CN107683257A - The composite of nanocrystal is absorbed containing UV - Google Patents

The composite of nanocrystal is absorbed containing UV Download PDF

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Publication number
CN107683257A
CN107683257A CN201680028055.0A CN201680028055A CN107683257A CN 107683257 A CN107683257 A CN 107683257A CN 201680028055 A CN201680028055 A CN 201680028055A CN 107683257 A CN107683257 A CN 107683257A
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composite
nano crystal
crystal material
amorphous
porous material
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C·W·贝尔
W·M·尤哈兹
M·E·希勒加斯
M·D·穆斯克
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Shepherd Color Co
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Shepherd Color Co
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    • C01F17/32—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6 oxide or hydroxide being the only anion, e.g. NaCeO2 or MgxCayEuO
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    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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Abstract

It is now discovered that the composite of the amorphous porous material with nano crystal material is a kind of UV absorbents included in its hole.Porous material is used as the pore matrix of nano crystal material support.The particle of nano crystal material is separation, it means that they are not connected to each other.In some embodiments, nano crystal material is entirely in the hole of porous material.In some embodiments, nano crystal material can stretch out from some or all holes of porous material.In some embodiments, nano crystal material is cerium oxide.In some embodiments, nanocrystal is that draw ratio is about 1 to about 1.5 2 to about 100nm in its size range most on major axis.

Description

The composite of nanocrystal is absorbed containing UV
Background technology
A kind of ultraviolet (UV) the just electromagnetic radiation form of wavelength between 10 and 400nm.Ultraviolet light has than visible ray Higher energy, and account for about the 10% of all luminous energy of sun transmitting.Due to the property of its strength, UV light has induced chemical anti- Should be with the ability of catalytic polymerization.Although beneficial in the case of some, ultraviolet also can be to organism and similar no life Body produces significant infringement.The absorption of ultraviolet radioactive causes degraded by photooxidation, high energy UV photons so that chemical bond not It is stable, and produce the approach that can reduce the material integrity under radiation.
Commonly referred to as the wave-length coverage of the electromagnetic spectrum portion of UV parts is more than 100nm and is less than 400nm.The scope is entered One step is subdivided into lower part：Wavelength is that UV-A, the wavelength between 315nm and 400nm are UV-B between 280nm and 315nm And UV-C of the wavelength between 100nm and 280nm.The UV-C light incident from the sun will not significantly penetrate atmosphere and ozone Layer, UV-B light is mainly absorbed by upper atmosphere, but is not completely absorbed.The intensity for reaching earth's surface changes with season, and right Intensity in equator is higher by a magnitude than limit.Although UV-A intensity is not so good as UV-B light, but UV spectrum more based on The region wanted.It penetrates cloud layer, and exists in any time for having daylight, no matter season or position.
Due to the destructiveness of ultraviolet radioactive, it is derivable potential to mitigate UV light substantial amounts of molecule and material have been developed Harm.Although initially effectively, organic UV absorbents are eventually degraded, it is necessary to can improve its use in more harsh environment The solution of the custom design in life-span or other additive.
These UV absorbents are used to strengthen the service life containing its product, coating, plastics or matrix.Functionally, They can dispose in the material with by reduce spoilage, holding structure integrality and packaging definition come provide packaging, into Divide, the protection of content.UV absorbents are added in cosmetics, face cream, washing lotion, protect the skin from the harmful of solar radiation Influence.On the woodenware dyestuff of decoration, vinyl products, floor or metal coating, UV absorbents help to maintain coating for combination Attachment to matrix, the layering of coating is minimized, contribute to the anticorrosion of metal, such as in automotive vehicles applications.UV absorbents increase Add the light resistance of toner, slow down the degraded of organic substrate such as wood-fibred and polymer, and increase durable vinyl, modeling Material and polymer product such as furniture, deck, floor, wallboard, outer goodses, furniture, waterproof cloth, agriculture fabric, automotive trim, fibre The service life of peacekeeping film etc..
Inorganic oxide provides the solution of the increase stability of a system, but due to its intrinsic high index of refraction, More see in opaque system.
Although being conventionally used in opaque system, the size of inorganic oxide UV absorbents can reduce to become It is bright.As the size of inorganic oxide is reduced beyond the wavelength of incident light, its opacity will reduce.
Known some inorganic substances are used as good UV absorbents.TiO2It is commonly used with ZnO in sun-screening agent, and CeO2It is more common in industrial woodwork coating.TiO2There is provided enough protections under the wavelength less than 350nm, but it can not be Enough absorptions are provided between 350nm and 400nm.ZnO provides bigger protection between 350nm and 400nm, but in acyclic acidic It can be less stable in border.Two oxides may each be photocatalytic activity, and other processing may be needed to protect Shield disposes their matrix from degraded.CeO2It is considered as most durable UV absorbents, there is provided photocatalytic activity, the height of reduction Acid resistance and high thermal stability.
However, for as durable, transparent and final effective UV absorbents applicatory extensively TiO2, ZnO or CeO2, it is necessary to reduce active nano crystalline size.Average diameter is the most useful less than 150nm particle diameter.Although traditionally use In opaque system, but the size of inorganic oxide UV absorbents can reduce to become transparent.With inorganic oxide Size is reduced beyond the wavelength of incident light, and its opacity will reduce.
These materials for being categorized as nano particle have uncommon challenge；Small size causes high surface area and very strong Agglomeration power, therefore, suitably dispersion is challenging, and generally these are provided as diluent liquid suspension. Suspension must have compatibility between the liquid containing UV absorbents and its medium that will be disposed.In water-based or solvent-borne type Nano particle UV absorbents in system need to carry out specific modification.
In addition, the security consideration exposed to powdered nano particle is not yet fully assessed.Many regulators are Carry out nano material breathing, intake and the review of topical application.The very small size of nano particle can allow particle migration to wear Skin, mucous layer are crossed, matrix, percolating filter is left or spreads far distance in atmosphere, increases breath exposure.These are closed Note not only influences manufacture method, the effectiveness and methods for using them of the absorbents of UV containing nano particle, has an effect on the long-term ring of nano particle Border influences, because they are eventually discharged into environment.
The content of the invention
A kind of UV absorbent composites comprising nano crystal material and porous material.Nano crystal material is porous In the hole of material, and it is separation.Nano crystal material includes cerium oxide.Optionally, there may be in porous material Other nano crystal material；Composite can be encapsulated by inorganic oxide；Or both.
A kind of UV absorbent composites comprising nano crystal material and porous material.Nano crystal material is porous In the hole of material.Nanocrystal is that draw ratio is about 1 to about 1.5 2 to about 100nm in its size range most on major axis.
Brief description of the drawings
The accompanying drawing for being incorporated to and forming the part of this specification is typically retouched exemplified with embodiment, and with being given above State and being described in detail for embodiment given below is used for the principle for explaining the disclosure together.
Fig. 1 a are the transmission electron microscope images of the composite of embodiment 1.Fig. 1 b are the composites of embodiment 4 Transmission electron microscope image.
Fig. 2 a are the transmission electron microscope images of the composite of embodiment 1.Fig. 2 b are the composites of embodiment 9 Transmission electron microscope image.
Fig. 3 is the UV, visible light transmitted spectrum of embodiment 15.
Fig. 4 is the UV-vis DRS spectrum of embodiment 1,2 and 3.
Fig. 5 is the UV-vis DRS spectrum of embodiment 1,4,5,6,7 and 8.
Fig. 6 is the UV-vis DRS spectrum of embodiment 1,9,10,11,12 and 13.
Fig. 7 is the UV, visible light transmitted light for the embodiment 1 and 3 being dispersed in as described in example 16 above in polystyrene resin Spectrum.
Fig. 8 is that the ultraviolet of embodiment 1,4,5,6,7 and 8 being dispersed in as described in example 16 above in polystyrene resin can See transmitted spectrum.
Fig. 9 is the purple for the embodiment 1,9,10,11,12 and 13 being dispersed in as described in example 16 above in polystyrene resin Outer transmission spectrum.
Figure 10 is to be dispersed in makrolon (PC) resin and be molded as the implementation of plastic chip as described in example 17 above The photo of example 1,4,5,6,7 and 8.
Figure 11 is to be dispersed in polystyrene (PS) resin and be molded as the implementation of plastic chip as described in example 16 above The photo of example 1,3,4,5,6,7,8,9,10,11,12 and 13.
Embodiment
It is now discovered that the composite of the amorphous porous material with nano crystal material is a kind of UV included in its hole Absorbent.Support of the random distribution of porous material endoporus as nano crystal material.Hole is separation, it means that they are not Connection.Hole carries the particle in nano crystal material and keeps them to separate, i.e. prevents them to be in contact with each other.Hole is open into more The surface of Porous materials.In some embodiments, nano crystal material is completely in the hole of porous material.In some embodiments In, nano crystal material can stretch out from some or all holes of porous material.In some embodiments, most of nanometer Crystalline material is in the hole of porous material.In some embodiments, most of nano crystal material is entirely in porous material In the hole of material.In some embodiments, nano crystal material is cerium oxide.In some embodiments, nanocrystal Material has 2nm to about 100nm nanocrystal size scope at it most on major axis, draw ratio is about 1 to about 1.5.It is nanocrystalline Body is monocrystalline.The particle of nano crystal material can be made up of multiple nanocrystals.
Porous material is inorganic amorphous materials.In some embodiments, the aperture in porous material be about 0.5nm extremely About 150nm, e.g., from about 0.5nm to about 100nm, about 0.5nm to about 80nm, about 1nm to about 80nm, about 1nm to about 50nm, about 2nm to about 50nm, about 3nm to about 40nm, about 5nm to about 150nm, about 5nm to about 100nm, about 5nm to about 75nm, about 5nm extremely About 50nm, about 10nm are to about 150nm, about 10nm to about 100nm, about 10nm to about 75nm, about 10nm to about 50nm.Aperture is more Diameter at Porous materials surface.Internal diameter can be with greater or lesser.In some embodiments, porous material has about 0.1 to about 4cm3/ g, e.g., from about 0.1 to about 2cm3/ g, about 0.1 to about 1cm3/ g, about 0.1 to about 0.8cm3/ g, about 0.25 to about 0.8cm3/ G, or about 0.25 to about 0.7cm3/ g accumulation pore volume.In some embodiments, porous material has about 0.5 μm to about 15 μm, e.g., from about 0.5 μm to about 10 μm, about 0.5 μm to about 7 μm, about 0.5 μm to about 5 μm or about 0.5 μm to about 3.5 μm of grain Footpath.Aperture, accumulation pore volume and the particle diameter of porous material can be described any combinations.
Manufacturer and grade depending on material, porous material can contain porose distribution.Most commonly, material contains hole The distribution in footpath, such as 16-24nm diameters, still have other grades to be described as containing diameter<100nm Kong Qun, its many hole point Cloth is still from 0.5nm to about 150nm.In addition, amorphous silica is characterised by that specific surface area is 25-750m2/ g, such as 100-390m2/ g and 80-190m2/g.In some embodiments, porous material has about 0.5 μm to about 350 μm, e.g., from about 0.3 μm to about 150 μm, e.g., from about 0.3 μm to about 100 μm, e.g., from about 0.3 μm to about 50 μm, e.g., from about 0.3 μm to about 20 μm, E.g., from about 5 μm to about 150 μm, e.g., from about 10 μm to about 150 μm, e.g., from about 0.3 μm to about 0.5 μm, about 0.8 μm to about 1.4 μm, About 2 μm to about 5 μm of particle diameter.Any number of abrasion, grinding or classification step can be used for the grain for reducing or changing porous material Footpath is distributed.Aperture, specific surface area and the particle diameter of porous material can be described any combinations.
In some embodiments, porous material is ceramics.In some embodiments, porous material is silica, Such as, but not limited to：Amorphous hot fumed silica (such as Cab-o-Sil, Syloid, Tixosil or Aerosil), nothing are fixed Shape precipitated silica (such as Zeolex, Zeosyl or Ultrasil) or naturally occurring silica (such as diatomite).
Nano crystal material is in the hole of porous material, therefore they are on or near the surface of porous material, not by Porous material is encapsulated completely.In some embodiments, nano crystal material is entrained in hole.In some embodiments, Nano crystal material is cerium oxide.The example of cerium oxide includes but is not limited to have empirical formula CexMyOzMaterial, Wherein 0.5<X≤1, and 0≤y≤1, and 2.0≤z≤7；Such as 0.5<X≤1, and 0≤y<0.5, and 2.0≤z≤7.Metal M Selected from Hf4+、Ta5+、W4+、Pr3+、Pr4+、Nd3+、Pm3+、Sm2+、Sm3+、Eu2+、Eu3+、Gd3+、Tb3+、Tb4+、Dy3+、Ho3+、Er3+、 Tm2+、Tm3+、Yb2+、Yb3+、Lu3+、V3+、V4+、V5+、Bi3+、Bi5+、Mo4+、Mo6+、Mg2+、Ti3+、Ti4+、Si4+、Zn2+、Al3+、 Zr4+、La3+、Sb5+、Nb5+、Co2+、Co3+、Mn2+、Mn3+、Ca2+、Sr2+、Ba2+、Fe4+、Fe3+、Fe2+、Cr3+、Sn4+、Y3+、Cu2+、 Cu3+Or its mixture；Such as V3+、V4+、V5+、Bi3+、Bi5+、Mo4+、Mo6+、Mg2+、Ti4+、Si4+、Zn2+、Al3+、Zr4+、La3+、 Sb5+、Nb5+、Co2+、Co3+、Mn2+、Mn3+、Ca2+、Sr2+、Ba2+、Fe4+、Fe3+、Fe2+、Cr3+、Sn4+Or its mixture；Or Ti4+、 Si4+、Zn2+、Co2+、Co3+、Ca2+、Sr2+、Ba2+、Fe4+、Fe3+、Fe2+、Cr3+、Sn4+Or its mixture.Example includes but unlimited In：CeO2、Ce0.9Ca0.2O2、Ce0.8Ca0.4O2、Ce2O3、Ce0.9Fe0.13O2、Ce0.6Cr0.53O2、SrTiO3、CeAlO3(Co, Zn)2SiO4.In some embodiments, nano crystal material is CeAlO3.In some embodiments, regardless of M, nanometer Crystalline material is about 2 to about 100nm in its crystal domain size scope most on major axis, and it is about 1 to about 1.5 to crystallize draw ratio.
In some embodiments, nano crystal material is about 2 to about in its crystal domain size scope most on major axis 100nm, such as：About 2nm to about 100nm, about 2nm to about 80nm, about 2nm to about 50nm, about 2nm to about 40nm, about 5nm extremely About 100nm, about 5nm are to about 80nm, about 5nm to about 75nm, about 5nm to about 50nm, about 5nm to about 40nm, about 5nm to about 30nm, about 10nm are to about 100nm, about 10nm to about 800nm, about 10nm to about 75nm, about 10nm to about 50nm.In some implementations In mode, crystallization draw ratio is about 1 to about 1.5.In some embodiments, the diameter of nano crystal material would be about 2nm extremely About 10nm, e.g., from about 2nm are to about 5nm or about 5nm to about 10nm.In some embodiments, draw ratio is about 1 to about 1.2.Receive Crystal domain size, crystal draw ratio and the diameter of rice crystalline material can be described any combinations.There may be multiple domain models Enclose.In some embodiments, more than one nano crystal material be present, and they there can be identical or different domain Scope.
In some embodiments, the structure of nano crystal material is cubic fluorite structure.In some embodiments, receive The structure of rice crystalline material is tetragonal.In some embodiments, the structure of nano crystal material is hexagonal crystal.In some realities Apply in mode, the structure of nano crystal material is Ca-Ti ore type.
In some embodiments, composite additionally comprises the second nano crystal material.Second nano crystal material is In the hole of porous material, and it is separation.Second nano crystal material is selected from TiO2、ZnO、MoO3、(Co,Zn)2SiO4、 SrTiO3And its mixture.In some embodiments, the second nano crystal material can be cerium oxide nanocrystals material Another composition.In some embodiments, the second nano crystal material its most on major axis it is nanocrystalline with 2nm to about 50nm Body size range, such as：About 2nm to about 100nm, about 2nm are to about 80nm, about 2nm to about 50nm, about 2nm about 40nm, about 5nm To about 100nm, about 5nm to about 80nm, about 5nm to about 75nm, about 5nm to about 50nm, about 5nm to about 40nm, about 5nm to about 30nm, about 10nm are to about 100nm, about 10nm to about 800nm, about 10nm to about 75nm, about 10nm to about 50nm.In some implementations In mode, crystal draw ratio is about 1 to about 1.5.Nanocrystal is monocrystalline.The particle of second nano crystal material can be by multiple Nanocrystal forms.In some embodiments, the second nano crystal material, which occupies, also contains cerium oxide nano in porous material The hole of crystalline material.
In some embodiments, the second Nanocrystalline materials are about 2 to about in its crystal domain size scope most on major axis 50nm, such as：About 2nm to about 100nm, about 2nm to about 80nm, from about 2nm to about 50nm, about 2nm to about 40nm, about 5nm to About 100nm, about 5nm are to about 80nm, about 5nm to about 75nm, about 5nm to about 50nm, about 5nm to about 40nm, about 5nm to about 30nm, about 10nm are to about 100nm, about 10nm to about 800nm, about 10nm to about 75nm, about 10nm to about 50nm.In some implementations In mode, crystal draw ratio is about 1 to about 1.5.In some embodiments, the diameter of the second nano crystal material would be about 2nm to about 10nm, e.g., from about 2nm are to about 5nm or about 5nm to about 10nm.In some embodiments, draw ratio is about 1 to about 1.2.Crystal domain size, crystal draw ratio and the diameter of second nano crystal material can be described any combinations.
In some embodiments, the second nano crystal material can exist with the structure different from nano crystal material. In some embodiments, TiO2Structure is anatase titanium dioxide, rutile-type or its combination.In some embodiments, TiO2It is nanocrystalline The average diameter of body is less than 100nm.In some embodiments, ZnO structures are wurtzite-type, zinc blend, Rochelle (Rochelle) salt or its combination.In some embodiments, the average diameter of ZnO nano crystal is less than 100nm.In some realities Apply in mode, MoO3Structure is iris, hexagonal crystal or its combination.In some embodiments, SrTiO3It is Ca-Ti ore type knot Structure.In some embodiments, (Co, Zn)2SiO4Structure is phenacite structure or has hexagonal crystal, water chestnut prismatic crystal or cubic crystalline form Willemite.
In some embodiments, the amount of total nano crystal material (including any second nano crystal material) is no more than multiple Between the weight % of 62.5 weight %, such as, but not limited to about 2 and about 62 of condensation material quality, about 5 and about 60 between weight %, about Between 5 and about 50 weight %, about 5 and about 43 between weight %, about 5 and about 40 between weight % and about 5 and about 35 weight % Between.
Powdered, undiluted form composite absorbs the wavelength of about 50% to about 100% between 200 and 375nm Light, such as absorb about 50% to about 75%, about 50% to about 70%, about 70% to about 80% and about 75% to about 100%.
In some embodiments, the average bulk aggregate size (bulk aggregate size) of composite is about 0.5 μm to about 300 μm, e.g., from about 0.5 μm to about 200 μm, about 0.5 μm to about 150 μm, about 0.5 μm to about 50 μm or about 0.5 μ M to about 20 μm.In some embodiments, the average bulk aggregate size of composite is about 0.2 μm to about 2 μm, e.g., from about 0.2 μm to about 1 μm, about 0.2 μm to about 0.8 μm or about 0.2 μm to about 0.5 μm.
Composite can be formed by just wet impregnation (incipient wetness) method.For example, by nanocrystal precursor Material is dissolved in solvent such as water.Porous material is added in solution to form viscogel.The liquid mixture of addition it is total Volume is less than or equal to the total pore volume of porous material.It is sufficiently mixed viscogel.Solvent tack gel is evaporated to produce Dry cake.Then dry cake is calcined on nanocrystal precursor decomposition temperature to produce composite.Can be by grinding as sprayed Grinding is processed further composite to reduce particle diameter or scattered agglomerate.
Nanocrystal precursor material is dissolved in solvent, and contains above-mentioned empirical formula (i.e. CexMyOz) needed for metal (one or more), generally with complementary anion.For example, NO3 -、Cl-、SO4 2-、CH3COO-、C5H7O2 -、C2O4 -、PO4 3-、 Br-、I-、CO3 2-And HCO3 -It is that can form solable matter in polarity or non-polar solven with one or more aforementioned metals Anion.In some embodiments, using more than one nanocrystal precursor material to form nano crystal material.One In a little embodiments, using only a kind of nanocrystal precursor material.During calcining, precursor material thermal decomposition aoxidizes for component Thing.
The solvent that can be used in the incipient wetness for preparing composite is can to dissolve nanometer at least in part Co-crystal former material, and the solvent of porous material will not be destroyed.
Composite comprising the second nano crystal material can be by including cerium oxide nanocrystals material for preparing Composite same procedure prepare.For preparing TiO2The precursor of second nano crystal material includes but is not limited to：Boronation Titanium, titanium chloride, titanium bromide, butanol titanium, titanium ethanolate, thylhexoic acid titanium, titantium hydride, isopropyl titanate, titanium nitride, titanium propanolate, lactic acid Titanium, titanium sulfate, titanyl sulfate and its mixture.Precursor for preparing the nano crystal materials of ZnO second includes but is not limited to：Second Sour zinc, zinc bromide, zinc chloride, zinc nitrate, butanol zinc, zinc carbonate, zinc citrate, zinc oxalate, zinc sulfate and its mixture.For Prepare MoO3The precursor of second nano crystal material includes but is not limited to：Acetic acid molybdenum, hydroboration molybdenum, molybdenum chloride, isopropanol molybdenum, sulphur Change molybdenum, molybdic acid, acetyl acetone, phosphomolybdic acid and its mixture.For preparing (Co, Zn)2SiO4Before second nano crystal material Body includes but is not limited to：Cobaltous bromide, cobalt chloride, cobalt edetate, cobalt hydroxide, isopropanol cobalt, cobalt nitrate and its mixture；With Strontium acetate, strontium bromide, strontium chloride, isopropanol strontium, strontium nitrate, strontium sulfate, strontium oxalate and its mixture.For preparing SrTiO3The The precursor of two nano crystal materials includes but is not limited to：Strontium acetate, strontium bromide, strontium chloride, isopropanol strontium, strontium nitrate, strontium sulfate, Strontium oxalate and its mixture；With titanium boride, titanium chloride, titanium bromide, butanol titanium, titanium ethanolate, thylhexoic acid titanium, titantium hydride, isopropyl Alcohol titanium, titanium nitride, titanium propanolate, lactic acid titanium, titanium sulfate, titanyl sulfate and its mixture.These precursor materials can be applied in combination To prepare the mixture of the second nano crystal material.
In some embodiments, composite portions or whole coating encapsulation.When composite is partially enclosed, At least half of composite is encapsulated, but coating need not be continuous.Example coating include Al, Zr, Si, Bi and W (or its mixing Thing) oxide and silicate, such as：SiO2、Al2O3、Bi2O3、Bi2SiO5、WO3、ZrO2.In some embodiments, coating Selected from SiO2And Al2O3.Coating can be formed from tungsten boride, tungsten chloride, ethanol tungsten, isopropanol tungsten, wolframic acid；Zirconium acetate, butanol Zirconium, zirconium carbonate, zirconium boride, zirconium bromide, zirconium oxycarbonate, zirconium chloride, basic zirconium chloride, zirconyl nitrate, zircoium hydride, zirconium iso-propoxide, Zirconium lactate, zirconium sulfate, propyl alcohol zirconium, zirconium；Bismuth acetate, bismuth bromide, bismuth citrate, waltherite, thylhexoic acid bismuth, hydroxide Bismuth, isopropanol bismuth, bismuth phosphate, bismuth sulfate, bismoclite, bismuth chloride, bismuth nitrate, novismuth, bismuth perchlorate；Silicic acid, tetrem Sour silicon, silicon chloride, silicon bromide, Iodotrimethylsilane, sodium metasilicate, tetraethyl orthosilicate, potassium silicate, cataloid, silane, Tetraethyl orthosilicate；Alum, aluminium acetate, aluminium bromide, aluminium chloride, aluminium butoxide, aluminium isopropoxide, aluminum nitrate, oxalic acid aluminium, sulfuric acid Aluminium, aluctyl, aluminium metaphosphate；And related compound, and its mixture.
Can by by the porous material containing nano crystal material with one or more through dissolving the water-based of parent material Or solvent-borne type metal salt or complex solution mixing carry out coating composite materials.It is optionally possible to for example with 3M NaOH, 3M H2SO4, phosphoric acid, ammonia, the pH of ammonium hydroxide or second acid-conditioning solution is to appropriate pH or stoichiometric proportion.PH is selected to cause gold Belong to the unstability of salting liquid.
In some embodiments, can containing one or more through dissolve raw material water-based or solvent-borne type metal salt or In the presence of complex solution, coating is formed on UV absorbent composites by mixing composite.It is optionally possible to Such as with 3M NaOH, 3M H2SO4, phosphoric acid, ammonia, the pH of ammonium hydroxide or second acid-conditioning solution is to appropriate pH or stoichiometry Than.PH is selected to cause the unstability of metal salt solution when added to UV absorbent composites.
In some embodiments, can be absorbed by the way that under agitation UV will be added to containing the solution through dissolved metal salt Coating is formed in 0.5 to 50 weight % solution of agent composite.Make solution before metal salt (one or more) precipitation Balance.Comparably begin to use the reaction of cataloid.Generally, metal alkoxide deposits materials are from alcoholic solution, wherein reagent Drive the hydrolysis of metal alkoxide and the formation of metal hydroxides or oxide.All reactions can contain or not contain other Auxiliary agent is complexed, and can be carried out at elevated temperatures, further to induce housing to be precipitated on UV absorbent composites And condensation.
Can be by carefully adjusting control precipitation reaction to the particle isoelectric point for being used for depositing colloidal particle or less than generation The pH of the instantaneous precipitation of metal oxide species.Acid or alkali be slowly added to be by under known speed with a small amount of acid or Alkalimetric titration and complete.Reaction rate shows according to the concentration of acid or alkali, the buffer capacity of solution, reaction temperature and addition speed Write change.In some embodiments, deposited material is deposited on porous particle, obtain can Thickness Measurement by Microwave uniform case.One In a little embodiments, the roughness and density of shell material change with composition.In some embodiments, inorganic oxide is encapsulated Material can occupy a part for the remaining pore structure of amorphous materials or is filled up completely with.
In some embodiments, encapsulating is the composite of more than one material.Can be by same by metal complex When be dissolved into water or solvent, and as described above exposed to UV absorbents compound come deposit encapsulating.For example, can be by using 3M H2SO4Slowly regulation pH deposits the solution of basic zirconium chloride and sodium metasilicate simultaneously from 12 to pH 8.In some embodiments, permit Perhaps cross reaction and compound are formed, and precursor material provides by-product deposition on or within porous matrix.
In some embodiments, encapsulating material without encasing UV absorbent composites completely.In some embodiments In, hole of the metal oxide covering containing nano crystal material.In some embodiments, can after encapsulating material deposition To add new mixed compounds, it produces the encapsulating of the organic or inorganic material containing entrainment.Equally, the deposition of encapsulating material Can be on porous material or the nano crystal material of exposure.
In some embodiments it may be desirable to the core material of coating is calcined to promote the crystallizing of shell material, closely knit, dehydration Or solidification, or any surface side joint hydroxyl condensation is encapsulated into oxide with being formed.Temperature and time depends on the material of composition Material, but example ranges are about 150 to about 1000 degrees Celsius, the residence time is about 30 to about 600 minutes.It can be forged by correction Temperature is burnt to adjust the formation of crystalline material, and glassy shell or amorphous metal oxide is formed to promote only to condense.In addition, should The formation that step can absorb nano crystal material with UV is completed or is respectively completed simultaneously；Individually or with multiple steps to increase Temperature.
Composite can be used for coating, such as coating, paint and varnish；Plastics；Fiber；Rubber；Elastomer；Film；Ink； Cosmetics；Ceramics, such as enamel, glass enamel；Fabric；Concrete；Deck；Metal coating；Furniture；Cement；Pitch；Woodenware applies Material；With similar object.Composite can be used for polymer substrate, such as, but not limited to heat-curable matrix and thermoplastic matrix, And for plastics and carton package, food contact application, automotive upholstery and automobile exterior trimming parts.
Laser labelling is by the way that article is produced into the work(of irreversible contrast color change on article exposed to laser beam Energy.When color change is patterned or delineated into character, picture or pattern, it is particularly useful.The technology is by for knowing Do not performed with some fields of decorative purpose.
The chemistry that laser marking additives produce observable contrast by the way that the laser under selective wavelength is converted into becomes Change to work.The article of laser marking additives containing effective dose is impacted by laser beam, and the additive in the region Chemical conversion is undergone, when checking under illumination, recognizable pair is produced between the irradiation zone of article and non-irradiated region Degree of ratio.Although checking that article is most common under visible light illumination, the definition of laser labelling need not use visible ray, Simply have by the contrast between the detectable article irradiation zone of some spectrum and non-irradiated region.
By adding to realizing many materials such as plastics and packaging exposed to the additive material of laser radiation sensitive Laser labelling.Cause color change exposed to laser, the basic color of itself and material is contrasted.UV absorbent composites can use Make laser marking additives.
Numerous optical maser wavelength pass flags can be utilized according to the chemical property of additive.When with UV laser treatments, UV absorbent composites are particularly useful.However, other optical maser wavelengths can be used for laser labelling UV absorbent composites.
Embodiment 1 is the cerium oxide of embedded amorphous silica matrix.The dioxy shown by transmission electron microscope SiClx Medium Culture CeO2The size of nanocrystal and distribution (Fig. 1 a) show random point of nanocrystal in the same size Cloth.It is clearly present amorphous silica and CeO2Separated region.The fine structure and porosity of amorphous silica can The domain for being described again to coalesce at random.
Some embodiments illustrate multiple functional uvs and absorb chemistry, and it is included in embodiment 2 and embodiment 3 opens up respectively The CeO modified with calcium or aluminium in the amorphous silica of embodiment 1 shown2.Compared with the composite of embodiment 1, these Change shows the change of color (referring to table 1) and UV reflectivity (referring to Fig. 4).
Embodiment 1 is encapsulated with amorphous silica, as shown in Figure 1 b, it occupies the hole of amorphous silica simultaneously Make discrete integration domain, generate material modified (embodiment 4) with compared with low surface area.Cladding is applied using following material to implement The material of example 1 generates the material of similar structure：Using amorphous silica (embodiment 4,5 and 6)；(implemented using zirconium oxide Example 7)；Using amorphous alumina (embodiment 8).When being dispersed in plastic matrix such as makrolon or polystyrene, these Material shows the photocatalytic activity of the plastic matrix of reduction compared with Example 1.
Contain CeO2With the second nano crystal material such as ZnO (embodiment 9) and TiO2The composite tool of (embodiment 10) There is the application as UV absorbents.Together with CeO2Carried secretly in amorphous silica the second nano crystal material result in The different hydridization attribute of body metal oxide.Protect metal oxide from acidleach in addition, amorphous silica provides Measure, and absorb metal oxide from organic substrate separation UV by using amorphous silica and make photocatalytic activity minimum Change.MoO3(embodiment 11), (Co, Zn)2SiO4(embodiment 12) and SrTiO3The composite of (embodiment 13) provides conduct The other benefit of the UV absorbents of other color space is obtained, referring to table 1.
Particle diameter, element composition and the crystal structure of each embodiment material are presented in table 2 and 3.Embodiment is intended to open Hair property, and non-claimed include or the example of limit.Particle diameter in table 2 is containing CeO2The amorphous titanium dioxide of material The size of silicon, rather than CeO2Or the size of other example UV absorbent oxides.By selecting appropriate amorphous porous dioxy SiClx simultaneously uses typical grinding and abrasion step, it is possible to achieve a diameter of 100nm to 400 μm of substantially any particle diameter.
Its crystal structure shown in chemical composition and table 3 shown in table 2 is the typical consequence that UV absorbs composite. Data confirm that can use amorphous silica to form CeO2Nanocrystal (embodiment 1)；Other metal is soluble in CeO in amorphous silica2In crystal structure (embodiment 3)；CeO2Amorphous silica material can be with other metals Amorphous oxide combines (embodiment 6 to 8)；It is (real that Multimetal oxide can be included in amorphous silica material Apply example 9 to 13)；And Multimetal oxide can be processed into a variety of nanocrystal (embodiments with different crystal structure 9th, 11,12 and 13)；And amorphous silica can be converted into crystalline silica (embodiment 4 and 11).When amorphous two When silica is converted into crystalline silica, composite loses its transparency.
By UV absorb compound UV absorbents that the combination of metal oxide and modified metal-oxide forms (embodiment 9 to 13) micro-structural is different from the material of embodiment 1 and the embodiment 4 to 8 of encapsulating.It is believed that the concentration increase of nanocrystal；Referring to Embodiment 9, Fig. 2 b are compared to embodiment 1, Fig. 2 a.The increase of nanocrystal density can influence color and UV absorbs.Additional suction The UV absorbance higher than embodiment 1 and lower reflectivity can be caused by receiving agent concentration.Embodiment 14 is from pure powdered samples Measure UV reflectivity.This is demonstrated in embodiment 13.
In embodiment 15, the UV absorbent compounds of embodiment 1 are dispersed in acrylic resin.UV spectrum (referring to Fig. 3) show the strong absorption (being less than 16% transmission) under less than 370nm wavelength.Occurs narrow mistake between 370nm and 450nm Area is crossed, wherein transmission sharply increases, transmissivity is more than 75%.From most of acutance for being absorbed into main transparent transition while refer to Show material visual appearance and color, and the transparency of the object containing UV absorbents.
When metal oxide is added into CeO2When in crystal structure, it is believed that lattice slightly deforms, and causes modified optics Property.By adding before calcined materials a small amount of metal salt jointly, dopant is added in element scale, to ensure Dopant is included in CeO2In structure.Compared with Example 1, add Ca for embodiment 2 and embodiment 3 adds Al and can be seen that The improvement that UV absorbs, referring to table 1.The UV spectrum of these three embodiments figure 4 illustrates.Compared with Example 1, because material is inhaled Increase is received, the reflection characteristic of embodiment 2 reduces in UV areas.Other desired characteristic is reflected under the wavelength more than 420nm The increase of rate.Compared with Example 1, embodiment 3 does not show the changes in optical properties under the wavelength more than 420nm, but Show that increased UV absorbs compared with Examples 1 and 2 under wavelength less than 365nm.The improvement, which confirms, draws small dopant Enter CeO2Have in structure for finely tuning optical property.By using the other metal dopants that can adjust optical properties of materials, Largely additional improvement can be carried out to UV absorbent composites.
It has been found that encapsulating UV absorbent composites show the improvement of weather resistance, the reduction of photocatalytic activity, Improved physical property；Relatively low specific surface area, low oil absorption ferric and uniform surface chemistry.Using inorganic oxide silica (embodiment 4 to 6)；Zirconium oxide (embodiment 7)；Or aluminum oxide (embodiment 8) encapsulating composite changes as shown in Figure 5 Optical property.
Composite containing a variety of nano crystal materials allows to finely tune optical property, such as UV absorbs and visible property. It is added to containing CeO2The example of the second nano crystal material in the UV absorbent composites of nano crystal material is：ZnO, Embodiment 9；TiO2, embodiment 10；MoO3, embodiment 11；(Co,Zn)SiO4, embodiment 12；And SrTiO2, embodiment 13.Fig. 6 Show the change of the limited proportionality between absorbance and transmissivity or reflectivity.For embodiment 9 and 10, from being absorbed to reflection Transformation is compared with Example 1 red shift, causes increased UV to absorb, but the transformation is not converted to the transmission more than 80% completely Rate, until well into the 450nm of visible spectrum.
Compared with Example 1, embodiment 11 shows desired sharp transformation between 360nm and 400nm.With embodiment 1 Material is compared, and embodiment 11,12 and 13 introduces blue shift in UV spectrum.Compared with Example 1, embodiment 11 and 13 improves UV Absorbent properties simultaneously reduce the visible absorbance at more than 400nm wavelength, both at desired attribute.
Embodiment 12 is blue material, referring to the color coordinates in the spectrum in Fig. 6 and table 1.It is coloured which demonstrate assigning The ability that material UV absorbs, and then give the same benefits for being derived from amorphous silica to the combination of these colored inorganics Thing.
UV absorbent composites can be used in article；The plastics of such as polystyrene are benefited from comprising UV absorbents Article such example.As shown in Example 16, embodiment 1 to 13 is included in polystyrene chip, and surveyed Optical transmission property is measured, as shown in figs.The CeO that Ca and Al is modified2UV absorbent composites and transparent polystyrene Compared to reducing<The transmission of 375nm UV light.By the way that comprising UV absorbents, the percent transmission close to~50% is reduced to< 1%.As shown in Figure 8, for the CeO of encapsulating2Amorphous silica material, measuring similar transmission reduces.With more The material of kind of nano crystal material shows similar trend, but due to the difference of UV absorbing materials, in embodiment 9 to 13 Each has the optic response slightly changed.The difference measured in optical characteristics and the main body powder shown in embodiment 14 The observation of spectrum is dry straightly corresponding.
The outward appearance of these composites is important, it is desirable that for many applications, transparent and colourless additive It is important.In addition, the matrix of protection should not be intended to them for they or the composition of article produces negative interaction.Such as table 1 chromatic number is combined with picture, and embodiment 17 is used to investigate visual characteristic of the embodiment material when being deployed in article.It is dispersed in Some embodiments (Figure 10) in makrolon are shown to change colour caused by the thermal degradation process of promotion.Embodiment 1 The discoloration of UV absorbents is significant.The material of the silica encapsulating of embodiment 4 to 6 has the discoloration that substantially reduces, and In appearance advantageously compared to the chip containing amorphous silica.
Figure 11 shows the visual appearance of some embodiments in polystyrene, and it closely reflects embodiment in table 1 Color value.
Although the disclosure is illustrated by describing some embodiments, and is had been described in considerable detail illustrative Embodiment, but applicant be not intended to constrain scope of the following claims or limited to this in any way Class details.Those skilled in the art are readily visible other advantage and modification.
Embodiment
The amorphous fumed silicas of embodiment 1- and CeO2Composite
In the presence of the solution containing be dissolved in 10mL deionized waters 50 gram of six nitric hydrate cerium (III), homogenizing Amorphous fumed silica (50 grams, 0.2mL/g pore volumes).Completely after homogenizing, the then drying composite at 100 DEG C, directly To all moisture of removing.Now, dry thick solid is ground into fine powder.Then pale powder is calcined extremely at 500 DEG C It is few 30 minutes, or until precursor decomposes completely.Then finished product is micronized to about 2 μm of ultimate size.The color of composite Shown in table 1.By by the sample of pure composite be fitted into the ultraviolet-uisible spectrophotometer equipped with diffusing reflection spheroid come Measure color.
The amorphous fumed silicas of embodiment 2- and Ce0.9Ca0.2O2Composite
Containing 29.17 gram of six nitric hydrate cerium (III) being dissolved in 6mL deionized waters and 0.83 gram of four nitric hydrate In the presence of the solution of calcium, amorphous fumed silica (30 grams, 0.2mL/g pore volumes) is homogenized.Completely after homogenizing, then exist Drying composite at 100 DEG C, until removing all moisture.Now, dry thick solid is ground into fine powder.Then 500 Pale powder is calcined at DEG C at least 30 minutes, or until precursor decomposes completely.Then finished product is micronized to about 2 μm final Particle diameter.The color of composite is shown in table 1.
The amorphous fumed silicas of embodiment 3- and CeAlO3Composite
In 19.9g Ce (NO3)3With Al (NO3)3(13%CeAlO3W/w in the presence of the aqueous solution), it is homogenized amorphous forging Silica (15.7g) processed.Completely after homogenizing, the then drying composite at 100 DEG C, until removing all moisture.Now, use Mortar and pestle are by dry thick solid grind into powder.Then pale powder is calcined at 1000 DEG C at least 240 minutes, or Until precursor decomposes completely.Then mixed in Wa Shi blenders (warring blender) through calcined powder.Composite Color is shown in table 1.
The amorphous fumed silica and CeO of embodiment 4- coated with silica2Composite
In 32.21g sodium silicate aqueous solutions (29%SiO2W/w in the presence of), it is homogenized the sample of undiluted composite (embodiment 1,10.78g).Completely after homogenizing, the then drying composite at 100 DEG C, until removing all moisture.Now, use Mortar and pestle are by dry thick solid grind into powder.Then pale powder at least 60 minutes, or directly is calcined at 500 DEG C Decomposed completely to precursor.Then with mortar and pestle through calcined powder.The color of composite is shown in table 1.
The amorphous fumed silica and CeO of embodiment 5- coated with silica2Composite
In 15.8g tetraethyl orthosilicates (29%SiO2W/w in the presence of), it is homogenized the sample of undiluted composite (embodiment 1,9.98g).Completely after homogenizing, the then drying composite at 100 DEG C, until removing all moisture.Now, with grinding Alms bowl and pestle are by dry thick solid grind into powder.Then pale powder is calcined at 500 DEG C at least 60 minutes, or until Precursor decomposes completely.Then with mortar and pestle through calcined powder.The color of composite is shown in table 1.
The amorphous fumed silica and CeO of embodiment 6- coated with silica2Composite
The sample (embodiment 1,58.61g) of undiluted composite is suspended in 1 liter of water, and by adding hydrogen-oxygen Change sodium and the pH of suspension is increased to 9.5.Suspension is heated to 90 DEG C, and 172.5g silicon is added with the speed of 0.7g/ minutes Acid sodium aqueous solution (6.5g SiO2), while dilute sulfuric acid is added so that the pH value of suspension is maintained at into about 9.5 with different rates.Will Suspension is cooled to room temperature and adjusts pH to about 7.Then washed by centrifugation, and then dried in atmosphere.Then Use Wa Shi blender combination drying samples.The color of composite is shown in table 1.
The amorphous fumed silica and CeO of embodiment 7- zirconium oxides cladding2Composite
In the presence of 22.75g butanol zirconiums (80%w/w n-butyl alcohols), the sample for being homogenized undiluted composite is (real Apply example 1,15.89g).Completely after homogenizing, the then drying composite at 100 DEG C, until removing all moisture.Now, mortar is used With pestle by dry thick solid grind into powder.Then pale powder at least 60 minutes, or until preceding is calcined at 500 DEG C Body decomposes completely.With mortar and pestle through calcined powder.The color of composite is shown in table 1.
The amorphous fumed silica and CeO of embodiment 8- alumina-coateds2Composite
In the presence of 25.26g aluminium isopropoxides (11%w/w isopropanols), the sample for being homogenized undiluted composite is (real Apply example 1,15.89g).Completely after homogenizing, the then drying composite at 100 DEG C, until removing all moisture.Now, mortar is used With pestle by dry thick solid grind into powder.Then pale powder at least 60 minutes, or until preceding is calcined at 500 DEG C Body decomposes completely.Then with mortar and pestle through calcined powder.The color of composite is shown in table 1.
The amorphous fumed silicas of embodiment 9-, ZnO and CeO2Composite
In 22.89g Zn (NO3)2In the presence of the aqueous solution (7%ZnO w/w), the sample of undiluted composite is homogenized (embodiment 1,10.00g).Completely after homogenizing, the then drying composite at 100 DEG C, until removing all moisture.Now, use Mortar and pestle are by dry thick solid grind into powder.Then pale powder at least 60 minutes, or directly is calcined at 500 DEG C Decomposed completely to precursor.Then with mortar and pestle through calcined powder.The color of composite is shown in table 1.
The amorphous fumed silicas of embodiment 10-, TiO2And CeO2Composite
In 16.18g TiOSO4The aqueous solution (7%TiO2W/w in the presence of), it is homogenized the sample of undiluted composite (embodiment 1,9.98g).Completely after homogenizing, the then drying composite at 100 DEG C, until removing all moisture.Now, with grinding Alms bowl and pestle are by dry thick solid grind into powder.Then pale powder is calcined at 500 DEG C at least 60 minutes, or until Precursor decomposes completely.Then with mortar and pestle through calcined powder.The color of composite is shown in table 1.
The amorphous fumed silicas of embodiment 11-, MoO3And CeO2Composite
In 18.5g NaMoO4The aqueous solution (20%MoO3W/w in the presence of), it is homogenized the sample of undiluted composite (embodiment 1,13.9g).Completely after homogenizing, the then drying composite at 100 DEG C, until removing all moisture.Now, with grinding Alms bowl and pestle are by dry thick solid grind into powder.Then pale powder at least 240 minutes, or directly is calcined at 1000 DEG C Decomposed completely to precursor.Then with mortar and pestle through calcined powder.The color of composite is shown in table 1.
The amorphous fumed silicas of embodiment 12-, (Co, Zn)2SiO4And CeO2Composite woodMaterial
In 20.7g Co (NO3)2With Zn (NO3)2In the presence of the aqueous solution (0.001CoZn mol/g), homogenizing is undiluted The sample (embodiment 1,16.7g) of composite.Completely after homogenizing, then the drying composite at 100 DEG C, all until removing Moisture.Now, with mortar and pestle by dry thick solid grind into powder.Then pale powder is calcined extremely at 1000 DEG C It is few 240 minutes, or until precursor decomposes completely.Then with mortar and pestle through calcined powder.The color of composite exists Shown in table 1.
The amorphous fumed silicas of embodiment 13-, SrTiO3And CeO2Composite
In 12.08g TiOSO4The aqueous solution (7%TiO2W/w in the presence of), it is (real to be homogenized undiluted composite sample Apply example 1,10.0g).Completely after homogenizing, the then drying composite at 100 DEG C, until removing all moisture.Now, mortar is used With pestle by dry thick solid grind into powder.Then in 15.8g Sr (NO3)2The aqueous solution (22%SrCO3W/w presence) Lower homogenizing pale powder.Completely after homogenizing, the then drying composite at 100 DEG C, until removing all moisture.Now, use Mortar and pestle are by dry thick solid grind into powder.Then pale powder is calcined at 1000 DEG C at least 240 minutes, or Until precursor decomposes completely.Then with mortar and pestle through calcined powder.The color of composite is shown in table 1.
Embodiment 14- measurement embodiments 1-13 UV reflectivity
It is powdered undiluted multiple in cuvette using the measurement of ultraviolet-visible spectrophotometer with diffusing reflection spheroid The UV reflectivity (including specular reflectivity) of the sample of condensation material.Spectrum is shown in Fig. 4,5 and 6.
Table 1：Embodiment 1-13 color
The vision opacity of embodiment 15- embodiments 1
Embodiment 1 (24%w/w) is dispersed in transparent acrylic resin system (Delstar DMR499), and is coated in On inert clear base material such as glass or quartz.The minimum thickness of dry film is 35 μm.When composite is more than between 475-750nm 70% it is transparent when, it is considered as visually transparent.Spectrum figure 3 illustrates.
The transmission of embodiment 16- embodiments 1 and 3-13
The sample (1%w/w) of composite is dispersed in polystyrene resin, and under 420 °F in injection machine mould It is moulded into plastic chip.The transmission of each chip is measured, is shown in figure 7 below, 8 and 9.
Embodiment 17- coats the plastic stability of sample
The sample (1%w/w) of composite is dispersed in makrolon (PC) resin, and in injection machine under 525 °F In be molded as plastic chip.The picture of chip is shown in figures 10 and 11.
Table 2：Embodiment 1-13 particle diameter and XRF composition
Table 3：The XRD compositions of embodiment 1,3-5 and 6-13

Claims (20)

1. a kind of UV absorbent composites comprising nano crystal material and amorphous porous material,
Wherein described nano crystal material be in the hole of the porous material, and be separation,
Wherein described nano crystal material includes cerium oxide.
2. the composite described in claim 1, wherein the nano crystal material has about 2nm to about at it most on major axis 100nm crystal domain size scope, and the crystal draw ratio is about 1 to about 1.5.
3. the composite any one of preceding claims, wherein the cerium oxide has following formula：
CexMyOz,
Wherein 0.5<X≤1,0≤y≤1, and 2.0≤z≤7, and
Metal M is selected from Hf4+、Ta5+、W4+、Pr3+、Pr4+、Nd3+、Pm3+、Sm2+、Sm3+、Eu2+、Eu3+、Gd3+、Tb3+、Tb4+、Dy3+、 Ho3+、Er3+、Tm2+、Tm3+、Yb2+、Yb3+、Lu3+、V3+、V4+、V5+、Bi3+、Bi5+、Mo4+、Mo6+、Mg2+、Ti3+、Ti4+、Si4+、 Zn2+、Al3+、Zr4+、La3+、Sb5+、Nb5+、Co2+、Co3+、Mn2+、Mn3+、Ca2+、Sr2+、Ba2+、Fe4+、Fe3+、Fe2+、Cr3+、Sn4 +、Y3+、Cu2+、Cu3+Or its mixture.
4. the composite any one of preceding claims, it includes the second nano crystal material,
Wherein described second nano crystal material be in the hole of the porous material, and be separation,
Wherein described second nano crystal material is selected from TiO2、ZnO、MoO3、(Co,Zn)2SiO4、SrTiO3And its mixture.
5. the composite described in claim 3, it includes the second nano crystal material,
Wherein described second nano crystal material be in the hole of the porous material, and be separation,
Wherein described second nano crystal material has following formula：
CexMyOz,
Wherein 0.5<X≤1,0≤y≤1, and 2.0≤z≤7, and
Metal M is selected from Hf4+、Ta5+、W4+、Pr3+、Pr4+、Nd3+、Pm3+、Sm2+、Sm3+、Eu2+、Eu3+、Gd3+、Tb3+、Tb4+、Dy3+、 Ho3+、Er3+、Tm2+、Tm3+、Yb2+、Yb3+、Lu3+、V3+、V4+、V5+、Bi3+、Bi5+、Mo4+、Mo6+、Mg2+、Ti3+、Ti4+、Si4+、 Zn2+、Al3+、Zr4+、La3+、Sb5+、Nb5+、Co2+、Co3+、Mn2+、Mn3+、Ca2+、Sr2+、Ba2+、Fe4+、Fe3+、Fe2+、Cr3+、Sn4 +、Y3+、Cu2+、Cu3+Or its mixture.
6. the composite any one of preceding claims, wherein the composite is at least in part by selected from without fixed One or more layers in shape silica, aluminum oxide, zirconium oxide, bismuth oxide, tungsten oxide and its mixture is encapsulated.
7. the composite any one of preceding claims, wherein the main body aggregate size of the composite is about 0.2 μm to about 300 μm.
8. the composite any one of claim 1-7, wherein the porous material is selected from amorphous fumedization Silicon, Amorphous precipitated silica, naturally occurring silica and combinations thereof.
9. the amount of the composite any one of preceding claims, wherein nano crystal material is no more than the composite wood Expect 62.5 weight % of quality.
10. the amount of the composite any one of preceding claims, wherein nano crystal material is the composite About the 5 of quality are to about 35 weight %.
11. the composite any one of preceding claims, wherein powdery, the composite of undiluted form are inhaled Receive incident light of the wavelength of about 50 to about 100% between 200 and 375nm.
12. a kind of UV absorbent composites comprising nano crystal material and amorphous porous material,
Wherein described nano crystal material be in the hole of the porous material,
Wherein described nano crystal material has 2nm to about 100nm crystal domain size scope, and the crystalline substance at it most on major axis Body draw ratio is about 1 to about 1.5.
13. the composite described in claim 12, wherein the nano crystal material includes cerium oxide.
14. the composite any one of claim 12-13, wherein the nano crystal material includes following formula：
CexMyOz,
Wherein 0.5<X≤1,0≤y≤1, and 2.0≤z≤7, and
Metal M is selected from Hf4+、Ta5+、W4+、Pr3+、Pr4+、Nd3+、Pm3+、Sm2+、Sm3+、Eu2+、Eu3+、Gd3+、Tb3+、Tb4+、Dy3+、 Ho3+、Er3+、Tm2+、Tm3+、Yb2+、Yb3+、Lu3+、V3+、V4+、V5+、Bi3+、Bi5+、Mo4+、Mo6+、Mg2+、Ti3+、Ti4+、Si4+、 Zn2+、Al3+、Zr4+、La3+、Sb5+、Nb5+、Co2+、Co3+、Mn2+、Mn3+、Ca2+、Sr2+、Ba2+、Fe4+、Fe3+、Fe2+、Cr3+、Sn4 +、Y3+、Cu2+、Cu3+Or its mixture.
15. the composite any one of claim 12-14, it includes the second nano crystal material,
Wherein described second nano crystal material be in the hole of the porous material, and be separation,
Wherein described second nano crystal material is selected from TiO2、ZnO、MoO3、SrTiO3、(Co,Zn)2SiO4And its mixture.
16. the composite any one of claim 12-15, wherein the composite is at least in part by selected from nothing One or more layers in amorphous silicon dioxide, aluminum oxide, zirconium oxide, bismuth oxide, tungsten oxide and its mixture is encapsulated.
17. the composite any one of claim 12-16, wherein the main body aggregate size of the composite is about 0.2 μm to about 300 μm.
18. the composite any one of claim 12-17, wherein the porous material is selected from amorphous fumed SiClx, Amorphous precipitated silica, naturally occurring silica and combinations thereof.
19. the ratio of the composite any one of claim 12-18, wherein nano crystal material and porous material is About 5 to about 35 weight %.
20. the composite any one of preceding claims, wherein the composite be added to plastics, paint, In ink, cosmetics, elastomer, rubber, wrapping paper or plastics, woodwork coating or dyestuff, or in metal, organic, polymerization or day Used in the presence of right product, or for protecting metal, organic, polymerization or natural products.
CN201680028055.0A 2015-03-30 2016-03-29 The composite of nanocrystal is absorbed containing UV Pending CN107683257A (en)

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