CN110053229A - One kind anti-fog haze function waterproof roll for building and preparation method - Google Patents
One kind anti-fog haze function waterproof roll for building and preparation method Download PDFInfo
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- CN110053229A CN110053229A CN201910322939.2A CN201910322939A CN110053229A CN 110053229 A CN110053229 A CN 110053229A CN 201910322939 A CN201910322939 A CN 201910322939A CN 110053229 A CN110053229 A CN 110053229A
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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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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 fields of anti-haze construction material, provide one kind anti-fog haze function waterproof roll for building and preparation method.This method forms coiled material layer raw material by polyvinyl chloride resin, plasticizer DOP, calcium zinc heat stabilizer, epoxidized soybean oil, filler-calcium carbonate, antioxidant, light stabilizer, anti- haze layer raw material is formed by ethylene-propylene-octene copolymer, three-dimensional manometer zinc oxide/molybdenum disulfide particles, antioxidant, light stabilizer, anti-fog haze function waterproof roll for building is made using double-layer coextrusion technique.It is compared with the traditional method, the waterproof roll of preparation of the invention, by adding three-dimensional manometer zinc oxide/molybdenum disulfide composite material in composite sheet material, impart the excellent anti-fog haze effect of waterproof roll, and preparation process is simple, and easy for construction, and can realize large area easily removes haze.
Description
Technical field
The invention belongs to the technical field of anti-haze construction material, provide a kind of anti-fog haze function waterproof roll for building and
Preparation method.
Background technique
With Chinese national economy sustainable growth and the continuous improvement of living standards of the people, environmental protection has become a kind of people and chases after
Seek the theme of healthy green living.And as coating requirement of the people to indoor exterior decoration is higher and higher, more people are selecting
During selecting functional coating, anti-fog haze environment-friendly type coating is considered emphatically, more and more people, which pursue, " gets close to nature, big gloomy
Fresh air as woods ", therefore, researching and developing, there is the coating of anti-fog haze effect to have great importance.
In recent years, haze pollution and indoor air quality issues were increasingly serious, and volatile organic contaminant is as haze
With one of the primary pollution source of room atmosphere pollution, the extensive concern of people is also therefore received.And for anti-haze effect
Construction material application become an important content, photocatalysis technology is such as used for the production of construction material, obtaining can anti-haze
Construction material, it is common at present mainly to have building coating etc., but building coating production technology is special, it is expensive, exist and apply
The defect of work difficulty.
Waterproof roll is mainly used for construction wall, roofing and tunnel, highway, refuse landfill etc., plays and resists
The rollable flexible building material product at web-like of one kind of extraneous rainwater, underground water leakage, as between engineering foundation and building
Ne-leakage connection, is the first barrier of entire engineering waterproofing, plays a crucial role to entire engineering.Waterproof roll exists
There is critically important status in the engineerings such as building, underground engineering, tank, with the development of science and technology, various macromolecule coiled materials
Develop also quickly.Therefore, anti-haze function can be combined with waterproof roll, realizes the purpose of anti-fog haze.
Certain effect has been achieved in terms of anti-fog haze technology, especially anti-fog haze construction material both at home and abroad at present.Wherein
Shi Liyi et al. has invented a kind of environment-friendly type photocatalystic outer wall coating and preparation method thereof (Chinese invention patent application number
200310109272.7), the invention is using inorganic/organic composite emulsion as film forming matter, by photochemical catalyst TiO2With function
The form of energy filler is dispersed therein, then is aided with auxiliary agent and other functional additives, prepares a kind of aqueous ring of normal temperature cure
Friendly coating.In addition, Wang Zhifei has invented a kind of anti-fog haze sand wall-like negative ion paint (Chinese invention patent application number of photocatalysis
201610741103.2), including following raw material: anti-15 ~ 60 parts by weight of haze basestocks, 10 ~ 70 parts by weight of granulated aggregate
With 10 ~ 30 parts by weight of binder；Anti- haze basestocks can eliminate the flue dust in haze, oily dirt, and sand dust etc. increases negative in air
Ion.
As it can be seen that the construction materials such as building coating in the prior art with anti-fog haze effect, remove haze carrying out large area
When, there are constructional difficulties, the disadvantages of anti-haze is ineffective.
Summary of the invention
In response to this, it is proposed that a kind of anti-fog haze function waterproof roll for building and preparation method, can assign anti-
The excellent anti-fog haze effect of water coiled material, and preparation process is simple, and easy for construction, can realize large area easily removes haze effect.
To achieve the above object, specific technical solution of the present invention is as follows:
A kind of preparation method of anti-fog haze function waterproof roll for building, by polyvinyl chloride resin, plasticizer DOP, calcium zinc heat stabilizer,
Epoxidized soybean oil, filler-calcium carbonate, antioxidant, light stabilizer form coiled material layer raw material, by ethylene-propylene-octene copolymer, three
It ties up nano zine oxide/molybdenum disulfide particles, antioxidant, light stabilizer and forms anti-haze layer raw material, by coiled material layer raw material and anti-haze layer
Coextruder is added in raw material, and anti-fog haze function waterproof roll for building, the specific steps of preparation are made using double-layer coextrusion technique
It is as follows:
(1) molybdenum disulfide nano sheet is subjected to cleaning intercalation pretreatment, be then impregnated in zinc acetate dihydrate/methanol solution, point
It dissipates uniformly, then sealing is placed in 24 ~ 48h of isothermal holding in 60 ~ 70 DEG C of constant temperature ovens, is heated to after reaction product filtering is taken out
It 450 ~ 500 DEG C, carries out cycle annealing and handles 1 ~ 2h, the molybdenum disulfide that surface forms zinc oxide seed layer is made；
(2) zinc acetate dihydrate, hexamethylenetetramine are added in distilled water and are configured to growth-promoting media, it is then that step (1) is obtained
The molybdenum disulfide that surface forms zinc oxide seed layer is scattered in growth-promoting media, is heated to 80 ~ 90 DEG C, 1 ~ 14h of isothermal reaction, so that
Molybdenum disulfide surface grows nano structure of zinc oxide, after product is centrifuged, then using deionized water clean 3 ~ 5 times,
The zinc salt of excess surface is removed, vacuum drying is finally ground to three-dimensional manometer zinc oxide/molybdenum disulfide that partial size is 5 ~ 15 μm
Grain；
(3) by polyvinyl chloride resin, plasticizer DOP, calcium zinc heat stabilizer, epoxidized soybean oil, filler-calcium carbonate, antioxidant, light stabilizer
In mixing investment kneader, 100 ~ 130 DEG C of 8 ~ 15min of kneading are warming up to, it will be in the mixed material investment main extruder after kneading
For squeezing out coiled material layer；Simultaneously by three-dimensional manometer zinc oxide/curing made from ethylene-propylene-octene copolymer, step (2)
Molybdenum particle, antioxidant, light stabilizer are added in secondary extruder after mixing for squeezing out anti-haze layer；It is gone to work using double-layer coextrusion
Skill prepares the waterproof roll that surface has anti-haze layer, finally hot-forming by three rollers, makes the anti-haze layer in surface and coiled material layer welding
It is compound, anti-fog haze function waterproof roll for building is made.
Step (1) successively cleans molybdenum disulfide nano sheet using dehydrated alcohol and acetone, cooperates ultrasonic wave added, no
Only cleaning effect is good, and can realize that intercalation pre-processes using ultrasonic wave added, can after immersing zinc acetate dihydrate/methanol solution
Seed layer is formed on molybdenum disulfide surface, establishes base in molybdenum disulfide surface construction three dimensional stress nano zine oxide structure to be subsequent
Plinth.Preferably, the cleaning process is first to be cleaned by ultrasonic 5 ~ 10min with dehydrated alcohol, then clean 5 ~ 10min with acetone；Each original
The parts by weight of material are 30 ~ 40 parts by weight of molybdenum disulfide nano sheet, 60 ~ 70 parts by weight of zinc acetate dihydrate/methanol solution；Described two
Zinc acetate dihydrate accounts for 15 ~ 20 parts by weight in water acetic acid zinc/methanol solution, remaining is methanol.
Step (2) is using zinc acetate dihydrate, hexamethylenetetramine as raw material, by controlling raw material proportioning and reaction temperature, with
Zinc oxide columnar arrays can be prepared in mild hydro-thermal reaction method, by the molybdenum disulfide table for having formed zinc oxide seed layer
Face epitaxial growth and the nano zine oxide structure for constructing three dimensional stress, so the significant increase specific surface area of composite photo-catalyst and
Catalytic activity has photocatalytic degradation nitrogen oxides, SO2, the aerosols precursor such as VOC function, such as check SO2 It is converted into
H2SO4, VOC be converted into the process of oxidized form organic matter, thus the basis that the particulate matter including removing PM2.5 is formed.Preferably,
The parts by weight of each raw material are 8 ~ 12 parts by weight of zinc acetate dihydrate, 5 ~ 8 parts by weight of hexamethylenetetramine, 40 ~ 57 weight of distilled water
Measure part, surface forms 30 ~ 40 parts by weight of molybdenum disulfide of zinc oxide seed layer.
Step (3) uses double-layer coextrusion technique, obtains having answering for anti-haze effect by co-extrusion on PVC waterproof roll surface
Close layer；Antioxidant selects phenolic antioxidant, can prevent or inhibit chain initiation reaction and chain growth by capturing peroxy radical
Reaction achievees the purpose that prevent oxidation have good rush for the performance of waterproof roll to terminate free chain reaction
Into effect；Light stabilizer selection has hydroperoxide decomposition, quenching excited oxygen, can capture free radical, circular regeneration itself
And the hindered amine light stabilizer of 4 kinds of abilities that itself can be cooperateed with, it is not only efficient light stabilizer, while being also efficient anti-
Oxygen agent.Preferably, the calcium zinc heat stabilizer is calcium zinc heat stabilizer CZ-1, calcium zinc heat stabilizer CZ-2, calcium zinc heat stabilizer
One of CZ-3, antioxidant are at least one of hydroquinone, thiobisphenol, 2,6-di-tert-butyl p-cresol, and light is stablized
Agent is at least one of light stabilizer 770, light stabilizer 622, light stabilizer 944, light stabilizer 783；
The parts by weight of each raw material of coiled material layer are 63 ~ 77 parts by weight of polyvinyl chloride resin, 2 ~ 4 parts by weight of plasticizer DOP, calcium zinc heat
1 ~ 2 parts by weight of stabilizer, 8 ~ 12 parts by weight of epoxidized soybean oil, 10 ~ 15 parts by weight of calcium carbonate, 1 ~ 2 parts by weight of antioxidant, light are stablized
1 ~ 2 parts by weight of agent；
The parts by weight of each raw material of anti-haze layer are 61 ~ 78 parts by weight of ethylene-propylene-octene copolymer, three-dimensional manometer oxidation
20 ~ 35 parts by weight of zinc/molybdenum disulfide particles, 1 ~ 2 parts by weight of antioxidant, 1 ~ 2 parts by weight of light stabilizer；
In the bilayer extrusion process, extrusion temperature is 150 ~ 180 DEG C, and extruder revolving speed is 300 ~ 400r/min；Three roller
Hot-forming temperature is 140 ~ 160 DEG C, and line pressure is 5 ~ 10MPa, and hot pressing speed is 500 ~ 600mm/min, molding waterproof
The coiled material layer of coiled material with a thickness of 0.8 ~ 2mm, anti-haze layer with a thickness of 0.4 ~ 1mm.
The present invention also provides the anti-fog haze function waterproof rolls for building that a kind of above-mentioned preparation method is prepared.This is anti-
Haze function waterproof roll is by polyvinyl chloride resin, plasticizer DOP, calcium zinc heat stabilizer, epoxidized soybean oil, filler-calcium carbonate, antioxygen
Agent, light stabilizer form coiled material layer raw material, by ethylene-propylene-octene copolymer, three-dimensional manometer zinc oxide/molybdenum disulfide particles,
Antioxidant, light stabilizer form anti-haze layer raw material, are made using double-layer coextrusion technique.Not only have the function of good anti-fog haze, and
And preparation and construction is simple.
The present invention provides a kind of anti-fog haze function waterproof roll for building and preparation methods, compared with prior art,
Prominent feature and excellent effect are:
1. waterproof roll prepared by the present invention has excellent anti-fog haze effect.
2. preparation method of the invention, by adding three-dimensional manometer zinc oxide/molybdenum disulfide composite wood in composite sheet material
Material, the significant increase specific surface area and catalytic activity of composite material, and then realize harmful gas in efficient catalytic degradation haze
The purpose of body.
3. preparation method of the invention, preparation process is simple, and easy for construction, and can realize large area easily removes haze.
4. anti-fog haze function waterproof roll for building produced by the present invention, by test, for the nitrogen oxides in haze
2h catalysis degradation modulus be 96 ~ 98%, for the SO in haze22h catalysis degradation modulus be 96 ~ 98%, for the VOC in haze
2h catalysis degradation modulus be 94 ~ 97%.
Specific embodiment
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
34kg molybdenum disulfide nano sheet is first cleaned by ultrasonic 7min with dehydrated alcohol, then cleans 7min with acetone, is then impregnated in
17kg zinc acetate dihydrate, 49kg methanol solution in, be uniformly dispersed, then sealing be placed in isothermal holding in 66 DEG C of constant temperature ovens
35h is heated to 470 DEG C after taking out reaction product filtering, carries out cycle annealing and handles 1.5h, and surface is made and forms zinc oxide kind
The molybdenum disulfide of sublayer；Then 9kg zinc acetate dihydrate, 7kg hexamethylenetetramine are added in 50kg distilled water and are configured to grow
Then liquid disperses the molybdenum disulfide that the surface 34kg forms zinc oxide seed layer in growth-promoting media, is heated to 86 DEG C, isothermal reaction
7h so that molybdenum disulfide surface grows nano structure of zinc oxide, after product is centrifuged, then cleaned using deionized water
4 times, the zinc salt of excess surface is removed, is dried in vacuo, three-dimensional manometer zinc oxide/curing that partial size is 10 μm is finally ground to
Molybdenum particle；Then by 71kg polyvinyl chloride resin, 3kg plasticizer DOP, 1kg calcium zinc heat stabilizer CZ-1,10kg epoxidized soybean oil,
12kg filler-calcium carbonate, 2kg hydroquinone, the mixing of 1kg light stabilizer 770 are put into kneader, are warming up to 108 DEG C of kneadings
11min will be used to squeeze out coiled material layer in the mixed material investment main extruder after kneading；Simultaneously by 70kg ethylene-propylene-octene
Copolymer, 27kg three-dimensional manometer zinc oxide/molybdenum disulfide particles, 1kg hydroquinone, 2kg light stabilizer 770 add after mixing
Enter for squeezing out anti-haze layer in secondary extruder, extrusion temperature is 170 DEG C, and extruder revolving speed is 360r/min；Using double-layer coextrusion
Technique preparation surface has the waterproof roll of anti-haze layer out, and finally hot-forming by three rollers, the hot-forming temperature of three rollers is
150 DEG C, line pressure 7MPa, hot pressing speed is 560mm/min, and the coiled material layer of molding waterproof roll is with a thickness of 1.2mm, anti-haze
Layer with a thickness of 0.8mm, anti-fog haze function waterproof roll for building is made.
Embodiment 2
33kg molybdenum disulfide nano sheet is first cleaned by ultrasonic 6min with dehydrated alcohol, then cleans 9min with acetone, is then impregnated in
16kg zinc acetate dihydrate, 51kg methanol solution in, be uniformly dispersed, then sealing be placed in isothermal holding in 62 DEG C of constant temperature ovens
44h is heated to 460 DEG C after taking out reaction product filtering, carries out cycle annealing and handles 2h, and surface is made and forms zinc oxide seed
The molybdenum disulfide of layer；Then 9kg zinc acetate dihydrate, 6kg hexamethylenetetramine are added in 52kg distilled water and are configured to growth-promoting media,
Then it disperses the molybdenum disulfide that the surface 33kg forms seed layer in growth-promoting media, is heated to 82 DEG C, isothermal reaction 12h, so that
Molybdenum disulfide surface grows nano structure of zinc oxide, after product is centrifuged, then using deionized water clean 3 times, go
Except the zinc salt of excess surface, vacuum drying is finally ground to three-dimensional manometer zinc oxide/molybdenum disulfide particles that partial size is 8 μm；
Then by 73kg polyvinyl chloride resin, 2kg plasticizer DOP, 2kg calcium zinc heat stabilizer CZ-2,9kg epoxidized soybean oil, 12kg filler carbon
Sour calcium, 1kg thiobisphenol, the mixing of 1kg light stabilizer 622 are put into kneader, 110 DEG C of kneading 12min are warming up to, after kneading
Mixed material investment main extruder in for squeezing out coiled material layer；Simultaneously by 74kg ethylene-propylene-octene copolymer, 24kg tri-
Dimension nano zine oxide/molybdenum disulfide particles, 1kg thiobisphenol, 1kg light stabilizer 622 are added after mixing in secondary extruder
For squeezing out anti-haze layer, extrusion temperature is 160 DEG C, and extruder revolving speed is 320r/min；Technique is gone out using double-layer coextrusion and prepares table
Face has the waterproof roll of anti-haze layer, finally hot-forming by three rollers, and the hot-forming temperature of three rollers is 145 DEG C, line pressure
For 6MPa, hot pressing speed is 520mm/min, the coiled material layer of molding waterproof roll with a thickness of 1mm, anti-haze layer with a thickness of
Anti-fog haze function waterproof roll for building is made in 0.5mm.
Embodiment 3
38kg molybdenum disulfide nano sheet is first cleaned by ultrasonic 9min with dehydrated alcohol, then cleans 6min with acetone, is then impregnated in
18kg zinc acetate dihydrate, 44kg methanol solution in, be uniformly dispersed, then sealing be placed in isothermal holding in 68 DEG C of constant temperature ovens
30h is heated to 480 DEG C after taking out reaction product filtering, carries out cycle annealing and handles 1h, and surface is made and forms zinc oxide seed
The molybdenum disulfide of layer；Then 11kg zinc acetate dihydrate, 7kg hexamethylenetetramine are added in 45kg distilled water and are configured to grow
Then liquid disperses the molybdenum disulfide that the surface 37kg forms seed layer in growth-promoting media, is heated to 88 DEG C, isothermal reaction 3h makes
Molybdenum disulfide surface grow nano structure of zinc oxide, after product is centrifuged, then using deionized water clean 5 times,
The zinc salt of excess surface is removed, vacuum drying is finally ground to three-dimensional manometer zinc oxide/molybdenum disulfide that partial size is 12 μm
Grain；Then 66kg polyvinyl chloride resin, 3kg plasticizer DOP, 2kg calcium zinc heat stabilizer CZ-3,11kg epoxidized soybean oil, 14kg are filled out
Expect that calcium carbonate, 2kg 2,6-di-tert-butyl p-cresol, the mixing of 2kg light stabilizer 944 are put into kneader, is warming up to 120 DEG C and pinches
10min is closed, will be used to squeeze out coiled material layer in the mixed material investment main extruder after kneading；It is simultaneously that 66kg ethylene-propylene-is pungent
Alkene copolymer, 30kg three-dimensional manometer zinc oxide/molybdenum disulfide particles, 2kg are to DBPC 2,6 ditertiary butyl p cresol, 2kg light stabilizer
944 are added in secondary extruder after mixing for squeezing out anti-haze layer, and extrusion temperature is 170 DEG C, and extruder revolving speed is 380r/
min；The waterproof roll that technique preparation surface has anti-haze layer, finally hot-forming by three rollers, three rollers are gone out using double-layer coextrusion
Hot-forming temperature is 155 DEG C, line pressure 8MPa, and hot pressing speed is 580mm/min, the coiled material layer of molding waterproof roll
With a thickness of 1.0mm, anti-haze layer with a thickness of 0.8mm, anti-fog haze function waterproof roll for building is made.
Embodiment 4
30kg molybdenum disulfide nano sheet is first cleaned by ultrasonic 5min with dehydrated alcohol, then cleans 5min with acetone, is then impregnated in
15kg zinc acetate dihydrate, 55kg methanol solution in, be uniformly dispersed, then sealing be placed in isothermal holding in 60 DEG C of constant temperature ovens
48h is heated to 450 DEG C after taking out reaction product filtering, carries out cycle annealing and handles 2h, and surface is made and forms zinc oxide seed
The molybdenum disulfide of layer；Then 8kg zinc acetate dihydrate, 8kg hexamethylenetetramine are added in 57kg distilled water and are configured to growth-promoting media,
Then it disperses the molybdenum disulfide that the surface 30kg forms seed layer in growth-promoting media, is heated to 80 DEG C, isothermal reaction 14h, so that
Molybdenum disulfide surface grows nano structure of zinc oxide, after product is centrifuged, then using deionized water clean 3 times, go
Except the zinc salt of excess surface, vacuum drying is finally ground to three-dimensional manometer zinc oxide/molybdenum disulfide particles that partial size is 5 μm；
Then by 77kg polyvinyl chloride resin, 2kg plasticizer DOP, 1kg calcium zinc heat stabilizer CZ-1,8kg epoxidized soybean oil, 10kg filler carbon
Sour calcium, kg hydroquinone, the mixing of 1kg light stabilizer 783 are put into kneader, 100 DEG C of kneading 15min are warming up to, after kneading
Mixed material investment main extruder in for squeezing out coiled material layer；Simultaneously by 78kg ethylene-propylene-octene copolymer, 20kg tri-
Dimension nano zine oxide/molybdenum disulfide particles, 1kg hydroquinone, 1kg light stabilizer 783 are added after mixing in secondary extruder
For squeezing out anti-haze layer, extrusion temperature is 150 DEG C, and extruder revolving speed is 400r/min；Technique is gone out using double-layer coextrusion and prepares table
Face has the waterproof roll of anti-haze layer, finally hot-forming by three rollers, and the hot-forming temperature of three rollers is 140 DEG C, line pressure
For 5MPa, hot pressing speed is 500mm/min, the coiled material layer of molding waterproof roll with a thickness of 0.8mm, anti-haze layer with a thickness of
Anti-fog haze function waterproof roll for building is made in 0.4mm.
Embodiment 5
40kg molybdenum disulfide nano sheet is first cleaned by ultrasonic 10min with dehydrated alcohol, then cleans 10min with acetone, is then impregnated
In 20kg zinc acetate dihydrate, 40kg methanol solution in, be uniformly dispersed, then sealing be placed in isothermal holding in 70 DEG C of constant temperature ovens
For 24 hours, 500 DEG C are heated to after reaction product filtering being taken out, cycle annealing is carried out and handles 1h, surface is made and forms zinc oxide seed
The molybdenum disulfide of layer；Then 12kg zinc acetate dihydrate, 8kg hexamethylenetetramine are added in 40kg distilled water and are configured to grow
Then liquid disperses the molybdenum disulfide that the surface 40kg forms seed layer in growth-promoting media, is heated to 90 DEG C, isothermal reaction 1h makes
Molybdenum disulfide surface grow nano structure of zinc oxide, after product is centrifuged, then using deionized water clean 5 times,
The zinc salt of excess surface is removed, vacuum drying is finally ground to three-dimensional manometer zinc oxide/molybdenum disulfide that partial size is 15 μm
Grain；Then 63kg polyvinyl chloride resin, 4kg plasticizer DOP, 2kg calcium zinc heat stabilizer CZ-2,12kg epoxidized soybean oil, 15kg are filled out
Expect that calcium carbonate, 2kg thiobisphenol, the mixing of 2kg light stabilizer 770 are put into kneader, is warming up to 130 DEG C of kneading 8min, will pinch
For squeezing out coiled material layer in mixed material investment main extruder after conjunction；Simultaneously by 61kg ethylene-propylene-octene copolymer,
35kg three-dimensional manometer zinc oxide/molybdenum disulfide particles, 2kg DBPC 2,6 ditertiary butyl p cresol, 2kg light stabilizer 783 are uniformly mixed
It is added in secondary extruder afterwards for squeezing out anti-haze layer, extrusion temperature is 180 DEG C, and extruder revolving speed is 400r/min；Using bilayer
Coextrusion processes prepare the waterproof roll that surface has anti-haze layer, finally hot-forming by three rollers, the hot-forming temperature of three rollers
Degree is 160 DEG C, line pressure 0MPa, and hot pressing speed is 600mm/min, the coiled material layer of molding waterproof roll with a thickness of 1.2mm,
Anti- haze layer with a thickness of 0.2mm, anti-fog haze function waterproof roll for building is made.
Comparative example 1
In waterproof roll preparation process, it is directly added into nano zine oxide, no molybdenum disulfide carrier, other preparation conditions and embodiment
5 is consistent.
Test method:
It takes waterproof roll to be cut into the sample of 15cm × 15cm, is placed in 1m3Haze test macro chamber in surveyed
Examination, the UVA ultraviolet light of the interior setting 30W of reaction chamber, is passed through haze, utilizes nitrogen oxides, SO2, TVOC test equipment tests respectively
Nitrogen oxides, SO2, TVOC test equipment initial concentration C0, initial concentration control is in 10mg/m3Or so, test concentrations are after 2h
C1, calculate 2h photocatalytic activity: ω=(C0 -C1)/C0。
The data obtained is as shown in table 1.
Table 1:
Claims (10)
1. a kind of preparation method of anti-fog haze function waterproof roll for building, which is characterized in that by polyvinyl chloride resin, plasticizer DOP,
Calcium zinc heat stabilizer, epoxidized soybean oil, filler-calcium carbonate, antioxidant, light stabilizer form coiled material layer raw material, by ethylene-propylene-
Octene copolymer, three-dimensional manometer zinc oxide/molybdenum disulfide particles, antioxidant, light stabilizer form anti-haze layer raw material, by coiled material layer
Coextruder is added in raw material and anti-haze layer raw material, and anti-fog haze function waterproof roll for building is made using double-layer coextrusion technique, makes
It is standby that specific step is as follows:
(1) molybdenum disulfide nano sheet is subjected to cleaning intercalation pretreatment, be then impregnated in zinc acetate dihydrate/methanol solution, point
It dissipates uniformly, then sealing is placed in 24 ~ 48h of isothermal holding in 60 ~ 70 DEG C of constant temperature ovens, is heated to after reaction product filtering is taken out
It 450 ~ 500 DEG C, carries out cycle annealing and handles 1 ~ 2h, the molybdenum disulfide that surface forms zinc oxide seed layer is made；
(2) zinc acetate dihydrate, hexamethylenetetramine are added in distilled water and are configured to growth-promoting media, it is then that step (1) is obtained
The molybdenum disulfide that surface forms zinc oxide seed layer is scattered in growth-promoting media, is heated to 80 ~ 90 DEG C, 1 ~ 14h of isothermal reaction, so that
Molybdenum disulfide surface grows nano structure of zinc oxide, after product is centrifuged, then using deionized water clean 3 ~ 5 times,
The zinc salt of excess surface is removed, vacuum drying is finally ground to three-dimensional manometer zinc oxide/molybdenum disulfide that partial size is 5 ~ 15 μm
Grain；
(3) by polyvinyl chloride resin, plasticizer DOP, calcium zinc heat stabilizer, epoxidized soybean oil, filler-calcium carbonate, antioxidant, light stabilizer
In mixing investment kneader, 100 ~ 130 DEG C of 8 ~ 15min of kneading are warming up to, it will be in the mixed material investment main extruder after kneading
For squeezing out coiled material layer；Simultaneously by three-dimensional manometer zinc oxide/curing made from ethylene-propylene-octene copolymer, step (2)
Molybdenum particle, antioxidant, light stabilizer are added in secondary extruder after mixing for squeezing out anti-haze layer；It is gone to work using double-layer coextrusion
Skill prepares the waterproof roll that surface has anti-haze layer, finally hot-forming by three rollers, makes the anti-haze layer in surface and coiled material layer welding
It is compound, anti-fog haze function waterproof roll for building is made.
2. a kind of preparation method of anti-fog haze function waterproof roll for building according to claim 1, it is characterised in that: step
(1) cleaning process is first to be cleaned by ultrasonic 5 ~ 10min with dehydrated alcohol, then clean 5 ~ 10min with acetone.
3. a kind of preparation method of anti-fog haze function waterproof roll for building according to claim 1, it is characterised in that: step
(1) parts by weight of each raw material are in, 30 ~ 40 parts by weight of molybdenum disulfide nano sheet, 60 ~ 70 weight of zinc acetate dihydrate/methanol solution
Part；Zinc acetate dihydrate accounts for 15 ~ 20 parts by weight in the zinc acetate dihydrate/methanol solution, remaining is methanol.
4. a kind of preparation method of anti-fog haze function waterproof roll for building according to claim 1, it is characterised in that: step
(2) parts by weight of each raw material are in, 8 ~ 12 parts by weight of zinc acetate dihydrate, 5 ~ 8 parts by weight of hexamethylenetetramine, distilled water 40 ~ 57
Parts by weight, surface form 30 ~ 40 parts by weight of molybdenum disulfide of zinc oxide seed layer.
5. a kind of preparation method of anti-fog haze function waterproof roll for building according to claim 1, it is characterised in that: step
(3) calcium zinc heat stabilizer be calcium zinc heat stabilizer CZ-1, calcium zinc heat stabilizer CZ-2, one in calcium zinc heat stabilizer CZ-3
Kind, antioxidant is at least one of hydroquinone, thiobisphenol, 2,6-di-tert-butyl p-cresol, and light stabilizer is stablized for light
At least one of agent 770, light stabilizer 622, light stabilizer 944, light stabilizer 783.
6. a kind of preparation method of anti-fog haze function waterproof roll for building according to claim 1, it is characterised in that: step
(3) parts by weight of each raw material of the coiled material layer are that 63 ~ 77 parts by weight of polyvinyl chloride resin, 2 ~ 4 parts by weight of plasticizer DOP, calcium zinc heat are steady
Determine 1 ~ 2 parts by weight of agent, 8 ~ 12 parts by weight of epoxidized soybean oil, 10 ~ 15 parts by weight of calcium carbonate, 1 ~ 2 parts by weight of antioxidant, light stabilizer
1 ~ 2 parts by weight.
7. a kind of preparation method of anti-fog haze function waterproof roll for building according to claim 1, it is characterised in that: step
(3) parts by weight of each raw material of anti-haze layer are, 61 ~ 78 parts by weight of ethylene-propylene-octene copolymer, three-dimensional manometer zinc oxide/
20 ~ 35 parts by weight of molybdenum disulfide particles, 1 ~ 2 parts by weight of antioxidant, 1 ~ 2 parts by weight of light stabilizer.
8. a kind of preparation method of anti-fog haze function waterproof roll for building according to claim 1, it is characterised in that: step
(3) in the double-deck extrusion process, extrusion temperature is 150 ~ 180 DEG C, and extruder revolving speed is 300 ~ 400r/min.
9. a kind of preparation method of anti-fog haze function waterproof roll for building according to claim 1, it is characterised in that: step
(3) the hot-forming temperature of three roller is 140 ~ 160 DEG C, and line pressure is 5 ~ 10MPa, and hot pressing speed is 500 ~ 600mm/min,
The coiled material layer of molding waterproof roll with a thickness of 0.8 ~ 2mm, anti-haze layer with a thickness of 0.4 ~ 1mm.
10. the anti-fog haze function waterproof roll for building that any one of claim 1 ~ 9 preparation method is prepared.
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