CN109517254A

CN109517254A - Organic/inorganic composite film piece and preparation method thereof with light selective absorbing and ageing-resistant function

Info

Publication number: CN109517254A
Application number: CN201710851495.2A
Authority: CN
Inventors: 曾晓飞; 韩玥; 王洁欣; 陈建峰
Original assignee: Beijing University of Chemical Technology
Current assignee: Beijing University of Chemical Technology
Priority date: 2017-09-19
Filing date: 2017-09-19
Publication date: 2019-03-26
Anticipated expiration: 2037-09-19
Also published as: CN109517254B

Abstract

The present invention discloses an organic inorganic composite film with light selective absorption and aging function, including polymers, multi -layer structure nano composite particles, plasticizers or soft agents and additives; : 45-99.8 parts of polymer, 0.2-40 parts of multi-layer structure nanocomposite particles, 0-45 parts of plasticizer or softener, 0-10 parts of auxiliary agent. The preparation method of the organic-inorganic composite membrane is also disclosed. The organic inorganic composite film provided by the present invention can be widely used in the fields of construction, aerospace, electronic information, rubber, plastic and other fields to prepare functional composite glass and transparent devices. The preparation method of the organic-inorganic composite film with photoselective absorption and aging resistance functions provided by the invention is simple and easy for large-scale production.

Description

Organic/inorganic composite film piece and its system with light selective absorbing and ageing-resistant function Preparation Method

Technical field

The present invention relates to field of nanocomposite materials, have light selective absorbing and ageing-resistant function more particularly, to one kind Organic/inorganic composite film piece and preparation method thereof.

Background technique

In recent years, with the continuous improvement of the rapid development of national economy and living standards of the people, need of the people to the energy It asks and is also rapidly increasing.China is that maximum developing country, energy consumption are continuously increased in the world.Building energy consumption has become me One of most important energy consumption element of state, accounts for about the 49.5% of social total energy consumption, is up to 55% in the near future.In order to pursue beauty It sees and improves brightness, glass is widely used in building, has become the necessity in people's life.It is examined from the energy is saved The characteristics of worry, glass transition heat, can frequently result in energy loss, and according to statistics, 40% energy loss is by glass door in building It is 2-3 times of developed country caused by window, therefore, research and development novel glass door and window power-saving technology is extremely urgent.

With being constantly progressive for science and technology, transparent nanocomposite causes extensively because it is with many unique performances On the one hand general concern maintains high light transmittance of the polymer in visible-range, on the other hand by binding function without Machine nano particle and the regulation barrier action for realizing ultraviolet and infrared ray, so that reducing heat transfer reaches energy-saving effect.Though So there are various adhering film to glass products now, still, cannot still take into account easy, easy-to-use, energy-saving safety the requirement of production. In modern architecture, in order to improve the energy-saving effect and security performance of glass door and window, hollow glass or doubling glass are mostly used greatly. Infrared ray can be obstructed but also absorb ultraviolet light by lacking in the prior art, while also ensure the material of service life, and by light Selective absorbing and the organic/inorganic composite film piece of ageing-resistant function are placed among hollow glass or doubling glass, can either be effective Above-mentioned problem is solved, and can be avoided the secondary work progress after building completion.Therefore, in door and window, energy-saving glass, building, boat Its aviation, electronic information, traditional fields such as rubber plastic and transparent nanocomposite have huge application value.

Summary of the invention

The invention solves first technical problem be to provide it is a kind of with light selective absorbing and ageing-resistant function Organic/inorganic composite film piece；The diaphragm can be widely applied on the fields such as building, space flight and aviation, electronic information, rubber, plastics make Standby functionality compound glass and transparent devices, can make glass and transparent devices have on the basis of keeping the transparency it is good every Heat and the performance for absorbing ultraviolet isolating infrared ray, and manufacture craft is simple, it is easily operated.

The invention solves second technical problem be to provide the production method of above-mentioned organic/inorganic composite film piece.

In order to solve the first technical problem mentioned above, invention adopts the following technical scheme that:

Organic/inorganic composite film piece with light selective absorbing and ageing-resistant function, including polymer, multilayered structure are received Rice composite particles, plasticizer or softening agent and auxiliary agent；Each component mass fraction are as follows: 45-99.8 parts of polymer, multilayered structure nanometer 0.2-40 parts of composite particles, plasticizer or 0-45 parts of softening agent, 0-10 parts of auxiliary agent.

As the further improvement of technical solution, the organic/inorganic composite film piece includes 50-90 parts of polymer, multilayer knot 0.5-30 parts of structure Nano composite granules, plasticizer or 1-30 parts of softening agent, 1-8 parts of auxiliary agent；Preferably, polymer 50-80 parts, more 1-20 parts of structure nano composite particles of layer, plasticizer or 15-30 parts of softening agent, 1-5 parts of auxiliary agent；Most preferably, polymer 60-70 Part, 3-10 parts of multilayered structure Nano composite granules, plasticizer or 20-30 parts of softening agent, 1-3 parts of auxiliary agent；

As the further improvement of technical solution, the organic/inorganic composite film piece with a thickness of 0.1-5mm.

As the further improvement of technical solution, the polymer be selected from polypropylene (referred to as: PP), polystyrene (referred to as: PS), polycarbonate (referred to as: PC), polymethyl methacrylate (referred to as: PMMA), acrylonitrile-butadiene-styrene copolymer (referred to as: ABS), polyvinyl chloride (referred to as: PVC), ethylene-vinyl acetate copolymer (referred to as: EVA), polyvinyl butyral (letter Claim: PVB), polyurethanes (referred to as: PU), poly terephthalic acid resinoid, epoxy resin, butadiene rubber, natural rubber, One of isoprene rubber, EP rubbers, butyl rubber, chlorohydrin rubber, silicon rubber are a variety of.

As the further improvement of technical solution, the plasticizer or softening agent are selected from dioctyl phthalate, the last of the ten Heavenly stems two Dioctyl phthalate, dibutyl sebacate, di-n-octyl phthalate, phthalic acid fourth in Triethyleneglycol di 2 ethylhexanoate Benzyl ester, dicyclohexyl phthalate, dibutyl phthalate, diisobutyl phthalate, repefral, Diethyl phthalate, diisooctyl phthalate, pine tar system rubber softener, fat oil system rubber softener, synthesis Rubber softener, petroleum rubber softener, coal tar system rubber softener it is one or more.

As the further improvement of technical solution, the auxiliary agent is selected from dispersing agent, antiheat agent, curing agent, toughener, emulsification Agent, defoaming agent, levelling agent, delustering agent, light stabilizer, antistatic agent it is one or more.

As the further improvement of technical solution, the multilayered structure Nano composite granules include: to obstruct with infrared ray The doping oxide inner layer of function, the metal oxide middle layer with ultraviolet radiation absorption function, having, which reduces metal oxide, urges Change the silica time outer layer of performance, and with the organic coating layer outermost layer for improving stability.

Preferably, the mass ratio of the doping oxide, metal oxide, silica and organic coating layer is 1: (0.1-0.33): (0.1-0.25): (0-0.1), particle size 5-100nm；It is highly preferred that the doping oxide, metal The mass ratio of oxide, silica and organic coating layer is 1:(0.1-0.33): (0.1-0.25): (0.01-0.1).

As the further improvement of technical solution, it is green that the doping oxide is selected from doped stannum oxide, doping vanadium oxide, tungsten One of copper class compound, molybdenum bronze class compound, tungsten bronze class compound are a variety of.

Preferably, the doped chemical in the doped stannum oxide is in the elements such as indium, antimony, titanium, zinc, tungsten, iron, silver, platinum It is one or more, the molar ratio of tin is 0.01-1:1 in doped chemical and tin oxide；It is highly preferred that the doped chemical and oxygen The molar ratio for changing tin in tin is 0.1-0.5:1.

Preferably, the doped chemical in the doping vanadium oxide is selected from one of tungsten, magnesium, aluminium or a variety of, doped chemical Molar ratio with the vanadium in vanadium oxide is 0.01-1:1；It is highly preferred that the molar ratio of the vanadium in the doped chemical and vanadium oxide For 0.1-0.5:1；

Preferably, the doping member in the tungsten bronze class compound, molybdenum bronze class compound or tungsten bronze class compound Element is one of metallic elements such as lithium, sodium, potassium, rubidium, caesium, magnesium, calcium, germanium, tin, aluminium, gallium, indium, silver, gold, titanium, bismuth and zirconium or two Kind, doped chemical is 0.01-1:1 with the molar ratio of tungsten and/or molybdenum total amount.It is highly preferred that the doped chemical and tungsten and/or molybdenum The molar ratio of total amount is 0.1-0.5:1.

As the further improvement of technical solution, the metal oxide with UV absorbing properties is selected from doping oxygen Change one or both of zinc and adulterated TiOx.

Preferably, the doped chemical in the doping zinc-oxide be selected from aluminium, calcium, gallium, cadmium, cerium, copper, iron, magnesium, tin, antimony, One of silver, nickel, titanium are a variety of, and the molar ratio of the doped chemical and zinc in zinc oxide is 0.001-1:1；It is highly preferred that The molar ratio of the doped chemical and zinc in zinc oxide is 0.01-0.5:1；

Preferably, the doped chemical in the adulterated TiOx is selected from one of zinc, cobalt, iron, tin, lanthanum etc. or a variety of, The molar ratio of titanium is 0.001-1:1 in the doped chemical and titanium oxide；It is highly preferred that titanium in the doped chemical and titanium oxide Molar ratio be 0.01-0.5:1.

As the further improvement of technical solution, the organic coating layer choosing is from octyl trimethoxy silane, three second of octyl Oxysilane, hexamethyldisilazane, 3- methacryloxypropyl trimethoxy silane, 3- methacryloxypropyl Triethoxysilane, six ruthenium trimethoxysilanes, six ruthenium triethoxysilanes, dimethyl polysiloxane, glycidol oxygen Propyl trimethoxy silicane, glycidyl-oxypropyl triethoxysilane, nine fluorine hexyl trimethoxysilanes, ten trifluoro octyls three It is methoxy silane, tridecafluoro-n-octyltriethoxysilane, amine propyl-triethoxysilicane, hexamethyldisilazane, lauric acid/dodecanoic acid, hard Resin acid, tannic acid, succinic acid, acrylic acid, oleic acid, isopropanol, polyvinyl alcohol, polyethylene glycol, lauryl sodium sulfate, dodecyl Benzene sulfonic acid sodium salt, sodium laurate, odium stearate, sodium acetate, enuatrol, polyoxyethylene, styrene, tween (polyoxyethylene sorbitol Alcohol acid anhydride monoleate), one of methyl methacrylate or a variety of；

To solve above-mentioned second technical problem, the organic/inorganic composite film of above-mentioned smooth selective absorbing and ageing-resistant function The preparation method of piece, includes the following steps:

S01, centrifugation phase inversion will be passed through to plasticizer or softening comprising the liquid dispersion of multilayered structure Nano composite granules Stable oily phase dispersion is formed in agent；

S02, it polymer is passed through into feed inlet with oily phase dispersion is respectively added in extruder, control extruder melt zone Temperature is 150-250 DEG C, carries out melting premix 1-30 minutes, while controlling extruder discharging mouth temperature is 150-280 DEG C, is carried out Melt blending squeezes out or control mold temperature is 140-250 DEG C, and light selective absorbing and resistance to old is made in mixture injection molding Change the organic/inorganic composite film piece of function；

Or use following steps:

S11, polymer is dissolved in liquid phase medium, certain density resin solution is made, then will include multilayer knot The liquid dispersion of structure Nano composite granules is added thereto, and is sufficiently stirred, after mixing, and solution system to be dried is obtained, and is gathered Closing concentration of the object in mixed liquor is 0.5-20wt%, obtains masterbatch after dry, and the content of polymer is 30- in masterbatch 90wt%, multilayered structure Nano composite granules content be 10-70wt%；

S12, plasticizer or softening agent and a certain amount of polymer is added in masterbatch obtained into step S11, is stirring It is added in extruder after full and uniform mixing in machine, while controlling extruder discharging mouth temperature is 150-280 DEG C, is melted Blending extrusion or control mold temperature are 140-250 DEG C, and light selective absorbing and ageing-resistant function is made in mixture injection molding The organic/inorganic composite film piece of energy；

For that diaphragm obtained can be cut, batched and be packed according still further to normal process steps convenient for sale.

As the further improvement of technical solution, step S01, in S11, the multilayered structure Nano composite granules liquid phase point Granular media includes multilayered structure Nano composite granules and liquid phase medium；In the multilayered structure Nano composite granules, inner layer be with The doping oxide of infrared ray barriers function, middle layer be the metal oxide with UV absorbing properties, secondary outer layer be with The silica of metal oxide oxidation catalyst performance is reduced, outermost layer is with the organic coating layer for improving stability；The multilayer Structure nano composite particles are evenly dispersed in liquid phase medium；

As the further improvement of technical solution, the liquid phase medium be selected from water, methanol, ethyl alcohol, ethylene glycol, isopropanol, Benzyl alcohol, toluene, dimethylbenzene, dimethyl sulfoxide, dimethylformamide, dimethyl acetamide, n-hexane, hexamethylene, acetone, fourth One of ketone, ethyl acetate, butyl acetate, phenol, cyclohexanone, tetrahydrofuran, halogenated alkane.

As the further improvement of technical solution, the preparation method of the multilayered structure Nano composite granules liquid dispersion Include the following steps:

S1. the raw material of inner layer doping oxide is dissolved in solvent and forms salting liquid, stirred evenly, adjust pH value, then Reducing agent is added, reaction solution is transferred to progress hydro-thermal or solvent thermal reaction in autoclave, is cooled to room temperature after complete reaction, Centrifuge washing, precipitation and separation obtain doping oxide nano particle；

S2. the raw material of middle layer metal oxide is dissolved in solvent and forms salting liquid, lye is then added, adjust pH value, After being sufficiently mixed, the obtained doping oxide nano particle of S1 is added and is reacted；It is cooled to room temperature after complete reaction, from Heart washing, precipitation and separation obtain metal oxide coating-doping oxide nano particles；

S3. silicon-containing compound is added in a certain amount of ethyl alcohol, lye is then added, adjust pH value, after being sufficiently mixed, The obtained metal oxide coating-doping oxide nano particles of S2 are added, stirs evenly, is reacted；After complete reaction It is cooled to room temperature；

S4. the raw material for surface coating layer being added into above-mentioned mixed liquor is reacted, and reaction product is spent washing, then It is scattered in liquid phase medium, obtains containing multilayered structure nano particle liquid phase transparent dispersion.

Liquid dispersion produced by the present invention containing multilayered structure Nano composite granules has ultraviolet and infrared resistance simultaneously Every function, it is seen that light Tou Guo Shuai≤85%, ultraviolet screener Shuai≤99%, infrared ray rejection rate Wei≤90%；And dispersion has There is good stability；Liquid dispersion places 5 months without precipitating.

Preferably, in step S1, the raw material of the inner layer doping oxide is including at least one oxide raw material and at least A kind of doped chemical raw material.The oxide raw material is selected from one of following substances or a variety of: stannous chloride, tin tetrachloride, Stannous sulfate, stannous oxalate, nitric acid tin, sulfuric acid alum, vanadic sulfate, dichloro vanadyl, vanadyl oxalate, hydrogen-oxygen vanadyl, vanadium pentoxide, Ammonium metavanadate, zinc acetate, tungsten hexachloride, tungsten tetrachloride, tungstate lithium, potassium tungstate, wolframic acid caesium, sodium tungstate, wolframic acid rubidium, cesium sulfate, Potassium sulfate, sodium sulphate, rubidium sulfate, lithium sulfate, ammonium paratungstate, ammonium metatungstate, positive ammonium tungstate, tungsten silicide, tungsten sulfide, chlorine oxygen tungsten, It is one tungstic acid hydrate, metamolybdic acid ammonium, positive ammonium molybdate, ammonium paramolybdate, molybdic acid, molybdenum silicide, molybdenum sulfide, chlorine oxygen molybdenum, alcohol oxygen molybdenum, phosphoric Molybdenum, molybdenum tetrachloride, molybdenum bromide, molybdenum fluoride, molybdenum carbide, oxidation of coal molybdenum；The doped chemical raw material is selected from the carbon containing doped chemical Hydrochlorate, bicarbonate, nitrate, nitrite, hydroxide, chloride, sulfate, sulphite, acylate, alkoxide, One of complex compound, oxyacid, oxysalt are a variety of；The solution concentration of all metal ions is 0.1-1.0M；

Preferably, in step S1 and S2, the solvent is selected from water, methanol, ethyl alcohol, acetone, butanone, ethyl acetate, acetic acid One of butyl ester, toluene, dimethylbenzene, n-hexane, hexamethylene are a variety of；

Preferably, in step S1, the reducing agent is selected from oxalic acid, citric acid, methanol, ethyl alcohol, ethylene glycol, 1,2- the third two Alcohol, 1,3- propylene glycol, glycerine, ethanol amine, triethanolamine, oleyl amine, oleic acid, ethylenediamine, hydrazine hydrate, ammonium oxalate, ammonium hydroxide, boron hydrogen Change one or both of sodium, potassium borohydride, hydrogen sulfide, sodium hypophosphite, mole of the reducing agent and tungsten and/or molybdenum total amount Than for 1.5-20:1 or 2-18:1 or 4-16:1 or 6-16:1 or 8-15:1 or 10-12:1；

Preferably, in step S1, the pH value that adjusts refers to that acidic materials, which are added, to be adjusted the pH to 1-6.5 of reaction solution or add Enter the pH to 7.5-12 that alkaline matter adjusts solution；Wherein, acidic materials be selected from hydrochloric acid, nitric acid, sulfuric acid, oxalic acid, citric acid and One or both of acetic acid；Alkaline matter is selected from sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, ethamine, ethyl alcohol Amine, ethylenediamine, dimethylamine, trimethylamine, triethylamine, propylamine, isopropylamine, 1,3- propane diamine, 1,2- propane diamine, tripropyl amine (TPA) and three second One or both of hydramine；

Preferably, in step S1, the hydro-thermal or solvent thermal reaction carry out in the absence of oxygen, reaction temperature 100- 300 DEG C, reaction time 1-48h.Reaction temperature can also be 100-300 DEG C or 100-250 DEG C or 100-200 DEG C or 100- 150 DEG C or 150-300 DEG C or 150-250 DEG C or 150-200 DEG C or 200-300 DEG C or 200-250 DEG C；Reaction time is also It can be 1-40h or 1-30h or 1-20h or 1-10h or 5-48h or 5-40h or 5-30h or 5-20h or 10-48h, or 10-40h or 10-30h or 20-48h；

Preferably, in step S2, the raw material of the middle layer metal oxide is selected from carbonate, the bicarbonate of corresponding metal It is salt, nitrate, nitrite, hydroxide, chloride, sulfate, sulphite, acylate, alkoxide, complex compound, oxygen-containing One of acid, oxysalt are a variety of, and solution concentration of the metal ion in salting liquid is 0.1-1.0M；It is preferred that 0.3- 0.8M；

Preferably, in step S2, the lye is selected from sodium hydroxide, potassium hydroxide, ammonium hydroxide, ethamine, ethanol amine, second two In amine, dimethylamine, trimethylamine, triethylamine, propylamine, isopropylamine, 1,3- propane diamine, 1,2- propane diamine, tripropyl amine (TPA) and triethanolamine One or more, concentration 0.1-1.0M, preferably 0.3-0.8M；

Preferably, in step S2, the pH is 7-11, and reaction temperature is 40-90 DEG C, reaction time 0.5-10h；More Preferably, the pH is 7-10, and reaction temperature is 50-80 DEG C, reaction time 1-7h；Most preferably, the pH is 8- 9, reaction temperature is 60-70 DEG C, reaction time 2-5h.

Preferably, in step S3, the silicon-containing compound is that ethyl orthosilicate, methyl orthosilicate, silester or silicon are molten One of glue is a variety of；

Preferably, in step S3, the lye is selected from sodium hydroxide, potassium hydroxide, ammonium hydroxide, ethamine, ethanol amine, second two In amine, dimethylamine, trimethylamine, triethylamine, propylamine, isopropylamine, 1,3- propane diamine, 1,2- propane diamine, tripropyl amine (TPA) and triethanolamine One or more, concentration 0.1-1.0M, preferably 0.3-0.8M；

Preferably, in step S3, the reaction temperature is 30-90 DEG C, reaction time 1-10h；It is highly preferred that described anti- Answering temperature is 40-70 DEG C, reaction time 1-7h；Most preferably, the reaction temperature is 60-70 DEG C, reaction time 2-5h；

Preferably, in step S4, the raw material of the surface coating layer is octyl trimethoxy silane, octyl triethoxysilicane Alkane, hexamethyldisilazane, 3- methacryloxypropyl trimethoxy silane, three ethoxy of 3- methacryloxypropyl Base silane, six ruthenium trimethoxysilanes, six ruthenium triethoxysilanes, dimethyl polysiloxane, glycidyl-oxypropyl three Methoxy silane, glycidyl-oxypropyl triethoxysilane, nine fluorine hexyl trimethoxysilanes, ten trifluoro octyl trimethoxies Silane, tridecafluoro-n-octyltriethoxysilane, amine propyl-triethoxysilicane, hexamethyldisilazane, lauric acid/dodecanoic acid, stearic acid, Tannic acid, succinic acid, acrylic acid, oleic acid, isopropanol, polyvinyl alcohol, polyethylene glycol, lauryl sodium sulfate, detergent alkylate sulphur Sour sodium, sodium laurate, odium stearate, sodium acetate, enuatrol, polyoxyethylene, styrene, tween (polyoxyethylene sorbitol acid anhydride Monoleate), methyl methacrylate；

Preferably, in step S4, the reaction temperature is 20-80 DEG C, reaction time 1-10h；

Preferably, in step S4, the organic solvent is selected from ethyl alcohol, normal propyl alcohol, acetone, ethyl acetate, butyl acetate, first One of benzene, dimethylbenzene, n-hexane, hexamethylene, dimethyl sulfoxide, dimethylformamide, dimethyl acetamide are a variety of.

Any range documented by the present invention includes any numerical value between end value and end value and end value or end value Between any subrange for being constituted of any number.

Unless otherwise specified, each raw material in the present invention can be obtained by commercially available purchase, equipment used in the present invention The conventional equipment in fields can be used or carried out referring to the prior art of fields.

Compared with prior art, the invention has the following beneficial effects:

1) the organic/inorganic composite film piece of smooth selective absorbing provided by the invention and ageing-resistant function, can be widely applied to Functional compound glass and transparent devices are prepared on the fields such as building, space flight and aviation, electronic information, traditional rubber plastic, it can Make glass and transparent devices on the basis of keeping the transparency with good heat-insulated and absorption ultraviolet isolating infrared ray performance；

2) preparation method of smooth selective absorbing provided by the invention and the organic/inorganic composite film piece of ageing-resistant function letter Single, simple process is easy, is easy to large-scale production.

Detailed description of the invention

Specific embodiments of the present invention will be described in further detail with reference to the accompanying drawing

Fig. 1 is the methylene blue catalytic performance figure of the composite particles liquid dispersion of embodiment 1；

Fig. 2 is the doubling glass ageing-resistant performance test chart of embodiment 19.

Specific embodiment

In order to illustrate more clearly of the present invention, below with reference to preferred embodiment, the present invention is described further.Ability Field technique personnel should be appreciated that following specifically described content is illustrative and be not restrictive, this should not be limited with this The protection scope of invention.

Embodiment 1

The preparation method of liquid dispersion containing multi-layer nano composite particles, includes the following steps:

S1. it weighs 0.99g sodium tungstate powder to be dissolved in 12.5mL deionized water, 15mL dust technology is added, centrifuge washing obtains Flaxen wolframic acid colloidal sol；It weighs 0.2g cesium sulfate powder to be dissolved in 46mL deionized water, and in the transfer of 40mL deionized water Self-control wolframic acid is stated, stirs 4h at room temperature；14mL ethylene glycol is added into above-mentioned mixed liquor, stirs 1h at room temperature, it is molten to obtain raw material Liquid；Above-mentioned raw materials solution is transferred in water heating kettle, temperature programming 2h to 230 DEG C at room temperature, reacts 20h.After complete reaction It is cooled to room temperature, is centrifuged and is precipitated, precipitation and separation obtains caesium tungsten bronze nano particle；

S2. it weighs 1.9g zinc acetate to be added in 30mL ethyl alcohol, stirring and dissolving at 60 DEG C obtains zinc solution；Weigh 1.2g Sodium hydroxide is dissolved in 25mL ethyl alcohol, obtains aqueous slkali, and lye is added in above-mentioned zinc solution and self-control caesium doping is added Tungsten oxide powder 1.38g, temperature maintain 60 DEG C and are stirred to react 3h, cooling, filtering, dehydrated alcohol washing, dry to get arriving institute Infrared light and UV double the barrier nano particle stated；

S3. 80mL ethyl alcohol is measured, 1.8g ethyl orthosilicate is added, the ethanol containing ammonia that 0.07mol/L is added adjusts pH React 5h at=9,60 DEG C, it is cooling, filtering, dehydrated alcohol washing, dry to get arriving Nano composite granules；

S4. Nano composite granules are dispersed in 50mL ethyl alcohol, 0.8g octyl trimethoxy silane is added, is reacted at 60 DEG C Reaction product deionized water and ethanol washing are then dispersed in dimethylformamide by 1.5h, obtain having ultraviolet and red The dispersion of the multilayered structure Nano composite granules of outer barriers function.

In liquid dispersion obtained, the internal layer of multi-layer nano composite particles is caesium tungsten bronze, and middle layer is zinc oxide, secondary outer Layer is silica, and outermost layer is octyl trimethoxy silane organic coating layer.Above-mentioned dispersion, which is diluted to concentration, is The solution of 10wt%, progress optical performance test, visible light transmittance 72%, rate of ultraviolet shield 99.1% are infrared Line rejection rate is 90%, places 5 months without precipitating.

Fig. 1 is the methylene blue catalytic performance figure of the composite particles liquid dispersion of the present embodiment；It can be seen by the figure O containing coated Si out₂The more uncoated SiO of dispersion₂The photo-catalysis capability of dispersion is declined, and lower than methylene blue itself Catalytic performance shows that photocatalysis can be effectively relieved in liquid dispersion obtained.

Embodiment 2

S1. it weighs 0.99g sodium tungstate powder to be dissolved in 12.5mL deionized water, 15mL dust technology is added, centrifuge washing obtains Flaxen wolframic acid colloidal sol；It respectively weighs 0.2g cesium sulfate and 0.2g sodium sulfate powder is dissolved in 46mL deionized water, and use 40mL Deionized water shifts above-mentioned self-control wolframic acid, stirs 4h at room temperature；25mL ethylene glycol is added into above-mentioned mixed liquor, stirs at room temperature 1h obtains material solution；Above-mentioned raw materials solution is transferred in water heating kettle, temperature programming 3h to 260 DEG C at room temperature, reaction is for 24 hours. Reaction product deionized water and ethanol washing obtain sodium caesium tungsten bronze nano particle；

S2. it weighs 1.38g zinc sulfate and 0.69g aluminium chloride is dissolved in 50mL ethyl alcohol, the sodium of the above-mentioned preparation of 0.56g is added Caesium tungsten bronze nano particle, adjusting pH using ethanol containing ammonia is 8, and 5h is reacted at 60 DEG C, is cooled to room after fully reacting Temperature is centrifuged and is precipitated, precipitation and separation, obtains infrared and UV double and obstructs nano particle；

S3. 80mL ethyl alcohol is measured, 1.6g silester is added, the ethanol containing ammonia that 0.07mol/L is added adjusts pH= React 2h at 9,70 DEG C, it is cooling, filtering, dehydrated alcohol washing, dry to get arriving Nano composite granules；

S4. Nano composite granules are dispersed in 50mL ethyl alcohol, three ethoxy of 0.1g 3- methacryloxypropyl is added Base silane reacts 1.5h at 60 DEG C, reaction product deionized water and ethanol washing is then dispersed in ethyl acetate, obtained To with ultraviolet and the multilayered structure Nano composite granules of infrared barrier function dispersions.

In liquid dispersion obtained, the internal layer of multi-layer nano composite particles is sodium caesium tungsten bronze, and middle layer is that aluminium adulterates oxygen Change zinc, secondary outer layer is silica, and outermost layer is 3- methacryloxypropyl organic coating layer.It will be upper It states dispersion and is diluted to the solution that concentration is 10wt%, carry out optical performance test, visible light transmittance 74%, ultraviolet light Shielding rate is 99.1%, and infrared ray rejection rate is 91%, places 5 months without precipitating.

Embodiment 3

S1. it prepares the vanadic anhydride solution 40ml containing 0.01mol/L, 0.008g oxalic acid is added and stirs into uniform molten Liquid.Into solution be added 1.67mg magnesium nitrate, stir evenly, by above-mentioned solution be put into reaction kettle in 240 reaction for 24 hours, from Heart washing, precipitation and separation obtain magnesium doping vanadium oxide nano particle；

S2. it weighs 0.6g zinc acetate to be dissolved in 40mL ethyl alcohol, and the above-mentioned magnesium doping vanadium oxide nanometer of 0.18g is added Grain, stirring 30min obtain mixed solution.By the mixed liquor of sodium hydroxide and dehydrated alcohol, (wherein, water and dehydrated alcohol volume ratio are 1:0.2, the concentration of sodium hydroxide are 0.11mol/L) it is slowly dropped in above-mentioned solution, 12h is stirred to react at 80 DEG C；Reaction It is cooled to room temperature after completely, is centrifuged and is precipitated, precipitation and separation obtains infrared and UV double and obstructs nano particle；

S3. 80mL ethyl alcohol is measured, 1.8g ethyl orthosilicate is added, reacts 5h at 60 DEG C, the ammonium hydroxide second of 0.07mol/L is added Alcoholic solution adjusts pH=9, cooling, filtering, dehydrated alcohol washing, dry to get arriving Nano composite granules；

S4. Nano composite granules are dispersed in 50mL ethyl alcohol, 0.1g octyltri-ethoxysilane is added, is reacted at 60 DEG C Reaction product deionized water and ethanol washing are then dispersed in acetone by 1.5h, obtain having ultraviolet and infrared barrier function The liquid dispersion of the multilayered structure Nano composite granules of energy.

In liquid dispersion obtained, the internal layer of multi-layer nano composite particles is that magnesium adulterates vanadium oxide, and middle layer is zinc oxide, Secondary outer layer is silica, and outermost layer is octyltri-ethoxysilane organic coating layer.Above-mentioned dispersion, which is diluted to concentration, is The solution of 10wt%, progress optical performance test, visible light transmittance 75%, rate of ultraviolet shield 99.2% are infrared Line rejection rate is 91%, places 5 months without precipitating.

Embodiment 4

S1. it weighs 2.11g molybdenum pentachloride and 0.84g potassium hydroxide is add to deionized water, after being sufficiently mixed, add Reaction solution, is then transferred in autoclave by 12.6g oxalic acid, reacts 42h at 210 DEG C；Reaction product deionized water and second Alcohol washing, obtains potassium molybdenum bronze nano particle；

S2. it weighs 6.7g titanium tetrachloride to be dissolved in 40mL methanol, 0.28mol/L sodium hydroxide ethanol solution is added to It states in metal salt solution, and adequately mixes, adjusting pH is 8, and the potassium molybdenum bronze of the above-mentioned preparation of 0.24g is added, anti-at 80 DEG C Answer 4h；It is cooled to room temperature, is centrifuged and is precipitated after fully reacting, precipitation and separation obtains infrared and UV double and obstructs nanometer Grain；

S3. 60mL ethyl alcohol is measured, 2g methyl orthosilicate is added, the ethanol containing ammonia that 0.07mol/L is added adjusts pH= React 2h at 9,70 DEG C, it is cooling, filtering, dehydrated alcohol washing, dry to get arriving Nano composite granules；

S4. Nano composite granules are dispersed in 50mL ethyl alcohol, 0.1g3- methacryloxypropyl trimethoxy is added Base silane reacts 3h at 50 DEG C, reaction product deionized water and ethanol washing is then dispersed in butyl acetate, obtained Liquid dispersion with ultraviolet and infrared barrier function multilayered structure Nano composite granules.

In liquid dispersion obtained, the internal layer of multi-layer nano composite particles is potassium molybdenum bronze, and middle layer is that aluminium adulterates dioxy Change titanium, secondary outer layer is silica, and outermost layer is 3- methacryloxypropyl trimethoxy silane organic coating layer.It will be upper It states dispersion and is diluted to the solution that concentration is 10wt%, carry out optical performance test, visible light transmittance 73%, ultraviolet light Shielding rate is 99.3%, and infrared ray rejection rate is 92%, places 5 months without precipitating.

Embodiment 5

S1. the dichloro oxygen vanadium solution 80ml containing 0.002mol/L is prepared, using sodium hydroxide titration to there is suspension.To The Al2O3 of 30mg is added in solution, stirs evenly, above-mentioned solution is put into reaction kettle, in 240 DEG C of reaction 20h；Reaction product With deionized water and ethanol washing, aluminium doping vanadium oxide nano particle is obtained；

S2. it weighs 2.36g titanium tetrachloride and 0.38g ferric nitrate is dissolved in 60mL acetone, by 0.62mol/L sodium hydroxide Acetone soln is added in above-mentioned metal salt solution, and adequately mixes, and adjusting pH is 9, and the ITO that the above-mentioned preparation of 0.6g is added receives Rice grain reacts 6h at 80 DEG C；Be cooled to room temperature, be centrifuged and precipitated after fully reacting, precipitation and separation, obtain it is infrared and UV double obstructs nano particle；

S3. 70mL ethyl alcohol is measured, 2.15g ethyl orthosilicate is added, the ethanol containing ammonia that 0.07mol/L is added adjusts pH 4h is reacted at=9,60 DEG C, cooling, filtering, dehydrated alcohol washing, drying are to get Nano composite granules；

S4. Nano composite granules are dispersed in 50mL ethyl alcohol, addition six ruthenium trimethoxysilane of 0.1g, it is anti-at 60 DEG C 1.5h is answered, by reaction product deionized water and ethanol washing, is then dispersed in dimethylbenzene, obtains that there is ultraviolet and infrared barrier The liquid dispersion of the multilayered structure Nano composite granules of function.

In liquid dispersion obtained, the internal layer of multi-layer nano composite particles is ITO, and middle layer is Fe2O3 doping titanium dioxide, Secondary outer layer is silica, and outermost layer is six ruthenium trimethoxysilane organic coating layers.Above-mentioned dispersion is diluted to concentration For the solution of 10wt%, optical performance test is carried out, visible light transmittance 78%, rate of ultraviolet shield 99.0% is red Outside line rejection rate is 92%, places 5 months without precipitating.

Embodiment 6

S1. it weighs 3.12g molybdenum pentachloride and 1.08g bismuth hydroxide is add to deionized water, after being sufficiently mixed, add Reaction solution, is then transferred in autoclave by 9.86g oxalic acid, reacts 32h at 260 DEG C；Reaction product deionized water and second Alcohol washing, obtains bismuth molybdenum bronze nano particle；

S2. it weighs 3.69g zinc sulfate and 1.45g nickel chloride is dissolved in 80mL ethyl alcohol, the bismuth of the above-mentioned preparation of 0.83g is added Molybdenum bronze nano particle, adjusting pH using ethanol containing ammonia is 10, reacts 6h at 70 DEG C；Room is cooled to after fully reacting Temperature is centrifuged and is precipitated, precipitation and separation, obtains infrared and UV double and obstructs nano particle；

S3. 60mL ethyl alcohol is measured, 1.89g silester is added, the ethanol containing ammonia that 0.07mol/L is added adjusts pH= React 6h at 9,70 DEG C, it is cooling, filtering, dehydrated alcohol washing, dry to get arriving Nano composite granules；

S4. Nano composite granules are dispersed in 50mL ethyl alcohol, 0.1g hexamethyldisilazane is added, is reacted at 50 DEG C Reaction product deionized water and ethanol washing are then dispersed in dimethyl sulfoxide by 2h, obtain having ultraviolet and infrared barrier The liquid dispersion of the multilayered structure Nano composite granules of function.

In liquid dispersion obtained, the internal layer of multilayered structure dual-functional nanometer composite particles is bismuth molybdenum bronze, and middle layer is Nickel doping zinc-oxide, secondary outer layer are silica, and outermost layer is hexamethyldisilazane organic coating layer.Above-mentioned dispersion is dilute The solution for being 10wt% to concentration is released, optical performance test, visible light transmittance 76% are carried out, rate of ultraviolet shield is 99.1%, infrared ray rejection rate is 91%, places 5 months without precipitating.

Embodiment 7

S1. it weighs 3.58g tin acetate and 1.69g nitric acid antimony is add to deionized water, after being sufficiently mixed, use 0.5mol/L It is 8 that ammonia spirit, which adjusts pH, is then transferred into autoclave, reacts 14h at 250 DEG C；Reaction product deionized water and second Alcohol washing, obtains ATO nano particle；

S2. it weighs 2.36g titanium tetrachloride and 0.38g cobalt nitrate is dissolved in 50mL acetone, by 0.62mol/L sodium hydroxide Acetone soln is added in above-mentioned metal salt solution, and adequately mixes, and adjusting pH is 9, and the ATO of the above-mentioned preparation of 0.67g is added Nano particle reacts 4h at 80 DEG C；It is cooled to room temperature, is centrifuged and is precipitated after fully reacting, precipitation and separation obtains red Outer and UV double obstructs nano particle；

S3. 70mL ethyl alcohol is measured, 2g silester is added, the ethanol containing ammonia that 0.07mol/L is added adjusts pH=9, 3h is reacted at 70 DEG C, cooling, filtering, dehydrated alcohol washing, drying are to get Nano composite granules；

S4. Nano composite granules are dispersed in 50mL ethyl alcohol, addition six ruthenium triethoxysilane of 0.1g, it is anti-at 70 DEG C 3h is answered, reaction product deionized water and ethanol washing are then dispersed in toluene, obtains that there is ultraviolet and infrared barrier function The liquid dispersion of the multilayered structure Nano composite granules of energy.

In liquid dispersion obtained, the internal layer of multi-layer nano composite particles is ATO, and middle layer is cobalt doped titanium dioxide, Secondary outer layer is silica, and outermost layer is six ruthenium triethoxysilane organic coating layers.Above-mentioned dispersion is diluted to concentration For the solution of 10wt%, optical performance test is carried out, visible light transmittance 70%, rate of ultraviolet shield 99.3% is red Outside line rejection rate is 93%, places 5 months without precipitating.

Embodiment 8

S2. it weighs 1.19g copper sulphate and 0.72g aluminium chloride is dissolved in 50mL ethyl alcohol, the sodium of the above-mentioned preparation of 0.56g is added Caesium tungsten bronze nano particle, adjusting pH using ethanol containing ammonia is 9, and 4h is reacted at 80 DEG C, is cooled to room after fully reacting Temperature is centrifuged and is precipitated, precipitation and separation, obtains infrared and UV double and obstructs nano particle；

S3. 80mL ethyl alcohol is measured, 1.6g silester is added, the ethanol containing ammonia that 0.07mol/L is added adjusts pH= 2h is reacted at 9,70 DEG C, cooling, filtering, dehydrated alcohol washing, drying are to get Nano composite granules；

S4. Nano composite granules are dispersed in 50mL ethyl alcohol, 0.1g dimethyl polysiloxane is added, is reacted at 50 DEG C Reaction product deionized water and ethanol washing are then dispersed in n-hexane by 5h, obtain having ultraviolet and infrared barrier function The liquid dispersion of the multilayered structure Nano composite granules of energy.

In liquid dispersion obtained, the internal layer of multi-layer nano composite particles is ATO, and middle layer is copper doped zinc oxide, secondary Outer layer is silica, and outermost layer is dimethyl polysiloxane organic coating layer.Above-mentioned dispersion, which is diluted to concentration, is The solution of 10wt%, progress optical performance test, visible light transmittance 79%, rate of ultraviolet shield 99.2% are infrared Line rejection rate is 92%, places 5 months without precipitating.

Embodiment 9

S1. 3.12g molybdenum pentachloride, 1.08g potassium hydroxide and 1.13g cesium hydroxide are weighed to be add to deionized water, is filled After dividing mixing, 15.65g oxalic acid is added, then reaction solution is transferred in autoclave, reacts 28h at 240 DEG C；Reaction produces Object deionized water and ethanol washing obtain potassium caesium molybdenum bronze nano particle；

S2. it weighs 2.36g titanium tetrachloride and 0.58g zinc nitrate is dissolved in 60mL acetone, by 0.62mol/L sodium hydroxide Acetone soln is added in above-mentioned metal salt solution, and adequately mixes, and adjusting pH is 9, and the potassium caesium of the above-mentioned preparation of 0.69g is added Molybdenum bronze nano particle reacts 6h at 80 DEG C；It is cooled to room temperature, is centrifuged and is precipitated after fully reacting, precipitation and separation obtains Nano particle is obstructed to infrared and UV double；

S3. 70mL ethyl alcohol is measured, 2.15g silica solution is added, the ethanol containing ammonia that 0.07mol/L is added adjusts pH=9, 4h is reacted at 70 DEG C, cooling, filtering, dehydrated alcohol washing, drying are to get Nano composite granules；

S4. Nano composite granules are dispersed in 50mL ethyl alcohol, 0.1g glycidoxypropyl trimethoxy silane are added, 4h is reacted at 60 DEG C, by reaction product deionized water and ethanol washing, is then dispersed in hexamethylene, obtains having ultraviolet and red The liquid dispersion of the multilayered structure Nano composite granules of outer barriers function.

In liquid dispersion obtained, the internal layer of multilayered structure composite particles is potassium caesium molybdenum bronze, and middle layer is zinc doping two Titanium oxide, secondary outer layer are silica, and outermost layer is glycidoxypropyl trimethoxy silane organic coating layer.By above-mentioned point Granular media is diluted to the solution that concentration is 10wt%, carries out optical performance test, visible light transmittance 77.3%, ultraviolet screen Covering rate is 99.2%, and infrared ray rejection rate is 94%, places 5 months without precipitating.

Embodiment 10

S1. it weighs 3.08g molybdenum pentachloride and 0.98g sodium hydroxide is add to deionized water, after being sufficiently mixed, add Reaction solution, is then transferred in autoclave by 9.86g oxalic acid, reacts 32h at 260 DEG C；Reaction product deionized water and second Alcohol washing, obtains sodium molybdenum bronze nano particle；

S2. it weighs 1.38g zinc sulfate and 0.89g magnesium chloride is dissolved in 50mL ethyl alcohol, the sodium of the above-mentioned preparation of 0.56g is added Molybdenum bronze nano particle, adjusting pH using ethanol containing ammonia is 8, and 5h is reacted at 80 DEG C, is cooled to room temperature after fully reacting, It is centrifuged and is precipitated, precipitation and separation obtains infrared and UV double and obstructs nano particle；

S4. Nano composite granules are dispersed in 50mL ethyl alcohol, 0.1g glycidoxypropyl trimethoxy silane are added, 4h is reacted at 60 DEG C, reaction product deionized water and ethanol washing are then dispersed in dimethyl acetamide, had The liquid dispersion of ultraviolet and infrared barrier function multilayered structure Nano composite granules.

In dispersion obtained, the internal layer of multilayered structure dual-functional nanometer composite particles is sodium molybdenum bronze, and middle layer is mixed for magnesium Miscellaneous zinc oxide, secondary outer layer are silica, and outermost layer is glycidoxypropyl trimethoxy silane organic coating layer.It will be above-mentioned Dispersion is diluted to the solution that concentration is 10wt%, carries out optical performance test, visible light transmittance 77%, ultraviolet screen Covering rate is 99.0%, and infrared ray rejection rate is 92%.

Embodiment 11

A kind of organic/inorganic composite film piece with light selective absorbing and ageing-resistant function, including polymer, multilayer knot Structure Nano composite granules, plasticizer；Each component mass fraction are as follows: 70 parts of polymer, 10 parts of multilayered structure Nano composite granules, increase 20 parts of agent of modeling.

Polymer in above-mentioned organic/inorganic composite film piece is EVA, and the internal layer of multi-layer nano composite particles is caesium tungsten bronze, Middle layer is zinc oxide, and secondary outer layer is silica, and outermost layer is octyl trimethoxy silane organic coating layer；Plasticizer is adjacent benzene Diformazan dioctyl phthalate.

The production method of above-mentioned organic/inorganic composite film piece, comprising the following steps:

1) EVA is dissolved in ethyl acetate, the dispersion of multilayered structure nano particle is added until completely dissolved, sufficiently It stirs, after mixing, obtains solution system to be dried, obtain masterbatch after dry；

2) plasticizer phthalic acid dioctyl ester is added in masterbatch obtained into step 1), it is full and uniform in blender Mixing, then, control extruder discharging mouth temperature are 160-240 DEG C, carry out melt blending extrusion, and the film with a thickness of 2mm is made Piece；

3) cutting, the packaging process that diaphragm is carried out according to normal process steps, are made organic/inorganic composite film piece finished product.

The dispersion that the multilayered structure nanoparticle dispersion uses embodiment 1 to prepare is more in the dispersion The internal layer of layer Nano composite granules is caesium tungsten bronze, and middle layer is zinc oxide, and secondary outer layer is silica, and outermost layer is octyl front three Oxysilane organic coating layer.Solid content 10wt%, granular one dimension size 20-100nm, liquid medium is ethyl acetate.

Resulting smooth selective absorbing and the organic/inorganic composite film piece of ageing-resistant function can be used as in hollow glass cavity The functional interlayer in portion.

Embodiment 12

A kind of organic/inorganic composite film piece with light selective absorbing and ageing-resistant function, including polymer, multilayer knot Structure Nano composite granules, plasticizer；Each component mass fraction are as follows: 60 parts of polymer, 35 parts of multilayered structure Nano composite granules, increase 5 parts of agent of modeling.

Polymer in above-mentioned organic/inorganic composite film piece is PVB, and the internal layer of multi-layer nano composite particles is that magnesium adulterates oxygen Change vanadium, middle layer is zinc oxide, and secondary outer layer is silica, and outermost layer is octyltri-ethoxysilane organic coating layer, plasticizer For Triethyleneglycol di 2 ethylhexanoate.

1) by the liquid dispersion of the nano particle containing multilayered structure by centrifugation phase inversion to Triethyleneglycol di 2 ethylhexanoate In；

2) mixture in PVB and step 1 is added in extruder by feed inlet, is premixed 20 minutes at 170 DEG C； Controlling extruder discharging mouth temperature is 180 DEG C, carries out melt blending extrusion, and the diaphragm with a thickness of 0.38mm is made；

3) cutting of sheet material being carried out according to normal process steps, being batched, packaging process, organic/inorganic composite film piece finished product is made.

The dispersion that the dispersion of the nano particle containing multilayered structure uses embodiment 3 to prepare, the dispersion The internal layer of middle multi-layer nano composite particles is that magnesium adulterates vanadium oxide, and middle layer is zinc oxide, and secondary outer layer is silica, and outermost layer is Octyltri-ethoxysilane organic coating layer, solid content 10wt%, granular one dimension size 20-80nm, liquid medium is ethyl alcohol.

The resulting organic/inorganic composite film piece with light selective absorbing and ageing-resistant function can be used as doubling glass Functional interlayer.

Embodiment 13

Repeat embodiment 11, the difference is that only: the polymer uses EVA；The multilayered structure nanometer is multiple It closes particle dispersion and uses the resulting dispersion of embodiment 4, wherein the internal layer of multilayered structure Nano composite granules is bismuth molybdenum bronze, Middle layer is nickel doping zinc-oxide, and secondary outer layer is silica, and outermost layer is hexamethyldisilazane organic coating layer, solid content 10wt%, granular one dimension size 25-60nm, liquid medium is toluene.

Embodiment 14

Repeat embodiment 11, the difference is that only: the polymer uses PVB；The multilayered structure nanometer is multiple It closes particle dispersion and uses the resulting dispersion of embodiment 7, wherein the internal layer of multi-layer nano composite particles in dispersion obtained For ATO, middle layer is cobalt doped titanium dioxide, and secondary outer layer is silica, and outermost layer is the organic packet of six ruthenium triethoxysilanes Coating, granular one dimension size 25-40nm, liquid medium is methanol.

Embodiment 15

Repeat embodiment 11, the difference is that only: the polymer uses PP；The multilayered structure is nano combined Particle dispersion uses the resulting dispersion of embodiment 9, wherein and the internal layer of multilayered structure composite particles is potassium caesium molybdenum bronze, in Layer is zinc doping titanium dioxide, and secondary outer layer is silica, and outermost layer is the organic packet of glycidoxypropyl trimethoxy silane Coating, solid content 10wt%, granular one dimension size 30-50nm, liquid medium is dimethylbenzene.

The resulting organic/inorganic composite film piece with light selective absorbing and ageing-resistant function can be used as hollow glass sky The functional interlayer in intracavitary portion.

Embodiment 16

Repeat embodiment 12, the difference is that only: the polymer uses PS；The multilayered structure is nano combined Particle dispersion uses the resulting dispersion of embodiment 2, wherein and the internal layer of multi-layer nano composite particles is sodium caesium tungsten bronze, in Layer is aluminium-doped zinc oxide, and secondary outer layer is silica, and outermost layer is that 3- methacryloxypropyl has Machine clad, solid content 10wt%, granular one dimension size 25-60nm, liquid medium is acetone.

Embodiment 17

Repeat embodiment 12, the difference is that only: the polymer uses PU；The multilayered structure is nano combined Particle dispersion uses the resulting dispersion of embodiment 5, wherein the internal layer of multi-layer nano composite particles is ITO, and middle layer is mixed for iron Miscellaneous titanium dioxide, secondary outer layer are silica, and outermost layer is six ruthenium trimethoxysilane organic coating layers, solid content 10wt%, granular one dimension size 10-20nm, liquid medium is toluene.

Embodiment 18

Repeat embodiment 12, the difference is that only: the polymer uses PMMA；The multilayered structure nanometer Grain dispersion uses the resulting dispersion of embodiment 6, wherein the internal layer of multilayered structure dual-functional nanometer composite particles is that bismuth molybdenum is green Copper, middle layer are nickel doping zinc-oxide, and secondary outer layer is silica, and outermost layer is hexamethyldisilazane organic coating layer, admittedly contain 10wt% is measured, granular one dimension size 23-54nm, liquid medium is ethyl acetate.

Embodiment 19

Doubling glass is prepared using conventional method:

Organic/inorganic composite film piece with light selective absorbing and ageing-resistant function made from embodiment 11 is placed in two Between block float glass, setting temperature is 180 DEG C, pressure 2.6kg/cm², pressure duration 20min, by being hot pressed into The method of type prepares doubling glass, and gained doubling glass is placed in radiation resistance testing machine and irradiates 80H progress ageing-resistant performance Test.

The optical performance test result of gained doubling glass is as follows: visible light transmittance 75%, rate of ultraviolet shield 99.7%, infrared ray rejection rate 90.3%.

Test result is as follows for the ageing-resistant performance of gained doubling glass: passing through 80H ultraviolet irradiation, it is seen that light transmission rate is almost It is constant, and the decline of doubling glass visible light transmittance made from normal film 30%, it effectively solves to a certain extent because of ultraviolet light The problem of irradiation performance declines.

Embodiment 20

Doubling glass is prepared using conventional method:

Organic/inorganic composite film piece with light selective absorbing and ageing-resistant function made from embodiment 12 is placed in two Between block float glass, setting temperature is 180 DEG C, pressure 2.6kg/cm², pressure duration 20min, by being hot pressed into The method of type prepares doubling glass, and gained doubling glass is placed in radiation resistance testing machine and irradiates 80H progress ageing-resistant performance Test.

The optical performance test result of gained doubling glass is as follows: visible light transmittance 73%, rate of ultraviolet shield 99.5%, infrared ray rejection rate 91.3%.

Test result is as follows for the ageing-resistant performance of gained doubling glass: passing through 80H ultraviolet irradiation, it is seen that light transmission rate is almost It is constant, and the decline of doubling glass visible light transmittance made from normal film 28%.

Embodiment 21

Doubling glass is prepared using conventional method:

Organic/inorganic composite film piece with light selective absorbing and ageing-resistant function made from embodiment 13 is placed in two Between block float glass, setting temperature is 180 DEG C, pressure 2.6kg/cm², pressure duration 20min, by being hot pressed into The method of type prepares doubling glass, and gained doubling glass is placed in radiation resistance testing machine and irradiates 80H progress ageing-resistant performance Test.

The optical performance test result of gained doubling glass is as follows: visible light transmittance 74%, rate of ultraviolet shield 98.9%, infrared ray rejection rate 90.7%.

Test result is as follows for the ageing-resistant performance of gained doubling glass: passing through 80H ultraviolet irradiation, it is seen that light transmission rate is almost It is constant, and the decline of doubling glass visible light transmittance made from normal film 29%.

Embodiment 22

Hollow glass is prepared using conventional method:

Organic/inorganic composite film piece with light selective absorbing and ageing-resistant function made from embodiment 12 is fixed on The centre of internal cavities, then again with binder by two sheet glass and sealing strip, glass bar bonding, sealing, centre is filled with drying Gas obtains hollow glass.

Resulting centre has the hollow glass performance of the organic/inorganic composite film of light selective absorbing and ageing-resistant function It is as follows: heat transfer coefficient 1.85W/m²K, shading coefficient 0.4 have good sunshade and energy-saving effect.

Comparative example 1

Using the raw material of embodiment 1, a kind of preparation method of hybrid dispersions, steps are as follows:

1) internal layer dispersion is prepared:

It weighs 0.99g sodium tungstate powder to be dissolved in 12.5mL deionized water, 15mL dust technology is added, centrifuge washing obtains yellowish The wolframic acid colloidal sol of color；It weighs 0.2g cesium sulfate powder to be dissolved in 46mL deionized water, and above-mentioned certainly with the transfer of 40mL deionized water Wolframic acid processed, stirs 4h at room temperature；14mL ethylene glycol is added into above-mentioned mixed liquor, stirs 1h at room temperature, obtains material solution；It will Above-mentioned raw materials solution is transferred in water heating kettle, temperature programming 2h to 230 DEG C at room temperature, reacts 20h；

2) it is cooled to room temperature, is centrifuged and is precipitated after complete reaction, precipitation and separation obtains caesium tungsten bronze nanometer Grain is added 0.6g cetyl trimethylammonium bromide, reaction 3h is carried out at 60 DEG C, by reaction product deionized water and ethyl alcohol Washing, is then dispersed in ethyl alcohol, obtains the caesium tungsten bronze nano particle liquid dispersion with infrared shielding performance；

3) middle layer dispersion is prepared；

It weighs 1.9g zinc acetate to be added in 30mL ethyl alcohol, stirring and dissolving at 60 DEG C obtains zinc solution；Weigh 1.2g hydrogen-oxygen Change sodium and be dissolved in 25mL ethyl alcohol, obtain aqueous slkali, lye is added in above-mentioned zinc solution, it is anti-that temperature maintains 60 DEG C of stirrings 3h is answered, cooling, filtering, dehydrated alcohol washing are then dispersed in ethyl alcohol, obtain the zinc-oxide nano with uv-shielding capacity Particle liquid dispersion；

4) outer layer dispersion is prepared；

80mL ethyl alcohol is measured, 1.8g ethyl orthosilicate is added, the ethanol containing ammonia that 0.07mol/L is added adjusts pH=9, 5h is reacted at 60 DEG C, cooling, filtering, dehydrated alcohol washing are scattered in ethyl alcohol, obtain nano SiO 2 particle solution dispersion Body；

5) it is mixed and stirred for each dispersion；

By internal layer dispersion obtained, middle layer dispersion and outer layer dispersion carry out physical mixed.

Obtained hybrid dispersions are diluted to the solution that concentration is 10wt%, carry out optical performance test, visible light-transmissive Rate is 72%, rate of ultraviolet shield 84%, and infrared ray rejection rate is 76%.Liquid dispersion, which is placed 4 months, precipitating.

Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair The restriction of embodiments of the present invention.For those of ordinary skill in the art, may be used also on the basis of the above description To make other variations or changes in different ways.Here all embodiments can not be exhaustive.It is all to belong to this hair The obvious changes or variations that bright technical solution is extended out are still in the scope of protection of the present invention.

Claims

1. The organic-inorganic composite diaphragm with photoselective absorption and anti-aging function is characterized in that: comprise polymer, multilayer structure nano-composite particle, plasticizer or softening agent and auxiliary agent; The mass fraction of each component is : 45-99.8 parts of polymer, 0.2-40 parts of multi-layer structure nanocomposite particles, 0-45 parts of plasticizer or softener, 0-10 parts of auxiliary agent.

2. The organic-inorganic composite membrane according to claim 1, characterized in that: the organic-inorganic composite membrane comprises 50-90 parts of polymer, 0.5-30 parts of multi-layered nanocomposite particles, plasticizer or softener 1-30 parts, 1-8 parts of additives; preferably, 50-80 parts of polymer, 1-20 parts of multi-layer nanocomposite particles, 15-30 parts of plasticizer or softener, 1-5 parts of additives ; Most preferably, 60-70 parts of polymer, 3-10 parts of multi-layer nanocomposite particles, 20-30 parts of plasticizer or softener, and 1-3 parts of auxiliary agent.

3. The organic-inorganic composite membrane according to claim 1, characterized in that: the thickness of the organic-inorganic composite membrane is 0.1-5 mm.

4. The organic-inorganic composite membrane according to claim 1, characterized in that: said polymer is selected from the group consisting of polypropylene, polystyrene, polycarbonate, polymethyl methacrylate, acrylonitrile-butadiene-benzene Ethylene copolymer, polyvinyl chloride, ethylene-vinyl acetate copolymer, polyvinyl butyral, polyurethane, Dupont SGP, polyethylene terephthalate resin, epoxy resin, butadiene rubber, natural rubber, One or more of isoprene rubber, ethylene propylene rubber, butyl rubber, chlorohydrin rubber, and silicone rubber;

Preferably, the plasticizer or softener is selected from dioctyl phthalate, dioctyl sebacate, dibutyl sebacate, triethylene glycol di-2-ethylhexanoate, o-phthalate Dioctyl phthalate, butyl benzyl phthalate, dicyclohexyl phthalate, dibutyl phthalate, diisobutyl phthalate, dimethyl phthalate, ortho Diethyl phthalate, diisodecyl phthalate, pine oil-based rubber softener, fatty oil-based rubber softener, synthetic rubber softener, petroleum-based rubber softener, coal tar-based rubber softener or more;

Preferably, the auxiliary agent is selected from one or more of dispersants, anti-heat agents, curing agents, toughening agents, emulsifiers, defoamers, leveling agents, matting agents, light stabilizers, and antistatic agents.

5. The organic-inorganic composite membrane according to claim 1, characterized in that: the multi-layer structure nanocomposite particles comprise: a doped oxide inner layer with an infrared blocking function, a metal oxide middle layer with an ultraviolet absorption function, a silica sub-outer layer with reduced metal oxide catalytic performance and an outermost organic coating layer with enhanced stability;

Preferably, the mass ratio of the doped oxide, metal oxide, silicon dioxide and organic coating layer is 1:(0.1-0.33):(0.1-0.25):(0-0.1), and the particle size is 5 -100nm; More preferably, the mass ratio of the doped oxide, metal oxide, silicon dioxide and organic coating layer is 1:(0.1-0.33):(0.1-0.25):(0.01-0.1);

Preferably, the doped oxide is selected from one or more of doped tin oxide, doped vanadium oxide, tungsten bronze compound, molybdenum bronze compound, and tungsten molybdenum bronze compound;

Preferably, the doping elements in the doped tin oxide are selected from one or more of elements such as indium, antimony, titanium, zinc, tungsten, iron, silver, platinum, etc., and the doping elements and tin in tin oxide The molar ratio is 0.01-1:1; more preferably, the molar ratio of the doping element to tin in tin oxide is 0.1-0.5:1;

Preferably, the doping element in the doped vanadium oxide is selected from one or more of tungsten, magnesium, and aluminum, and the molar ratio of the doping element to vanadium in the vanadium oxide is 0.01-1:1; more preferably Preferably, the molar ratio of the doping element to vanadium in vanadium oxide is 0.1-0.5:1;

Preferably, the doping elements in the tungsten bronze compound, molybdenum bronze compound or tungsten molybdenum bronze compound are lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, germanium, tin, aluminum, gallium, indium, One or two of metal elements such as silver, gold, titanium, bismuth and zirconium, the molar ratio of the doping element to the total amount of tungsten and/or molybdenum is 0.01-1:1, more preferably, the doping element The molar ratio to the total amount of tungsten and/or molybdenum is 0.1-0.5:1;

Preferably, the metal oxide with ultraviolet absorbing function is selected from one or both of doped zinc oxide and doped titanium oxide;

Preferably, the doping elements in the doped zinc oxide are selected from one or more of aluminum, calcium, gallium, cadmium, cerium, copper, iron, magnesium, tin, antimony, silver, nickel, titanium, so The molar ratio of the doping element to zinc in zinc oxide is 0.001-1:1; more preferably, the molar ratio of the doping element to zinc in zinc oxide is 0.001-0.5:1;

Preferably, the doping element in the doped titanium oxide is selected from one or more of zinc, cobalt, iron, tin, lanthanum, etc., and the molar ratio of the doping element to titanium in the titanium oxide is 0.001- 0.5:1; more preferably, the molar ratio of the doping element to titanium in titanium oxide is 0.001-0.3:1;

Preferably, the organic coating layer is selected from octyltrimethoxysilane, octyltriethoxysilane, hexamethyldisilazane, 3-methacryloxypropyltrimethoxysilane, 3 -Methacryloxypropyltriethoxysilane, Hexadecyltrimethoxysilane, Hexadecyltriethoxysilane, Dimethicone, Glycidoxypropyltrimethoxysilane, Glycidyloxypropyltriethoxysilane, nonafluorohexyltrimethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, aminopropyltriethoxysilane, six Methyldisilazane, Lauryl Acid, Stearic Acid, Tannic Acid, Succinic Acid, Acrylic Acid, Oleic Acid, Isopropyl Alcohol, Polyvinyl Alcohol, Polyethylene Glycol, Sodium Lauryl Sulfate, Dodecane Sodium phenylbenzenesulfonate, sodium laurate, sodium stearate, sodium acetate, sodium oleate, polyoxyethylene, styrene, Tween (polyoxyethylene sorbitan monooleate), methyl methacrylate one or more of.

6. the preparation method of the organic-inorganic composite diaphragm with above-mentioned photoselective absorption and anti-aging function as claimed in claim 1-5, is characterized in that, comprises the steps:

S01. The hydraulic dispersing body containing multi -layer nano -composite particles forms a stable oil phase dispersion in the plasticizer or soft agent;

S02. Add the polymer and the oil phase dispersion into the extruder respectively through the feed port, control the temperature of the melting section of the extruder at 150-250°C, perform melt premixing for 1-30 minutes, and simultaneously control the output of the extruder The temperature of the feed port is 150-280°C, melt blending and extrusion or control the mold temperature at 140-250°C, and injection molding the mixed raw materials to obtain an organic-inorganic composite film with light selective absorption and aging resistance;

Or use the following steps:

S11, dissolving the polymer in the liquid phase medium to make a resin solution with a certain concentration, then adding the liquid phase dispersion containing multi-layer structure nanocomposite particles to it, fully stirring and mixing uniformly, to obtain the solution system to be dried, The concentration of the polymer in the mixed liquid is 0.5-20wt%, and the masterbatch is obtained after drying, the content of the polymer in the masterbatch is 30-90wt%, and the content of the multilayer structure nanocomposite particles is 10-70wt%;

S12. Add a plasticizer or softener and a certain amount of polymer to the masterbatch prepared in step S11, mix it fully and uniformly in the mixer, and then add it to the extruder, and control the outlet of the extruder at the same time The temperature is 150-280 ° C, and the temperature of the mixing or controlling the mold is 140-250 ° C, and the mixed raw material injection molding is made of organic inorganic composite film that selectively absorbs and aging aging.

7. according to the preparation method of the described organic-inorganic composite membrane of claim 6, it is characterized in that: in step S01, S11, described multilayer structure nanocomposite particle liquid phase dispersion comprises multilayer structure nanocomposite particle and liquid phase medium ; In the multi-layer structure nanocomposite particles, the inner layer is a doped oxide with an infrared barrier function, the middle layer is a metal oxide with an ultraviolet absorption function, and the second outer layer is silicon dioxide that reduces the catalytic performance of the metal oxide The outermost layer is an organic coating layer with stability; the multi -layer nano -composite particles are evenly dispersed in the liquid medium.

8.根据权利要求7所述有机无机复合膜片的制备方法，其特征在于：所述液相介质选自水、甲醇、乙醇、乙二醇、异丙醇、苯甲醇、甲苯、二甲苯、 Die metamyramine, di metamimamide, di methalium acetamide, orthopedic hexane, cyclopen, acetone, cytone, ethyl acetate, acetate, phenol, cycloetone, tetrahydraxu, halide alkane hydrocarbons A sort of.

9. according to the preparation method of the described organic-inorganic composite diaphragm of claim 7, it is characterized in that, the preparation method of described multi-layer structure nano-composite particle liquid dispersion, comprises the steps:

S1. Dissolve the oxide-doped raw material in the inner layer in a solvent to form a salt solution, stir evenly, adjust the pH value, then add a reducing agent and transfer the reaction solution to an autoclave for hydrothermal or solvothermal reaction. After the reaction is complete Cool to room temperature, centrifugal washing, separation and precipitation, obtaining doped oxide nano particles;

S2. Dissolve the raw material of the middle layer metal oxide in a solvent to form a salt solution, then add lye, adjust the pH value, and after mixing fully, add the doped oxide nanoparticles obtained in S1 to react; after the reaction is complete, cool to Room temperature, centrifugal washing, separation and precipitation, obtained metal oxides to cover the doped oxide nanoparticles;

S3. adding the silicon-containing compound to a certain amount of ethanol, then adding lye, adjusting the pH value, and after fully mixing, adding the metal oxide-coated doped oxide nanoparticles obtained in S2, stirring evenly, and performing the reaction; Cool to room temperature after the reaction is complete;

S4. Adding a surface coating layer to the above mixed solution for reaction, washing the reaction product with water, and then dispersing it in the liquid phase medium to obtain a liquid phase transparent dispersion containing multi-layer structure nanoparticles.

10. The preparation method of the organic-inorganic composite membrane according to claim 9, characterized in that: in step S1, the raw material of the inner doped oxide includes at least one oxide raw material and at least one doping element raw materialThe oxide raw material is selected from one or more of the following substances: stannous chloride, tin tetrachloride, stannous sulfate, stannous oxalate, tin nitrate, alum sulfate, vanadyl sulfate, vanadyl dichloride , vanadium oxalate, vanadium hydroxide, vanadium pentoxide, ammonium metavanadate, zinc acetate, tungsten hexachloride, tungsten tetrachloride, lithium tungstate, potassium tungstate, cesium tungstate, sodium tungstate, tungsten Rubidium acid, cesium sulfate, potassium sulfate, sodium sulfate, rubidium sulfate, lithium sulfate, ammonium paratungstate, ammonium metatungstate, ammonium orthotungstate, tungsten silicide, tungsten sulfide, tungsten oxychloride, tungstic acid monohydrate, ammonium metamolybdate, Ammonium orthomolybdate, ammonium paramolybdate, molybdenum acid, molybdenum silicide, molybdenum sulfide, molybdenum oxychloride, molybdenum oxyalkoxide, molybdenum pentachloride, molybdenum tetrachloride, molybdenum bromide, molybdenum fluoride, molybdenum carbide, carbon oxide Molybdenum; the doping element raw material is selected from carbonates, bicarbonates, nitrates, nitrites, hydroxides, chlorides, sulfates, sulfites, organic acid salts, alkoxides containing doping elements , One or more in one or more oxygenic acid, oxide, and oxide;

Preferably, the solution concentration of all metal ions in the raw material of the inner layer doped oxide is 0.1-1.0M; more preferably, the solution concentration of all metal ions in the raw material of the inner layer doped oxide is 0.3-0.8M;

Preferably, in steps S1 and S2, the solvent is selected from one or more of water, methanol, ethanol, acetone, butanone, ethyl acetate, butyl acetate, toluene, xylene, n-hexane, and cyclohexane kind;

Preferably, in step S1, the reducing agent is selected from oxalic acid, citric acid, methanol, ethanol, ethylene glycol, 1,2-propanediol, 1,3-propanediol, glycerol, ethanolamine, triethanolamine, oleylamine, One or both of oleic acid, ethylenediamine, hydrazine hydrate, ammonium oxalate, ammonia water, sodium borohydride, potassium borohydride, hydrogen sulfide, sodium hypophosphite, the reducing agent and the total amount of tungsten and/or molybdenum Moore is 1.5-20: 1, or 2-18: 1, or 4-16: 1, or 6-16: 1, or 8-15: 1, or 10-12: 1;

Preferably, in step S1, adjusting the pH value refers to adding an acidic substance to adjust the pH of the reaction solution to 1-6.5 or adding an alkaline substance to adjust the pH of the solution to 7.5-12; wherein the acidic substance is selected from hydrochloric acid, nitric acid, One or both of sulfuric acid, oxalic acid, citric acid and acetic acid; alkaline substances are selected from sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, ethylamine, ethanolamine, ethylenediamine, dimethylamine, Trifartine, tithamine, propionine, glycerophils, 1,3-propionine, 1,2-propionine, tatabine, and titolylamine;

Preferably, in step S1, the water heat or solvent thermal reaction is performed under anaerobic conditions, and the reaction temperature is 100-300 ° C, and the reaction time is 1-48h;

Preferably, in step S2, the raw material of the middle metal oxide is selected from carbonates, bicarbonates, nitrates, nitrites, hydroxides, chlorides, sulfates, sulfites, organic One or more of acid salts, alkoxides, complexes, oxyacids, and oxyacids, the solution concentration of metal ions in the salt solution is 0.1-1.0M; preferably 0.3-0.8M;

Preferably, in step S2, the alkali solution is selected from sodium hydroxide, potassium hydroxide, ammonia, ethyleine, ethylelamine, ethyleine, dihamine, triamine, propionine, albumin, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 3-1,1,2-propyaline, tiopropyne, and titolylamine, with a concentration of 0.1-1.0m, preferably 0.3-0.8m;

Preferably, in step S2, the pH is 7-11, the reaction temperature is 40-90°C, and the reaction time is 0.5-10h; more preferably, the pH is 7-10, and the reaction temperature is 50-80 °C, the reaction time is 1-5h; most preferably, the pH is 8-9, the reaction temperature is 60-70°C, and the reaction time is 2-4h;

Preferably, in step S3, the silicon-containing compound is one or more of ethyl orthosilicate, methyl orthosilicate, ethyl silicate or silica sol, and the mass ratio of the silicon-containing compound to ethanol is 1:40-50;

Preferably, in step S3, the lye is selected from sodium hydroxide, potassium hydroxide, ammonia water, ethylamine, ethanolamine, ethylenediamine, dimethylamine, trimethylamine, triethylamine, propylamine, isopropylamine, 1, 3-1,1,2-propyaline, tiopropyne, and titolylamine, with a concentration of 0.1-1.0m, preferably 0.3-0.8m;

Preferably, in step S3, the reaction temperature is 30-90°C, and the reaction time is 1-10h; more preferably, the reaction temperature is 40-70°C, and the reaction time is 1-7h; most preferably, the The reaction temperature is 60-70 ° C, and the response time is 2-5H;

Preferably, in step S4, the raw materials of the surface covering layer are Cincin-based trigaine, cindian triaxyxyxane, hexal axer silicane, 3-methyl acryl oxyl oxyl oxyl Oxygenosiline, 3-methyl acryl oxyl oxygenol tritenol, hexalized trimethyl oxygne, hexalized triaxids silicane, diharocytosiline, and shrinking glycerol oxygenol Trimethylexyoxyne, shrinking glycerol oxygenidyxyxyxyxyne, ninetefluoro hexyl oxygenne, thirtyl -fluorinel oxygenne, thirtyl -fluorinel oxygne, and amine. Oxygenne, hexmethyl siruscanane, duodrotic acid, ductic acid, stiffic acid, tannic acid, butad acid, acrylic acid, oleic acid, isopropyl, polyethylene, polyethylene glycol, duolius, dulate sulfuric acid sulfuric acid Sodium, sodium phenyl -sodium phenylsulzenate, sodium laurel, sodium liphamine, sodium acetate, sodium acetate, polyoxide, styrene, vomitin (polyoxyethylene pearl anhydride monopoline), Methyl etchrite;

Preferably, in step S4, the reaction temperature is 20-80 ° C, and the reaction time is 1-10H;

Preferably, in step S4, the organic solvent is selected from ethanol, n-propanol, acetone, ethyl acetate, butyl acetate, toluene, xylene, n-hexane, cyclohexane, dimethyl sulfoxide, dimethyl One or more of methalmamide and dihalium acetyide.