CN110053229B - Anti-haze functional waterproof roll for building and preparation method thereof - Google Patents
Anti-haze functional waterproof roll for building and preparation method thereof Download PDFInfo
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- CN110053229B CN110053229B CN201910322939.2A CN201910322939A CN110053229B CN 110053229 B CN110053229 B CN 110053229B CN 201910322939 A CN201910322939 A CN 201910322939A CN 110053229 B CN110053229 B CN 110053229B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0021—Combinations of extrusion moulding with other shaping operations combined with joining, lining or laminating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
- B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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- E—FIXED CONSTRUCTIONS
- E02—HYDRAULIC ENGINEERING; FOUNDATIONS; SOIL SHIFTING
- E02D—FOUNDATIONS; EXCAVATIONS; EMBANKMENTS; UNDERGROUND OR UNDERWATER STRUCTURES
- E02D31/00—Protective arrangements for foundations or foundation structures; Ground foundation measures for protecting the soil or the subsoil water, e.g. preventing or counteracting oil pollution
- E02D31/002—Ground foundation measures for protecting the soil or subsoil water, e.g. preventing or counteracting oil pollution
- E02D31/006—Sealing of existing landfills, e.g. using mining techniques
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- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
- E04B1/00—Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
- E04B1/62—Insulation or other protection; Elements or use of specified material therefor
- E04B1/66—Sealings
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- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04D—ROOF COVERINGS; SKY-LIGHTS; GUTTERS; ROOF-WORKING TOOLS
- E04D5/00—Roof covering by making use of flexible material, e.g. supplied in roll form
- E04D5/10—Roof covering by making use of flexible material, e.g. supplied in roll form by making use of compounded or laminated materials, e.g. metal foils or plastic films coated with bitumen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention belongs to the technical field of anti-haze building materials, and provides a waterproof roll with an anti-haze function for buildings and a preparation method thereof. The method comprises the steps of preparing coil layer raw materials from PVC resin, a plasticizer DOP, a calcium-zinc heat stabilizer, epoxidized soybean oil, calcium carbonate filler, an antioxidant and a light stabilizer, preparing the haze-resistant raw materials from an ethylene-propylene-octene copolymer, three-dimensional nano zinc oxide/molybdenum disulfide particles, the antioxidant and the light stabilizer, and preparing the haze-resistant functional waterproof coil for the building by adopting a double-layer co-extrusion process. Compared with the traditional method, the prepared waterproof coiled material has the advantages that the three-dimensional nano zinc oxide/molybdenum disulfide composite material is added into the composite coiled material, so that the waterproof coiled material is endowed with an excellent anti-haze effect, the preparation process is simple, the construction is convenient, and the large-area haze removal can be easily realized.
Description
Technical Field
The invention belongs to the technical field of anti-haze building materials, and provides a waterproof roll with an anti-haze function for buildings and a preparation method thereof.
Background
With the continuous increase of national economy and the continuous improvement of the living standard of people in China, environmental protection becomes a main melody for people to pursue healthy and green life. With the higher requirements of people on the indoor and outdoor decoration coatings, more people pay more attention to the haze-resistant environment-friendly coatings in the process of selecting the functional coatings, and more people pursue 'fresh air close to nature and in the shape of a forest', so that the research and development of the coatings with the haze-resistant effect are of great significance.
In recent years, the problems of haze pollution and indoor air quality are becoming more serious, and volatile organic pollutants are also widely concerned by people as one of main pollution sources of haze and indoor air pollution. The application of the building material with the haze-resistant function becomes an important content, for example, the photocatalysis technology is used for producing the building material to obtain the building material capable of resisting haze, at present, common building coatings and the like mainly exist, but the building coatings are special in production process and high in cost, and have the defect of difficult construction.
The waterproof coiled material is mainly used for building walls, roofs, tunnels, highways, refuse landfills and the like, can be curled into a roll-shaped flexible building material product for resisting external rainwater and underground water leakage, is used as a leakage-free connection between an engineering foundation and a building, is a waterproof first barrier of the whole engineering, and plays a vital role in the whole engineering. The waterproof coiled material has an important position in projects such as buildings, underground projects, water storage pools and the like, and various high polymer coiled materials are developed quickly along with the development of scientific technology. Therefore, can combine anti haze function and waterproofing membrane, realize the purpose of anti haze.
At present, the anti-haze technology at home and abroad, in particular to the anti-haze building material, has achieved certain effect. Wherein Schlieiver et al have invented an environment-friendly photocatalytic exterior wall coating and its preparation method (Chinese patent application No. 200310109272.7), the invention adopts inorganic/organic composite emulsion as film-forming material, and uses photocatalyst TiO as film-forming material2Dispersing the functional filler in the paint in the form of functional filler, and adding auxiliary agents and other functional additives to prepare the normal-temperature-cured water-based environment-friendly paint. In addition, Wangshei invented a photocatalytic haze sand resistant wall-shaped anion coating (Chinese patent application No. 201610741103.2), which comprises the following raw materials in parts by weight: 15-60 parts of a haze-resistant base material, 10-70 parts of a particle aggregate and 10-30 parts of a binder; the anti-haze base material can eliminate smoke dust, oil dust, sand dust and the like in haze, and increase negative ions in air.
It is thus clear that building materials such as architectural coatings with anti haze effect among the prior art have the construction difficulty when removing the haze by a large scale, and anti haze effect is not good shortcoming.
Disclosure of Invention
Aiming at the situation, the anti-haze waterproof roll for the building and the preparation method are provided, the waterproof roll can have an excellent anti-haze effect, the preparation process is simple, the construction is convenient, and the large-area haze removal effect can be easily realized.
In order to achieve the purpose, the invention relates to the following specific technical scheme:
a preparation method of a haze-resistant functional waterproof roll for buildings comprises the steps of preparing roll layer raw materials from PVC resin, a plasticizer DOP, a calcium-zinc heat stabilizer, epoxidized soybean oil, calcium carbonate filler, an antioxidant and a light stabilizer, preparing haze-resistant raw materials from an ethylene-propylene-octene copolymer, three-dimensional nano zinc oxide/molybdenum disulfide particles, the antioxidant and the light stabilizer, adding the roll layer raw materials and the haze-resistant raw materials into a co-extruder, and preparing the haze-resistant functional waterproof roll for buildings by adopting a double-layer co-extrusion process, wherein the preparation method comprises the following specific steps:
(1) cleaning and intercalating molybdenum disulfide nanosheets, then soaking the molybdenum disulfide nanosheets in a zinc acetate dihydrate/methanol solution, uniformly dispersing, then sealing and placing the molybdenum disulfide nanosheets in a constant-temperature oven at 60-70 ℃ for heat preservation treatment for 24-48 h, filtering and taking out reaction products, heating the reaction products to 450-500 ℃, and carrying out constant-temperature annealing treatment for 1-2 h to prepare molybdenum disulfide with a zinc oxide seed layer formed on the surface;
(2) adding zinc acetate dihydrate and hexamethylenetetramine into distilled water to prepare a growth solution, dispersing molybdenum disulfide which is prepared in the step (1) and has a zinc oxide seed layer formed on the surface into the growth solution, heating to 80-90 ℃, reacting at a constant temperature for 1-14 h to enable a zinc oxide nano structure to grow on the surface of the molybdenum disulfide, centrifuging a product after the reaction is finished, cleaning for 3-5 times by using deionized water, removing redundant zinc salt on the surface, drying in vacuum, and finally grinding to obtain three-dimensional nano zinc oxide/molybdenum disulfide particles with the particle size of 5-15 mu m;
(3) mixing PVC resin, a plasticizer DOP, a calcium-zinc heat stabilizer, epoxidized soybean oil, filler calcium carbonate, an antioxidant and a light stabilizer, putting the mixture into a kneading machine, heating the mixture to 100-130 ℃, kneading the mixture for 8-15 min, and putting the kneaded mixture into a main extruder for extruding a coil layer; simultaneously mixing the ethylene-propylene-octene copolymer, the three-dimensional nano zinc oxide/molybdenum disulfide particles prepared in the step (2), an antioxidant and a light stabilizer uniformly, and adding the mixture into a secondary extruder for extruding the haze-resistant layer; preparing a waterproof roll with a haze-resistant layer on the surface by adopting a double-layer co-extrusion process, and finally performing three-roller hot press molding to weld and compound the haze-resistant layer on the surface and the roll layer to obtain the haze-resistant functional waterproof roll for buildings.
In the step (1), the molybdenum disulfide nanosheets are sequentially cleaned by absolute ethyl alcohol and acetone, and ultrasonic assistance is matched, so that the cleaning effect is good, the intercalation pretreatment can be realized by utilizing the ultrasonic assistance, and after the molybdenum disulfide nanosheets are immersed in a zinc acetate dihydrate/methanol solution, a seed layer can be formed on the surface of the molybdenum disulfide, so that a foundation is laid for the subsequent construction of a three-dimensional nano zinc oxide structure on the surface of the molybdenum disulfide. Preferably, the cleaning process comprises firstly ultrasonically cleaning the glass substrate for 5-10 min by using absolute ethyl alcohol and then cleaning the glass substrate for 5-10 min by using acetone; the weight parts of the raw materials are 30-40 parts of molybdenum disulfide nanosheets and 60-70 parts of zinc acetate dihydrate/methanol solution; the zinc acetate dihydrate/methanol solution contains 15-20 parts by weight of zinc acetate dihydrate and the balance of methanol.
Zinc acetate dihydrate and hexamethylenetetramine are used as raw materials in the step (2), a zinc oxide columnar array can be prepared by a mild hydrothermal reaction method by controlling the raw material proportion and the reaction temperature, and a three-dimensional nano zinc oxide structure is constructed by epitaxial growth on the surface of molybdenum disulfide of a formed zinc oxide seed layer, SO that the specific surface area and the catalytic activity of the composite photocatalyst are greatly improved, and the nitrogen oxide and SO are degraded by photocatalysis2VOC, or other aerosol precursors, e.g. suppression of SO2 Conversion to H2SO4And the VOC is converted into oxidation type organic matters, so that the basis of the formation of particulate matters including PM2.5 is removed. Preferably, the raw materials comprise, by weight, 8-12 parts of zinc acetate dihydrate, 5-8 parts of hexamethylenetetramine, 40-57 parts of distilled water and 30-40 parts of molybdenum disulfide with a zinc oxide seed layer formed on the surface.
Step (3) a double-layer co-extrusion process is adopted, and a composite layer with the anti-haze effect is obtained on the surface of the PVC waterproof roll through co-extrusion; the antioxidant is selected from phenol antioxidants, and can prevent or inhibit chain initiation reaction and chain growth reaction by capturing peroxy radicals, so that the free radical chain reaction is stopped, the purpose of preventing oxidation is achieved, and the antioxidant has good promotion effect on the performance of the waterproof coiled material; the light stabilizer is selected from hindered amine light stabilizers which have the capabilities of decomposing hydroperoxide, quenching excited oxygen, capturing free radicals, recycling and 4 self-synergistic functions, and the hindered amine light stabilizers are not only high-efficiency light stabilizers but also high-efficiency antioxidants. Preferably, the calcium-zinc heat stabilizer is one of calcium-zinc heat stabilizer CZ-1, calcium-zinc heat stabilizer CZ-2 and calcium-zinc heat stabilizer CZ-3, the antioxidant is at least one of hydroquinone, thiobisphenol and 2, 6-di-tert-butyl-p-cresol, and the light stabilizer is at least one of light stabilizer 770, light stabilizer 622, light stabilizer 944 and light stabilizer 783;
the coil layer comprises, by weight, 63-77 parts of PVC resin, 2-4 parts of plasticizer DOP, 1-2 parts of calcium-zinc heat stabilizer, 8-12 parts of epoxidized soybean oil, 10-15 parts of calcium carbonate, 1-2 parts of antioxidant and 1-2 parts of light stabilizer;
the haze-resistant layer comprises 61-78 parts by weight of an ethylene-propylene-octene copolymer, 20-35 parts by weight of three-dimensional nano zinc oxide/molybdenum disulfide particles, 1-2 parts by weight of an antioxidant and 1-2 parts by weight of a light stabilizer;
in the double-layer extrusion process, the extrusion temperature is 150-180 ℃, and the rotating speed of an extruder is 300-400 r/min; the three-roller hot press molding temperature is 140-160 ℃, the linear pressure is 5-10 MPa, the hot press speed is 500-600 mm/min, the thickness of the coil layer of the molded waterproof roll is 0.8-2 mm, and the thickness of the haze-preventing layer is 0.4-1 mm.
The invention also provides the anti-haze waterproof roll for the building, which is prepared by the preparation method. The haze-resistant functional waterproof roll is prepared by a double-layer co-extrusion process, wherein the roll layer raw material consists of PVC resin, a plasticizer DOP, a calcium-zinc heat stabilizer, epoxidized soybean oil, filler calcium carbonate, an antioxidant and a light stabilizer, and the haze-resistant layer raw material consists of an ethylene-propylene-octene copolymer, three-dimensional nano zinc oxide/molybdenum disulfide particles, the antioxidant and the light stabilizer. Not only has good anti haze function, but also is simple to prepare and construct.
The invention provides a haze-resistant waterproof coiled material for buildings and a preparation method thereof, and compared with the prior art, the haze-resistant waterproof coiled material has the outstanding characteristics and excellent effects that:
1. the waterproof coiled material prepared by the invention has an excellent anti-haze effect.
2. According to the preparation method, the three-dimensional nano zinc oxide/molybdenum disulfide composite material is added into the composite coiled material, so that the specific surface area and the catalytic activity of the composite material are greatly improved, and the aim of efficiently catalyzing and degrading harmful gases in haze is fulfilled.
3. The preparation method disclosed by the invention is simple in preparation process, convenient to construct and capable of easily realizing large-area haze removal.
4. Through tests, the 2h catalytic degradation rate of the prepared waterproof roll with the haze-resistant function for buildings is 96-98% for nitrogen oxides in haze, and the 2h catalytic degradation rate of the waterproof roll with the haze-resistant function for SO in haze is 96-98% for SO in haze2The 2h catalytic degradation rate is 96-98%, and the 2h catalytic degradation rate of VOC in haze is 94-97%.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Example 1
Ultrasonically cleaning 34kg of molybdenum disulfide nanosheets with absolute ethyl alcohol for 7min, cleaning with acetone for 7min, then soaking in a solution of 17kg of zinc acetate dihydrate and 49kg of methanol, uniformly dispersing, sealing, placing in a constant-temperature oven at 66 ℃ for heat preservation for 35h, filtering reaction products, taking out, heating to 470 ℃, and carrying out constant-temperature annealing for 1.5h to obtain molybdenum disulfide with a zinc oxide seed layer formed on the surface; adding 9kg of zinc acetate dihydrate and 7kg of hexamethylenetetramine into 50kg of distilled water to prepare a growth solution, dispersing 34kg of molybdenum disulfide with a zinc oxide seed layer formed on the surface into the growth solution, heating to 86 ℃, reacting at constant temperature for 7 hours to enable a zinc oxide nano structure to grow on the surface of the molybdenum disulfide, centrifuging a product after the reaction is finished, cleaning for 4 times by using deionized water to remove redundant zinc salt on the surface, drying in vacuum, and finally grinding to obtain three-dimensional nano zinc oxide/molybdenum disulfide particles with the particle size of 10 mu m; then 71kg of PVC resin, 3kg of plasticizer DOP, 1kg of calcium-zinc heat stabilizer CZ-1, 10kg of epoxidized soybean oil, 12kg of filler calcium carbonate, 2kg of hydroquinone and 1kg of light stabilizer 770 are mixed and put into a kneader, the mixture is heated to 108 ℃ and kneaded for 11min, and the kneaded mixture is put into a main extruder for extruding a coil layer; simultaneously, 70kg of ethylene-propylene-octene copolymer, 27kg of three-dimensional nano zinc oxide/molybdenum disulfide particles, 1kg of hydroquinone and 2kg of light stabilizer 770 are uniformly mixed and then added into a secondary extruder for extruding the haze-resistant layer, wherein the extrusion temperature is 170 ℃, and the rotation speed of the extruder is 360 r/min; preparing a waterproof roll with a haze-resistant layer on the surface by adopting a double-layer co-extrusion process, and finally carrying out three-roller hot press molding at the temperature of 150 ℃, the linear pressure of 7MPa and the hot press speed of 560mm/min to obtain a waterproof roll with the haze-resistant layer for buildings, wherein the thickness of the roll layer of the molded waterproof roll is 1.2mm, and the thickness of the haze-resistant layer is 0.8 mm.
Example 2
Ultrasonically cleaning 33kg of molybdenum disulfide nanosheets with absolute ethyl alcohol for 6min, cleaning with acetone for 9min, then soaking in a solution of 16kg of zinc acetate dihydrate and 51kg of methanol, uniformly dispersing, sealing, placing in a constant-temperature oven at 62 ℃ for heat preservation treatment for 44h, filtering reaction products, taking out, heating to 460 ℃, and carrying out constant-temperature annealing treatment for 2h to obtain molybdenum disulfide with a zinc oxide seed layer formed on the surface; adding 9kg of zinc acetate dihydrate and 6kg of hexamethylenetetramine into 52kg of distilled water to prepare a growth solution, dispersing 33kg of molybdenum disulfide with a seed layer formed on the surface into the growth solution, heating to 82 ℃, reacting at a constant temperature for 12 hours to enable a zinc oxide nano structure to grow on the surface of the molybdenum disulfide, centrifuging a product after the reaction is finished, cleaning for 3 times by using deionized water to remove redundant zinc salt on the surface, drying in vacuum, and finally grinding to obtain three-dimensional nano zinc oxide/molybdenum disulfide particles with the particle size of 8 mu m; then 73kg of PVC resin, 2kg of plasticizer DOP, 2kg of calcium-zinc heat stabilizer CZ-2, 9kg of epoxidized soybean oil, 12kg of filler calcium carbonate, 1kg of thiobisphenol and 1kg of light stabilizer 622 are mixed and put into a kneader, the mixture is heated to 110 ℃ and kneaded for 12min, and the kneaded mixture is put into a main extruder for extruding a coil layer; simultaneously, 74kg of ethylene-propylene-octene copolymer, 24kg of three-dimensional nano zinc oxide/molybdenum disulfide particles, 1kg of thiobisphenol and 1kg of light stabilizer 622 are uniformly mixed and then added into a sub-extruder for extruding the haze resistant layer, wherein the extrusion temperature is 160 ℃, and the rotation speed of the extruder is 320 r/min; preparing a waterproof roll with a haze-resistant layer on the surface by adopting a double-layer co-extrusion process, and finally performing three-roller hot press molding at the temperature of 145 ℃, the linear pressure of 6MPa and the hot press speed of 520mm/min to obtain a waterproof roll with the haze-resistant layer thickness of 1mm and the haze-resistant layer thickness of 0.5mm, thereby obtaining the haze-resistant functional waterproof roll for buildings.
Example 3
Ultrasonically cleaning 38kg of molybdenum disulfide nanosheets with absolute ethyl alcohol for 9min, cleaning with acetone for 6min, then soaking in a solution of 18kg of zinc acetate dihydrate and 44kg of methanol, uniformly dispersing, sealing, placing in a constant-temperature oven at 68 ℃ for heat preservation treatment for 30h, filtering reaction products, taking out, heating to 480 ℃, and carrying out constant-temperature annealing treatment for 1h to obtain molybdenum disulfide with a zinc oxide seed layer formed on the surface; adding 11kg of zinc acetate dihydrate and 7kg of hexamethylenetetramine into 45kg of distilled water to prepare a growth solution, dispersing 37kg of molybdenum disulfide with a seed layer formed on the surface into the growth solution, heating to 88 ℃, reacting at a constant temperature for 3 hours to enable a zinc oxide nano structure to grow on the surface of the molybdenum disulfide, centrifuging a product after the reaction is finished, cleaning for 5 times by using deionized water to remove redundant zinc salt on the surface, drying in vacuum, and finally grinding to obtain three-dimensional nano zinc oxide/molybdenum disulfide particles with the particle size of 12 mu m; then 66kg of PVC resin, 3kg of plasticizer DOP, 2kg of calcium-zinc heat stabilizer CZ-3, 11kg of epoxidized soybean oil, 14kg of filler calcium carbonate, 2kg of 2, 6-di-tert-butyl-p-cresol and 2kg of light stabilizer 944 are mixed and put into a kneader, the mixture is heated to 120 ℃ and kneaded for 10min, and the kneaded mixture is put into a main extruder for extruding a coil layer; simultaneously, 66kg of ethylene-propylene-octene copolymer, 30kg of three-dimensional nano zinc oxide/molybdenum disulfide particles, 2kg of p-2, 6-di-tert-butyl-p-cresol and 2kg of light stabilizer 944 are uniformly mixed and then added into a sub-extruder for extruding the haze-resistant layer, wherein the extrusion temperature is 170 ℃, and the rotation speed of the extruder is 380 r/min; preparing a waterproof roll with a haze-resistant layer on the surface by adopting a double-layer co-extrusion process, and finally carrying out three-roller hot press molding at the temperature of 155 ℃, the linear pressure of 8MPa and the hot press speed of 580mm/min to obtain a waterproof roll with the haze-resistant layer for buildings, wherein the thickness of the roll layer of the molded waterproof roll is 1.0mm, and the thickness of the haze-resistant layer is 0.8 mm.
Example 4
Ultrasonically cleaning 30kg of molybdenum disulfide nanosheets with absolute ethyl alcohol for 5min, cleaning with acetone for 5min, then soaking in a solution of 15kg of zinc acetate dihydrate and 55kg of methanol, uniformly dispersing, sealing, placing in a constant-temperature oven at 60 ℃ for heat preservation treatment for 48h, filtering reaction products, taking out, heating to 450 ℃, and carrying out constant-temperature annealing treatment for 2h to obtain molybdenum disulfide with a zinc oxide seed layer formed on the surface; adding 8kg of zinc acetate dihydrate and 8kg of hexamethylenetetramine into 57kg of distilled water to prepare a growth solution, dispersing 30kg of molybdenum disulfide with a seed layer formed on the surface in the growth solution, heating to 80 ℃, reacting at a constant temperature for 14h to enable a zinc oxide nano structure to grow on the surface of the molybdenum disulfide, centrifuging a product after the reaction is finished, cleaning for 3 times by using deionized water to remove redundant zinc salt on the surface, drying in vacuum, and finally grinding to obtain three-dimensional nano zinc oxide/molybdenum disulfide particles with the particle size of 5 mu m; then 77kg of PVC resin, 2kg of plasticizer DOP, 1kg of calcium-zinc heat stabilizer CZ-1, 8kg of epoxidized soybean oil, 10kg of filler calcium carbonate, kg of hydroquinone and 1kg of light stabilizer 783 are mixed and put into a kneader, the mixture is heated to 100 ℃ and kneaded for 15min, and the kneaded mixture is put into a main extruder for extruding a coil layer; simultaneously, 78kg of ethylene-propylene-octene copolymer, 20kg of three-dimensional nano zinc oxide/molybdenum disulfide particles, 1kg of hydroquinone and 1kg of light stabilizer 783 are uniformly mixed and then added into a sub-extruder for extruding the haze-resistant layer, wherein the extrusion temperature is 150 ℃, and the rotation speed of the extruder is 400 r/min; preparing a waterproof roll with a haze-resistant layer on the surface by adopting a double-layer co-extrusion process, and finally performing three-roller hot press molding at the temperature of 140 ℃, the linear pressure of 5MPa and the hot press speed of 500mm/min to obtain a waterproof roll with the haze-resistant layer thickness of 0.8mm and the haze-resistant layer thickness of 0.4mm, thereby obtaining the haze-resistant waterproof roll for buildings.
Example 5
Ultrasonically cleaning 40kg of molybdenum disulfide nanosheets with absolute ethyl alcohol for 10min, cleaning with acetone for 10min, then soaking in a solution of 20kg of zinc acetate dihydrate and 40kg of methanol, uniformly dispersing, sealing, placing in a constant-temperature oven at 70 ℃, carrying out heat preservation treatment for 24h, filtering reaction products, taking out, heating to 500 ℃, and carrying out constant-temperature annealing treatment for 1h to obtain molybdenum disulfide with a zinc oxide seed layer formed on the surface; then adding 12kg of zinc acetate dihydrate and 8kg of hexamethylenetetramine into 40kg of distilled water to prepare a growth solution, then dispersing 40kg of molybdenum disulfide with a seed layer formed on the surface into the growth solution, heating to 90 ℃, reacting at constant temperature for 1h to enable a zinc oxide nano structure to grow on the surface of the molybdenum disulfide, centrifuging the product after the reaction is finished, cleaning for 5 times by using deionized water to remove redundant zinc salt on the surface, drying in vacuum, and finally grinding to obtain three-dimensional nano zinc oxide/molybdenum disulfide particles with the particle size of 15 mu m; then 63kg of PVC resin, 4kg of plasticizer DOP, 2kg of calcium-zinc heat stabilizer CZ-2, 12kg of epoxidized soybean oil, 15kg of filler calcium carbonate, 2kg of thiobisphenol and 2kg of light stabilizer 770 are mixed and put into a kneader, the mixture is heated to 130 ℃ and kneaded for 8min, and the kneaded mixture is put into a main extruder for extruding a coil layer; simultaneously, 61kg of ethylene-propylene-octene copolymer, 35kg of three-dimensional nano zinc oxide/molybdenum disulfide particles, 2kg of 2, 6-di-tert-butyl-p-cresol and 2kg of light stabilizer 783 are uniformly mixed and then added into a sub-extruder for extruding the haze-resistant layer, wherein the extrusion temperature is 180 ℃, and the rotation speed of the extruder is 400 r/min; preparing a waterproof roll with a haze-resistant layer on the surface by adopting a double-layer co-extrusion process, and finally carrying out three-roller hot press molding at the temperature of 160 ℃, the linear pressure of 0MPa and the hot press speed of 600mm/min to obtain a waterproof roll with the haze-resistant layer for buildings, wherein the thickness of the roll layer of the molded waterproof roll is 1.2mm, and the thickness of the haze-resistant layer is 0.2 mm.
Comparative example 1
In the preparation process of the waterproof roll, the nano zinc oxide is directly added, no molybdenum disulfide carrier is used, and other preparation conditions are consistent with those of the embodiment 5.
The test method comprises the following steps:
cutting the waterproof coiled material into 15cm × 15cm samples, and placing in 1m3The haze test system is characterized in that a test box is used for testing, a 30W UVA ultraviolet lamp is arranged in a reaction chamber, haze is introduced, and nitrogen oxide and SO are utilized2And a TVOC test instrument respectively tests nitrogen oxide and SO2Initial concentration C of TVOC test instrument0The initial concentration is controlled at 10mg/m3About, the test concentration after 2h is C1And calculating the 2h photocatalytic degradation rate: ω = (C)0 -C1）/ C0。
The data obtained are shown in Table 1.
Table 1:
Claims (9)
1. a preparation method of a haze-resistant functional waterproof roll for buildings is characterized in that roll layer raw materials are composed of PVC resin, a plasticizer DOP, a calcium-zinc heat stabilizer, epoxidized soybean oil, filler calcium carbonate, an antioxidant and a light stabilizer, haze-resistant layer raw materials are composed of an ethylene-propylene-octene copolymer, three-dimensional nano zinc oxide/molybdenum disulfide particles, the antioxidant and the light stabilizer, the roll layer raw materials and the haze-resistant layer raw materials are added into a co-extruder, and a double-layer co-extrusion process is adopted to prepare the haze-resistant functional waterproof roll for buildings, wherein the preparation method comprises the following specific steps:
(1) cleaning and intercalating molybdenum disulfide nanosheets, then soaking the molybdenum disulfide nanosheets in a zinc acetate dihydrate/methanol solution, uniformly dispersing, then sealing and placing the molybdenum disulfide nanosheets in a constant-temperature oven at 60-70 ℃ for heat preservation treatment for 24-48 h, filtering and taking out reaction products, heating the reaction products to 450-500 ℃, and carrying out constant-temperature annealing treatment for 1-2 h to prepare molybdenum disulfide with a zinc oxide seed layer formed on the surface;
(2) adding zinc acetate dihydrate and hexamethylenetetramine into distilled water to prepare a growth solution, dispersing molybdenum disulfide which is prepared in the step (1) and has a zinc oxide seed layer formed on the surface into the growth solution, heating to 80-90 ℃, reacting at a constant temperature for 1-14 h to enable a zinc oxide nano structure to grow on the surface of the molybdenum disulfide, centrifuging a product after the reaction is finished, cleaning for 3-5 times by using deionized water, removing redundant zinc salt on the surface, drying in vacuum, and finally grinding to obtain three-dimensional nano zinc oxide/molybdenum disulfide particles with the particle size of 5-15 mu m; the weight parts of the raw materials are as follows: 8-12 parts of zinc acetate dihydrate, 5-8 parts of hexamethylenetetramine, 40-57 parts of distilled water and 30-40 parts of molybdenum disulfide with a zinc oxide seed layer formed on the surface;
(3) mixing PVC resin, a plasticizer DOP, a calcium-zinc heat stabilizer, epoxidized soybean oil, filler calcium carbonate, an antioxidant and a light stabilizer, putting the mixture into a kneading machine, heating the mixture to 100-130 ℃, kneading the mixture for 8-15 min, and putting the kneaded mixture into a main extruder for extruding a coil layer; simultaneously mixing the ethylene-propylene-octene copolymer, the three-dimensional nano zinc oxide/molybdenum disulfide particles prepared in the step (2), an antioxidant and a light stabilizer uniformly, and adding the mixture into a secondary extruder for extruding the haze-resistant layer; preparing a waterproof roll with a haze-resistant layer on the surface by adopting a double-layer co-extrusion process, and finally performing three-roller hot press molding to weld and compound the haze-resistant layer on the surface and the roll layer to obtain the haze-resistant functional waterproof roll for buildings.
2. The preparation method of the anti-haze functional waterproof roll for the building as claimed in claim 1, wherein the preparation method comprises the following steps: and (2) the cleaning process in the step (1) is that firstly absolute ethyl alcohol is used for ultrasonic cleaning for 5-10 min, and then acetone is used for cleaning for 5-10 min.
3. The preparation method of the anti-haze functional waterproof roll for the building as claimed in claim 1, wherein the preparation method comprises the following steps: the weight parts of the raw materials in the step (1) are 30-40 parts of molybdenum disulfide nanosheets and 60-70 parts of zinc acetate dihydrate/methanol solution; the zinc acetate dihydrate/methanol solution contains 15-20 parts by weight of zinc acetate dihydrate and the balance of methanol.
4. The preparation method of the anti-haze functional waterproof roll for the building as claimed in claim 1, wherein the preparation method comprises the following steps: the calcium-zinc heat stabilizer in the step (3) is one of calcium-zinc heat stabilizer CZ-1, calcium-zinc heat stabilizer CZ-2 and calcium-zinc heat stabilizer CZ-3, the antioxidant is at least one of hydroquinone, thiobisphenol and 2, 6-di-tert-butyl-p-cresol, and the light stabilizer is at least one of light stabilizer 770, light stabilizer 622, light stabilizer 944 and light stabilizer 783.
5. The preparation method of the anti-haze functional waterproof roll for the building as claimed in claim 1, wherein the preparation method comprises the following steps: the coil layer in the step (3) comprises, by weight, 63-77 parts of PVC resin, 2-4 parts of plasticizer DOP, 1-2 parts of calcium-zinc heat stabilizer, 8-12 parts of epoxidized soybean oil, 10-15 parts of calcium carbonate, 1-2 parts of antioxidant and 1-2 parts of light stabilizer.
6. The preparation method of the anti-haze functional waterproof roll for the building as claimed in claim 1, wherein the preparation method comprises the following steps: the haze-resistant layer is prepared from 61-78 parts by weight of an ethylene-propylene-octene copolymer, 20-35 parts by weight of three-dimensional nano zinc oxide/molybdenum disulfide particles, 1-2 parts by weight of an antioxidant, and 1-2 parts by weight of a light stabilizer.
7. The preparation method of the anti-haze functional waterproof roll for the building as claimed in claim 1, wherein the preparation method comprises the following steps: and (3) in the double-layer extrusion process, the extrusion temperature is 150-180 ℃, and the rotating speed of an extruder is 300-400 r/min.
8. The preparation method of the anti-haze functional waterproof roll for the building as claimed in claim 1, wherein the preparation method comprises the following steps: the three-roller hot press molding temperature in the step (3) is 140-160 ℃, the linear pressure is 5-10 MPa, the hot press speed is 500-600 mm/min, the thickness of the coil layer of the molded waterproof roll is 0.8-2 mm, and the thickness of the haze-preventing layer is 0.4-1 mm.
9. The anti-haze functional waterproof roll for buildings, which is prepared by the preparation method of any one of claims 1 to 8.
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