Self-cleaning anti-fouling artificial outer wall composite insulation marble film material and preparation method thereof

Abstract

The invention relates to the technical field of membrane material production, in particular to a self-cleaning anti-fouling artificial outer wall composite heat preservation marble membrane material and a preparation method thereof. The self-cleaning anti-fouling artificial outer wall composite heat preservation marble film material is prepared from the following raw materials in parts by weight: 30 to 40 parts of polyvinylidene fluoride, 3 to 6 parts of functional additive, 3 to 5 parts of auxiliary additive, 2 to 4 parts of anti-ultraviolet agent, 3 to 6 parts of N, N-dimethylacetamide and 2 to 5 parts of antioxidant, the self-cleaning anti-pollution artificial outer wall composite thermal insulation marble film material prepared by the invention not only has better thermal insulation performance, but also has excellent self-cleaning anti-pollution performance, so that the quality of the self-cleaning anti-pollution artificial outer wall composite thermal insulation marble film material is effectively ensured.

Description

Technical Field

[0001] The invention relates to the technical field of membrane material production, in particular to a self-cleaning and anti-fouling artificial exterior wall composite thermal insulation marble membrane material and a preparation method thereof. Background Art

[0002] Marble is a metamorphic rock formed by the high temperature and high pressure in the earth's crust, which causes the structure, texture and mineral composition of the original rocks to change. Marble is mainly composed of calcite, limestone, serpentine and dolomite. Its main component is calcium carbonate. Marble has attracted the attention of consumers with its gorgeous appearance and very practical features. The texture of each marble floor tile is different. Marble is widely used in the building exterior wall industry because of its clear texture, smooth and delicate, bright and fresh.

[0003] In the patent document with application number "CN2021110 51961.1" and titled "An easily peelable protective film for artificial marble and its preparation method", it is recorded that "the weight composition of the raw materials is as follows: 80-100 parts of polyethylene, 20-30 parts of polyolefin, 2-5 parts of 2,5-furandicarboxylic acid, 0.5-1.5 parts of antioxidant, 0.5-1.5 parts of plasticizer, and 0.5-1.0 parts of lubricant. The inventors of this application have found through practice that the combination of polyethylene, polyolefin and 2,5-furandicarboxylic acid works together to overcome the aforementioned defects. The prepared protective film has excellent strength and toughness, good weather resistance and adhesion stability, and the peeling force does not increase significantly after several days or long-term application, and is easy to remove. When it is removed, there is no residual glue left on the artificial marble table top, and no shadow is left."

[0004] Although the membrane material manufactured by the above patent document has advantages such as weather resistance, its self-cleaning, anti-fouling and thermal insulation performance is relatively insufficient and still needs further improvement. Based on this, the present invention provides a self-cleaning, anti-fouling artificial exterior wall composite thermal insulation marble membrane material and a preparation method thereof to solve the above technical problems. Summary of the invention

[0005] The purpose of the present invention is to provide a self-cleaning and anti-fouling artificial exterior wall composite thermal insulation marble membrane material and a preparation method thereof. The prepared self-cleaning and anti-fouling artificial exterior wall composite thermal insulation marble membrane material not only has good thermal insulation performance, but also has excellent self-cleaning and anti-fouling performance, effectively ensuring its quality.

[0006] To achieve the above object, the present invention provides the following technical solutions: The first aspect of the present invention provides a self-cleaning and anti-fouling artificial exterior wall composite thermal insulation marble membrane material, which is composed of the following raw materials in parts by weight: 30 to 40 parts of polyvinylidene fluoride, 3 to 6 parts of functional additives, 3 to 5 parts of auxiliary additives, 2 to 4 parts of UV protection agents, 3 to 6 parts of N, N-dimethylacetamide and 2 to 5 parts of antioxidants.

[0007] Furthermore, the preparation process of the functional additive is as follows: The aluminum silicate fiber is ultrasonically dispersed in deionized water at a solid-liquid ratio of 0.02-0.06 g / mL for 20-30 minutes, and then γ-glycidyloxypropyltrimethoxysilane (0.02%-0.08% by weight of the aluminum silicate fiber) is added thereto, and the mixture is treated at 240-260 r / min and 40-50° C. for 30-40 minutes. After filtration, the mixture is dried at 70-90° C. to constant weight to obtain modified aluminum silicate fiber. According to the solid-liquid ratio of 0.24-0.28 g / mL, an appropriate amount of modified base material is ultrasonically dispersed in an appropriate amount of deionized water and mixed for 30-40 minutes, and then 2.4%-6.4% of the modified base material mass of modified aluminum silicate fiber is added thereto, and the mixture is treated at 340-540 r / min for 10-15 minutes, and then treated at 100-110°C for 300-320 minutes. After filtration, the mixture is washed with deionized water for 2-4 times, and dried at 70-90°C to constant weight to obtain a functional additive.

[0008] Furthermore, the preparation process of the modified base material is as follows: A proper amount of hollow ceramic microbeads is placed in an 8% to 12% acrylic acid aqueous solution at a dosage ratio of 0.8 to 1.2 g / mL, stirred at 120 to 220 r / min for 20 to 30 min, and then ammonium persulfate is added thereto. Stirring is continued for 70 to 78 min under a nitrogen atmosphere at 60 to 68° C. After suction filtration, the obtained filter cake is washed 2 to 4 times with anhydrous ethanol and deionized water respectively, then dried at 70 to 90° C. to constant weight, and then placed in a muffle furnace at 550 to 570° C. for 100 to 120 min to obtain a base material; An appropriate amount of the base material is placed in deionized water at a dosage ratio of 0.02 to 0.12 g / mL and ultrasonically dispersed for 20 to 30 minutes, and then 0.08% to 0.16% of the mass of the base material of γ-glycidyloxypropyltrimethoxysilane is added thereto, and the base material is treated at 220 to 240 r / min and 40 to 50° C. for 30 to 40 minutes. After filtration, the base material is dried at 70 to 90° C. to constant weight to obtain a modified base material.

[0009] Furthermore, the amount of ammonium persulfate added is 0.08% to 0.22% of the mass of the hollow ceramic microspheres.

[0010] Furthermore, the preparation process of the auxiliary agent is as follows: The composite material is placed in a 0.14% to 0.24% potassium permanganate aqueous solution at a dosage ratio of 0.04 to 0.12 g / mL, stirred at 220 to 240 r / min for 20 to 30 minutes, and then a 0.12% to 0.32% manganese acetate aqueous solution is added thereto, and the mixture is stirred for 100 to 120 minutes at 35 to 40°C, and then left to stand for 140 to 150 minutes; After completion, centrifuge, wash the centrifugal product with deionized water 2 to 4 times, and dry it in a drying oven at 50 to 60° C. to constant weight to obtain an auxiliary agent; Wherein, the addition amount of the manganese acetate aqueous solution is 0.04% to 0.08% of the mass of the composite material.

[0011] Furthermore, the composite material is formed by mixing powder and nano silicon dioxide in a mass ratio of 1:0.5 to 0.7.

[0012] Furthermore, the preparation process of the powder is as follows: Add an appropriate amount of aluminum nitrate nonahydrate in deionized water at a dosage ratio of 0.04 to 0.12 g / mL, and stir at 120 to 140 r / min for 10 to 14 minutes to obtain a first solution; Add an appropriate amount of sodium acetate in deionized water at a dosage ratio of 0.03 to 0.09 g / mL, and stir at 120 to 140 r / min for 10 to 14 minutes to obtain a second solution; The first solution and the second solution are mixed in a mass ratio of 1:0.6-0.8, and treated at 192-196° C. for 12-14 min. The obtained product is washed with anhydrous ethanol and deionized water for 2-4 times, respectively, and then dried at 50-60° C. for 300-340 min, and crushed to 100-200 meshes to obtain a powder.

[0013] Furthermore, the anti-ultraviolet agent is selected from any one of ferric oxide and zinc oxide.

[0014] Furthermore, the antioxidant is selected from any one of antioxidant 1010, antioxidant 1076, and antioxidant CA.

[0015] The second aspect of the present invention: also provides a method for preparing the above self-cleaning and anti-fouling artificial exterior wall composite thermal insulation marble membrane material, comprising the following steps: Step 1, accurately weighing polyvinylidene fluoride, UV protection agent, functional additive, auxiliary additive, UV protection agent, N,N-dimethylacetamide and antioxidant, and grinding the antioxidant functional additive and auxiliary additive in a grinding mill to obtain grinding powder; Then, polyvinylidene fluoride, N,N-dimethylacetamide and ground powder are put into a mixing equipment for mixing and stirring. After being evenly mixed, they are evenly scraped on the template, and then dried at a temperature of 80-82°C to form a film. After being taken out, cooled and peeled off, a self-cleaning and anti-fouling artificial exterior wall composite insulation marble membrane product is obtained.

[0016] Compared with the prior art, the present invention has the following beneficial effects: In the present invention, polyvinylidene fluoride, functional additives, auxiliary additives, anti-ultraviolet agents, N, N-dimethylacetamide and antioxidants are used as raw materials, and the antioxidant functional additives and auxiliary additives are ground to obtain a ground powder, and then the polyvinylidene fluoride, anti-ultraviolet agents, N, N-dimethylacetamide and ground powder are put into a mixing device for mixing and stirring. After being evenly mixed, they are evenly scraped on the template, and then dried to form a film, taken out and cooled and peeled off to obtain a self-cleaning and anti-fouling artificial exterior wall composite thermal insulation marble membrane finished product. The self-cleaning and anti-fouling artificial exterior wall composite thermal insulation marble membrane prepared by the present invention not only has good thermal insulation performance, but also has excellent self-cleaning and anti-fouling performance, which effectively guarantees its quality. The self-cleaning and anti-fouling artificial exterior wall composite thermal insulation marble membrane provided by the present invention and its preparation method have a broader market prospect and are more suitable for promotion. DETAILED DESCRIPTION

[0017] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0018] Example 1: This example provides a self-cleaning and anti-fouling artificial exterior wall composite thermal insulation marble membrane material, which is composed of the following raw materials in parts by weight: 30 parts of polyvinylidene fluoride, 3 parts of functional additives, 3 parts of auxiliary additives, 2 parts of UV protection agents, 3 parts of N,N-dimethylacetamide and 2 parts of antioxidants.

[0019] In this embodiment, it should be noted that polyvinylidene fluoride was purchased from Dongguan Zhanyu Plastic Raw Materials Co., Ltd.

[0020] The preparation process of the functional additive is as follows: The aluminum silicate fiber was ultrasonically dispersed in deionized water at a solid-liquid ratio of 0.02 g / mL for 20 minutes, and then γ-glycidyloxypropyltrimethoxysilane (0.02% by weight of the aluminum silicate fiber) was added thereto, and the mixture was treated at 240 r / min and 40°C for 30 minutes. After filtration, the mixture was dried at 70°C to constant weight to obtain modified aluminum silicate fiber. An appropriate amount of the modified base was ultrasonically dispersed in an appropriate amount of deionized water at a solid-liquid ratio of 0.24 g / mL and mixed for 30 minutes. Then, 2.4% of the modified aluminum silicate fiber by mass of the modified base was added thereto, and the mixture was treated at 340 r / min for 10 minutes, and then at 100°C for 300 minutes. After filtration, the mixture was washed twice with deionized water and dried at 70°C to constant weight to obtain a functional additive.

[0021] Further, the preparation process of the modified base material is as follows: An appropriate amount of hollow ceramic microbeads was placed in an 8% acrylic acid aqueous solution at a dosage ratio of 0.8 g / mL, stirred at 120 r / min for 20 min, and then ammonium persulfate was added thereto. The mixture was stirred for 70 min under a nitrogen atmosphere at 60° C. After suction filtration, the obtained filter cake was washed twice with anhydrous ethanol and deionized water, respectively, and then dried at 70° C. to constant weight, and then placed in a muffle furnace at 550° C. for 100 min to obtain a base material. An appropriate amount of the base material was placed in deionized water at a dosage ratio of 0.02 g / mL and ultrasonically dispersed for 20 minutes. Then, 0.08% of the mass of the base material of γ-glycidyloxypropyltrimethoxysilane was added thereto, and the mixture was treated at 220 r / min and 40°C for 30 minutes. After filtration, the mixture was dried at 70°C to constant weight to obtain a modified base material.

[0022] In this embodiment, it should be noted that aluminum silicate fibers were purchased from Hebei Runhuabang New Material Technology Co., Ltd., hollow ceramic microspheres were purchased from Shijiazhuang Hualang Mineral Products Trading Co., Ltd., and acrylic acid was purchased from Sinopharm Chemical Reagent Co., Ltd.

[0023] Furthermore, the amount of ammonium persulfate added is 0.08% of the mass of the hollow ceramic microspheres.

[0024] The preparation process of the auxiliary agent is as follows: The composite material was placed in a 0.14% potassium permanganate aqueous solution at a dosage ratio of 0.04 g / mL, stirred at 220 r / min for 20 min, and then a 0.12% manganese acetate aqueous solution was added thereto, stirred for 100 min at 35°C, and then allowed to stand for 140 min; After completion, centrifuge, wash the centrifugal product twice with deionized water, and dry it in a drying oven at 50°C to constant weight to obtain an auxiliary agent; The added amount of manganese acetate aqueous solution is 0.04% of the mass of the composite material.

[0025] Furthermore, the composite material is mixed by powder and nano silicon dioxide in a mass ratio of 1:0.5.

[0026] Furthermore, the powder preparation process is as follows: An appropriate amount of aluminum nitrate nonahydrate was added to deionized water at a dosage ratio of 0.04 g / mL, and stirred at 120 r / min for 10 min to obtain a first solution; Add an appropriate amount of sodium acetate in deionized water at a dosage ratio of 0.03 g / mL, and stir at 120 r / min for 10 min to obtain a second solution; The first solution and the second solution were mixed in a mass ratio of 1:0.6, treated at 192°C for 12 min, the obtained product was washed twice with anhydrous ethanol and deionized water respectively, then dried at 50°C for 300 min, and crushed to 100 mesh to obtain a powder.

[0027] Among them, the UV protection agent is ferric oxide.

[0028] The antioxidant used is antioxidant 1010.

[0029] In this embodiment, it should be noted that the antioxidant 1010 is a commercially available product purchased from BASF (China) Co., Ltd.

[0030] In addition, this embodiment also provides a method for preparing the self-cleaning and anti-fouling artificial exterior wall composite thermal insulation marble membrane material, comprising the following steps: Step 1, accurately weighing polyvinylidene fluoride, functional additives, auxiliary additives, UV protection agent, N,N-dimethylacetamide and antioxidant, and grinding the antioxidant functional additives and auxiliary additives in a grinding mill to obtain grinding powder; Then put polyvinylidene fluoride, UV protection agent, N,N-dimethylacetamide and ground powder into a mixing equipment for mixing and stirring. After being evenly mixed, evenly apply it on the template, and then dry it at 80°C to form a film. After being taken out, cooled and peeled off, a self-cleaning and anti-fouling artificial exterior wall composite insulation marble membrane material is obtained.

[0031] Example 2: The preparation method of the self-cleaning and anti-fouling artificial exterior wall composite thermal insulation marble membrane provided in this example is basically the same as that in Example 1, except that: the specific raw material composition and the specific preparation method of the self-cleaning and anti-fouling artificial exterior wall composite thermal insulation marble membrane in this example are different; the specific raw material composition and the specific preparation method of the self-cleaning and anti-fouling artificial exterior wall composite thermal insulation marble membrane in this example are as follows: The self-cleaning and anti-fouling artificial exterior wall composite thermal insulation marble membrane material is composed of the following raw materials in parts by weight: 35 parts of polyvinylidene fluoride, 4 parts of functional additives, 4 parts of auxiliary additives, 3 parts of anti-ultraviolet agents, 4 parts of N,N-dimethylacetamide and 3 parts of antioxidants.

[0032] In this embodiment, it should be noted that polyvinylidene fluoride was purchased from Dongguan Zhanyu Plastic Raw Materials Co., Ltd.

[0033] The preparation process of the functional additive is as follows: The aluminum silicate fiber was ultrasonically dispersed in deionized water at a solid-liquid ratio of 0.04 g / mL for 25 minutes, and then γ-glycidyloxypropyltrimethoxysilane (0.06% by weight of the aluminum silicate fiber) was added thereto, and the mixture was treated at 250 r / min and 45°C for 35 minutes. After filtration, the mixture was dried at 80°C to constant weight to obtain modified aluminum silicate fiber. An appropriate amount of the modified base material was ultrasonically dispersed in an appropriate amount of deionized water at a solid-liquid ratio of 0.26 g / mL and mixed for 35 minutes. Then, 4.4% of the modified base material weight of modified aluminum silicate fiber was added thereto, and the mixture was treated at 440 r / min for 12 minutes, and then at 100-110° C. for 300-320 minutes. After filtration, the mixture was washed three times with deionized water and dried at 80° C. to constant weight to obtain a functional additive.

[0034] Further, the preparation process of the modified base material is as follows: An appropriate amount of hollow ceramic microbeads was placed in a 10% acrylic acid aqueous solution at a dosage ratio of 1 g / mL, stirred at 1270 r / min for 25 min, and then ammonium persulfate was added thereto. The mixture was stirred for 74 min under a nitrogen atmosphere at 64° C. After suction filtration, the obtained filter cake was washed three times with anhydrous ethanol and deionized water, respectively, and then dried at 80° C. to constant weight, and then placed in a muffle furnace at 560° C. for 110 min to obtain a base material. An appropriate amount of the base material was placed in deionized water at a dosage ratio of 0.07 g / mL and ultrasonically dispersed for 25 minutes. Then, 0.12% of the mass of the base material of γ-glycidyloxypropyltrimethoxysilane was added thereto, and the mixture was treated at 230 r / min and 45°C for 35 minutes. After filtration, the mixture was dried at 80°C to constant weight to obtain a modified base material.

[0035] In this embodiment, it should be noted that aluminum silicate fibers were purchased from Hebei Runhuabang New Material Technology Co., Ltd., hollow ceramic microspheres were purchased from Shijiazhuang Hualang Mineral Products Trading Co., Ltd., and acrylic acid was purchased from Sinopharm Chemical Reagent Co., Ltd.

[0036] Furthermore, the amount of ammonium persulfate added is 0.15% of the mass of the hollow ceramic microspheres.

[0037] The preparation process of the auxiliary agent is as follows: The composite material was placed in a 0.19% potassium permanganate aqueous solution at a dosage ratio of 0.08 g / mL, stirred at 230 r / min for 25 min, and then a 0.22% manganese acetate aqueous solution was added thereto, stirred for 110 min at 37°C, and then allowed to stand for 145 min; After completion, centrifuge, wash the centrifugal product three times with deionized water, and dry it in a drying oven at 55°C to constant weight to obtain an auxiliary agent; The added amount of manganese acetate aqueous solution is 0.06% of the mass of the composite material.

[0038] Furthermore, the composite material is mixed by powder and nano silicon dioxide in a mass ratio of 1:0.6.

[0039] Furthermore, the powder preparation process is as follows: An appropriate amount of aluminum nitrate nonahydrate was added to deionized water at a dosage ratio of 0.08 g / mL, and stirred at 130 r / min for 12 min to obtain a first solution; An appropriate amount of sodium acetate was added to deionized water at a dosage ratio of 0.06 g / mL, and stirred at 130 r / min for 12 min to obtain a second solution; The first solution and the second solution were mixed in a mass ratio of 1:0.7, treated at 194°C for 13 min, the obtained product was washed three times with anhydrous ethanol and deionized water respectively, then dried at 55°C for 320 min, and crushed to 150 mesh to obtain a powder.

[0040] Among them, zinc oxide is used as the UV protection agent.

[0041] Antioxidant 1076 was selected as the antioxidant.

[0042] In addition, this embodiment also provides a method for preparing the self-cleaning and anti-fouling artificial exterior wall composite thermal insulation marble membrane material, comprising the following steps: Step 1, accurately weighing polyvinylidene fluoride, functional additives, auxiliary additives, UV protection agent, N,N-dimethylacetamide and antioxidant, and grinding the antioxidant functional additives and auxiliary additives in a grinding mill to obtain grinding powder; Then put polyvinylidene fluoride, UV protection agent, N,N-dimethylacetamide and ground powder into a mixing equipment for mixing and stirring. After being evenly mixed, evenly apply it on the template, and then dry it at 81°C to form a film. After taking out, cooling and peeling, a self-cleaning and anti-fouling artificial exterior wall composite insulation marble membrane product is obtained.

[0043] Example 3: The preparation method of the self-cleaning and anti-fouling artificial exterior wall composite thermal insulation marble membrane provided in this example is basically the same as that in Example 1, except that: the specific raw material composition and the specific preparation method of the self-cleaning and anti-fouling artificial exterior wall composite thermal insulation marble membrane in this example are different; the specific raw material composition and the specific preparation method of the self-cleaning and anti-fouling artificial exterior wall composite thermal insulation marble membrane in this example are as follows: The self-cleaning and anti-fouling artificial exterior wall composite thermal insulation marble membrane material is composed of the following raw materials in parts by weight: 40 parts of polyvinylidene fluoride, 6 parts of functional additives, 5 parts of auxiliary additives, 4 parts of anti-ultraviolet agents, 6 parts of N,N-dimethylacetamide and 5 parts of antioxidants.

[0044] In this embodiment, it should be noted that polyvinylidene fluoride was purchased from Dongguan Zhanyu Plastic Raw Materials Co., Ltd.

[0045] The preparation process of the functional additive is as follows: The aluminum silicate fiber was ultrasonically dispersed in deionized water at a solid-liquid ratio of 0.06 g / mL for 30 minutes, and then γ-glycidyloxypropyltrimethoxysilane (0.08% by weight of the aluminum silicate fiber) was added thereto, and the mixture was treated at 260 r / min and 50° C. for 40 minutes. After filtration, the mixture was dried at 90° C. to constant weight to obtain modified aluminum silicate fiber. An appropriate amount of the modified base material was ultrasonically dispersed in an appropriate amount of deionized water at a solid-liquid ratio of 0.28 g / mL and mixed for 40 minutes. Then, 6.4% of the modified base material by mass of modified aluminum silicate fiber was added thereto, and the mixture was treated at 540 r / min for 15 minutes, and then at 110°C for 320 minutes. After filtration, the mixture was washed with deionized water for 4 times and dried at 90°C to constant weight to obtain a functional additive.

[0046] Further, the preparation process of the modified base material is as follows: An appropriate amount of hollow ceramic microbeads was placed in an acrylic acid aqueous solution with a concentration of 12% at a dosage ratio of 1.2 g / mL, and stirred at 220 r / min for 30 min. Ammonium persulfate was then added thereto, and the mixture was stirred for 78 min under a nitrogen atmosphere at 68° C. After suction filtration, the obtained filter cake was washed 4 times with anhydrous ethanol and deionized water, respectively, and then dried at 90° C. to constant weight, and then placed in a muffle furnace at 570° C. for 120 min to obtain a base material. An appropriate amount of the base material was placed in deionized water at a dosage ratio of 0.12 g / mL and ultrasonically dispersed for 30 minutes. Then, 0.16% of the mass of the base material of γ-glycidyloxypropyltrimethoxysilane was added thereto, and the mixture was treated at 240 r / min and 50° C. for 40 minutes. After filtration, the mixture was dried at 90° C. to constant weight to obtain a modified base material.

[0047] In this embodiment, it should be noted that aluminum silicate fibers were purchased from Hebei Runhuabang New Material Technology Co., Ltd., hollow ceramic microspheres were purchased from Shijiazhuang Hualang Mineral Products Trading Co., Ltd., and acrylic acid was purchased from Sinopharm Chemical Reagent Co., Ltd.

[0048] Furthermore, the amount of ammonium persulfate added is 0.22% of the mass of the hollow ceramic microspheres.

[0049] The preparation process of the auxiliary agent is as follows: The composite material was placed in a 0.24% potassium permanganate aqueous solution at a dosage ratio of 0.12 g / mL, stirred at 240 r / min for 30 min, and then a 0.32% manganese acetate aqueous solution was added thereto, stirred for 120 min at 40°C, and then allowed to stand for 150 min; After completion, centrifuge, wash the centrifugal product with deionized water 4 times, and dry it in a drying oven at 60°C to constant weight to obtain an auxiliary agent; The added amount of manganese acetate aqueous solution is 0.08% of the mass of the composite material.

[0050] Furthermore, the composite material is mixed by powder and nano silicon dioxide in a mass ratio of 1:0.7.

[0051] Furthermore, the powder preparation process is as follows: An appropriate amount of aluminum nitrate nonahydrate was added to deionized water at a dosage ratio of 0.12 g / mL, and stirred at 140 r / min for 14 minutes to obtain a first solution; An appropriate amount of sodium acetate was added to deionized water at a dosage ratio of 0.09 g / mL, and stirred at 140 r / min for 14 min to obtain a second solution; The first solution and the second solution were mixed in a mass ratio of 1:0.8, treated at 196°C for 14 minutes, the obtained product was washed 4 times with anhydrous ethanol and deionized water respectively, then dried at 60°C for 340 minutes, and crushed to 200 mesh to obtain a powder.

[0052] Among them, the UV protection agent is ferric oxide.

[0053] The antioxidant used is antioxidant CA.

[0054] In addition, this embodiment also provides a method for preparing the self-cleaning and anti-fouling artificial exterior wall composite thermal insulation marble membrane material, comprising the following steps: Step 1, accurately weighing polyvinylidene fluoride, functional additives, auxiliary additives, UV protection agent, N,N-dimethylacetamide and antioxidant, and grinding the antioxidant functional additives and auxiliary additives in a grinding mill to obtain grinding powder; Then put polyvinylidene fluoride, UV protection agent, N,N-dimethylacetamide and ground powder into a mixing equipment for mixing and stirring. After being evenly mixed, evenly apply it on the template, and then dry it at 82°C to form a film. After taking out, cooling and peeling it off, a self-cleaning and anti-fouling artificial exterior wall composite insulation marble membrane product is obtained.

[0055] Comparative Example 1: The difference from Example 1 is that the same amount of functional additives are used in this example.

[0056] Comparative Example 2: The difference from Example 1 is that in this example, an equal amount of hollow ceramic microspheres is used to replace the modified base material.

[0057] Comparative Example 3: The difference from Example 1 is that in this example, an equal amount of nano-silicon dioxide is used to replace the auxiliary additive.

[0058] Performance test: The self-cleaning and anti-fouling artificial exterior wall composite thermal insulation marble membrane samples provided in Examples 1 to 3 and Comparative Examples 1 to 3 are marked as Examples 1 to 3 and Comparative Examples 1 to 3, respectively; and the relevant properties of the self-cleaning and anti-fouling artificial exterior wall composite thermal insulation marble membrane provided in Examples 1 to 3 and Comparative Examples 1 to 3 are tested as follows: 1. Thermal insulation test: The test method is: use a thermal constant analyzer to test the thermal conductivity of the sample.

[0059] 2. Contact angle test: The test method is: using SDC-500 fully automatic water drop angle contact angle instrument for testing.

[0060] The obtained test data are recorded in Table 1 and Table 2 below.

[0061]

[0062]

[0063] By comparing and analyzing the relevant data in Table 1 and Table 2, it can be seen that the self-cleaning and anti-fouling artificial exterior wall composite thermal insulation marble membrane material prepared by the present invention not only has good thermal insulation performance, but also has excellent self-cleaning and anti-fouling performance, which effectively guarantees its quality. This shows that the self-cleaning and anti-fouling artificial exterior wall composite thermal insulation marble membrane material and the preparation method thereof provided by the present invention have a broader market prospect and are more suitable for promotion.

[0064] In the description of this specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0065] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to the specific implementation methods described. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. Self-cleaning and anti-fouling artificial exterior wall composite thermal insulation marble membrane material, characterized in that: The invention is composed of the following raw materials in parts by weight: 30 to 40 parts of polyvinylidene fluoride, 3 to 6 parts of functional additives, 3 to 5 parts of auxiliary additives, 2 to 4 parts of UV protection agents, 3 to 6 parts of N,N-dimethylacetamide and 2 to 5 parts of antioxidants; The preparation process of the auxiliary agent is as follows: The composite material is placed in a 0.14% to 0.24% potassium permanganate aqueous solution at a dosage ratio of 0.04 to 0.12 g / mL, stirred at 220 to 240 r / min for 20 to 30 minutes, and then a 0.12% to 0.32% manganese acetate aqueous solution is added thereto, and the mixture is stirred for 100 to 120 minutes at 35 to 40°C, and then left to stand for 140 to 150 minutes; After completion, centrifuge, wash the centrifugal product with deionized water 2 to 4 times, and dry it in a drying oven at 50 to 60° C. to constant weight to obtain an auxiliary agent; Wherein, the addition amount of the manganese acetate aqueous solution is 0.04% to 0.08% of the mass of the composite material; The composite material is prepared by mixing powder and nano silicon dioxide in a mass ratio of 1:0.5 to 0.7; The preparation process of the powder is as follows: Add an appropriate amount of aluminum nitrate nonahydrate in deionized water at a dosage ratio of 0.04 to 0.12 g / mL, and stir at 120 to 140 r / min for 10 to 14 minutes to obtain a first solution; Add an appropriate amount of sodium acetate in deionized water at a dosage ratio of 0.03 to 0.09 g / mL, and stir at 120 to 140 r / min for 10 to 14 minutes to obtain a second solution; The first solution and the second solution are mixed in a mass ratio of 1:0.6-0.8, and treated at 192-196° C. for 12-14 minutes. The obtained product is washed with anhydrous ethanol and deionized water for 2-4 times, respectively, and then dried at 50-60° C. for 300-340 minutes, and crushed to 100-200 meshes to obtain a powder; The functional additive is prepared by mixing the modified base material in deionized water once, adding the modified aluminum silicate fiber therein for secondary mixing, and then heat-insulating, filtering, washing and drying.

2. The self-cleaning and anti-fouling artificial exterior wall composite thermal insulation marble membrane material according to claim 1 is characterized in that: The preparation process of the modified aluminum silicate fiber is as follows: The aluminum silicate fiber was ultrasonically dispersed in deionized water at a solid-liquid ratio of 0.02-0.06 g / mL for 20-30 minutes, and then 0.02%-0.08% of γ-glycidyloxypropyltrimethoxysilane by weight of the aluminum silicate fiber was added thereto. The mixture was treated at 240-260 r / min and 40-50° C. for 30-40 minutes. After filtration, the mixture was dried at 70-90° C. to constant weight to obtain modified aluminum silicate fiber.

3. The self-cleaning and anti-fouling artificial exterior wall composite thermal insulation marble membrane material according to claim 1, characterized in that: The first mixing is to ultrasonically disperse an appropriate amount of modified base material in an appropriate amount of deionized water at a solid-liquid ratio of 0.24 to 0.28 g / mL and mix for 30 to 40 minutes; the added mass of the modified aluminum silicate fiber is 2.4% to 6.4% of the mass of the modified base material; the rotation speed of the second mixing is 340 to 540 r / min, and the time is 10 to 15 minutes; the condition of the heat preservation treatment is to treat at 100 to 110°C for 300 to 320 minutes.

4. The self-cleaning and anti-fouling artificial exterior wall composite thermal insulation marble membrane material according to claim 1, characterized in that: The preparation process of the modified base material is as follows: A proper amount of hollow ceramic microbeads is placed in an 8% to 12% acrylic acid aqueous solution at a dosage ratio of 0.8 to 1.2 g / mL, stirred at 120 to 220 r / min for 20 to 30 min, and then ammonium persulfate is added thereto. Stirring is continued for 70 to 78 min under a nitrogen atmosphere at 60 to 68° C. After suction filtration, the obtained filter cake is washed 2 to 4 times with anhydrous ethanol and deionized water respectively, then dried at 70 to 90° C. to constant weight, and then placed in a muffle furnace at 550 to 570° C. for 100 to 120 min to obtain a base material; An appropriate amount of the base material is placed in deionized water at a dosage ratio of 0.02 to 0.12 g / mL and ultrasonically dispersed for 20 to 30 minutes, and then 0.08% to 0.16% of the mass of the base material of γ-glycidyloxypropyltrimethoxysilane is added thereto, and the base material is treated at 220 to 240 r / min and 40 to 50° C. for 30 to 40 minutes. After filtration, the base material is dried at 70 to 90° C. to constant weight to obtain a modified base material.

5. The self-cleaning and anti-fouling artificial exterior wall composite thermal insulation marble membrane material according to claim 4, characterized in that: The amount of ammonium persulfate added is 0.08% to 0.22% of the mass of the hollow ceramic microspheres.

6. The self-cleaning and anti-fouling artificial exterior wall composite thermal insulation marble membrane material according to claim 1, characterized in that: The anti-ultraviolet agent is selected from any one of ferric oxide and zinc oxide.

7. The self-cleaning and anti-fouling artificial exterior wall composite thermal insulation marble membrane material according to claim 1, characterized in that: The antioxidant is selected from any one of antioxidant 1010, antioxidant 1076, and antioxidant CA.

8. The method for preparing the self-cleaning and anti-fouling artificial exterior wall composite thermal insulation marble membrane according to any one of claims 1 to 7, characterized in that: The following steps are involved: Step 1, accurately weighing polyvinylidene fluoride, functional additives, auxiliary additives, UV protection agent, N,N-dimethylacetamide and antioxidant, and grinding the antioxidant functional additives and auxiliary additives in a grinding mill to obtain grinding powder; Then put polyvinylidene fluoride, UV protection agent, N,N-dimethylacetamide and ground powder into a mixing equipment for mixing and stirring. After being evenly mixed, evenly apply it on the template, and then dry it at a temperature of 80-82°C to form a film. After being taken out, cooled and peeled off, a self-cleaning and anti-fouling artificial exterior wall composite insulation marble membrane product is obtained.

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