CN117207622B - PVDF composite anti-aging film for waterproof coiled material, preparation method and waterproof coiled material - Google Patents
PVDF composite anti-aging film for waterproof coiled material, preparation method and waterproof coiled material Download PDFInfo
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- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 claims description 6
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
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Abstract
The invention discloses a PVDF composite anti-aging film for a waterproof coiled material, a preparation method and the waterproof coiled material, and belongs to the technical field of roof covering layers. The waterproof coiled material comprises a substrate layer, a first waterproof layer arranged on the upper surface of the substrate layer, a second waterproof layer arranged on the lower surface of the substrate layer, glue layers respectively arranged on the upper surface of the first waterproof layer and the lower surface of the second waterproof layer, a first anti-aging layer and a second anti-aging layer respectively arranged on the surface of the glue layers, wherein the first waterproof layer and the second waterproof layer are SBS asphalt, the glue layers are polyurethane glue, and the first anti-aging layer and the second anti-aging layer are PVDF composite anti-aging films. Compared with the prior art, the waterproof coiled material prepared by the invention has better ultraviolet aging resistance and corrosion resistance, can be used in an outdoor environment for a long time, and can effectively protect a substrate from being corroded by ultraviolet rays and chemical substances.
Description
Technical Field
The invention relates to the technical field of building waterproof materials, in particular to a PVDF composite anti-aging film for a waterproof coiled material, a preparation method and the waterproof coiled material.
Background
A waterproofing membrane is a material used in construction, engineering and other applications, the main function of which is to provide waterproofing protection. The waterproofing membrane is generally composed of a multi-layered material including a base material layer and a waterproofing layer. The substrate layer is typically made of polymer modified materials such as polyester, polyethylene, polypropylene, and the like, and reinforcing materials such as fiberglass mat. The waterproof layer may be made of different materials, such as asphalt, polymer modified asphalt, polymer film, etc. The combination of these layers provides the waterproofing and mechanical properties of the waterproofing membrane.
In the prior art, asphalt coiled materials are one of traditional waterproof coiled materials and are made of asphalt or asphalt modified materials. Has better waterproof performance and durability, and is generally used for waterproofing buildings such as roofs, basement, tunnels and the like. The polymer coiled material is waterproof coiled material made of polymer material, such as polyethylene, polypropylene, etc. They have good flexibility and chemical resistance. TPO coiled material is Thermoplastic Polyolefin (TPO) waterproof coiled material made of polyolefin, plastic, elastomer and other materials. Has excellent weather resistance, chemical resistance and mechanical property, and can be widely applied to roof and underground engineering. The PVC coiled material is a waterproof coiled material made of polyvinyl chloride (PVC) material, has good weather resistance and chemical resistance, and is commonly used for waterproofing basements, pools and coating layers. The self-adhesive coiled material is a waterproof coiled material with a self-adhesive back surface, does not need external adhesive, is convenient and quick to construct, and is commonly used for roof waterproofing and basement waterproofing.
The PVDF (polyvinylidene fluoride) composite anti-aging film is a material with good ultraviolet aging resistance. In the prior art, an anti-aging agent, such as an ultraviolet absorber, a light stabilizer and the like, is usually added into the PVDF film in the preparation process. The additives can absorb or stabilize ultraviolet rays, delay the aging process of the PVDF film, and improve the weather resistance and the service life of the PVDF film. The PVDF film may be composited with other materials such as fiberglass, nanomaterials, and the like. The introduction of the composite material can enhance the mechanical property and ageing resistance of the film and improve the durability and stability of the film. However, the ultraviolet aging resistance and corrosion resistance of the PVDF film in the prior art need to be further improved.
The Chinese patent application CN110528788A discloses a PVDF (polyvinylidene fluoride) composite TPO sun-proof anti-aging composite membrane for a waterproof coiled material and a preparation method thereof, wherein the composite membrane is composed of a PVDF membrane, a glue layer, a TPO layer, an adhesive layer and a release layer which are sequentially arranged, wherein: the thickness of the PVDF film is 0.015-0.025 mm, and the width is 860-1920 mm; the thickness of the glue layer is 0.0003-0.0005 mm, and the width is 860-1920 mm; the thickness of the TPO layer is 2-5 mm, and the width is 900-1100 mm; the thickness of the adhesive layer is 1-2 mm, and the width is 1060-2120 mm; the thickness of the release layer is 0.03-0.04 mm, and the width is 1060-2120 mm. The anti-ultraviolet light-resistant metal roof can be directly used for the single-layer roof and the metal roof, the exposed anti-ultraviolet light-resistant life of the thermoplastic polyolefin elastomer (TPO) sheet is only about 5-10 years, the service life is prolonged to 25 years, the requirements of the new municipal administration and building waterproof general specification are met, and the maintenance cost is greatly reduced. However, the ultraviolet aging resistance and corrosion resistance of the composite film prepared by the invention still have defects.
Disclosure of Invention
In view of the defect of poor ultraviolet aging resistance and corrosion resistance of the PVDF film in the prior art, the invention aims to solve the technical problem of providing the PVDF composite anti-aging film for the waterproof coiled material, which has good ultraviolet aging resistance and corrosion resistance, a preparation method and the waterproof coiled material.
In order to achieve the above object, the present invention adopts the following technical scheme:
the utility model provides a waterproofing membrane, includes the substrate layer, the substrate layer is the glass fiber felt layer, still including setting up the first waterproof layer at substrate layer upper surface, set up the second waterproof layer at substrate layer lower surface, first waterproof layer upper surface and second waterproof layer lower surface are provided with the glue layer respectively, glue layer surface is provided with first ageing resistance layer and second ageing resistance layer respectively.
Preferably, the first waterproof layer and the second waterproof layer are SBS asphalt.
Preferably, the glue layer is polyurethane glue.
Preferably, the first aging resistant layer and the second aging resistant layer are PVDF composite aging resistant films.
The preparation method of the waterproof coiled material comprises the following steps:
coating a layer of SBS asphalt on the upper and lower surfaces of the glass fiber felt layer respectively to obtain a first waterproof layer and a second waterproof layer, wherein the coating thickness is 1.5-3 mm; coating polyurethane glue on the upper surface of the first waterproof layer and the lower surface of the second waterproof layer, wherein the thickness of the glue layer is 4-10 mu m, and respectively adhering PVDF composite anti-aging films on the surfaces of the glue layers to obtain the waterproof coiled material.
The PVDF composite anti-aging film is prepared by the following steps of:
s1, adding 0.5-0.7 part of zirconium tetrachloride and 0.3-0.5 part of 2-amino terephthalic acid into 140-160 parts of mixed solvent, performing ultrasonic treatment, and stirring at 100-300 rpm for 30-60 min at room temperature to obtain a uniform solution; stirring at 50-200 rpm for 10-30 h at 110-130 ℃, cooling to room temperature, pouring out supernatant, collecting solid matters, respectively washing with N, N-dimethylformamide and methanol for 1-3 times, centrifuging, and drying in vacuum to obtain coarse materials;
s2, adjusting the pH of 180-220 parts of Tris buffer solution to 8-9 by using 0.5-2 mol/L hydrochloric acid, adding 0.3-0.5 part of coarse material prepared in the step S1, performing ultrasonic treatment, adding 0.1-0.3 part of dopamine, stirring 20~50 h,8000~12000rpm at room temperature of 100-300 rpm, centrifuging for 3-8 min, collecting solid, washing for 1-3 times by using water, and performing vacuum drying to obtain a grafted material;
s3, mixing 10-20 parts of polyvinylidene fluoride, 80-90 parts of caprolactam and 0.3-0.5 part of the grafting material prepared in the step S2 with 0.1-0.3 part of a modifier, stirring at 100-300 rpm for 10-30 min, heating at 160-180 ℃ for 1-3 h, and degassing for 4-8 h to obtain a to-be-coated liquid; preheating a quartz glass plate to 160-180 ℃, scraping the liquid to be coated onto the quartz glass plate by using a film scraper, then rapidly immersing the quartz glass plate in water at 20-35 ℃ for cooling to obtain a cooling film, and immersing the cooling film in the water for 5-20 hours to obtain the PVDF composite anti-aging film, wherein the thickness of the PVDF composite anti-aging film is 300-500 mu m.
Preferably, the mixed solvent is N, N-dimethylformamide and glacial acetic acid according to the mass ratio of 1: and 0.5-2.
The preparation method of the modifier comprises the following steps of:
z1, mixing 0.5-2 parts of titanium dioxide with 15-25 parts of 0.5-2 mol/L sodium hydroxide aqueous solution, stirring at 100-300 rpm for 20-40 min, heating to 140-160 ℃ and maintaining for 1-3 h, adjusting pH to 1-2 with 0.5-2 mol/L hydrochloric acid, washing with water and drying to obtain a pretreated substance;
z2, uniformly mixing 4-6 parts of dimethylol urea and 4-6 parts of 2, 4-diamino-1, 3, 5-triazine for 0.5-3 hours, calcining in a muffle furnace at 500-600 ℃ for 1-5 hours, and cooling to room temperature to obtain powder; adding 0.5-2 parts of the pretreated matter prepared in the step Z1 and 2-4 parts of the powder into 80-120 parts of absolute ethyl alcohol, carrying out ultrasonic treatment, adding 0.5-2 parts of 1H, 2H-perfluoro decyl trichlorosilane, stirring at 100-300 rpm for 5-20 hours at 70-90 ℃, collecting precipitate, washing and drying to obtain the modifier.
Preferably, the ultrasonic time is 0.5-4 h, the ultrasonic power is 200-600W, and the ultrasonic frequency is 20-60 kHz.
The polar nature and hydrogen bond interaction of the dopamine in the invention are helpful for enhancing the interaction between the grafting material and the polyvinylidene fluoride, thereby improving the overall compatibility of the system. The dispersibility of the grafting material in the to-be-coated liquid is good, and the crystallinity and ultraviolet stability of the anti-aging film are improved. With the introduction of dopamine, the anti-aging membrane has the advantages that additional functional groups are provided, and hydrogen bonds are established between polyvinylidene fluoride molecules and a plurality of hydroxyl groups on the surface of the dopamine, so that the anti-aging membrane ultraviolet stability is enhanced. The obtained anti-aging film not only has excellent chemical stability, mechanical strength and ultraviolet stability, but also has excellent acid resistance, alkali resistance and chlorine resistance.
The pretreatment substance is successfully inserted into the two-dimensional porous powder in the preparation method of the modifier, so that intermolecular force is generated, the modifier has strong photocatalytic activity, obvious inhibition effect on a photo-generated product is realized, and the effective electron transfer between semiconductors is utilized to induce electron hole pair recombination, so that the rate of the photo-generated electron hole pair recombination is reduced to the minimum. Under the irradiation of ultraviolet rays, the photocatalyst consisting of powder and pretreatment in the anti-aging film can well separate photo-generated electron-hole pairs. In addition, the curled porous structure of the powder and the rod-shaped structure of the pretreatment provide reaction sites for photocatalytic reaction, generate strong oxidizing property, not only can degrade pollutants, but also can damage the cell walls of bacteria, cause leakage of intracellular substances, finally kill bacteria, reduce exposure of the anti-aging film to severe environments such as acid, alkali and salt solution, and improve corrosion resistance.
Fluorinated modification is performed with 1H, 2H-perfluorodecyl trichlorosilane to improve the dispersibility and stability. The prepared anti-aging film still keeps superhydrophobic after continuous soaking and ultraviolet irradiation, and has good chemical stability. This shows that the coating has excellent uv stability, which is attributable to the excellent photo-oxidative aging resistance of polyvinylidene fluoride and 1h,2 h-perfluorodecyl trichlorosilane. The anti-aging film can effectively prevent the influence of aqueous solution, and endows the anti-aging film with good water resistance.
Compared with the prior art, the invention has the beneficial effects that:
1) The waterproof coiled material prepared by the invention has ultraviolet ageing resistance and corrosion resistance, and the PVDF composite ageing resistance film in the waterproof coiled material has good ultraviolet ageing resistance. The PVDF material has higher weather resistance, can effectively resist the irradiation and oxidation of solar ultraviolet rays, and prolongs the service life of coiled materials.
2) The waterproof coiled material prepared by the invention has corrosion resistance, and the SBS asphalt in the waterproof coiled material has good corrosion resistance as a waterproof layer. The SBS asphalt has excellent acid-base resistance and chemical corrosion resistance, can protect the base material from being corroded by chemical substances, and improves the durability and stability of the coiled material.
3) The PVDF composite anti-aging film introduces a modifier in the preparation process so as to improve the anti-aging performance of the PVDF composite anti-aging film. The introduction of the modifier can improve the stability of the film material, enhance the oxidation resistance and ultraviolet aging resistance of the film material, promote the improvement of hydrophobicity, and further improve the durability and the service life of the waterproof coiled material.
Detailed Description
The main material sources are as follows:
SBS asphalt: bode , bode New Polymer materials, inc., cat: JH-7401.
Glass fiber felt layer: city New Senrong composite material Co., ltd., model: 34.
polyurethane glue: dongguan city, ming Tai chemical technology Co., ltd., model: TS-8810.
Titanium dioxide: shandong you polymerization chemical engineering Co., ltd., crystal form: rutile type, cat No.: 01.
tris buffer: new material only limited in shandong, product number: 1688.
polyvinylidene fluoride: the Yuyao city bang superplasticizer company, brand: 6020.
example 1
The preparation method of the waterproof coiled material comprises the following steps:
the waterproof coiled material comprises a substrate layer, the substrate layer is a glass fiber felt layer, the waterproof coiled material further comprises a first waterproof layer arranged on the upper surface of the substrate layer, a second waterproof layer arranged on the lower surface of the substrate layer, glue layers are respectively arranged on the upper surface of the first waterproof layer and the lower surface of the second waterproof layer, and a first anti-aging layer and a second anti-aging layer are respectively arranged on the surface of the glue layers. Wherein the first waterproof layer and the second waterproof layer are SBS asphalt; the glue layer is polyurethane glue; the first aging resistant layer and the second aging resistant layer are PVDF composite aging resistant films; coating a layer of SBS asphalt on the upper and lower surfaces of the glass fiber felt layer respectively to obtain a first waterproof layer and a second waterproof layer, wherein the coating thickness is 2mm; coating polyurethane glue on the upper surface of the first waterproof layer and the lower surface of the second waterproof layer, wherein the thickness of the glue layers is 5 mu m, and respectively adhering PVDF composite anti-aging films on the surfaces of the glue layers to obtain the waterproof coiled material.
The preparation method of the PVDF composite anti-aging film comprises the following steps:
s1, adding 0.6g of zirconium tetrachloride and 0.4g of 2-amino terephthalic acid into 150g of mixed solvent, carrying out ultrasonic treatment for 30min, wherein the ultrasonic power is 400W, the ultrasonic frequency is 40kHz, and the mixed solvent is N, N-dimethylformamide and glacial acetic acid according to the mass ratio of 1:1, and then stirring for 45min at 200rpm at room temperature to obtain a uniform solution; stirring at 120 ℃ at 100rpm for 24 h, cooling to room temperature, pouring out supernatant, collecting solid substances, washing with N, N-dimethylformamide and methanol for 3 times respectively, centrifuging, and vacuum drying to obtain coarse materials;
s2, adjusting the pH of 200g of Tris buffer solution to 8.5 by using 1mol/L hydrochloric acid, then adding 0.4g of coarse material prepared in the step S1, carrying out ultrasonic treatment for 2 hours, wherein the ultrasonic power is 400W, the ultrasonic frequency is 40kHz, then adding 0.2g of dopamine, stirring at 200rpm for 48 hours at room temperature, centrifuging at 10000rpm for 5 minutes, collecting solid, washing with water for 3 times, and carrying out vacuum drying to obtain grafted material;
s3, mixing 15g of polyvinylidene fluoride, 84.4g of caprolactam, 0.4g of the grafting material prepared in the step S2 and 0.2g of modifier, stirring at 200rpm for 20min, heating at 170 ℃ for 2h, and degassing for 6h to obtain a to-be-coated liquid; preheating a quartz glass plate to 170 ℃, scraping the liquid to be coated on the quartz glass plate by using a film scraper, then quickly immersing the quartz glass plate in water at 30 ℃ for cooling to obtain a cooling film, and immersing the cooling film in the water for 12 hours to obtain the PVDF composite anti-aging film, wherein the thickness of the PVDF composite anti-aging film is 400 mu m.
The preparation method of the modifier comprises the following steps:
z1, mixing 1g of titanium dioxide with 20g of 1mol/L sodium hydroxide aqueous solution, stirring for 30min at 200rpm, then heating to 150 ℃ and keeping for 2h, adjusting the pH to 1.5 by using 1mol/L hydrochloric acid, and washing and drying by using water to obtain a pretreatment substance;
z2, uniformly mixing 5g of dimethylol urea and 5g of 2, 4-diamino-1, 3, 5-triazine for 1h, calcining for 3 hours at 550 ℃ in a muffle furnace, and cooling to room temperature to obtain powder; 1g of the pretreatment prepared in the step Z1 and 3g of the powder are added into 100 g absolute ethyl alcohol, the ultrasonic power is 300W, the ultrasonic frequency is 40kHz, 1g of 1H, 2H-perfluoro decyl trichlorosilane is added, the mixture is stirred at 200rpm at 80 ℃ for 12h, the precipitate is collected, washed and dried, and the modifier is obtained.
Comparative example 1
The preparation method of the waterproof coiled material is basically the same as that of the embodiment 1, and the only difference is that: the PVDF composite anti-aging film is different in preparation method.
The preparation method of the PVDF composite anti-aging film comprises the following steps:
s1, adding 0.6g of zirconium tetrachloride and 0.4g of 2-amino terephthalic acid into 150g of mixed solvent, carrying out ultrasonic treatment for 30min, wherein the ultrasonic power is 400W, the ultrasonic frequency is 40kHz, and the mixed solvent is N, N-dimethylformamide and glacial acetic acid according to the mass ratio of 1:1, and then stirring for 45min at 200rpm at room temperature to obtain a uniform solution; stirring at 120 ℃ at 100rpm for 24 h, cooling to room temperature, pouring out supernatant, collecting solid substances, washing with N, N-dimethylformamide and methanol for 3 times respectively, centrifuging, and vacuum drying to obtain coarse materials;
s2, adjusting the pH of 200g of Tris buffer solution to 8.5 by using 1mol/L hydrochloric acid, then adding the coarse material prepared in the step S1 of 0.4g, performing ultrasonic dispersion for 2 hours, wherein the ultrasonic power is 400W, the ultrasonic frequency is 40kHz, centrifuging at 10000rpm for 5 minutes, collecting solids, washing with water for 3 times, and performing vacuum drying to obtain fine materials;
s3, mixing 15g of polyvinylidene fluoride, 84.4g of caprolactam, 0.4g of the fine materials prepared in the step S2 and 0.2g of modifier, stirring at 200rpm for 20min, heating at 170 ℃ for 2h, and degassing for 6h to obtain a liquid to be coated; preheating a quartz glass plate to 170 ℃, scraping the liquid to be coated on the quartz glass plate by using a film scraper, then quickly immersing the quartz glass plate in water at 30 ℃ for cooling to obtain a cooling film, and immersing the cooling film in the water for 12 hours to obtain the PVDF composite anti-aging film, wherein the thickness of the PVDF composite anti-aging film is 400 mu m.
The preparation method of the modifier is the same as that of the example 1.
Comparative example 2
The preparation method of the waterproof coiled material is basically the same as that of the embodiment 1, and the only difference is that: the preparation methods of the modifier are different.
The preparation method of the modifier comprises the following steps: uniformly mixing 5g of dimethylol urea and 5g of 2, 4-diamino-1, 3, 5-triazine for 1h, calcining for 3 hours at 550 ℃ in a muffle furnace, and cooling to room temperature to obtain powder; 3g of the powder is added into 100 g absolute ethyl alcohol, 1h of ultrasonic wave with the ultrasonic power of 300W and the ultrasonic frequency of 40kHz, 1g of 1H, 2H-perfluoro decyl trichlorosilane is added, and the mixture is stirred at 200rpm for 12h at 80 ℃, and the precipitate is collected, washed and dried to obtain the modifier.
The PVDF composite anti-aging film was prepared in the same manner as in example 1.
Comparative example 3
The preparation method of the waterproof coiled material is basically the same as that of the embodiment 1, and the only difference is that: the preparation methods of the modifier are different.
The preparation method of the modifier comprises the following steps:
z1, mixing 1g of titanium dioxide with 20g of 1mol/L sodium hydroxide aqueous solution, stirring for 30min at 200rpm, then heating to 150 ℃ and keeping for 2h, adjusting the pH to 1.5 by using 1mol/L hydrochloric acid, and washing and drying by using water to obtain a pretreatment substance;
z2, uniformly mixing 5g of dimethylol urea and 5g of 2, 4-diamino-1, 3, 5-triazine for 1h, calcining for 3 hours at 550 ℃ in a muffle furnace, and cooling to room temperature to obtain powder; 1g of the pretreated product prepared in the step Z1 and 3g of powder are added into 100 g absolute ethyl alcohol, ultrasonic wave 1h is carried out, ultrasonic power is 300W, ultrasonic frequency is 40kHz, stirring is carried out at 80 ℃ and 200rpm for 12h, precipitate is collected, washed and dried, and the modifier is obtained.
The PVDF composite anti-aging film was prepared in the same manner as in example 1.
Comparative example 4
The preparation method of the waterproof coiled material is basically the same as that of the embodiment 1, and the only difference is that: the PVDF composite anti-aging film is different in preparation method.
The preparation method of the PVDF composite anti-aging film comprises the following steps:
s1, adding 0.6g of zirconium tetrachloride and 0.4g of 2-amino terephthalic acid into 150g of mixed solvent, carrying out ultrasonic treatment for 30min, wherein the ultrasonic power is 400W, the ultrasonic frequency is 40kHz, and the mixed solvent is N, N-dimethylformamide and glacial acetic acid according to the mass ratio of 1:1, and then stirring for 45min at 200rpm at room temperature to obtain a uniform solution; stirring at 120 ℃ at 100rpm for 24 h, cooling to room temperature, pouring out supernatant, collecting solid substances, washing with N, N-dimethylformamide and methanol for 3 times respectively, centrifuging, and vacuum drying to obtain coarse materials;
s2, adjusting the pH of 200g of Tris buffer solution to 8.5 by using 1mol/L hydrochloric acid, then adding the coarse material prepared in the step S1 of 0.4g, performing ultrasonic dispersion for 2 hours, wherein the ultrasonic power is 400W, the ultrasonic frequency is 40kHz, centrifuging at 10000rpm for 5 minutes, collecting solids, washing with water for 3 times, and performing vacuum drying to obtain fine materials;
s3, mixing 15g of polyvinylidene fluoride, 84.4g of caprolactam and 0.4g of the fine materials prepared in the step S2, stirring at 200rpm for 20min, heating at 170 ℃ for 2h, and degassing for 6h to obtain a to-be-coated liquid; preheating a quartz glass plate to 170 ℃, scraping the liquid to be coated on the quartz glass plate by using a film scraper, then quickly immersing the quartz glass plate in water at 30 ℃ for cooling to obtain a cooling film, and immersing the cooling film in the water for 12 hours to obtain the PVDF composite anti-aging film, wherein the thickness of the PVDF composite anti-aging film is 400 mu m.
Test example 1
Ultraviolet aging resistance test
The test instrument is an ultraviolet aging tester of Tianjin Weisi laboratory instruments, and the test conditions comprise: the ultraviolet lamp has a wavelength of 280-400nm and an irradiation intensity of 1000W/m 2 The irradiation distance was 50mm. The waterproof coiled material prepared by the invention is put into an ultraviolet aging tester, the temperature is set to be 60 ℃, the irradiation is started, the irradiation time is 4 hours each time, and then the waterproof coiled material is taken out and immersed into saturated brine for one cycle. The waterproof coiled materials are subjected to water contact angle test before irradiation and after 48 hours of irradiation, and each group of test is performed three times, and an average value is obtained. The test results are shown in Table 1.
TABLE 1 ultraviolet aging resistance test results
Test example 2
Corrosion resistance test
The waterproof coiled materials prepared by the invention are respectively soaked in corrosive solutions with certain concentration, such as: 2mol/L hydrochloric acid, 2mol/LNaOH aqueous solution, saturated sodium chloride aqueous solution and the like are soaked for 120d, the membrane is taken out of a soaking container after the soaking is finished, the membrane is soaked in water for 48h after being washed clean by water, and is taken out and is dried under the condition of 25 ℃ at a ventilation position for quality testing, and the quality degradation rate is inspected. The test results are shown in Table 2.
TABLE 2 Corrosion resistance test results
From the test data in tables 1 and 2, it can be seen that the waterproof coiled material prepared in example 1 of the present invention has excellent ultraviolet aging resistance and corrosion resistance. Example 1 is probably due to the polar nature of dopamine and the hydrogen bonding interactions helping to enhance the interaction between the graft and polyvinylidene fluoride, as compared to comparative example 1, thereby improving the overall compatibility of the system. The dispersibility of the grafting material in the to-be-coated liquid is good, and the crystallinity and ultraviolet stability of the anti-aging film are improved. With the introduction of dopamine, the anti-aging membrane has the advantages that additional functional groups are provided, and hydrogen bonds are established between polyvinylidene fluoride molecules and a plurality of hydroxyl groups on the surface of the dopamine, so that the anti-aging membrane ultraviolet stability is enhanced. The obtained anti-aging film not only has excellent chemical stability, mechanical strength and ultraviolet stability, but also has excellent acid resistance, alkali resistance and chlorine resistance.
Example 1 is probably because the pretreatment is successfully inserted into the two-dimensional porous powder in the preparation method of the modifier of the present invention, thereby generating intermolecular forces, the modifier has strong photocatalytic activity, has a remarkable inhibitory effect on the photo-generated product, and minimizes the rate of photo-generated electron-hole pair recombination by inducing electron-hole pair recombination by using efficient electron transfer between semiconductors, as compared with comparative example 2. Under the irradiation of ultraviolet rays, the photocatalyst consisting of powder and pretreatment in the anti-aging film can well separate photo-generated electron-hole pairs. In addition, the curled porous structure of the powder and the rod-shaped structure of the pretreatment provide reaction sites for photocatalytic reaction, generate strong oxidizing property, not only can degrade pollutants, but also can damage the cell walls of bacteria, cause leakage of intracellular substances, finally kill bacteria, reduce exposure of the anti-aging film to severe environments such as acid, alkali and salt solution, and improve corrosion resistance.
Example 1 is probably due to the fluorinated modification of 1H, 2H-perfluorodecyl trichlorosilane to improve the dispersibility and stability thereof, as compared with comparative example 3. The prepared anti-aging film still keeps superhydrophobic after continuous soaking and ultraviolet irradiation, and has good chemical stability. This shows that the coating has excellent uv stability, which is attributable to the excellent photo-oxidative aging resistance of polyvinylidene fluoride and 1h,2 h-perfluorodecyl trichlorosilane. The anti-aging film can effectively prevent the influence of aqueous solution, and endows the anti-aging film with good water resistance.
Claims (9)
1. The waterproof coiled material is characterized by comprising a substrate layer, a first waterproof layer arranged on the upper surface of the substrate layer, a second waterproof layer arranged on the lower surface of the substrate layer, a glue layer respectively arranged on the upper surface of the first waterproof layer and the lower surface of the second waterproof layer, and a first anti-aging layer and a second anti-aging layer respectively arranged on the surface of the glue layer;
the first aging resistant layer and the second aging resistant layer are PVDF composite aging resistant films;
the preparation method of the PVDF composite anti-aging film comprises the following steps of, by weight:
s1, adding 0.5-0.7 part of zirconium tetrachloride and 0.3-0.5 part of 2-amino terephthalic acid into 140-160 parts of mixed solvent, performing ultrasonic treatment, and stirring at 100-300 rpm for 30-60 min at room temperature to obtain a uniform solution; stirring at 50-200 rpm for 10-30 h at 110-130 ℃, cooling to room temperature, pouring out supernatant, collecting solid matters, respectively washing with N, N-dimethylformamide and methanol for 1-3 times, centrifuging, and drying in vacuum to obtain coarse materials;
s2, adjusting the pH of 180-220 parts of Tris buffer solution to 8-9 by using 0.5-2 mol/L hydrochloric acid, adding 0.3-0.5 part of coarse material prepared in the step S1, performing ultrasonic treatment, adding 0.1-0.3 part of dopamine, stirring 20~50 h,8000~12000rpm at room temperature of 100-300 rpm, centrifuging for 3-8 min, collecting solid, washing for 1-3 times by using water, and performing vacuum drying to obtain a grafted material;
s3, mixing 10-20 parts of polyvinylidene fluoride, 80-90 parts of caprolactam and 0.3-0.5 part of the grafting material prepared in the step S2 with 0.1-0.3 part of a modifier, stirring at 100-300 rpm for 10-30 min, heating at 160-180 ℃ for 1-3 h, and degassing for 4-8 h to obtain a to-be-coated liquid; preheating a quartz glass plate to 160-180 ℃, scraping the liquid to be coated on the quartz glass plate by using a film scraper, then quickly immersing the quartz glass plate in water at 20-35 ℃ for cooling to obtain a cooling film, and immersing the cooling film in the water for 5-20 hours to obtain a PVDF composite anti-aging film, wherein the thickness of the PVDF composite anti-aging film is 300-500 mu m;
the preparation method of the modifier comprises the following steps of:
z1, mixing 0.5-2 parts of titanium dioxide with 15-25 parts of 0.5-2 mol/L sodium hydroxide aqueous solution, stirring at 100-300 rpm for 20-40 min, heating to 140-160 ℃ and maintaining for 1-3 h, adjusting pH to 1-2 with 0.5-2 mol/L hydrochloric acid, washing with water and drying to obtain a pretreated substance;
z2, uniformly mixing 4-6 parts of dimethylol urea and 4-6 parts of 2, 4-diamino-1, 3, 5-triazine for 0.5-3 hours, calcining in a muffle furnace at 500-600 ℃ for 1-5 hours, and cooling to room temperature to obtain powder; adding 0.5-2 parts of the pretreated matter prepared in the step Z1 and 2-4 parts of powder into 80-120 parts of absolute ethyl alcohol, carrying out ultrasonic treatment, adding 0.5-2 parts of 1H, 2H-perfluoro decyl trichlorosilane, stirring at 100-300 rpm for 5-20 hours at 70-90 ℃, collecting precipitate, washing and drying to obtain a modifier;
the mixed solvent is N, N-dimethylformamide and glacial acetic acid according to the mass ratio of 1: and 0.5-2.
2. A water-resistant roll as claimed in claim 1, characterized in that: the ultrasonic time is 0.5-4 h, the ultrasonic power is 200-600W, and the ultrasonic frequency is 20-60 kHz.
3. A water-resistant roll as claimed in claim 1, characterized in that: the first waterproof layer and the second waterproof layer are SBS asphalt.
4. A water-resistant roll as claimed in claim 1, characterized in that: the glue layer is polyurethane glue.
5. The method of any one of claims 1 to 4, comprising the steps of: coating a layer of SBS asphalt on the upper and lower surfaces of the glass fiber felt layer respectively to obtain a first waterproof layer and a second waterproof layer, wherein the coating thickness is 1.5-3 mm; coating polyurethane glue on the upper surface of the first waterproof layer and the lower surface of the second waterproof layer, wherein the thickness of the glue layer is 4-10 mu m, and respectively adhering PVDF composite anti-aging films on the surfaces of the glue layers to obtain the waterproof coiled material.
6. The method for preparing the PVDF composite anti-aging film is characterized by comprising the following steps of:
s1, adding 0.5-0.7 part of zirconium tetrachloride and 0.3-0.5 part of 2-amino terephthalic acid into 140-160 parts of mixed solvent, performing ultrasonic treatment, and stirring at 100-300 rpm for 30-60 min at room temperature to obtain a uniform solution; stirring at 50-200 rpm for 10-30 h at 110-130 ℃, cooling to room temperature, pouring out supernatant, collecting solid matters, respectively washing with N, N-dimethylformamide and methanol for 1-3 times, centrifuging, and drying in vacuum to obtain coarse materials;
s2, adjusting the pH of 180-220 parts of Tris buffer solution to 8-9 by using 0.5-2 mol/L hydrochloric acid, adding 0.3-0.5 part of coarse material prepared in the step S1, performing ultrasonic treatment, adding 0.1-0.3 part of dopamine, stirring 20~50 h,8000~12000rpm at room temperature of 100-300 rpm, centrifuging for 3-8 min, collecting solid, washing for 1-3 times by using water, and performing vacuum drying to obtain a grafted material;
s3, mixing 10-20 parts of polyvinylidene fluoride, 80-90 parts of caprolactam and 0.3-0.5 part of the grafting material prepared in the step S2 with 0.1-0.3 part of a modifier, stirring at 100-300 rpm for 10-30 min, heating at 160-180 ℃ for 1-3 h, and degassing for 4-8 h to obtain a to-be-coated liquid; preheating a quartz glass plate to 160-180 ℃, scraping the liquid to be coated on the quartz glass plate by using a film scraper, then quickly immersing the quartz glass plate in water at 20-35 ℃ for cooling to obtain a cooling film, and immersing the cooling film in the water for 5-20 hours to obtain a PVDF composite anti-aging film, wherein the thickness of the PVDF composite anti-aging film is 300-500 mu m;
the preparation method of the modifier comprises the following steps of:
z1, mixing 0.5-2 parts of titanium dioxide with 15-25 parts of 0.5-2 mol/L sodium hydroxide aqueous solution, stirring at 100-300 rpm for 20-40 min, heating to 140-160 ℃ and maintaining for 1-3 h, adjusting pH to 1-2 with 0.5-2 mol/L hydrochloric acid, washing with water and drying to obtain a pretreated substance;
z2, uniformly mixing 4-6 parts of dimethylol urea and 4-6 parts of 2, 4-diamino-1, 3, 5-triazine for 0.5-3 hours, calcining in a muffle furnace at 500-600 ℃ for 1-5 hours, and cooling to room temperature to obtain powder; adding 0.5-2 parts of the pretreated matter prepared in the step Z1 and 2-4 parts of the powder into 80-120 parts of absolute ethyl alcohol, carrying out ultrasonic treatment, adding 0.5-2 parts of 1H, 2H-perfluoro decyl trichlorosilane, stirring at 100-300 rpm for 5-20 hours at 70-90 ℃, collecting precipitate, washing and drying to obtain the modifier.
7. The method of PVDF composite anti-aging film according to claim 6, wherein: the mixed solvent is N, N-dimethylformamide and glacial acetic acid according to the mass ratio of 1: and 0.5-2.
8. The method of PVDF composite anti-aging film according to claim 6, wherein: the ultrasonic time is 0.5-4 h, the ultrasonic power is 200-600W, and the ultrasonic frequency is 20-60 kHz.
9. A PVDF composite anti-aging film, characterized in that it is prepared by the method of any one of claims 6 to 8.
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| GB202007915D0 (en) * | 2020-05-27 | 2020-07-08 | G2O Water Tech Limited | Oil and water separation membrane |
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