areas is severe, which affects the service life of PVC. Therefore, there is an increasing market demand for research on the acid and corrosion resistance of PVC films.

[0003] The rapid development of nanotechnology and material modification technologies has provided new approaches for improving the acid and corrosion resistance of PVC films. By introducing nanomaterials with specialized functions or chemically modifying the PVC matrix, its corrosion resistance can be effectively enhanced. However, how to significantly improve the acid and corrosion resistance of PVC films while maintaining their original excellent properties, while also balancing processability and cost-effectiveness, remains a challenge in current research. Therefore, developing an acid- and corrosion-resistant PVC film based on the introduction of specialized nanomaterials has become a pressing technical challenge for those skilled in the art. Summary of the Invention

[0004] Technical problems solved In view of the above-mentioned shortcomings of the prior art, the present invention provides an acid-resistant and corrosion-resistant PVC film and a preparation method thereof, which can effectively solve the problem of poor acid and corrosion resistance of the prior art PVC film.

[0005] Technical Solution

[0006] To achieve the above objectives, the present invention is implemented through the following technical solutions: An acid-resistant and corrosion-resistant PVC film, comprising the following components: PVC powder, boron nitride-modified graphene oxide, double-layer coated modified aluminum pigment, modified material, heat stabilizer, plasticizer, silane coupling agent KH-550, nano-calcium carbonate, and titanium dioxide; The boron nitride modified graphene oxide is prepared with hydroxylated boron nitride and graphene oxide as main raw materials; The double-layer coated modified aluminum pigment is prepared by double-coating the silicon dioxide coated aluminum pigment with aluminum oxide; The modified material is a nano boron nitride chip modified carbon fiber nano material.

[0007] Furthermore, the preparation method of the hydroxylated boron nitride is: Disperse 2-3g of boron nitride powder in 100mL of 2mol / L sodium hydroxide solution, then pour it into a ball mill containing 40g of large agate balls and 60g of small agate balls and ball mill at a speed of 200r / min for 22-24h. After removing the agate balls, wash it with 0.1mol / L hydrochloric acid solution for 3-5 times, then repeatedly re-neutralize it with deionized water, and dry it in a vacuum drying oven at 60℃ for 72h to obtain hydroxylated boron nitride.

[0008] Furthermore, the preparation steps of the boron nitride modified graphene oxide are: Step 1: Weigh 1-2 g of graphene oxide and disperse it in 400 mL of N,N-dimethylformamide for ultrasonic treatment. Then, add 40 mL of silane coupling agent KH-550 and 2-3 g of dicyclohexylcarbodiimide. After stirring, the mixture is recorded as a mixed component. Step 2: After the mixed components are filtered, the filter cake is rinsed three times with tetrahydrofuran and anhydrous ethanol in sequence, and then redispersed in 400 mL of anhydrous ethanol. 60 mL of deionized water and 10 mL of acetic acid are added and stirred for reaction. The resultant is recorded as the reaction component; Step 3: Add 0.5-0.7 g of hydroxylated boron nitride to the reaction components, condense and reflux at 78° C. for 5-6 hours, then filter with anhydrous ethanol and deionized water 3-5 times in sequence, and dry to obtain boron nitride-modified graphene oxide.

[0009] Furthermore, the ultrasonic treatment method in step 1 is ultrasonic dispersion at a power of 200 W for 5 hours, the stirring treatment method in step 1 is stirring at a stirring speed of 200 r / min at a temperature of 70°C for 12 hours, the stirring reaction method in step 2 is stirring at a stirring speed of 300 r / min at room temperature for 1 hour, and the drying treatment method in step 3 is drying at a temperature of 80°C for 24 hours.

[0010] Furthermore, the preparation steps of the silica-coated aluminum pigment are: Step A: Pour 2-3 mL of ethyl orthosilicate into 10-15 mL of anhydrous ethanol and stir until evenly, which is recorded as the first drop. Pour 20-30 mL of anhydrous ethanol and 1-2 mL of ethylenediamine into 50 mL of deionized water and stir until evenly, which is recorded as the second drop. Step B, 2-3 g of aluminum pigment and 20-30 mL of anhydrous ethanol were poured into a flask for mixing and dispersion, and the first and second droplets were added simultaneously at a dripping rate of 1 drop / s. After the dripping, the mixture was reacted at a temperature of 40° C. for 12 h, and then aged for 3 h, filtered, washed three times with anhydrous ethanol, and dried to be recorded as the reaction product; Step C: Pour the reaction product into 20-30 mL of anhydrous ethanol, add 9-10 mL of silane coupling agent KH-570 and 2-3 mL of deionized water after ultrasonic treatment, react at 40° C. for 2-3 hours, filter, and finally dry at 50° C. for 4 hours to obtain a silica-coated aluminum pigment.

[0011] Furthermore, the method for uniform stirring in step A is stirring at a stirring speed of 500 r / min for 10 minutes, the method for mixing and dispersing in step B is stirring at a stirring speed of 300 r / min for 30 minutes, the method for drying in step B is drying at a temperature of 60°C for 4 hours, and the method for ultrasonic treatment in step C is ultrasonic dispersion at a power of 300 w for 15 minutes.

[0012] Furthermore, the preparation steps of the double-layer coated modified aluminum pigment are: Step i, weighing 5-6 g of aluminum isopropoxide and dissolving it in 50-60 mL of deionized water, stirring at 200 rpm for 24 h at a temperature of 50° C. to prepare a gel component; Step ii, weigh 3-4g of silica-coated aluminum pigment and dissolve it in 50mL of anhydrous ethanol. After ultrasonic dispersion at a power of 200W for 30min, the gel component is added dropwise at a drop rate of 1 drop / s. After the addition is completed, react for 4h and then age for 12h. After filtration, it is placed at a temperature of 50°C and dried for 8h to obtain a double-layer coated modified aluminum pigment.

[0013] Furthermore, the preparation method of the modified material is: Weigh 1-2g of silane coupling agent KH-570 and dissolve it in 500mL of dimethylformamide. Add 1-2g of carbon fiber and stir at a stirring speed of 400r / min for 30min. After standing for 4h, add 0.5g of nano-boron nitride chip, stir at a stirring speed of 500r / min for 30min, and then stand for 2h. After filtering, place it in an oven at 100℃ and bake it for 2h. After cooling to room temperature, the obtained material is the modified material.

[0014] A method for preparing an acid-resistant and corrosion-resistant PVC film, the preparation method comprising: S1. Weigh 90-100 parts by weight of PVC powder, 1-2 parts of boron nitride modified graphene oxide, 1-2 double-layer coated modified aluminum pigments, 1-2 parts of modified materials, 3-4 parts of heat stabilizer, 16-50 parts of plasticizer, 2-5 parts of silane coupling agent KH-550, 15-30 parts of nano-calcium carbonate, and 3-10 parts of titanium dioxide into an internal mixer, mix them at low speed, and then perform internal mixing and plasticization. The obtained mixture is recorded as the primary plastic component; S2. Pour the primary plastic component into an open mill and perform secondary plasticization at a temperature of 160-170°C, and then extrude it through a screw machine at a temperature of 165-180°C. The obtained component is recorded as the secondary plastic component; S3. The plasticized components are subjected to 5-roll calendering molding. The temperatures of the 5-roll calender are 175-180°C for roller No. 1, 178-185°C for roller No. 2, 180-190°C for roller No. 3, 185-195°C for roller No. 4, and 180-190°C for roller No. 5. The film is then embossed, cooled, and rolled up to obtain an acid-resistant and corrosion-resistant PVC film.

[0015] Furthermore, the low-speed mixing method in S1 is to mix at a speed of 50-300 r / min for 50-90s and then at a speed of 400-600 r / min for 150-200s under the conditions of a mixing temperature of 80-110°C and a mixing current of 320-360A. The mixing and plasticizing temperature in S1 is 150-170°C.

[0016] Beneficial effects The present invention provides an acid-resistant and corrosion-resistant PVC film and a preparation method thereof. Compared with the existing known technology, the present invention has the following beneficial effects: 1. The present invention can significantly improve the acid and corrosion resistance of PVC film by introducing boron nitride-modified graphene oxide and double-layer coated modified aluminum pigment, and can also effectively resist the erosion of acidic substances and corrosive environments, thereby extending the service life of PVC film; wherein, boron nitride-modified graphene oxide combines the advantages of boron nitride and graphene oxide. Boron nitride has good chemical stability and thermal stability, while graphene oxide has excellent mechanical properties and conductivity. The two are effectively combined through chemical modification to form a composite material with excellent acid and corrosion resistance and mechanical properties; the double-layer coated modified aluminum pigment is a double-layer protective structure formed by double-coating the silica-coated aluminum pigment with aluminum oxide, which can effectively isolate the aluminum pigment from direct contact with the external environment, thereby improving the stability and corrosion resistance of the aluminum pigment. At the same time, the double-layer coating also maintains the metallic luster and decorative effect of the aluminum pigment.

[0017] 2. The addition of nano-boron nitride chip modified carbon fiber nanomaterials in the present invention can enhance the mechanical strength of the PVC film, making it have better wear resistance, tear resistance and tensile strength. Nano-boron nitride chips have excellent mechanical properties and thermal stability. By combining them with carbon fiber nanomaterials, a composite material with excellent performance can be formed, thereby effectively improving the strength and toughness of the PVC film while maintaining the lightweight of the material. DETAILED DESCRIPTION

[0018] To make the objectives, technical solutions, and advantages of the embodiments of the present invention more clear, the technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0019] The present invention will be further described below with reference to the embodiments.

[0020] The sources of some components in the Examples and Comparative Examples are as follows: PVC powder, PVC type 5 powder with a degree of polymerization of 1000; Boron nitride powder, National Nitrogen Technology Co., Ltd.; Sodium hydroxide, Laiyang Fine Chemical Plant; Hydrochloric acid, Laiyang Fine Chemical Plant; Graphene oxide, Hangzhou Yanqu Information Technology Co., Ltd.; N,N-dimethylformamide, Shanghai Aladdin Biochemical Technology Co., Ltd.; Silane coupling agent KH-550, Shanghai Aladdin Biochemical Technology Co., Ltd.; Dicyclohexylcarbodiimide, Shanghai Aladdin Biochemical Technology Co., Ltd.; Tetrahydrofuran, Shanghai Aladdin Biochemical Technology Co., Ltd.; Anhydrous ethanol, Shanghai Aladdin Biochemical Technology Co., Ltd.; Ethyl orthosilicate, Sinopharm Chemical Reagent Co., Ltd.; Ethylenediamine, Nanjing Xinhuayuan Chemical Co., Ltd.; Aluminum pigment, Anhui Aoya Alloy Co., Ltd.; Silane coupling agent KH-570, Sinopharm Chemical Reagent Co., Ltd.; Aluminum isopropoxide, Wuhan Smack Biotechnology Co., Ltd.; Dimethylformamide, Jinan Qichen Chemical Co., Ltd.; Carbon fiber, 100-400 mesh, Shanghai Lishuo Composite Materials Technology Co., Ltd.; Nano boron nitride wafers, Liaoning Boronda Technology Co., Ltd.; Heat stabilizer, liquid barium zinc stabilizer, Nantong Aidewang Chemical Co., Ltd. Plasticizer, diisononyl phthalate, Shanghai MacLean Biochemical Technology Co., Ltd.; Nano calcium carbonate, Hebei Huishun Mining Co., Ltd.; Titanium dioxide, chloride process rutile titanium dioxide.

[0021] Example 1 The present embodiment provides an acid-resistant and corrosion-resistant PVC film, which is composed of the following components: PVC powder, boron nitride-modified graphene oxide, double-layer coated modified aluminum pigment, modified material, heat stabilizer, plasticizer, silane coupling agent KH-550, nano-calcium carbonate, and titanium dioxide; Boron nitride modified graphene oxide is prepared with hydroxylated boron nitride and graphene oxide as main raw materials; Wherein, the preparation method of hydroxylated boron nitride is: 2g of boron nitride powder was dispersed in 100mL of 2mol / L sodium hydroxide solution, then poured into a ball mill containing 40g of large agate balls and 60g of small agate balls and ball milled at a speed of 200r / min for 22h. After removing the agate balls, the solution was washed three times with a 0.1mol / L hydrochloric acid solution, then repeatedly re-neutralized with deionized water, and dried in a vacuum drying oven at 60°C for 72h to obtain hydroxylated boron nitride.

[0022] The preparation steps of boron nitride modified graphene oxide are: Step 1: Weigh 1 g of graphene oxide and disperse it in 400 mL of N,N-dimethylformamide, ultrasonically disperse it at a power of 200 W for 5 h, then add 40 mL of silane coupling agent KH-550 and 2 g of dicyclohexylcarbodiimide, and stir at a temperature of 70 ° C and a stirring speed of 200 r / min for 12 h. The result is recorded as the mixed component; Step 2: After the mixed components were filtered, the filter cake was rinsed three times with tetrahydrofuran and anhydrous ethanol in sequence, and then redispersed in 400 mL of anhydrous ethanol. After adding 60 mL of deionized water and 10 mL of acetic acid, the mixture was stirred at room temperature at a stirring speed of 300 r / min for 1 hour. The result was recorded as the reaction component; Step 3: Add 0.5 g of hydroxylated boron nitride to the reaction components, condense and reflux at 78° C. for 5 h, then filter with anhydrous ethanol and deionized water three times in sequence, and dry at 80° C. for 24 h to obtain boron nitride-modified graphene oxide.

[0023] Double-layer coated modified aluminum pigment is prepared by double-coating the silica-coated aluminum pigment with aluminum oxide; The preparation steps of the silica-coated aluminum pigment are as follows: Step A: Pour 2 mL of ethyl orthosilicate into 10 mL of anhydrous ethanol and stir at a stirring speed of 500 r / min for 10 minutes to obtain the first drop. Pour 20 mL of anhydrous ethanol and 1 mL of ethylenediamine into 50 mL of deionized water and stir at a stirring speed of 500 r / min for 10 minutes to obtain the second drop. Step B, 2 g of aluminum pigment and 20 mL of anhydrous ethanol were poured into a flask and stirred at a stirring speed of 300 r / min for 30 min, and the first drop and the second drop were added simultaneously at a dripping rate of 1 drop / s. After the dripping, the mixture was reacted at a temperature of 40°C for 12 h, then aged for 3 h, filtered, and washed three times with anhydrous ethanol, and dried at a temperature of 60°C for 4 h. The reaction product was recorded; Step C: Pour the reaction product into 20 mL of anhydrous ethanol, ultrasonically disperse it at a power of 300 W for 15 minutes, add 9 mL of silane coupling agent KH-570 and 2 mL of deionized water, react at a temperature of 40°C for 2 hours, filter it, and finally dry it at a temperature of 50°C for 4 hours to obtain a silica-coated aluminum pigment.

[0024] The preparation steps of double-layer coated modified aluminum pigment are as follows: Step i: 5 g of aluminum isopropoxide was weighed and dissolved in 50 mL of deionized water, and the mixture was stirred at 200 rpm for 24 h at 50° C. to prepare a gel component; Step ii, weigh 3g of silica-coated aluminum pigment and dissolve it in 50mL of anhydrous ethanol. After ultrasonic dispersion at a power of 200W for 30min, the gel component is added dropwise at a drop rate of 1 drop / s. After the dropwise reaction is completed for 4h, it is aged for 12h, filtered and dried at a temperature of 50°C for 8h to obtain a double-layer coated modified aluminum pigment.

[0025] The modified material is nano-boron nitride chip modified carbon fiber nanomaterial.

[0026] Wherein, the preparation method of the modified material is: Weigh 1g of silane coupling agent KH-570 and dissolve it in 500mL of dimethylformamide. Add 1g of carbon fiber and stir at a stirring speed of 400r / min for 30min. After standing for 4h, add 0.5g of nano-boron nitride wafer, stir at a stirring speed of 500r / min for 30min, and then stand for 2h. After filtering, place it in an oven at 100℃ and bake it for 2h. After cooling to room temperature, the obtained material is the modified material.

[0027] A method for preparing an acid-resistant and corrosion-resistant PVC film, the preparation method comprising: S1. Weigh 90 parts by weight of PVC powder, 1 part of boron nitride modified graphene oxide, 1 double-layer coated modified aluminum pigment, 1 part of modified material, 3 parts of heat stabilizer, 16 parts of plasticizer, 2 parts of silane coupling agent KH-550, 15 parts of nano-calcium carbonate and 3 parts of titanium dioxide into a banbury mixer, mix them at low and high speed, and then perform banburying and plasticizing. The obtained mixture is recorded as the primary plastic component. The low and high speed mixing method is as follows: under the conditions of a banburying temperature of 80° C. and a banburying current of 320A, first mix at a speed of 50 r / min for 50 s, then mix at a speed of 400 r / min for 150 s, and the banburying and plasticizing temperature is 150° C. S2, pouring the primary plastic component into an open mill for secondary plasticization at a temperature of 160°C, and then extruding through a screw machine at a temperature of 165°C, and the obtained product is recorded as the secondary plastic component; S3. The plasticized components are subjected to 5-roll calendering molding. The temperatures of the 5-roll calender are 175°C for roller No. 1, 178°C for roller No. 2, 180°C for roller No. 3, 185°C for roller No. 4, and 180°C for roller No. 5. The film is then embossed, cooled, and rolled up to obtain an acid-resistant and corrosion-resistant PVC film.

[0028] Example 2 The present embodiment provides an acid-resistant and corrosion-resistant PVC film, which is composed of the following components: PVC powder, boron nitride-modified graphene oxide, double-layer coated modified aluminum pigment, modified material, heat stabilizer, plasticizer, silane coupling agent KH-550, nano-calcium carbonate, and titanium dioxide; Boron nitride modified graphene oxide is prepared with hydroxylated boron nitride and graphene oxide as main raw materials; Wherein, the preparation method of hydroxylated boron nitride is: 3g of boron nitride powder was dispersed in 100mL of 2mol / L sodium hydroxide solution, then poured into a ball mill containing 40g of large agate balls and 60g of small agate balls and ball milled at a speed of 200r / min for 24h. After removing the agate balls, the mixture was washed 5 times with a 0.1mol / L hydrochloric acid solution, then repeatedly re-neutralized with deionized water, and dried in a vacuum drying oven at 60°C for 72h to obtain hydroxylated boron nitride.

[0029] The preparation steps of boron nitride modified graphene oxide are: Step 1, weighing 2 g of graphene oxide and dispersing it in 400 mL of N, N-dimethylformamide and ultrasonically dispersing it at a power of 200 W for 5 h, then adding 40 mL of silane coupling agent KH-550 and 3 g of dicyclohexylcarbodiimide, stirring at a temperature of 70 ° C and a stirring speed of 200 r / min for 12 h, the result is recorded as the mixed component; Step 2: After the mixed components were filtered, the filter cake was rinsed three times with tetrahydrofuran and anhydrous ethanol in sequence, and then redispersed in 400 mL of anhydrous ethanol. After adding 60 mL of deionized water and 10 mL of acetic acid, the mixture was stirred at room temperature at a stirring speed of 300 r / min for 1 hour. The result was recorded as the reaction component; Step 3: Add 0.7 g of hydroxylated boron nitride to the reaction components, condense and reflux at 78° C. for 6 h, then filter with anhydrous ethanol and deionized water 5 times in sequence, and dry at 80° C. for 24 h to obtain boron nitride-modified graphene oxide.

[0030] Double-layer coated modified aluminum pigment is prepared by double-coating the silica-coated aluminum pigment with aluminum oxide; The preparation steps of the silica-coated aluminum pigment are as follows: Step A: Pour 3 mL of ethyl orthosilicate into 15 mL of anhydrous ethanol and stir at a stirring speed of 500 r / min for 10 minutes to obtain the first drop. Pour 30 mL of anhydrous ethanol and 2 mL of ethylenediamine into 50 mL of deionized water and stir at a stirring speed of 500 r / min for 10 minutes to obtain the second drop. Step B, 3g of aluminum pigment and 30mL of anhydrous ethanol were poured into a flask and stirred at a stirring speed of 300r / min for 30min, and the first drop and the second drop were added simultaneously at a dripping rate of 1 drop / s. After the dripping, the mixture was reacted at a temperature of 40°C for 12h, then aged for 3h, filtered and washed three times with anhydrous ethanol, and dried at a temperature of 60°C for 4h. The reaction product was recorded; Step C: Pour the reaction product into 30 mL of anhydrous ethanol, ultrasonically disperse it at a power of 300 W for 15 minutes, add 10 mL of silane coupling agent KH-570 and 3 mL of deionized water, react at a temperature of 40°C for 3 hours, filter it, and finally dry it at a temperature of 50°C for 4 hours to obtain a silica-coated aluminum pigment.

[0031] The preparation steps of double-layer coated modified aluminum pigment are as follows: Step i: 6 g of aluminum isopropoxide was weighed and dissolved in 60 mL of deionized water, and the mixture was stirred at 50° C. and 200 rpm for 24 h to prepare a gel component; Step ii, weigh 4 g of silica-coated aluminum pigment and dissolve it in 50 mL of anhydrous ethanol. After ultrasonic dispersion at a power of 200 W for 30 min, the gel component was added dropwise at a drop rate of 1 drop / s. After the dropwise reaction, the mixture was reacted for 4 h and then aged for 12 h. After filtration, it was placed at a temperature of 50 ° C and dried for 8 h to obtain a double-layer coated modified aluminum pigment.

[0032] The modified material is nano-boron nitride chip modified carbon fiber nanomaterial.

[0033] Wherein, the preparation method of the modified material is: Weigh 2g of silane coupling agent KH-570 and dissolve it in 500mL of dimethylformamide. Add 2g of carbon fiber and stir at a stirring speed of 400r / min for 30min. After standing for 4h, add 0.5g of nano-boron nitride chip, stir at a stirring speed of 500r / min for 30min, and then stand for 2h. After filtering, place it in an oven at 100℃ and bake it for 2h. After cooling to room temperature, the obtained material is the modified material.

[0034] A method for preparing an acid-resistant and corrosion-resistant PVC film, the preparation method comprising: S1. Weigh 100 parts of PVC powder, 2 parts of boron nitride modified graphene oxide, 2 double-layer coated modified aluminum pigments, 2 parts of modified material, 4 parts of heat stabilizer, 50 parts of plasticizer, 5 parts of silane coupling agent KH-550, 30 nano-calcium carbonate and 10 parts of titanium dioxide by weight, pour them into a banbury mixer, mix them at low and high speed, and then perform banburying plasticization. The result is recorded as the primary plastic component, wherein the low and high speed mixing method is under the conditions of a banburying temperature of 110° C. and a banburying current of 360A, first mixing at a speed of 300 r / min for 90 seconds, then mixing at a speed of 600 r / min for 200 seconds, and the banburying plasticization temperature is 170° C.; S2, pouring the primary plastic component into an open mill for secondary plasticization at a temperature of 170°C, and then extruding it through a screw machine at a temperature of 180°C, and the obtained result is recorded as the secondary plastic component; S3. The plasticized components are subjected to 5-roll calendering molding. The temperatures of the 5-roll calender are 180°C for roller No. 1, 185°C for roller No. 2, 190°C for roller No. 3, 195°C for roller No. 4, and 190°C for roller No. 5. The film is then embossed, cooled, and rolled up to obtain an acid-resistant and corrosion-resistant PVC film.

[0035] Example 3 The present embodiment provides an acid-resistant and corrosion-resistant PVC film, which is composed of the following components: PVC powder, boron nitride-modified graphene oxide, double-layer coated modified aluminum pigment, modified material, heat stabilizer, plasticizer, silane coupling agent KH-550, nano-calcium carbonate, and titanium dioxide; Boron nitride modified graphene oxide is prepared with hydroxylated boron nitride and graphene oxide as main raw materials; Wherein, the preparation method of hydroxylated boron nitride is: 3g of boron nitride powder was dispersed in 100mL of 2mol / L sodium hydroxide solution, then poured into a ball mill containing 40g of large agate balls and 60g of small agate balls and ball milled at a speed of 200r / min for 23h. After removing the agate balls, the mixture was washed four times with a 0.1mol / L hydrochloric acid solution, then repeatedly re-neutralized with deionized water, and dried in a vacuum drying oven at 60°C for 72h to obtain hydroxylated boron nitride.

[0036] The preparation steps of boron nitride modified graphene oxide are: Step 1, weighing 2 g of graphene oxide and dispersing it in 400 mL of N, N-dimethylformamide and ultrasonically dispersing it at a power of 200 W for 5 h, then adding 40 mL of silane coupling agent KH-550 and 3 g of dicyclohexylcarbodiimide, stirring at a temperature of 70 ° C and a stirring speed of 200 r / min for 12 h, the result is recorded as the mixed component; Step 2: After the mixed components were filtered, the filter cake was rinsed three times with tetrahydrofuran and anhydrous ethanol in sequence, and then redispersed in 400 mL of anhydrous ethanol. After adding 60 mL of deionized water and 10 mL of acetic acid, the mixture was stirred at room temperature at a stirring speed of 300 r / min for 1 hour. The result was recorded as the reaction component; Step 3: Add 0.6 g of hydroxylated boron nitride to the reaction components, condense and reflux at 78° C. for 6 h, then filter with anhydrous ethanol and deionized water four times in sequence, and dry at 80° C. for 24 h to obtain boron nitride-modified graphene oxide.

[0037] Double-layer coated modified aluminum pigment is prepared by double-coating the silica-coated aluminum pigment with aluminum oxide; The preparation steps of the silica-coated aluminum pigment are as follows: Step A: Pour 3 mL of ethyl orthosilicate into 13 mL of anhydrous ethanol and stir at a stirring speed of 500 r / min for 10 minutes to obtain the first drop. Pour 25 mL of anhydrous ethanol and 2 mL of ethylenediamine into 50 mL of deionized water and stir at a stirring speed of 500 r / min for 10 minutes to obtain the second drop. Step B, 3g of aluminum pigment and 25mL of anhydrous ethanol were poured into a flask and stirred at a stirring speed of 300r / min for 30min, and the first drop and the second drop were added simultaneously at a dripping rate of 1 drop / s. After the dripping, the mixture was reacted at a temperature of 40°C for 12h, then aged for 3h, filtered and washed three times with anhydrous ethanol, and dried at a temperature of 60°C for 4h. The reaction product was recorded; Step C: Pour the reaction product into 25 mL of anhydrous ethanol, ultrasonically disperse it at a power of 300 W for 15 minutes, add 10 mL of silane coupling agent KH-570 and 3 mL of deionized water, react at a temperature of 40°C for 3 hours, filter it, and finally dry it at a temperature of 50°C for 4 hours to obtain a silica-coated aluminum pigment.

[0038] The preparation steps of double-layer coated modified aluminum pigment are as follows: Step i: Weigh 6 g of aluminum isopropoxide and dissolve it in 55 mL of deionized water. Stir the mixture at 50° C. and 200 rpm for 24 h to prepare a gel component. Step ii, weigh 4 g of silica-coated aluminum pigment and dissolve it in 50 mL of anhydrous ethanol. After ultrasonic dispersion at a power of 200 W for 30 min, the gel component was added dropwise at a drop rate of 1 drop / s. After the dropwise reaction, the mixture was reacted for 4 h and then aged for 12 h. After filtration, it was placed at a temperature of 50 ° C and dried for 8 h to obtain a double-layer coated modified aluminum pigment.

[0039] The modified material is nano-boron nitride chip modified carbon fiber nanomaterial.

[0040] Wherein, the preparation method of the modified material is: Weigh 2g of silane coupling agent KH-570 and dissolve it in 500mL of dimethylformamide. Add 2g of carbon fiber and stir at a stirring speed of 400r / min for 30min. After standing for 4h, add 0.5g of nano-boron nitride chip, stir at a stirring speed of 500r / min for 30min, and then stand for 2h. After filtering, place it in an oven at 100℃ and bake it for 2h. After cooling to room temperature, the obtained material is the modified material.

[0041] A method for preparing an acid-resistant and corrosion-resistant PVC film, the preparation method comprising: S1. Weigh 95 parts of PVC powder, 2 parts of boron nitride modified graphene oxide, 2 double-layer coated modified aluminum pigments, 2 parts of modified materials, 3 parts of heat stabilizer, 30 parts of plasticizer, 3 parts of silane coupling agent KH-550, 22 parts of nano calcium carbonate and 6 parts of titanium dioxide into a banbury mixer, mix them at low and high speed, and then perform banburying plasticization. The obtained components are recorded as primary plastic components. The low and high speed mixing method is as follows: under the conditions of a banburying temperature of 95° C. and a banburying current of 340A, first mix at a speed of 200 r / min for 60 seconds, then mix at a speed of 500 r / min for 180 seconds, and the banburying plasticization temperature is 160° C. S2. Pour the primary plastic component into an open mill and perform secondary plasticization at a temperature of 165°C, and then extrude it through a screw machine at a temperature of 175°C. The obtained component is recorded as the secondary plastic component; S3. The plasticized components are subjected to 5-roll calendering molding. The temperatures of the 5-roll calender are 178°C for roller No. 1, 182°C for roller No. 2, 186°C for roller No. 3, 190°C for roller No. 4, and 185°C for roller No. 5. The film is then embossed, cooled, and rolled up to obtain an acid-resistant and corrosion-resistant PVC film.

[0042] Comparative Example 1 The acid-resistant and corrosion-resistant PVC film and its preparation method provided in this comparative example are roughly the same as those in Example 1, with the main difference being that the boron nitride-modified graphene oxide in Example 1 is replaced with unmodified graphene oxide in this comparative example.

[0043] Comparative Example 2 The acid-resistant and corrosion-resistant PVC film and its preparation method provided in this comparative example are roughly the same as those in Example 1, with the main difference being that this comparative example replaces the double-layer coated modified aluminum pigment in Example 1 with the silica-coated aluminum pigment in Example 1.

[0044] Comparative Example 3 The acid-resistant and corrosion-resistant PVC film and its preparation method provided in this comparative example are substantially the same as those in Example 1, with the main difference being that the modified material in Example 1 is replaced with unmodified carbon fiber in this comparative example.

[0045] Performance Testing The acid-resistant and corrosion-resistant PVC films prepared in Examples 1-3 and Comparative Examples 1-3 are marked as Example 1, Example 2, Example 3, Comparative Example 1, Comparative Example 2, and Comparative Example 3, respectively. The performance of Examples 1-3 and Comparative Examples 1-3 was tested. The specific testing methods and test items are as follows: 1. The corrosion resistance of Examples 1-3 and Comparative Examples 1-3 was tested with reference to the QB / T3801-1999 standard, and the obtained corrosion degree data were recorded in the following table; 2. The tensile strength of Examples 1-3 and Comparative Examples 1-3 was tested with reference to the standard of GB / T1040.1-2018, and the obtained tensile strength data were recorded in the following table; 3. The impact strength of Examples 1-3 and Comparative Examples 1-3 was tested with reference to the standard of GB / T1043.1-2008, and the obtained impact strength data are recorded in the following table;

[0046] As shown in the data in the above table, the corrosion resistance and mechanical properties of the acid-resistant and corrosion-resistant PVC films in Examples 1-3 are better than those in Comparative Examples 1-3, indicating that the addition of boron nitride-modified graphene oxide, double-layer coated modified aluminum pigment and modified materials for synergistic modification during the preparation of the acid-resistant and corrosion-resistant PVC film can improve the corrosion resistance and mechanical properties of the PVC film.

[0047] It should be noted that, in this document, relational terms such as first and second, etc., are used only to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply the existence of any such actual relationship or order between these entities or operations. Moreover, the terms "comprises," "comprising," or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article, or device comprising a series of elements includes not only those elements, but also other elements not explicitly listed, or elements inherent to such process, method, article, or device. In the absence of further limitations, an element defined by the phrase "comprising a ..." does not exclude the presence of other identical elements in the process, method, article, or device comprising the element.

[0048] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements will not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the various embodiments of the present invention.

Claims

1. An acid-resistant and corrosion-resistant PVC film, characterized in that: The acid-resistant and corrosion-resistant PVC film is composed of the following components: PVC powder, boron nitride-modified graphene oxide, double-layer coated modified aluminum pigment, modified material, heat stabilizer, plasticizer, silane coupling agent KH-550, nano calcium carbonate and titanium dioxide; The boron nitride modified graphene oxide is prepared with hydroxylated boron nitride and graphene oxide as main raw materials; The double-layer coated modified aluminum pigment is prepared by double-coating the silicon dioxide coated aluminum pigment with aluminum oxide; The modified material is a nano boron nitride chip modified carbon fiber nano material.

2. The acid-resistant and corrosion-resistant PVC film according to claim 1, characterized in that: The preparation method of the hydroxylated boron nitride is: Disperse 2-3g of boron nitride powder in 100mL of 2mol / L sodium hydroxide solution, then pour it into a ball mill containing 40g of large agate balls and 60g of small agate balls and ball mill at a speed of 200r / min for 22-24h. After removing the agate balls, wash it with 0.1mol / L hydrochloric acid solution for 3-5 times, then repeatedly re-neutralize it with deionized water, and dry it in a vacuum drying oven at 60℃ for 72h to obtain hydroxylated boron nitride.

3. The acid-resistant and corrosion-resistant PVC film according to claim 1, characterized in that: The preparation steps of the boron nitride modified graphene oxide are: Step 1: Weigh 1-2 g of graphene oxide and disperse it in 400 mL of N,N-dimethylformamide for ultrasonic treatment. Then, add 40 mL of silane coupling agent KH-550 and 2-3 g of dicyclohexylcarbodiimide. After stirring, the mixture is recorded as a mixed component. Step 2: After the mixed components are filtered, the filter cake is rinsed three times with tetrahydrofuran and anhydrous ethanol in sequence, and then redispersed in 400 mL of anhydrous ethanol. 60 mL of deionized water and 10 mL of acetic acid are added and stirred for reaction. The resultant is recorded as the reaction component; Step 3: Add 0.5-0.7 g of hydroxylated boron nitride to the reaction components, condense and reflux at 78° C. for 5-6 hours, then filter with anhydrous ethanol and deionized water 3-5 times in sequence, and dry to obtain boron nitride-modified graphene oxide.

4. The acid-resistant and corrosion-resistant PVC film according to claim 3, characterized in that: The ultrasonic treatment method in step 1 is ultrasonic dispersion at a power of 200 W for 5 hours, the stirring treatment method in step 1 is stirring at a stirring speed of 200 r / min at a temperature of 70°C for 12 hours, the stirring reaction method in step 2 is stirring at a stirring speed of 300 r / min at room temperature for 1 hour, and the drying treatment method in step 3 is drying at a temperature of 80°C for 24 hours.

5. The acid-resistant and corrosion-resistant PVC film according to claim 1, characterized in that: The preparation steps of the silica-coated aluminum pigment are: Step A: Pour 2-3 mL of ethyl orthosilicate into 10-15 mL of anhydrous ethanol and stir until evenly, which is recorded as the first drop. Pour 20-30 mL of anhydrous ethanol and 1-2 mL of ethylenediamine into 50 mL of deionized water and stir until evenly, which is recorded as the second drop. Step B, 2-3 g of aluminum pigment and 20-30 mL of anhydrous ethanol were poured into a flask for mixing and dispersion, and the first and second droplets were added simultaneously at a dripping rate of 1 drop / s. After the dripping, the mixture was reacted at a temperature of 40° C. for 12 h, and then aged for 3 h, filtered, washed three times with anhydrous ethanol, and dried to be recorded as the reaction product; Step C: Pour the reaction product into 20-30 mL of anhydrous ethanol, add 9-10 mL of silane coupling agent KH-570 and 2-3 mL of deionized water after ultrasonic treatment, react at 40° C. for 2-3 hours, filter, and finally dry at 50° C. for 4 hours to obtain a silica-coated aluminum pigment.

6. The acid-resistant and corrosion-resistant PVC film according to claim 5, characterized in that: The method for uniform stirring in step A is stirring at a stirring speed of 500 r / min for 10 minutes, the method for mixing and dispersing in step B is stirring at a stirring speed of 300 r / min for 30 minutes, the method for drying in step B is drying at a temperature of 60°C for 4 hours, and the method for ultrasonic treatment in step C is ultrasonic dispersion at a power of 300 w for 15 minutes.

7. The acid-resistant and corrosion-resistant PVC film according to claim 1, characterized in that: The preparation steps of the double-layer coated modified aluminum pigment are: Step i, weighing 5-6 g of aluminum isopropoxide and dissolving it in 50-60 mL of deionized water, stirring at 200 rpm for 24 h at a temperature of 50° C. to prepare a gel component; Step ii, weigh 3-4g of silica-coated aluminum pigment and dissolve it in 50mL of anhydrous ethanol. After ultrasonic dispersion at a power of 200W for 30min, the gel component is added dropwise at a drop rate of 1 drop / s. After the addition is completed, react for 4h and then age for 12h. After filtration, it is placed at a temperature of 50°C and dried for 8h to obtain a double-layer coated modified aluminum pigment.

8. The acid-resistant and corrosion-resistant PVC film according to claim 1, characterized in that: The preparation method of the modified material is: Weigh 1-2g of silane coupling agent KH-570 and dissolve it in 500mL of dimethylformamide. Add 1-2g of carbon fiber and stir at a stirring speed of 400r / min for 30min. After standing for 4h, add 0.5g of nano-boron nitride chip, stir at a stirring speed of 500r / min for 30min, and then stand for 2h. After filtering, place it in an oven at 100℃ and bake it for 2h. After cooling to room temperature, the obtained material is the modified material.

9. The method for preparing an acid-resistant and corrosion-resistant PVC film according to any one of claims 1 to 8, characterized in that: The preparation method is: S1. Weigh 90-100 parts by weight of PVC powder, 1-2 parts of boron nitride modified graphene oxide, 1-2 double-layer coated modified aluminum pigments, 1-2 parts of modified materials, 3-4 parts of heat stabilizer, 16-50 parts of plasticizer, 2-5 parts of silane coupling agent KH-550, 15-30 parts of nano-calcium carbonate, and 3-10 parts of titanium dioxide into an internal mixer, mix them at low speed, and then perform internal mixing and plasticization. The obtained mixture is recorded as the primary plastic component; S2. Pour the primary plastic component into an open mill and perform secondary plasticization at a temperature of 160-170°C, and then extrude it through a screw machine at a temperature of 165-180°C. The obtained component is recorded as the secondary plastic component; S3. The plasticized components are subjected to 5-roll calendering molding. The temperatures of the 5-roll calender are 175-180°C for roller No. 1, 178-185°C for roller No. 2, 180-190°C for roller No. 3, 185-195°C for roller No. 4, and 180-190°C for roller No.

5. The film is then embossed, cooled, and rolled up to obtain an acid-resistant and corrosion-resistant PVC film.

10. The method for preparing an acid-resistant and corrosion-resistant PVC film according to claim 9, characterized in that: The low-speed mixing method in S1 is to mix at a speed of 50-300 r / min for 50-90s, and then mix at a speed of 400-600 r / min for 150-200s under the conditions of a mixing temperature of 80-110°C and a mixing current of 320-360A. The mixing and plasticizing temperature in S1 is 150-170°C.

Images