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

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

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CN109517254A
CN109517254A CN201710851495.2A CN201710851495A CN109517254A CN 109517254 A CN109517254 A CN 109517254A CN 201710851495 A CN201710851495 A CN 201710851495A CN 109517254 A CN109517254 A CN 109517254A
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acid
oxide
organic
film piece
composite film
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CN109517254B (en
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曾晓飞
韩玥
王洁欣
陈建峰
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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Abstract

The invention discloses a kind of organic/inorganic composite film piece with light selective absorbing and ageing-resistant function, including polymer, multilayered structure Nano composite granules, plasticizer or softening agent and auxiliary agent；Each component mass fraction are as follows: 45-99.8 parts of polymer, 0.2-40 parts of multilayered structure Nano composite granules, plasticizer or 0-45 parts of softening agent, 0-10 parts of auxiliary agent.Also disclose the preparation method of the organic/inorganic composite film piece.Organic/inorganic composite film piece provided by the invention can be widely applied to be used to prepare functional compound glass and transparent devices on the fields such as building, space flight and aviation, electronic information, rubber, plastics.The preparation method of smooth selective absorbing provided by the invention and the organic/inorganic composite film piece of ageing-resistant function is simple, is easy to 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
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 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
The preparation method of liquid dispersion containing multi-layer nano composite particles, includes the following steps:
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
The preparation method of liquid dispersion containing multi-layer nano composite particles, includes the following steps:
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
The preparation method of liquid dispersion containing multi-layer nano composite particles, includes the following steps:
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
The preparation method of liquid dispersion containing multi-layer nano composite particles, includes the following steps:
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
The preparation method of liquid dispersion containing multi-layer nano composite particles, includes the following steps:
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
The preparation method of liquid dispersion containing multi-layer nano composite particles, includes the following steps:
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 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
The preparation method of liquid dispersion containing multi-layer nano composite particles, includes the following steps:
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
The preparation method of liquid dispersion containing multi-layer nano composite particles, includes the following steps:
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；
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 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.
The production method of above-mentioned organic/inorganic composite film piece, comprising the following steps:
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.
The resulting organic/inorganic composite film piece with light selective absorbing and ageing-resistant function can be used as doubling glass Functional interlayer.
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.
The resulting organic/inorganic composite film piece with light selective absorbing and ageing-resistant function can be used as doubling glass Functional interlayer.
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.
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 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.
The resulting organic/inorganic composite film piece with light selective absorbing and ageing-resistant function can be used as doubling glass Functional interlayer.
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.
The resulting organic/inorganic composite film piece with light selective absorbing and ageing-resistant function can be used as doubling glass Functional interlayer.
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 (10)

1. the organic/inorganic composite film piece with light selective absorbing and ageing-resistant function, it is characterised in that: more including polymer Layer structure nano composite particles, plasticizer or softening agent and auxiliary agent；Each component mass fraction are as follows: 45-99.8 parts of polymer, multilayer 0.2-40 parts of structure nano composite particles, plasticizer or 0-45 parts of softening agent, 0-10 parts of auxiliary agent.
2. organic/inorganic composite film piece according to claim 1, it is characterised in that: the organic/inorganic composite film piece includes poly- Close object 50-90 parts, 0.5-30 parts of multilayered structure Nano composite granules, plasticizer or 1-30 parts of softening agent, 1-8 parts of auxiliary agent；It is preferred that Ground, 50-80 parts of polymer, 1-20 parts of multilayered structure Nano composite granules, plasticizer or 15-30 parts of softening agent, 1-5 parts of auxiliary agent； Most preferably, polymer 60-70 parts, 3-10 parts of multilayered structure Nano composite granules, plasticizer or 20-30 parts of softening agent, auxiliary agent 1-3 parts.
3. organic/inorganic composite film piece according to claim 1, it is characterised in that: the thickness of the organic/inorganic composite film piece For 0.1-5mm.
4. organic/inorganic composite film piece according to claim 1, it is characterised in that: the polymer is selected from polypropylene, polyphenyl Ethylene, polycarbonate, polymethyl methacrylate, acrylonitrile-butadiene-styrene copolymer, polyvinyl chloride, ethyl vinyl acetate It is ethylene copolymer, polyvinyl butyral, polyurethanes, Du Pont SGP, poly terephthalic acid resinoid, epoxy resin, suitable One of buna, natural rubber, isoprene rubber, EP rubbers, butyl rubber, chlorohydrin rubber, silicon rubber are a variety of；
Preferably, the plasticizer or softening agent be selected from dioctyl phthalate, dioctyl sebacate, dibutyl sebacate, Triethyleneglycol di 2 ethylhexanoate, di-n-octyl phthalate, BBP(Butyl Benzyl Phthalate, dicyclohexyl phthalate, Dibutyl phthalate, diisobutyl phthalate, repefral, diethyl phthalate, adjacent benzene two Formic acid diisodecyl ester, pine tar system rubber softener, fat oil system rubber softener, synthetic rubber softening agent, petroleum rubber are soft Agent, coal tar system rubber softener it is one or more；
Preferably, the auxiliary agent is selected from dispersing agent, antiheat agent, curing agent, toughener, emulsifier, defoaming agent, levelling agent, delustring Agent, light stabilizer, antistatic agent it is one or more.
5. organic/inorganic composite film piece according to claim 1, it is characterised in that: the multilayered structure Nano composite granules packet Include: the doping oxide inner layer with infrared ray barriers function, the metal oxide middle layer with ultraviolet radiation absorption function have Reduce the silica time outer layer of metal oxide oxidation catalyst 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 aoxidize The mass ratio of object, silica and organic coating layer is 1:(0.1-0.33): (0.1-0.25): (0.01-0.1)；
Preferably, the doping oxide is selected from doped stannum oxide, doping vanadium oxide, tungsten bronze class compound, molybdenum bronze class Close one of object, tungsten bronze class compound or a variety of；
Preferably, the doped chemical in the doped stannum oxide in the elements such as indium, antimony, titanium, zinc, tungsten, iron, silver, platinum one Kind is a variety of, and 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 tin oxide The molar ratio of middle 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 and oxygen The molar ratio for changing the vanadium in vanadium is 0.01-1:1；It is highly preferred that the doped chemical and the molar ratio of the vanadium in vanadium oxide are 0.1-0.5:1；
Preferably, the doped chemical in the tungsten bronze class compound, molybdenum bronze class compound or tungsten bronze class compound is One or both of metallic elements such as lithium, sodium, potassium, rubidium, caesium, magnesium, calcium, germanium, tin, aluminium, gallium, indium, silver, gold, titanium, bismuth and zirconium, The molar ratio of doped chemical and tungsten and/or molybdenum total amount is 0.01-1:1, it is highly preferred that the doped chemical and tungsten and/or molybdenum are total The molar ratio of amount is 0.1-0.5:1；
Preferably, the metal oxide with ultraviolet radiation absorption function in doping zinc-oxide and adulterated TiOx one Kind or two kinds；
Preferably, the doped chemical in the doping zinc-oxide be selected from aluminium, calcium, gallium, cadmium, cerium, copper, iron, magnesium, tin, antimony, silver, nickel, One of titanium is 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 described mix The molar ratio of miscellaneous element and zinc in zinc oxide is 0.001-0.5:1；
Preferably, the doped chemical in the adulterated TiOx is selected from one of zinc, cobalt, iron, tin, lanthanum etc. or a variety of, described The molar ratio of titanium is 0.001-0.5:1 in doped chemical and titanium oxide；It is highly preferred that titanium in the doped chemical and titanium oxide Molar ratio is 0.001-0.3:1；
Preferably, the organic coating layer choosing is from octyl trimethoxy silane, octyltri-ethoxysilane, two silicon nitrogen of hexamethyl Alkane, 3- methacryloxypropyl trimethoxy silane, 3- methacryloxypropyl, six decyls three Methoxy silane, dimethyl polysiloxane, glycidoxypropyl trimethoxy silane, is shunk at six ruthenium triethoxysilanes Glycidoxypropyl triethoxysilane, nine fluorine hexyl trimethoxysilanes, ten trifluoro octyl trimethoxy silanes, ten trifluoro octyls Triethoxysilane, amine propyl-triethoxysilicane, hexamethyldisilazane, lauric acid/dodecanoic acid, stearic acid, tannic acid, succinic acid, propylene It is acid, oleic acid, isopropanol, polyvinyl alcohol, polyethylene glycol, lauryl sodium sulfate, neopelex, sodium laurate, hard Resin acid sodium, sodium acetate, enuatrol, polyoxyethylene, styrene, tween (polyoxyethylene sorbitan monooleate), methyl-prop One of e pioic acid methyl ester is a variety of.
6. the organic/inorganic composite film piece as claimed in claims 1-5 with above-mentioned smooth selective absorbing and ageing-resistant function Preparation method, which comprises the steps of:
S01, centrifugation phase inversion will be passed through into plasticizer or softening agent comprising the liquid dispersion of multilayered structure Nano composite granules Form stable oily phase dispersion；
S02, it polymer is passed through into feed inlet with oily phase dispersion is respectively added in extruder, control extruder melt zone temperature It is 150-250 DEG C, carries out melting premix 1-30 minutes, 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 resistance to old is made in mixed raw material 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 received comprising multilayered structure The liquid dispersion of rice composite particles is added thereto, and is sufficiently stirred, after mixing, is obtained solution system to be dried, polymer Concentration in mixed liquor is 0.5-20wt%, obtains masterbatch after dry, in masterbatch the content of polymer be 30-90wt%, it is more The content of layer structure nano composite particles is 10-70wt%；
S12, plasticizer or softening agent and a certain amount of polymer is added in masterbatch obtained into step S11, in blender It is added it in extruder after full and uniform mixing, 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 resistance to old is made in mixed raw material injection molding Change the organic/inorganic composite film piece of function.
7. the preparation method of organic/inorganic composite film piece according to claim 6, it is characterised in that: step S01, in S11, institute Stating multilayered structure Nano composite granules liquid dispersion includes multilayered structure Nano composite granules and liquid phase medium；The multilayer knot In structure Nano composite granules, inner layer is the doping oxide with infrared ray barriers function, and middle layer is with ultraviolet radiation absorption function The metal oxide of energy, secondary outer layer are with the silica for reducing metal oxide oxidation catalyst performance, and outermost layer is with raising The organic coating layer of stability；The multilayered structure Nano composite granules are evenly dispersed in liquid phase medium.
8. the preparation method of organic/inorganic composite film piece according to claim 7, it is characterised in that: the liquid phase medium is selected from Water, methanol, ethyl alcohol, ethylene glycol, isopropanol, benzyl alcohol, toluene, dimethylbenzene, dimethyl sulfoxide, dimethylformamide, dimethyl Acetamide, n-hexane, hexamethylene, acetone, butanone, ethyl acetate, butyl acetate, phenol, cyclohexanone, tetrahydrofuran, alkyl halide One of hydrocarbon.
9. the preparation method of organic/inorganic composite film piece according to claim 7, which is characterized in that the multilayered structure nanometer The preparation method of composite particles liquid dispersion, includes the following steps:
S1. the raw material of inner layer doping oxide is dissolved in solvent and forms salting liquid, stirred evenly, adjusted pH value, be then added Reaction solution is transferred in autoclave and carries out hydro-thermal or solvent thermal reaction by reducing agent, is cooled to room temperature after complete reaction, is centrifuged 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, sufficiently After mixing, the obtained doping oxide nano particle of S1 is added and is reacted；It is cooled to room temperature after complete reaction, centrifugation is washed It washs, precipitation and separation, obtains 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, be added The obtained metal oxide coating-doping oxide nano particles of S2, stir evenly, are reacted；It cools down after complete reaction To room temperature；
S4. surface coating layer is added into above-mentioned mixed liquor to be reacted, reaction product is spent into washing, is then dispersed in liquid phase In medium, obtain containing multilayered structure nano particle liquid phase transparent dispersion.
10. the preparation method of organic/inorganic composite film piece according to claim 9, it is characterised in that: in step S1, in described The raw material of layer doping oxide includes at least one oxide raw material and at least one doped chemical raw material.The oxide raw material 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, four chlorinations Tungsten, it is tungstate lithium, potassium tungstate, wolframic acid caesium, sodium tungstate, wolframic acid rubidium, cesium sulfate, potassium sulfate, sodium sulphate, rubidium sulfate, lithium sulfate, secondary It is ammonium tungstate, ammonium metatungstate, positive ammonium tungstate, tungsten silicide, tungsten sulfide, chlorine oxygen tungsten, a tungstic acid hydrate, metamolybdic acid ammonium, positive ammonium molybdate, secondary Ammonium molybdate, molybdic acid, molybdenum silicide, molybdenum sulfide, chlorine oxygen molybdenum, alcohol oxygen molybdenum, molybdenum pentachloride, molybdenum tetrachloride, molybdenum bromide, molybdenum fluoride, carbonization Molybdenum, oxidation of coal molybdenum；The doped chemical raw material be selected from carbonate containing doped chemical, bicarbonate, nitrate, nitrite, One of hydroxide, chloride, sulfate, sulphite, acylate, alkoxide, complex compound, oxyacid, oxysalt Or it is a variety of；
Preferably, the solution concentration of all metal ions in the raw material of the inner layer doping oxide is 0.1-1.0M；It is more excellent Selection of land, the solution concentration of all metal ions in the raw material of the inner layer doping oxide are 0.3-0.8M；
Preferably, in step S1 and S2, the solvent be selected from water, methanol, ethyl alcohol, acetone, butanone, ethyl acetate, butyl acetate, One of 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-PD, 1, 3-propanediol, glycerine, ethanol amine, triethanolamine, oleyl amine, oleic acid, ethylenediamine, hydrazine hydrate, ammonium oxalate, ammonium hydroxide, sodium borohydride, The molar ratio of one or both of potassium borohydride, hydrogen sulfide, sodium hypophosphite, the reducing agent and tungsten and/or molybdenum total amount 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, 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 alkali is added Property substance adjust solution pH to 7.5-12；Wherein, acidic materials are selected from hydrochloric acid, nitric acid, sulfuric acid, oxalic acid, citric acid and acetic acid One or both of；Alkaline matter is selected from sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, ethamine, ethanol amine, second Diamines, dimethylamine, trimethylamine, triethylamine, propylamine, isopropylamine, 1,3- propane diamine, 1,2- propane diamine, tripropyl amine (TPA) and triethanolamine One or both of；
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；
Preferably, in step S2, the raw material of the middle layer metal oxide is selected from carbonate, bicarbonate, the nitre of corresponding metal Hydrochlorate, hydroxide, chloride, sulfate, sulphite, acylate, alkoxide, complex compound, oxyacid, contains nitrite One of oxygen hydrochlorate is 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, ethylenediamine, two One of methylamine, trimethylamine, triethylamine, propylamine, isopropylamine, 1,3- propane diamine, 1,2- propane diamine, tripropyl amine (TPA) and triethanolamine Or a variety of, 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 Ground, the pH are 7-10, and reaction temperature is 50-80 DEG C, reaction time 1-5h；Most preferably, the pH is 8-9, instead Answering temperature is 60-70 DEG C, reaction time 2-4h；
Preferably, in step S3, the silicon-containing compound is in ethyl orthosilicate, methyl orthosilicate, silester or silica solution It is one or more, the mass ratio of the silicon-containing compound and ethyl alcohol is 1:40-50；
Preferably, in step S3, the lye is selected from sodium hydroxide, potassium hydroxide, ammonium hydroxide, ethamine, ethanol amine, ethylenediamine, two One of methylamine, trimethylamine, triethylamine, propylamine, isopropylamine, 1,3- propane diamine, 1,2- propane diamine, tripropyl amine (TPA) and triethanolamine Or a variety of, 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 the reaction temperature Degree 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 be octyl trimethoxy silane, octyltri-ethoxysilane, Hexamethyldisilazane, 3- methacryloxypropyl trimethoxy silane, 3- methacryloxypropyl triethoxy Silane, six ruthenium trimethoxysilanes, six ruthenium triethoxysilanes, dimethyl polysiloxane, glycidyl-oxypropyl front three Oxysilane, glycidyl-oxypropyl triethoxysilane, nine fluorine hexyl trimethoxysilanes, ten trifluoro octyl trimethoxy silicon Alkane, tridecafluoro-n-octyltriethoxysilane, amine propyl-triethoxysilicane, hexamethyldisilazane, lauric acid/dodecanoic acid, stearic acid, tan Acid, succinic acid, acrylic acid, oleic acid, isopropanol, polyvinyl alcohol, polyethylene glycol, lauryl sodium sulfate, dodecyl benzene sulfonic acid Sodium, sodium laurate, odium stearate, sodium acetate, enuatrol, polyoxyethylene, styrene, tween (polyoxyethylene sorbitol acid anhydride list Oleate), 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 be selected from ethyl alcohol, normal propyl alcohol, acetone, ethyl acetate, butyl acetate, toluene, One of dimethylbenzene, n-hexane, hexamethylene, dimethyl sulfoxide, dimethylformamide, dimethyl acetamide are a variety of.
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CN114890667A (en) * 2022-06-13 2022-08-12 晓恩医药包装材料(安庆)有限公司 Neutral borosilicate glass medicinal tube with light-shielding function and preparation method thereof
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