WO2015055115A1 - 透明阻燃隔热防紫外高分子复合贴膜及其制备方法和用途 - Google Patents

透明阻燃隔热防紫外高分子复合贴膜及其制备方法和用途 Download PDF

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WO2015055115A1
WO2015055115A1 PCT/CN2014/088598 CN2014088598W WO2015055115A1 WO 2015055115 A1 WO2015055115 A1 WO 2015055115A1 CN 2014088598 W CN2014088598 W CN 2014088598W WO 2015055115 A1 WO2015055115 A1 WO 2015055115A1
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retardant
flame
functional layer
heat
nano
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French (fr)
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陈建峰
韩兴威
曾晓飞
王洁欣
陈国术
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CHIZHOU ENP TECHNOLOGY CO LTD
Beijing University of Chemical Technology
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CHIZHOU ENP TECHNOLOGY CO LTD
Beijing University of Chemical Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/05—Forming flame retardant coatings or fire resistant coatings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/002—Processes for applying liquids or other fluent materials the substrate being rotated
    • B05D1/005—Spin coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2201/00—Polymeric substrate or laminate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2252/00—Sheets
    • B05D2252/10—Applying the material on both sides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/304—Insulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/71—Resistive to light or to UV
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2429/00—Characterised by the use 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 an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2429/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes

Definitions

  • the invention relates to the field of polymer-inorganic nanoparticle composite composite film, in particular to a transparent flame-retardant heat-insulating anti-UV polymer composite film and a preparation method thereof.
  • China's economy has prospered, urban construction has developed rapidly, and the beautiful modern buildings have decorated the inner city.
  • urban construction and development it also brings about social problems with high energy and resource consumption.
  • China's building energy consumption accounts for 40% of social energy consumption, while indoor heating and air conditioning refrigeration consumes energy.
  • the consumption is about 65% of the building energy consumption.
  • What is even more shocking is that more than 50% of the temperature control energy efficiency brought by heating and air conditioning is lost from the glass windows of buildings with unsatisfactory energy-saving effects, so the energy-saving renovation of doors and windows in existing buildings Energy conservation is crucial.
  • reducing the high energy consumption of buildings has become an urgent need for sustainable development in China and has become the focus of the country's current work.
  • the energy-saving glass film on the market in China is mainly occupied by several foreign brands such as V-KOOL, Ray-Ban, 3M (3M), Federal (ATI) and Johnson (Johnson).
  • the market lacks products of local independent brands.
  • the development of China's domestic energy-saving glass film provides a broad space for development, and also provides the impetus for the development of energy-saving glass film preparation technology.
  • UV light As we all know, ultraviolet light, as a kind of non-visible light, has a specific lethality and is called "invisible killer" by the scientific community.
  • Ultraviolet rays are classified according to the length of their wavelengths: the wavelength of the UV-A band is 320 ⁇ 400nm; UV-B is 280-320nm; UV-C is 100-280nm; short-wave ultraviolet light can pass through the dermis, and medium wave can enter the dermis.
  • the vast majority of UV-B can be absorbed by the skin and damage DNA. When DNA is destroyed, cells will die or develop into uncontrollable cancer cells.
  • the causes of many of the diseases that can be diagnosed today are related to ultraviolet radiation.
  • UV shielding films and infrared thermal insulation film materials on the market are prepared by using organic high molecular polymer as a substrate, so the film itself has certain flammability; at present, the film material can be applied not only to glass.
  • Transparent materials and devices such as windows, protective films, containers and electronic components have also been widely used in construction, transportation, electronics, aerospace, medicine, etc.
  • polymer materials account for a large proportion. Therefore, the flame retardant properties of the film materials are particularly important in these fields; in addition, in the traditional application fields of film materials (such as the construction industry and the automotive industry), glass and other non-combustible building materials are attached to the surface.
  • a functional type of film product is very likely to become a fire source or a flame propagation medium; therefore, it has been important to develop a glass film that combines various functions such as flame retardant, infrared barrier and ultraviolet shielding, and It also has broad market prospects.
  • the first technical problem to be solved by the present invention is to provide a transparent flame-retardant and heat-insulating anti-ultraviolet polymer composite film, which has high transparency, good flame retardant effect and thermal insulation performance. Excellent and UV resistant.
  • the present invention adopts the following technical solutions:
  • a transparent flame-retardant and heat-insulating anti-ultraviolet polymer composite film comprises a flame-retardant functional layer, a heat-insulating functional layer, an ultraviolet-proof functional layer and a substrate layer.
  • the polymer composite film is, in order from top to bottom, a flame retardant functional layer, a substrate layer, a heat insulating functional layer and an ultraviolet shielding functional layer.
  • the transparent flame-retardant and heat-insulating anti-ultraviolet polymer composite film has a thickness of 1 um to 500 um, Preferably, the transparent flame-retardant and heat-insulating anti-ultraviolet polymer composite film has a thickness of 1 um to 300 um.
  • the transparent flame-retardant and heat-insulating anti-ultraviolet polymer composite film has a visible light transmittance of more than 80%, an ultraviolet light transmittance of less than 1%, and a near-infrared light transmittance of less than 10%.
  • the flame-retardant functional layer is composed of 10 to 50% by weight of the inorganic nano-flame retardant, 50 to 70% by weight of the high-molecular polymer, and 0 to 20% by weight of the auxiliary agent; preferably, the flame-retardant functional layer is composed of inorganic nano-resistance 30 to 50% by weight of the fuel, 50 to 70% by weight of the polymer, and 0 to 20% of the plastic auxiliary;
  • the thickness of the flame-retardant functional layer is 100 nm to 100 um; preferably, the inorganic nano flame retardant is selected from the group consisting of nano magnesium hydroxide, nano aluminum hydroxide, zinc borate, antimony trioxide, and ⁇ -molybdenum trioxide. Or a mixture of several; more preferably, the inorganic nano flame retardant is selected from the group consisting of nano magnesium hydroxide or nano aluminum hydroxide;
  • the inorganic nano flame retardant has a morphology of a cuboidal shape, a spherical shape, a rod shape, a ribbon shape, a needle shape, a sheet shape or a sea urchin shape; more preferably, the inorganic nano flame retardant has a sheet shape.
  • the nano magnesium hydroxide is prepared as follows:
  • the magnesium salt is selected from one or more of the group consisting of magnesium sulfate, magnesium nitrate, magnesium chloride, and magnesium acetate.
  • the concentration of the magnesium salt solution is from 1% by weight to 35% by weight.
  • the organic solvent is selected from one or more of the following: methanol, ethanol, ethylene glycol, isopropanol, glycerol, butanol, acetone, methyl ethyl ketone, ethyl acetate, butyl acetate, benzene, Toluene, xylene, dimethyl sulfoxide, tetrahydrofuran.
  • the alkali liquid is selected from one or more of the following: a sodium hydroxide solution, a potassium hydroxide solution, and ammonia water;
  • the sodium hydroxide solution is a solution in which sodium hydroxide is dissolved in water or an organic solvent;
  • the potassium hydroxide solution is a solution of potassium hydroxide dissolved in water or an organic solvent;
  • the organic solvent is selected from one or more of the following: methanol, ethanol, ethylene glycol, isopropanol, glycerol, Butanol, acetone, methyl ethyl ketone, ethyl acetate, butyl acetate, benzene, toluene, xylene, dimethyl sulfoxide, tetrahydrofuran Methane, n-hexane, cyclohexane.
  • the concentration of the lye is from 1% by weight to 40% by weight; preferably, the concentration of the lye is from 1% by weight to 25% by weight.
  • the obtained magnesium salt solution and the alkali solution are separately placed in a storage tank, and the temperature is maintained at 20 to 70 °C.
  • the reaction temperature is 20 to 70 ° C; more preferably, the reaction temperature is 25 to 60 ° C; most preferably, the reaction temperature is 25 to 55 ° C.
  • the supergravity rotating bed reactor is selected from the group consisting of a rotating packed bed supergravity rotating bed reactor, a baffled supergravity rotating bed reactor, a spiral channel supergravity rotating bed reactor, and a stator-rotor supergravity A rotating bed reactor or a rotating disc supergravity rotating bed reactor; preferably, the rotating bed has a rotor speed of 300 to 5000 rpm; preferably, the rotor of the rotating bed has a rotational speed of 600 to 2500 rpm.
  • the molar flow ratio of the magnesium salt solution to the lye in the rotary packed bed is 0.2 to 3.5:1; preferably, the linear velocity of the magnesium salt solution into the rotary packed bed is 2 to 7 m. /s, the lye is 2 ⁇ 8m / s.
  • the sleeve type annular microchannel reactor comprises an outer tube and an inner tube forming a sleeve, and an annular gap is left between the inner tube and the outer tube to form an annular microchannel, and the annular microchannel
  • the radial spacing is from 100 micrometers to 5 millimeters.
  • the outer tube is provided with a continuous phase inlet and an outlet.
  • One end of the inner tube is provided with a dispersed phase inlet, the other end is closed, and the closed end is in the shape of a cone or a bullet, at the closed end.
  • the adjacent columnar inner tube wall is provided with micropores along the circumferential direction of the wall, the pore diameter range of the pores is 0.05-100 micrometers, the columnar inner tube wall opening ratio is 3% to 60%, and the micropores on the inner tube are Disperse phase exports.
  • the volume flow ratio of the magnesium salt solution to the lye in the cannulated annular microchannel reactor is (0.5 to 10):1.
  • the flow rate of the magnesium salt solution into the outer tube of the sleeve type annular microchannel reactor is 1 to 6 L/min, and the flow rate of the alkali liquid into the inner tube of the sleeve type annular microchannel reactor is 0.2 to 2 L. /min.
  • step (2) a plurality of sleeve-type annular microchannel reactors are used in parallel.
  • a centrifugal pump, a peristaltic pump or a metering pump is used with a flow meter to adjust the injection rate of the reaction solution.
  • the surfactant is selected from one or more of the following: cetyltrimethylammonium bromide, sodium lauryl sulfate, sodium oleate, polyvinylpyrrolidone, poly Ethylene glycol, ⁇ -aminopropyltriethoxysilane, ⁇ -glycidyloxypropyltrimethoxysilane, ⁇ -methacryloyloxy Propyltrimethoxysilane, N-( ⁇ -aminoethyl)- ⁇ -aminopropyltrimethoxysilane, N-( ⁇ -aminoethyl)- ⁇ -aminopropyltriethoxysilane, N- --(aminoethyl)- ⁇ -aminopropylmethyldimethoxysilane, oleic acid, stearic acid, zinc stearate, sodium hard acid, titanate, polyvinyl alcohol.
  • the modification is carried out in a modified tank, the modification temperature is 30 to 95 ° C, and the modification time is 0.5 to 5 h; preferably, the modification temperature is 40 to 90 ° C, and the modification time is 1 ⁇ 4h; optimally, the modification temperature is 50-80 ° C, and the modification time is 1.5-4 h.
  • the surfactant coating layer accounts for 1% to 40% of the mass fraction of the modified magnesium hydroxide particles; preferably, the surfactant coating layer accounts for the modified magnesium hydroxide.
  • the mass fraction of the particles is from 2% to 30%; most preferably, the surfactant coating layer accounts for 5% to 25% by mass of the modified magnesium hydroxide particles.
  • the standing time is 0.5 to 5 hours.
  • the preparation method of the nano aluminum hydroxide is similar to the preparation method of the nano magnesium hydroxide.
  • the heat insulating functional layer is composed of a near infrared ray absorbing agent or a heat shielding agent of 5 to 50% by weight, a high molecular polymer of 60 to 80% by weight, and an auxiliary agent of 0 to 35% by weight; and the thickness of the heat insulating functional layer is 100 nm to 150 um.
  • the near-infrared absorbing agent or heat-shielding agent is selected from the group consisting of nano-indium tin oxide, nano-tin-tin-oxide, nano-tungsten oxide, various tungsten bronze or lanthanum hexaboride. ;
  • the near-infrared absorbing agent or the heat-shielding agent has a topography, a spherical shape, a rod shape, a ribbon shape, a needle shape, a sheet shape or a sea urchin shape; more preferably, the near infrared absorbing agent Or the shape of the heat shielding agent is cuboid or spherical.
  • the ultraviolet protection functional layer is composed of 4 to 60 wt% of an inorganic nano UV absorber, 40 to 96 wt% of a polymer, and 0 to 30 wt% of an auxiliary agent; the thickness of the ultraviolet protection functional layer is 100 nm to 50 ⁇ m;
  • the inorganic nano-UV absorber is selected from the group consisting of nano zinc oxide, nano titanium dioxide, nano cerium oxide, doped nano zinc oxide, doped nano titanium dioxide, or coated with any of the above nanoparticles as a core. a mixture of one or more of the core-shell structure composite metal oxide nanoparticles of silica; more preferably, the inorganic nano-UV absorber is selected from the group consisting of nano-zinc oxide coated with silica;
  • the inorganic nano-ultraviolet absorber has a morphology of a cuboid, a sphere, a rod, a ribbon, a needle, a sheet or a sea urchin; more preferably, the inorganic nano-UV absorber has a morphology of a cubic Shape or sphere.
  • the high molecular polymer is selected from the group consisting of polyvinyl butyral (PVB), polyvinylpyrrolidone (PVP), polyacrylate polymers, polysiloxane polymers, polyurethane polymers, and poly pairs. a copolymer or blend of any one or more of a phthalate polymer, polystyrene (PS) or polycarbonate (PC);
  • the high molecular polymer of the flame retardant functional layer is selected from the group consisting of polysiloxane polymers; more preferably, the high molecular polymer of the flame retardant functional layer is selected from the group consisting of polydimethylsiloxane and polyparaphenylene One of propylene glycol formate (PPT).
  • PPT propylene glycol formate
  • the auxiliary agent is selected from the group consisting of diethyl phthalate, dioctyl phthalate, dibutyl phthalate, tributyl phosphate, triphenyl phosphate, tricresyl phosphate, and bismuth Dibutyl acrylate, acrylic acid copolymer, non-reactive modified polysiloxane, H88, ethylene glycol monobutyl ether, diethylene glycol dibutyl ether, polyether modified silicone wetting agent, organic Silicone defoamer, polyether defoamer, polyvinylpyrrolidone, various ionic surfactants, fatty alcohol polyoxyethylene ether, stearyltrimethylammonium chloride, N,N-bis-hydroxyl Methyl-N-(3'-dialkoxy-2'-hydroxypropyl)methylammonium sulfate, hard amide propyl- ⁇ -hydroxyethyl-dimethylammonium nitrate.
  • the second technical problem to be solved by the present invention is to provide a method for preparing a transparent flame-retardant and heat-insulating anti-ultraviolet polymer composite film, which has simple preparation process, low production cost, easy realization of large-scale industrialization, and has important social and social Economic value and broad market prospects.
  • the present invention adopts the following technical solutions:
  • a preparation method of transparent flame-retardant heat-insulating anti-ultraviolet polymer composite film comprising the following preparation steps:
  • the film-forming stock solution of the flame-retardant functional layer obtained in the step (1) is coated on the substrate by knife coating, transfer, spraying, dipping, roll coating, spin coating, extrusion molding or calender molding. Curing at ⁇ 150 ° C or UV light;
  • the film forming stock solution obtained in the step (1) is coated in the step (2) by knife coating, transfer, spraying, dipping, roll coating, spin coating, extrusion molding or calender molding. Another substrate One side, then cured at 80-150 ° C or UV light;
  • step 3 Coating, transferring, spraying, dipping, rolling, spin coating, extrusion molding or calendering of the film forming raw material of the ultraviolet shielding functional layer obtained in the step (1) is carried out in the step 3).
  • the heat-insulating functional layer is cured at 80-150 ° C or ultraviolet light; the product is transparent flame-retardant heat-insulating anti-UV polymer composite film.
  • the dispersion medium in the step (1) is a mixture of one or more of water, methanol, ethanol, n-heptane, n-hexane, cyclohexane, toluene, xylene, ethyl acetate or butyl acetate.
  • the transparent polymer film substrate is selected from the group consisting of polyethylene terephthalate (PET), polycarbonate (PC), polystyrene (PS), polyethylene (PE), and polypropylene (PP). Or one of polyvinyl chloride (PVC).
  • PET polyethylene terephthalate
  • PC polycarbonate
  • PS polystyrene
  • PE polyethylene
  • PP polypropylene
  • PVC polyvinyl chloride
  • the third technical problem to be solved by the present invention is to provide a transparent flame-retardant heat-insulating and ultraviolet-proof polymer composite film, and the transparent flame-retardant heat-insulating and ultraviolet-proof polymer composite film provided by the invention can be used for glass and window.
  • Transparent materials and devices such as protective films, containers and electronic components are mainly used in construction, transportation, electronics, aerospace, medicine and other fields.
  • the invention has the beneficial effects that the transparent flame-retardant and heat-insulating ultraviolet-proof polymer composite film of the invention has a visible light transmittance of more than 80%, an ultraviolet light transmittance of less than 1%, and a near-infrared light transmittance of less than 10%, and energy saving. The effect is remarkable and it also has excellent flame retardant ability.
  • the flame-retardant functional layer high-molecular polymer of the transparent flame-retardant and heat-insulating anti-UV polymer composite film of the invention is preferably a polysiloxane resin, so that the transparent flame-retardant heat-insulating and anti-UV polymer composite film can be imparted with self-cleaning ability. .
  • the preparation method of the transparent flame-retardant and heat-insulating anti-ultraviolet polymer composite film of the invention is simple and easy to produce, has low production cost, and is suitable for large-scale industrial production.
  • the transparent flame-retardant and heat-insulating anti-ultraviolet polymer composite film of the invention can be applied to many fields such as human life, work, transportation, adventure, space engineering, display, special engineering and the like.
  • FIG. 1 is a structural view of a transparent flame-retardant and heat-insulating anti-UV polymer composite film of the present invention.
  • Example 2 is a UV-Vis-NIR spectrum diagram of a transparent flame-retardant and heat-insulating anti-UV polymer composite film prepared in Example 8 of the present invention.
  • Example 4 is a photograph of a polymer composite film prepared in Example 8 of the present invention.
  • Figure 5 is a photograph of a dispersion of a dispersion containing Mg(OH) 2 nanoparticles in Example 1 of the present invention.
  • Fig. 6 is a photograph of a solid of a dispersion containing ZnO nanoparticles in Example 1 of the present invention.
  • Figure 7 is a photograph of a polymer composite film prepared in Example 9 of the present invention.
  • ZnO, ITO, ATO, and LaB 6 used in the present invention are commercially available products;
  • H88 is a commercially available product, for example, produced by Hubei Laisi Chemical New Material Co., Ltd.; various types of tungsten bronze particles are synthesized according to the following documents: Chongshen Guo ,Shu Yin,Lijun Huang,Lu Yang and Tsugio Sato.Discovery of an excellent IR with a broad working waveband:CsxWO3nanorods.Chem.Commun.,2011,47,8853-8855.
  • optical properties of the films prepared according to the invention were determined using a UV-2501 UV-Vis spectrophotometer.
  • the flame retardancy of the film material was tested using a JF-3 oxygen index meter.
  • the agent or a solution of a certain concentration thereof is uniformly mixed to obtain a film-forming stock solution.
  • the mass ratio of Mg(OH) 2 to PDMS in this step is about 30:70.
  • ITO indium tin oxide
  • PVB polyvinyl butyral
  • the ZnO nanoparticles are dispersed in an appropriate amount of ethanol to form a transparent dispersion containing ZnO nanoparticles.
  • the transparent dispersion containing ZnO nanoparticles and polyvinyl butyral (PVB) were thoroughly mixed to obtain a film-forming stock solution of the ultraviolet-protective functional layer.
  • the ZnO:PVB in the film forming stock solution is about 5:95.
  • the LaB 6 nanoparticles were dispersed in an appropriate amount of ethanol to form a transparent dispersion containing LaB 6 nanoparticles.
  • the transparent dispersion containing LaB 6 nanoparticles is mixed with polyvinyl butyral (PVB) and an auxiliary agent to obtain a film-forming stock solution of the heat insulating functional layer.
  • PVB polyvinyl butyral
  • the ZnO nanoparticles are dispersed in a certain amount of ethanol to form a transparent dispersion containing ZnO nanoparticles.
  • the transparent dispersion containing ZnO nanoparticles is mixed with PVB to obtain a film-forming stock solution of the ultraviolet-protective functional layer.
  • the mass ratio of ZnO to PVB in this step is about 5:95.
  • the film-forming stock solution of the flame-retardant functional layer obtained in the step (1) is coated on the PET substrate by spraying, and cured at 80 ° C;
  • Mg (OH) 2 nanoparticles dispersed in toluene to form Mg (OH) 2 containing a transparent dispersion liquid; containing Mg (OH) 2 with a transparent dispersion liquid polyethylene terephthalate and additives
  • the film-forming film forming solution of the flame-retardant functional layer is obtained by mixing uniformly.
  • the mass ratio of Mg(OH) 2 to PDMS in this step is about 40:60.
  • the transparent dispersion containing ITO and ATO nanoparticles is mixed with PVB and an appropriate amount of auxiliary agent to obtain a film-forming stock solution of the heat insulating functional layer.
  • the ZnO nanoparticles are dispersed in a certain amount of ethanol to form a transparent dispersion containing ZnO nanoparticles.
  • the dispersion containing the ZnO nanoparticles is mixed with the PVB to obtain a film-forming stock solution of the ultraviolet-protective functional layer.
  • the mass ratio of ZnO to PVB in this step is about 5:95.
  • the film forming stock solution of the anti-UV functional layer obtained in the step (1) is applied onto the heat insulating functional layer obtained in the step (3) by a doctor blade method, and cured at 80 ° C; Insulation and anti-UV polymer composite film. Its performance is shown in Table 1.
  • the K x WO 3 nanoparticles were dispersed in an appropriate amount of ethanol to form a transparent dispersion containing LaB 6 nanoparticles.
  • the ZnO nanoparticles are dispersed in a certain amount of ethanol to form a transparent dispersion containing ZnO nanoparticles.
  • the transparent dispersion containing ZnO nanoparticles is mixed with PVB to obtain a film-forming stock solution of the ultraviolet-protective functional layer.
  • the mass ratio of ZnO to PVB in this step is about 5:95.
  • the film-forming stock solution of the flame-retardant functional layer obtained in the step (1) is coated on the PET substrate by spin coating, and cured under irradiation with an ultraviolet lamp;
  • the film forming stock solution of the anti-UV functional layer obtained in the step (1) is coated on the heat insulating functional layer obtained in the step (3) by spin coating, and cured under ultraviolet light irradiation; Insulation and anti-UV polymer composite film. Its performance is shown in Table 1.
  • Al(OH) 3 is dispersed in an appropriate amount of toluene to form a transparent dispersion containing Al(OH) 3 .
  • An appropriate amount of PPT and an auxiliary agent are added to a transparent dispersion containing Al(OH) 3 and stirred and mixed uniformly to obtain a film-forming stock solution of the flame-retardant functional layer.
  • the mass ratio of Al(OH) 3 , PPT and auxiliary in this step is about 28:70:2.
  • the ZnO nanoparticles were dispersed in an appropriate amount of ethanol to obtain a transparent dispersion containing ZnO nanoparticles.
  • the transparent dispersion containing ZnO nanoparticles is mixed with PVB to obtain a film-forming stock solution of the ultraviolet-protective functional layer.
  • the ZnO:PVB in the film forming stock solution is about 5:95.
  • ITO indium tin oxide
  • the ZnO nanoparticles are dispersed in a certain amount of ethanol to form a transparent dispersion containing ZnO nanoparticles.
  • the transparent dispersion liquid containing ZnO nanoparticles is sufficiently mixed with PVB to obtain a film-forming stock solution of the ultraviolet-proof functional layer.
  • the mass ratio of ZnO to PVB in this step is about 20:80.
  • ITO indium tin oxide
  • the transparent dispersion containing ZnO nanoparticles is mixed with PVB to obtain a film-forming stock solution of the ultraviolet-protective functional layer.
  • the film-forming stock solution of the anti-UV functional layer obtained in the step (1) is coated on the heat insulating functional layer obtained in the step (3) by a roll coating method, and cured at 80 ° C; Insulation and anti-UV polymer composite film. Its performance is shown in Table 1.
  • Al(OH) 3 is dispersed in an appropriate amount of butyl acetate to form a transparent dispersion containing Al(OH) 3 .
  • An appropriate amount of PPT and an appropriate amount of auxiliary agent are added to the transparent dispersion containing Al(OH) 3 and uniformly mixed to obtain a film-forming stock solution of the flame-retardant functional layer.
  • the mass ratio of Al(OH) 3 , PPT and auxiliary in this step is about 38:60:2.
  • the nanoparticle mixture of ITO, ATO and WO 3 is dispersed in an appropriate amount of ethanol, wherein the mass ratio of ITO:ATO:WO 3 is 1.5:1.5:2, forming a transparent layer containing (ITO, ATO, WO 3 ) nanoparticles Dispersions.
  • the ZnO nanoparticles are dispersed in an appropriate amount of ethanol to form a transparent dispersion containing ZnO nanoparticles.
  • the transparent dispersion liquid containing ZnO nanoparticles is sufficiently mixed with PVB to obtain a film-forming stock solution of the ultraviolet-proof functional layer.
  • the film forming stock solution of the ultraviolet shielding functional layer obtained in the step (1) is applied to the heat insulating functional layer obtained in the step (3) by extrusion molding, and cured at 80 ° C; Flame-retardant and heat-insulating anti-UV polymer composite film. Its performance is shown in Table 1.
  • Example 4 was repeated except that the near-infrared absorber or the heat-shielding agent were potassium tungsten bronze (K x WO 3 ), tantalum tungsten bronze (Cs x WO 3 ), and tantalum tungsten bronze (Rb x WO 3 ). ), potassium antimony tungsten bronze (K x Cs y WO 3 ), ammonium tungsten bronze ((NH 4 ) x WO 3 ), nano tungsten oxide (WO 3 ) or lanthanum hexaboride (LaB 6 ).
  • K x WO 3 potassium tungsten bronze
  • Cs x WO 3 tantalum tungsten bronze
  • Rb x WO 3 tantalum tungsten bronze
  • K x Cs y WO 3 potassium antimony tungsten bronze
  • ammonium tungsten bronze (NH 4 ) x WO 3 )
  • nano tungsten oxide WO 3
  • LaB 6 lanthanum hexaboride
  • Example 4 was repeated except that the inorganic nano-UV absorbers were respectively silica-coated nano zinc oxide (ZnO) and nano titanium dioxide (TiO 2 ).
  • Example 4 was repeated except that the polymer was polyvinyl butyral (PVB), polyvinylpyrrolidone (PVP), polystyrene (PS), polycarbonate (PC), poly Ethylene terephthalate (PET) or polyurethane (PU).
  • PVB polyvinyl butyral
  • PVP polyvinylpyrrolidone
  • PS polystyrene
  • PC polycarbonate
  • PET poly Ethylene terephthalate
  • PU polyurethane
  • Example 4 was repeated except that the plastic auxiliaries were dioctyl phthalate (DOP), dibutyl sebacate (DBS), H88 leveling agent, polyoxyethylene oxypropylene glycerol ( GPE), triethylene glycol di-2-ethylhexanoate (3G8) or photoinitiator 184.
  • DOP dioctyl phthalate
  • DBS dibutyl sebacate
  • H88 leveling agent polyoxyethylene oxypropylene glycerol
  • GPE polyoxyethylene oxypropylene glycerol
  • G8 triethylene glycol di-2-ethylhexanoate

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Abstract

本发明公开了一种透明阻燃隔热防紫外高分子复合贴膜，该透明阻燃隔热防紫外高分子复合贴膜自上而下依次为：阻燃功能层、基片层、隔热功能层和防紫外功能层，膜厚度为1um～500um，其可见光透过率大于80％，紫外光透过率小于1％，近红外光的透过率小于10％。本发明还公开了透明阻燃隔热防紫外高分子复合贴膜的制备方法，本发明的透明阻燃隔热防紫外高分子复合贴膜的制备工艺简便易行，生产成本低，适于大规模的工业化生产。本发明的透明阻燃隔热防紫外高分子复合贴膜，可以用于玻璃、视窗、保护膜、容器和电子元件等透明的材料和器件上，在建筑、交通、电子、航天航空、医药等诸多领域具有广泛的应用前景。

Description

透明阻燃隔热防紫外高分子复合贴膜及其制备方法和用途 技术领域
本发明涉及聚合物-无机纳米粒子合成复合薄膜领域，特别涉及一种透明阻燃隔热防紫外高分子复合贴膜及其制备方法。
背景技术
近年来，党中央国务院相继出台了国家能源消耗20％的明文，节能已经受到中央政府前所未有的高度关注。随着国家节能政策的相继出台，节能在全社会范围内掀起了热潮。
在这股节能热潮中，节能玻璃贴膜已经成为新经济增长的最大亮点。纵观中国玻璃贴膜市场，无论是建筑业、汽车业，还是IT产品，对于玻璃贴膜的潜在需求都是惊人的，所以采用新兴的有机-无机纳米粒子复合技术合成复合玻璃贴膜具有重要的战略意义。
近年来我国经济繁荣，城市建设发展迅猛，美轮美奂的现代化建筑将内座城市装点得绚丽多姿。然而，在城市建设发展的同时也带来了能源和资源消耗居高不下的社会问题，据有关统计，目前我国建筑能耗占社会能耗的40％，而室内采暖和空调制冷所消耗的能耗约占建筑能耗的65％，更为震惊的是采暖和空调所带来的控温能效有50％以上从节能效果不理想的建筑物玻璃窗流失掉，因而门窗节能改造在既有建筑节能中至关重要。为此，降低建筑高能耗已经成为我国可持续发展的迫切需求，成为国家当前工作中的重点。现在在欧美的许多发达国家，为了提高门窗的节能效率，有超过70％的建筑采用节能玻璃贴膜来进行节能改造。这是值得我国学习的经验，这也为节能玻璃在我国的发展提供了难得的机遇。
目前我国市场上的节能玻璃贴膜主要被威固(V-KOOL)、雷朋、3M(3M)、联邦(ATI)、强生(Johnson)几大国外品牌占据，市场上缺少本土自主品牌的产品，这位我国本土节能玻璃贴膜的发展提供了广阔的发展空间，也为节能玻璃贴膜的制备技术的发展提供了动力。
众所周知，紫外线作为一种非可视光线，具有特定的杀伤力，被科学界称为“无形杀手”。紫外线按照其波长的长短分为：UV-A波段的波长为320～ 400nm；UV-B为280～320nm；UV-C为100～280nm；短波紫外线可穿过真皮，中波则可进入真皮。中波紫外线UV-B的极大部分可以被皮肤吸收，损害DNA，当DNA遭到破坏，细胞会因此而死亡或者发展成为不可控的癌细胞。目前可以诊断出的许多疾病的诱因均与紫外辐射有关。而从20世纪20年代以来，由于碳氟系溶剂和氟利昂的大量使用，大气层中臭氧层遭到严重的破坏，致使到达地球表面的紫外线不断增加。为此，人们花费了很大的人力物力对“无形杀手”采取有效的防护措施，研究开发研制各种防紫外线材料。目前市场上已经有多重紫外屏蔽材料问世，但是，现有的紫外屏蔽材料还是存在着诸如：可见光的透过率较低，对红外光区无吸收，加工生产成本过高等不足，仍具有很大的改进空间。
目前市场上的众多紫外屏蔽膜、红外隔热膜材料都是以有机高分子聚合物为基材制备得到的，因而膜的本身也具有一定的可燃性；目前，膜材料不仅仅可以应用在玻璃、视窗、保护膜、容器和电子元件等透明的材料和器件上，在建筑、交通、电子、航空航天、医药等领域也得到了广泛的应用，在这些特殊的领域中高分子材料占有很大比重，因而在这些领域中膜材料的阻燃性能就显得尤为重要；此外，在膜材料的传统应用领域(如建筑行业和汽车行业)中，玻璃等原本不可燃的建筑材料在其表面贴上各种功能型的贴膜制品后就极有可能成为火源或是火焰的传播介质；因而研制开发出一种集阻燃、红外阻隔和紫外屏蔽等多种功能于一身的玻璃贴膜具有重要意义，而且还具有广阔的市场前景。
发明内容
本发明要解决的第一个技术问题是提供一种透明阻燃隔热防紫外高分子复合贴膜，该透明阻燃隔热防紫外高分子复合贴膜的透明度高、阻燃效果好、隔热性能优异且兼具防紫外线功能。
为解决第一个技术问题，本发明采用下述技术方案：
一种透明阻燃隔热防紫外高分子复合贴膜，包括阻燃功能层、隔热功能层、防紫外功能层和基片层。
优选地，所述高分子复合贴膜自上而下依次为：阻燃功能层、基片层、隔热功能层和防紫外功能层。
优选地，所述透明阻燃隔热防紫外高分子复合贴膜的厚度为1um～500um， 优选地，透明阻燃隔热防紫外高分子复合贴膜的厚度为1um～300um。
优选地，所述透明阻燃隔热防紫外高分子复合贴膜的可见光透过率大于80％，紫外光透过率小于1％，近红外光的透过率小于10％。
优选地，所述阻燃功能层由无机纳米阻燃剂10～50wt％、高分子聚合物50～70wt％和助剂0～20wt％组成；优选地，所述阻燃功能层由无机纳米阻燃剂30～50wt％、高分子聚合物50～70wt％和塑料助剂0～20％组成；
阻燃功能层的厚度为100nm～100um；优选地，所述无机纳米阻燃剂选自纳米氢氧化镁、纳米氢氧化铝、硼酸锌、三氧化二锑、α-三氧化钼等任意一种或几种的混合物；更优选地，所述无机纳米阻燃剂选自纳米氢氧化镁或纳米氢氧化铝；
优选地，所述无机纳米阻燃剂形貌为立方形、球形、棒状、带状、针状、片状或海胆形；更优选地，所述无机纳米阻燃剂形貌为片状。
优选地，所述纳米氢氧化镁按下述步骤制备：
(1)将镁盐溶于水或有机溶剂中，得到镁盐溶液；将碱溶于水或有机溶剂中，得碱液；
(2)将镁盐溶液和碱液加入到超重力旋转填充床或套管式环形微通道反应器中反应，反应后得到氢氧化镁悬浊液；
(3)将表面活性剂加入到氢氧化镁悬浊液中进行改性；改性后静置改性液；
(4)将改性液过滤、洗涤；得到所需是的纳米氢氧化镁颗粒。
镁盐选自下列物质中的一种或多种：硫酸镁、硝酸镁、氯化镁、醋酸镁。
镁盐溶液的浓度为1wt％～35wt％。
所述有机溶剂选自下列物质中的一种或多种：甲醇、乙醇、乙二醇、异丙醇、丙三醇、丁醇、丙酮、丁酮、乙酸乙酯、乙酸丁酯、苯、甲苯、二甲苯、二甲基亚砜、四氢呋喃。
所述碱液选自下列物质中的一种或多种：氢氧化钠溶液、氢氧化钾溶液、氨水；所述氢氧化钠溶液为氢氧化钠溶于水或有机溶剂形成的溶液；所述氢氧化钾溶液为氢氧化钾溶于水或有机溶剂形成的溶液；所述有机溶剂选自下列物质中的一种或多种：甲醇、乙醇、乙二醇、异丙醇、丙三醇、丁醇、丙酮、丁酮、乙酸乙酯、乙酸丁酯、苯、甲苯、二甲苯、二甲基亚砜、四氢呋 喃、正己烷、环己烷。
所述碱液的浓度为1wt％～40wt％；优选地，所述碱液的浓度为1wt％～25wt％。
步骤(1)中，将得到的镁盐溶液和碱液分别置于储槽中，保持温度为20～70℃。
步骤(2)中，反应温度为20～70℃；更优选地，反应温度为25～60℃；最优选地，反应温度为25～55℃。
步骤(2)中，所述超重力旋转床反应器选自旋转填充床超重力旋转床反应器、折流式超重力旋转床反应器、螺旋通道超重力旋转床反应器、定-转子超重力旋转床反应器或旋转碟片超重力旋转床反应器；优选地，旋转床的转子转速为300～5000rpm；优选地，转床的转子转速为600～2500rpm。
步骤(2)中，通入旋转填充床中镁盐溶液与碱液的摩尔流速比是0.2～3.5:1；优选地，所述镁盐溶液通入旋转填充床的喷口线速度为2～7m/s，碱液为2～8m/s。
步骤(2)中，所述套管式环形微通道反应器由一根外管和一根内管构成套管，在内管、外管之间留有环隙构成环形微通道，环形微通道径向间距为100微米～5毫米，外管上设有连续相进口和出口，内管一端设有分散相进口，另一端闭合，且闭合端外形为圆锥体或子弹头状，在与闭合端相邻的柱状内管管壁上沿壁周向布有微孔，微孔孔径范围为0.05～100微米，柱状内管管壁开孔率为3％～60％，内管上的微孔为分散相出口。
步骤(2)中，通入套管式环形微通道反应器中的镁盐溶液与碱液的体积流量比为(0.5～10):1。
步骤(2)中，镁盐溶液通入套管式环形微通道反应器外管的流量为1～6L/min，碱液通入套管式环形微通道反应器内管的流量为0.2～2L/min。
步骤(2)中，采用多个套管式环形微通道反应器并联。
步骤(2)中，采用离心泵、蠕动泵或计量泵附带流量计调节反应溶液注入速率。
步骤(3)中，所述表面活性剂选自下列物质中的一种或多种:十六烷基三甲基溴化铵、十二烷基硫酸钠、油酸钠、聚乙烯吡咯烷酮、聚乙二醇、γ-氨丙基三乙氧基硅烷、γ-缩水甘油醚氧丙基三甲氧基硅烷、γ-甲基丙烯酰氧基 丙基三甲氧基硅烷、N-(β-氨乙基)-γ-氨丙基三甲氧基硅烷、N-(β-氨乙基)-γ-氨丙基三乙氧基硅烷、N-β-(氨乙基)-γ-氨丙基甲基二甲氧基硅烷、油酸、硬脂酸、硬脂酸锌、硬质酸钠、钛酸酯、聚乙烯醇。
步骤(3)中，所述改性在改性罐中进行，改性温度为30～95℃，改性时间为0.5～5h；优选地，改性温度为40～90℃，改性时间为1～4h；最优地，改性温度为50～80℃，改性时间为1.5～4h。
步骤(3)中，所述表面活性剂包覆层占改性后氢氧化镁颗粒的质量分数为1％～40％；优选地，所述表面活性剂包覆层占改性后氢氧化镁颗粒的质量分数为2％～30％；最优选地，所述表面活性剂包覆层占改性后氢氧化镁颗粒的质量分数为5％～25％。
步骤(3)中，所述静置时间为0.5～5h。
优选地，所述的纳米氢氧化铝的制备方法类似于纳米氢氧化镁的制备方法。
优选地，所述隔热功能层由近红外吸收剂或热屏蔽剂5～50wt％、高分子聚合物60～80wt％和助剂0～35wt％组成；隔热功能层的厚度为100nm～150um；优选地，所述的近红外吸收剂或热屏蔽剂选自纳米氧化铟锡、纳米氧化锡锑、纳米氧化钨、各种钨青铜或六硼化镧中的任意一种或几种的混合物；
优选地，所述的近红外吸收剂或是热屏蔽剂的形貌为立方形、球形、棒状、带状、针状、片状抑或是海胆形；更优选地，所述的近红外吸收剂或是热屏蔽剂的形貌为立方形或球形。
优选地，所述防紫外功能层由无机纳米紫外吸收剂4～60wt％、高分子聚合物40～96wt％和助剂0～30wt％组成；防紫外功能层的厚度为100nm～50um；
优选地，所述的无机纳米紫外吸收剂选自纳米氧化锌、纳米二氧化钛、纳米氧化铈、掺杂纳米氧化锌、掺杂纳米二氧化钛，或是以上述任意一种纳米颗粒为核，表面包覆二氧化硅的核-壳结构复合金属氧化物纳米颗粒中的一种或几种的混合物；更优选地，所述的无机纳米紫外吸收剂选自表面包覆二氧化硅的纳米氧化锌；
优选地，所述的无机纳米紫外吸收剂形貌为立方形、球形、棒状、带状、针状、片状抑或是海胆形；更优选地，所述的无机纳米紫外吸收剂形貌为立方形或球形。
优选地，所述高分子聚合物选自聚乙烯醇缩丁醛(PVB)、聚乙烯吡咯烷酮(PVP)、聚丙烯酸酯类聚合物、聚硅氧烷类聚合物、聚氨酯类聚合物、聚对苯二甲酸酯类聚合物、聚苯乙烯(PS)或聚碳酸酯(PC)中的任意一种或几种的共聚物或共混物；
优选地，阻燃功能层的高分子聚合物选自为聚硅氧烷类聚合物；更优选地，阻燃功能层的高分子聚合物选自聚二甲基硅氧烷和聚对苯二甲酸丙二醇酯(PPT)中的一种。
优选地，所述助剂选自邻苯二甲酸二乙酯、邻苯二甲酸二辛酯、邻苯二甲酸二丁酯、磷酸三丁酯、磷酸三苯酯、磷酸三甲苯酯、癸二酸二丁酯、丙烯酸共聚物、非反应型改性聚硅氧烷、H88、乙二醇单丁醚、二乙二醇二丁醚、聚醚改性聚硅氧烷类润湿剂、有机硅类消泡剂、聚醚类消泡剂、聚乙烯吡咯烷酮、各类离子型表面活性剂、脂肪醇聚氧乙烯醚、硬脂基三甲基氯化铵、N,N-双-羟乙基-N-(3‘于二烷氧基-2‘-羟基丙基)甲氨硫酸甲酯盐、硬质酰胺丙基-β-羟乙基-二甲基硝酸氨。硬质羟胺丙基-β-羟乙基-二甲基磷酸三氢氨、乙氧基月桂酷胺，甘油-硬脂酸酯、二硫代氨基甲酸钠、十二烷基磺酸钠中的一种或几种。
本发明要解决的第二个技术问题是提供一种透明阻燃隔热防紫外高分子复合贴膜的制备方法，该方法制备工艺简单，生产成本低，易于实现大规模工业化，具有重要的社会和经济价值和广阔的市场前景。
为解决第二个技术问题，本发明采用下述技术方案：
一种透明阻燃隔热防紫外高分子复合贴膜的制备方法，包括如下制备步骤：
(1)将各个功能层的功能型纳米粒子分散到适当的分散介质中，形成均匀透明的分散液；将透明分散液与的高分子聚合物和助剂或其一定浓度的溶液混合均匀，得到各个功能层的成膜原液。
(2)将步骤(1)中所得到的阻燃功能层成膜原液采用刮涂、转印、喷涂、浸渍、辊涂、旋涂、挤出成型或压延成型法覆于基片上，在80～150℃或紫外灯照射下固化；
(3)将步骤(1)中所得到隔热功能层的成膜原液采用刮涂、转印、喷涂、浸渍、辊涂、旋涂、挤出成型或压延成型法覆于步骤(2)中的基片的另 一侧，然后在80～150℃或紫外灯照射下固化；
(4)将步骤(1)中所得到的防紫外功能层的成膜原液刮涂、转印、喷涂、浸渍、辊涂、旋涂、挤出成型或压延成型法覆于步骤3)中得到的隔热功能层上，在80～150℃或紫外灯照射下固化；得到产品透明阻燃隔热防紫外高分子复合贴膜。
优选地，步骤(1)所述分散介质是水、甲醇、乙醇、正庚烷、正己烷、环己烷、甲苯、二甲苯、乙酸乙酯或乙酸丁酯的一种或几种的混合物。
优选地，所述的透明高分子膜基选自聚对苯二甲酸乙二醇酯(PET)、聚碳酸酯(PC)、聚苯乙烯(PS)、聚乙烯(PE)、聚丙烯(PP)或聚氯乙烯(PVC)中的一种。
本发明要解决的第三个技术问题是提供一种透明阻燃隔热防紫外高分子复合贴膜的用途，本发明所提供的透明阻燃隔热防紫外高分子复合贴膜可以用于玻璃、视窗、保护膜、容器和电子元件等透明的材料和器件上，主要在建筑、交通、电子、航空航天、医药等领域应用。
本发明的有益效果是本发明的透明阻燃隔热防紫外高分子复合贴膜的可见光透过率大于80％，紫外光透过率小于1％，近红外光的透过率小于10％，节能效果显著，还具有优异的阻燃能力。
本发明的透明阻燃隔热防紫外高分子复合贴膜的阻燃功能层高分子聚合物优选为聚硅氧烷类树脂，这样可以赋予透明阻燃隔热防紫外高分子复合贴膜以自清洁能力。本发明的透明阻燃隔热防紫外高分子复合贴膜的制备方法生产工艺简便易行，生产成本低，适于大规模的工业化生产。
本发明的透明阻燃隔热防紫外高分子复合贴膜，可以应用在人类生活、工作、交通、探险、空间工程、展示、特种工程等诸多领域。
附图说明
图1为本发明透明阻燃隔热防紫外高分子复合贴膜的结构图。
图2为本发明实施例8所制备的透明阻燃隔热防紫外高分子复合贴膜的UV-Vis-NIR光谱图。
图3为本发明实施例7所制备的透明阻燃隔热防紫外高分子复合贴膜的阻燃功能层接触角示意图，其中阻燃功能层接触角CA＝117.8±2°。
图4为本发明实施例8所制备的高分子复合贴膜的实物照片。
图5为本发明实施例1中含有Mg(OH)2纳米颗粒的分散液的实物照片。
图6为本发明实施例1中含有ZnO纳米颗粒的分散液的实物照片。
图7为本发明实施例9所制备的高分子复合贴膜的实物照片。
具体实施方式
本发明中所使用的ZnO、ITO、ATO、LaB6为市售商品；H88为市售商品，例如湖北来斯化工新材料有限公司有生产；各类钨青铜颗粒按下述文献合成：Chongshen Guo，Shu Yin,Lijun Huang,Lu Yang and Tsugio Sato.Discovery of an excellent IR absorbent with a broad working waveband:CsxWO3nanorods.Chem.Commun.,2011,47,8853-8855.
Chongshen Guo，Shu Yin,Qaing Dong and Tsugio Sato.Near-infrared absorption properties of RbxWO3nanoparticles.Cryst.Eng.Commun.,2012,14,7727-7732.Chongshen Guo，Shu Yin,Qaing Dong and Tsugio Sato.The near infrared absorption properties of W18O49.RSC.Advances.,2012,2,5041-5043.
Lingxiao Liu,XiaoLi Dong,Xiangwen Liu,Fei Shi and Tsugio Sato.Solvothermal synthesis an characterization of tungsten oxides with controllable morphology and crystal phase.J.Alloy.Compd.,2011,509,1482-1488.
Chongshen Guo，Shu Yin,and Tsugio Sato.Effects of crystallization atmosphere on the near-infrared absorbtion and electroconductive properties of tungsten bronze type MxWO3(M＝Na,K).J.Am.Ceram.Soc.,95,1634-1639.
Chongshen Guo，Shu Yin,Lijun Huang and Tsugio Sato.Synthesis of one-dimensional potassium tungsten bronze with excellent near-infrared absorption property.ACS Appl.Mater.Interfaces.,2011,3,2794-2799.
Chongshen Guo，Shu Yin,Yunfang Huang,Qaing Dong and Tsugio Sato.Synthesis of W18O49nanorod via ammonium tungsten oxide and its interasting optical properties.Langmuir.2011,27,12172-12178.
Hiromitsu Takeda and Kenji Adachi.Near infrared absoption of tungsten oxide nanoparticle dispertions.,J.Am.Ceram.Soc.,2007,90,2059-2061.
采用UV-2501型紫外-可见分光光度计测定本发明所制备的薄膜的光学性能。
采用JF-3型氧指数测定仪对膜材料的阻燃性能进行测试。
实施例1：
(1)将纳米氢氧化镁(Mg(OH)2)纳米颗粒分散到甲苯中，形成含有Mg(OH)2的透明分散液；将上述含有Mg(OH)2的透明分散液与PDMS和助剂或其一定浓度的溶液混合均匀，得到成膜原液。此步骤中的Mg(OH)2与PDMS的质量比约为30:70。
将纳米氧化铟锡(ITO)分散到适量的乙醇中，形成含有ITO的透明分散液；将上述含有ITO的透明分散液与聚乙烯缩丁醛(PVB)和助剂充分搅拌均匀得到隔热功能层的成膜原液。此步骤中各主要组分的质量比为ITO:PVB:助剂＝5:75:20。
将ZnO纳米粒子分散到适量的乙醇中，形成含有ZnO纳米粒子的透明分散液。将含有ZnO纳米粒子的透明分散液与聚乙烯缩丁醛(PVB)充分混合得到防紫外功能层的成膜原液。成膜原液中的ZnO:PVB约为5:95。
(2)将步骤(1)中所得到的阻燃功能层成膜原液采用旋涂法覆于PET基片上，在80℃下固化；
(3)将步骤(1)中所得到隔热功能层的成膜原液采用旋涂法覆于在步骤(2)中的基片的另一侧，在80℃下固化；
(4)将步骤(1)中所得到的防紫外功能层的成膜原液采用旋涂法覆于在步骤(3)中得到的隔热功能层上，在80℃下固化；得到产品透明阻燃隔热防紫外高分子复合贴膜。其性能见表1。
实施例2：
(1)将30份的纳米氢氧化铝(Al(OH)3)分散到甲苯中，形成含有Al(OH)3的透明分散液。将上述含有Al(OH)3的透明分散液与PDMS和适量的助剂混合均匀得到成膜原液。此步骤中的Al(OH)3与PDMS的质量比约为30:70。
将LaB6纳米粒子分散到适量的乙醇中，形成含有LaB6纳米粒子的透明分散液。将含有LaB6纳米粒子的透明分散液与聚乙烯缩丁醛(PVB)和助剂混合均匀得到隔热功能层的成膜原液。此步骤中各主要组分的质量比为LaB6:PVB:助剂＝5:75:20。
将ZnO纳米粒子分散到一定量的的乙醇中，形成含有ZnO纳米粒子的透明分散液。将含有ZnO纳米粒子的透明分散液与PVB混合均匀得到防紫外功能层的成膜原液。此步骤中的ZnO与PVB的质量比约为5:95。
(2)将步骤(1)中所得到的阻燃功能层成膜原液采用喷涂法覆于PET基片上，在80℃下固化；
(3)将步骤(1)中所得到隔热功能层的成膜原液采用喷涂法覆于步骤(2)中的基片的另一侧，在80℃下固化；
(6)将步骤(1)中所得到的防紫外功能层的成膜原液采用喷涂法覆于步骤(3)中得到的隔热功能层上，在80℃下固化；得到产品透明阻燃隔热防紫外高分子复合贴膜。其性能见表1。
实施例3：
(1)将Mg(OH)2纳米颗粒分散到甲苯中，形成含有Mg(OH)2的透明分散液；将含有Mg(OH)2的透明分散液与聚对苯二甲酸丙二醇酯以及助剂混合均匀得到阻燃功能层的成膜成膜原液。此步骤中的Mg(OH)2与PDMS的质量比约为40:60。
将ITO和ATO的混合物(ITO：ATO＝w1:w2＝1:1)分散到一定量的乙醇中，形成含有ITO和ATO纳米粒子的透明分散液。将含有ITO和ATO纳米粒子的透明分散液与PVB以及适量的助剂混合均匀得到隔热功能层的成膜原液。此步骤中各主要组分的质量比为(ITO和ATO):PVB:助剂＝5:75:20。
将ZnO纳米粒子分散到一定量的的乙醇中，形成含有ZnO纳米粒子的透明分散液。将含有ZnO纳米粒子的分散液与的PVB混合均匀得到防紫外功能层的成膜原液。此步骤中的ZnO与PVB的质量比约为5:95。
(2)将步骤(1)中所得到的阻燃功能层成膜原液采用刮涂法覆于PET基片上，在80℃下固化；
(3)将步骤(1)中所得到隔热功能层的成膜原液采用刮涂法覆于步骤(2)中的基片的另一侧，在80℃下固化；
(4)将步骤(1)中所得到的防紫外功能层的成膜原液采用刮涂法覆于步骤(3)中得到的隔热功能层上，在80℃下固化；得到产品透明阻燃隔热防紫外高分子复合贴膜。其性能见表1。
实施例4：
(1)将Mg(OH)2纳米颗粒分散到甲苯中，形成含有Mg(OH)2的透明分散液；将上述得到的含有Mg(OH)2的透明分散液与聚对苯二甲酸丙二醇酯(PPT)以及适量的助剂混合均匀后得到阻燃功能层的成膜原液。此步骤中的Mg(OH)2 与PPT的质量比约为30:70。
将KxWO3纳米粒子分散到适量的乙醇中形成含有LaB6纳米粒子的透明分散液。将含有KxWO3纳米粒子的透明分散液与PVB和适量的助剂，充分搅拌均匀得到隔热功能层的成膜原液。此步骤中各主要组分的质量比为KxWO3:PVB:助剂＝5:75:20。
将ZnO纳米粒子分散到一定量的的乙醇中，形成含有ZnO纳米粒子的透明分散液。将含有ZnO纳米粒子的透明分散液与PVB混合均匀得到防紫外功能层的成膜原液。此步骤中的ZnO与PVB的质量比约为5:95。
(2)将步骤(1)中所得到的阻燃功能层成膜原液采用旋涂法覆于PET基片上，在紫外灯照射下固化；
(3)将步骤(1)中所得到隔热功能层的成膜原液采用旋涂法覆于步骤(2)中的基片的另一侧，在紫外灯照射下固化；
(4)将步骤(1)中所得到的防紫外功能层的成膜原液采用旋涂法覆于步骤(3)中得到的隔热功能层上，在紫外灯照射下固化；得到产品透明阻燃隔热防紫外高分子复合贴膜。其性能见表1。
实施例5：
(1)将Al(OH)3分散到适量的甲苯中，形成含有Al(OH)3的透明分散液。将适量的PPT以及助剂加入到含有Al(OH)3的透明分散液中，搅拌混合均匀后得到阻燃功能层的成膜原液。此步骤中的Al(OH)3、PPT以及助剂的质量比约为28:70:2。
将纳米氧化铟锡ITO分散到适量的乙醇中，形成含有ITO的透明分散液；将上述含有ITO的透明分散液与聚乙烯缩丁醛(PVB)和助剂混均匀得到隔热功能层的成膜原液。此步骤中各主要组分的质量比为ITO:PVB:助剂＝5:75:20。
将ZnO纳米粒子分散到适量的乙醇中，得到含有ZnO纳米粒子的透明分散液。将含有ZnO纳米粒子的透明分散液与PVB混合均匀得到防紫外功能层的成膜原液。成膜原液中的ZnO:PVB约为5:95。
(2)将步骤(1)中所得到的阻燃功能层成膜原液采用喷涂法覆于PET基片上，在紫外灯照射下固化；
(3)将步骤(1)中所得到隔热功能层的成膜原液采用喷涂法覆于步骤(2)中的基片的另一侧，在紫外灯照射下固化；
(4)将步骤(1)中所得到的防紫外功能层的成膜原液采用喷涂法覆于步骤(3)中得到的隔热功能层上，在紫外灯照射下固化；得到产品透明阻燃隔热防紫外高分子复合贴膜。其性能见表1。
实施例6：
(1)将Mg(OH)2纳米颗粒分散到甲苯中，形成含有Mg(OH)2的透明分散液；将上述透明分散液与聚对苯二甲酸丙二醇酯充分混合均匀得到成膜原液。此步骤中的Mg(OH)2与PPT的质量比约为30:70。
将纳米氧化铟锡(ITO)分散到适量的乙醇中，形成含有ITO的透明分散液；将上述含有ITO的透明分散液与聚乙烯缩丁PVB以及适量的助剂充分混合均匀得到隔热功能层的成膜原液。此步骤中各主要组分的质量比为ITO:PVB:助剂＝25:65:10。
将ZnO纳米粒子分散到一定量的的乙醇中，形成含有ZnO纳米粒子的透明分散液。将含有ZnO纳米粒子的透明分散液中与PVB充分混合均匀得到防紫外功能层的成膜原液。此步骤中的ZnO与PVB的质量比约为20:80。
(2)将步骤(1)中所得到的阻燃功能层成膜原液采用压延法覆于PET基片上，在80℃下固化；
(3)将步骤(1)中所得到隔热功能层的成膜原液采用压延法覆于步骤(2)中的基片的另一侧，在80℃下固化；
(4)将步骤(1)中所得到的防紫外功能层的成膜原液采用压延法覆于步骤(3)中得到的隔热功能层上，在80℃下固化；得到产品透明阻燃隔热防紫外高分子复合贴膜。其性能见表1。
实施例7：
(1)将Mg(OH)2纳米颗粒分散到甲苯中，形成含有Mg(OH)2的透明分散液；将上述透明分散液与聚对苯二甲酸丙二醇酯(PPT)以及适量的助剂充分混合均匀得到成膜原液。此步骤中的Mg(OH)2与PPT的质量比约为40:60。
将纳米氧化铟锡(ITO)分散到适量的乙醇中，形成含有ITO的透明分散液；向上述含有ITO的透明分散液中加聚乙烯缩丁PVB和助剂，充分搅拌混合均匀得到隔热功能层的成膜原液。此步骤中各主要组分的质量比为ITO:PVB:助剂＝35:55:10。
将ZnO纳米粒子分散到一定量的乙醇中，形成含有ZnO纳米粒子的分散 液。将含有ZnO纳米粒子的透明分散液与PVB混合均匀得到防紫外功能层的成膜原液。
(2)将步骤(1)中所得到的阻燃功能层成膜原液采用辊涂法覆于PET基片上，在80℃下固化；
(3)将步骤(1)中所得到隔热功能层的成膜原液采用辊涂法覆于步骤(2)中的基片的另一侧，在80℃下固化；
(4)将步骤(1)中所得到的防紫外功能层的成膜原液采用辊涂法覆于步骤(3)中得到的隔热功能层上，在80℃下固化；得到产品透明阻燃隔热防紫外高分子复合贴膜。其性能见表1。
实施例8：
(1)将Al(OH)3分散到适量的乙酸丁酯中，形成含有Al(OH)3的透明分散液。将适量的PPT和适量的助剂加入到含有Al(OH)3的透明分散液中，混合均匀后得到阻燃功能层的成膜原液。此步骤中的Al(OH)3、PPT以及助剂的质量比约为38:60:2。
将ITO、ATO和WO3的纳米粒子混合物分散到适量的乙醇中，其中，ITO：ATO：WO3的质量比为1.5:1.5:2，形成含有(ITO、ATO、WO3)纳米粒子的透明分散液。向含有上述纳米粒子的透明分散液中加入一定比例的PVB和助剂混合均匀得到隔热功能层的成膜原液。此步骤中各主要组分的质量比为(ITO、ATO、WO3):PVB:助剂＝5:75:20。
将ZnO纳米粒子分散到适量的乙醇中，形成含有ZnO纳米粒子的透明分散液。将含有ZnO纳米粒子的透明分散液中与PVB充分混合均匀得到防紫外功能层的成膜原液。其中各组分的质量比为ZnO:PVB＝10:90。
(2)将步骤(1)中所得到的阻燃功能层成膜原液采用挤出成型法覆于PET基片上，在80℃下固化；
(3)将步骤(1)中所得到隔热功能层的成膜原液采用挤出成型法覆于步骤(4)中的基片的另一侧，在80℃下固化；
(4)将步骤(1)中所得到的防紫外功能层的成膜原液采用挤出成型法涂覆于步骤(3)中得到的隔热功能层上，在80℃下固化；得到产品透明阻燃隔热防紫外高分子复合贴膜。其性能见表1。
表1 实施例1-8所制备的透明阻燃隔热防紫外高分子复合贴膜的性能
Figure PCTCN2014088598-appb-000001
实施例9-15：
重复实施例4，其不同之处仅在于，近红外吸收剂或热屏蔽剂分别为钾钨青铜(KxWO3)、铯钨青铜(CsxWO3)、铷钨青铜(RbxWO3)、钾铯钨青铜(KxCsyWO3)、铵钨青铜((NH4)xWO3)、纳米氧化钨(WO3)或六硼化镧(LaB6)。
实施例16-17：
重复实施例4，其不同之处仅在于，无机纳米紫外吸收剂分别为二氧化硅包覆的纳米氧化锌(ZnO)、纳米二氧化钛(TiO2)。
实施例18-23：
重复实施例4，其不同之处仅在于，高分子聚合物分别为聚乙烯醇缩丁醛(PVB)、聚乙烯吡咯烷酮(PVP)、聚苯乙烯(PS)、聚碳酸酯(PC)、聚对苯二甲酸乙二醇酯(PET)或聚氨基甲酸酯(PU)。
实施例24-29：
重复实施例4，其不同之处仅在于，塑料助剂分别为邻苯二甲酸二辛酯(DOP)、癸二酸二丁酯(DBS)、H88流平剂、聚氧乙烯氧丙烯甘油(GPE)、三甘醇二-2-乙基己酸酯(3G8)或光引发剂184。
显然，本发明的上述实施例仅仅是为清楚地说明本发明所作的举例，而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无法对所有的实施方式予以穷举。凡是属于本发明的技术方案所引伸出的显而易见的变化或变动仍处于本发明的保护范围之列。

Claims (10)

  1. 一种透明阻燃隔热防紫外高分子复合贴膜，其特征在于：包括阻燃功能层、隔热功能层、防紫外功能层和基片层。
  2. 根据权利要求1所述的透明阻燃隔热防紫外高分子复合贴膜，其特征在于：优选地，所述高分子复合贴膜自上而下依次为：阻燃功能层、基片层、隔热功能层和防紫外功能层。
    优选地，所述透明阻燃隔热防紫外高分子复合贴膜的厚度为1um～500um，优选地，透明阻燃隔热防紫外高分子复合贴膜的厚度为1um～300um。
  3. 根据权利要求1所述的透明阻燃隔热防紫外高分子复合贴膜，其特征在于：优选地，所述阻燃功能层由无机纳米阻燃剂10～50wt％、高分子聚合物50～70wt％和助剂0～20wt％组成；阻燃功能层的厚度为100nm～100um；优选地，所述无机纳米阻燃剂选自纳米氢氧化镁、纳米氢氧化铝、硼酸锌、三氧化二锑、α-三氧化钼中的任意一种或几种的混合物；更优选地，所述无机纳米阻燃剂选自纳米氢氧化镁或纳米氢氧化铝；
    优选地，所述无机纳米阻燃剂形貌为立方形、球形、棒状、带状、针状、片状或海胆形；更优选地，所述无机纳米阻燃剂形貌为片状；
    优选地，所述纳米氢氧化镁按下述步骤制备：
    (1)将镁盐溶于水或有机溶剂中，得到镁盐溶液；将碱溶于水或有机溶剂中，得碱液；
    (2)将镁盐溶液和碱液加入到分子混合强化反应器(特征为：分子混合特征时间小于成核诱导期时间)中，优选地加入到超重力旋转填充床或微通道反应器中反应，反应后得到氢氧化镁悬浊液；
    (3)将表面活性剂加入到氢氧化镁悬浊液中进行改性；改性后静置改性液；
    (4)将改性液过滤、洗涤；得到所需是的纳米氢氧化镁颗粒；
    镁盐选自下列物质中的一种或多种：硫酸镁、硝酸镁、氯化镁、醋酸镁；
    镁盐溶液的浓度为1wt％～35wt％；
    所述有机溶剂选自下列物质中的一种或多种：甲醇、乙醇、乙二醇、异丙醇、丙三醇、丁醇、丙酮、丁酮、乙酸乙酯、乙酸丁酯、苯、甲苯、二甲 苯、二甲基亚砜、四氢呋喃；
    所述碱液选自下列物质中的一种或多种：氢氧化钠溶液、氢氧化钾溶液、氨水；所述氢氧化钠溶液为氢氧化钠溶于水或有机溶剂形成的溶液；所述氢氧化钾溶液为氢氧化钾溶于水或有机溶剂形成的溶液；所述有机溶剂选自下列物质中的一种或多种：甲醇、乙醇、乙二醇、异丙醇、丙三醇、丁醇、丙酮、丁酮、乙酸乙酯、乙酸丁酯、苯、甲苯、二甲苯、二甲基亚砜、四氢呋喃、正己烷、环己烷；
    所述碱液的浓度为1wt％～40wt％；优选地，所述碱液的浓度为1wt％～25wt％；
    步骤(1)中，将得到的镁盐溶液和碱液分别置于储槽中，保持温度为20～70℃；
    步骤(2)中，反应温度为20～70℃；更优选地，反应温度为25～60℃；最优选地，反应温度为25～55℃；
    步骤(2)中，所述超重力旋转床反应器选自旋转填充床超重力旋转床反应器、折流式超重力旋转床反应器、螺旋通道超重力旋转床反应器、定-转子超重力旋转床反应器或旋转碟片超重力旋转床反应器；优选地，旋转床的转子转速为300～5000rpm；优选地，转床的转子转速为600～2500rpm；
    步骤(2)中，通入旋转填充床中镁盐溶液与碱液的摩尔流速比是0.2～3.5:1；优选地，所述镁盐溶液通入旋转填充床的喷口线速度为2～7m/s，碱液为2～8m/s；
    步骤(2)中，所述微通道反应器由一根外管和一根内管构成套管，在内管、外管之间留有环隙构成环形微通道，环形微通道径向间距为100微米～5毫米，外管上设有连续相进口和出口，内管一端设有分散相进口，另一端闭合，且闭合端外形为圆锥体或子弹头状，在与闭合端相邻的柱状内管管壁上沿壁周向布有微孔，微孔孔径范围为0.05～100微米，柱状内管管壁开孔率为3％～60％，内管上的微孔为分散相出口；
    步骤(2)中，通入套管式环形微通道反应器中的镁盐溶液与碱液的体积流量比为(0.5～10):1；
    步骤(2)中，镁盐溶液通入套管式环形微通道反应器外管的流量为1～6L/min，碱液通入套管式环形微通道反应器内管的流量为0.2～2L/min；
    步骤(2)中，采用多个套管式环形微通道反应器并联；
    步骤(2)中，采用离心泵、蠕动泵或计量泵附带流量计调节反应溶液注入速率；
    步骤(3)中，所述表面活性剂选自下列物质中的一种或多种:十六烷基三甲基溴化铵、十二烷基硫酸钠、油酸钠、聚乙烯吡咯烷酮、聚乙二醇、γ-氨丙基三乙氧基硅烷、γ-缩水甘油醚氧丙基三甲氧基硅烷、γ-甲基丙烯酰氧基丙基三甲氧基硅烷、N-(β-氨乙基)-γ-氨丙基三甲氧基硅烷、N-(β-氨乙基)-γ-氨丙基三乙氧基硅烷、N-β-(氨乙基)-γ-氨丙基甲基二甲氧基硅烷、油酸、硬脂酸、硬脂酸锌、硬质酸钠、钛酸酯、聚乙烯醇；
    步骤(3)中，所述改性在改性罐中进行，改性温度为30～95℃，改性时间为0.5～5h；优选地，改性温度为40～90℃，改性时间为1～4h；最优地，改性温度为50～80℃，改性时间为1.5～4h；
    步骤(3)中，所述表面活性剂包覆层占改性后氢氧化镁颗粒的质量分数为1％～40％；优选地，所述表面活性剂包覆层占改性后氢氧化镁颗粒的质量分数为2％～30％；最优选地，所述表面活性剂包覆层占改性后氢氧化镁颗粒的质量分数为5％～25％；
    步骤(3)中，所述静置时间为0.5～5h。
  4. 根据权利要求1所述的透明阻燃隔热防紫外高分子复合贴膜，其特征在于：优选地，所述隔热功能层由近红外吸收剂或热屏蔽剂5～50wt％、高分子聚合物60～80wt％和助剂0～35wt％组成；隔热功能层的厚度为100nm～150um；优选地，所述的近红外吸收剂或热屏蔽剂选自纳米氧化铟锡、纳米氧化锡锑、纳米氧化钨、各种钨青铜或六硼化镧中的任意一种或几种的混合物；
    优选地，所述的近红外吸收剂或是热屏蔽剂的形貌为立方形、球形、棒状、带状、针状、片状抑或是海胆形；更优选地，所述的近红外吸收剂或是热屏蔽剂的形貌为立方形或球形。
  5. 根据权利要求1所述的透明阻燃隔热防紫外高分子复合贴膜，其特征在于：优选地，所述防紫外功能层由无机纳米紫外吸收剂4～60wt％、高分子聚合物40～96wt％和助剂0～30wt％组成；防紫外功能层的厚度为100nm～50um；
    优选地，所述的无机纳米紫外吸收剂选自纳米氧化锌、纳米二氧化钛、 纳米氧化铈、掺杂纳米氧化锌、掺杂纳米二氧化钛，或是以上述任意一种纳米颗粒为核，表面包覆二氧化硅的核-壳结构复合金属氧化物纳米颗粒中的一种或几种的混合物；更优选地，所述的无机纳米紫外吸收剂选自表面包覆二氧化硅的纳米氧化锌；
    优选地，所述的无机纳米紫外吸收剂形貌为立方形、球形、棒状、带状、针状、片状抑或是海胆形；更优选地，所述的无机纳米紫外吸收剂形貌为立方形或球形。
  6. 根据权利要求3-5中任一所述的透明阻燃隔热防紫外高分子复合贴膜，其特征在于：优选地，所述高分子聚合物选自聚乙烯醇缩丁醛、聚乙烯吡咯烷酮、聚丙烯酸酯类聚合物、聚硅氧烷类聚合物、聚氨酯类聚合物、聚对苯二甲酸酯类聚合物、聚苯乙烯或聚碳酸酯中的任意一种或几种的共聚物或共混物；更优选地，所述阻燃功能层的高分子聚合物选自聚硅氧烷类聚合物或聚对苯二甲酸酯类聚合物中的一种或几种共聚物或共混物；最优选地，所述阻燃功能层的高分子聚合物选自聚二甲基硅氧烷和聚对苯二甲酸丙二醇酯中的一种；
    优选地，所述助剂选自邻苯二甲酸二乙酯、邻苯二甲酸二辛酯、邻苯二甲酸二丁酯、磷酸三丁酯、磷酸三苯酯、磷酸三甲苯酯、癸二酸二丁酯、丙烯酸共聚物、非反应型改性聚硅氧烷、流平剂H88、乙二醇单丁醚、二乙二醇二丁醚、聚醚改性聚硅氧烷类润湿剂、有机硅类消泡剂、聚醚类消泡剂、聚乙烯吡咯烷酮、各类离子型表面活性剂、脂肪醇聚氧乙烯醚、硬脂基三甲基氯化铵、N,N-双-羟乙基-N-(3‘于二烷氧基-2‘-羟基丙基)甲氨硫酸甲酯盐、硬质酰胺丙基-β-羟乙基-二甲基硝酸氨。硬质羟胺丙基-β-羟乙基-二甲基磷酸三氢氨、乙氧基月桂酷胺，甘油-硬脂酸酯、二硫代氨基甲酸钠、十二烷基磺酸钠中的一种或几种。
  7. 如权利要求1-6所述的透明阻燃隔热防紫外高分子复合贴膜的制备方法，其特征在于：包括如下制备步骤：
    (1)将各个功能层的功能型纳米粒子分散到适当的分散介质中，形成均匀透明的分散液；将透明分散液与高分子聚合物和助剂或其一定浓度的溶液混合均匀，得到各个功能层的成膜原液。
    (2)将步骤(1)中所得到的阻燃功能层成膜原液采用刮涂、转印、喷 涂、浸渍、辊涂、旋涂、挤出成型或压延成型法覆于基片上，在80～150℃或紫外灯照射下固化；
    (3)将步骤(1)中所得到隔热功能层的成膜原液采用刮涂、转印、喷涂、浸渍、辊涂、旋涂、挤出成型或压延成型法覆于步骤(2)中的基片的另一侧，然后在80～150℃或紫外灯照射下固化；
    (4)将步骤(1)中所得到的防紫外功能层的成膜原液刮涂、转印、喷涂、浸渍、辊涂、旋涂、挤出成型或压延成型法覆于步骤3)中得到的隔热功能层上，在80～150℃或紫外灯照射下固化；得到产品透明阻燃隔热防紫外高分子复合贴膜。
  8. 根据权利要求7所述的透明阻燃隔热防紫外高分子复合贴膜的制备方法，其特征在于：优选地，步骤(1)所述分散介质是水、甲醇、乙醇、正庚烷、正己烷、环己烷、甲苯、二甲苯、乙酸乙酯或乙酸丁酯的一种或几种的混合物。
  9. 根据权利要求1所述的透明阻燃隔热防紫外高分子复合贴膜的基片选自透明高分子膜基片。所述的透明高分子膜基片选自聚对苯二甲酸乙二醇酯(PET)、聚碳酸酯(PC)、聚苯乙烯(PS)、聚乙烯(PE)、聚丙烯(PP)或聚氯乙烯(PVC)中的一种。
  10. 如权利要求1-6所述的透明阻燃隔热防紫外高分子复合贴膜的用途，其特征在于：本发明所提供的透明阻燃隔热防紫外高分子复合贴膜可以用于玻璃、视窗、保护膜、容器和电子元件等透明的材料和器件上，主要在建筑、交通、电子、航天航空、医药等领域应用。
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CN117946434A (zh) * 2024-03-26 2024-04-30 中北大学 基于peg和mwcnt-cooh结合静电自组装法的阻燃相变膜及其制备方法和应用
CN117946434B (zh) * 2024-03-26 2024-06-11 中北大学 基于peg和mwcnt-cooh结合静电自组装法的阻燃相变膜及其制备方法和应用

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