Nanometric tin-containing metal oxide particle and dispersion, and preparation method and application thereof

Abstract

There is disclosed a tin-containing metal oxide nanoparticle, which has an index of dispersion degree less than 7 and a narrow particle size distribution which is defined as steepness ratio less than 3. There is disclosed dispersion, paint, shielding film and their glass products which comprise the said nanoparticles. Besides, there are also disclosed processes of making the tin-containing metal oxide nanoparticle and their dispersion. The tin-containing metal oxide nanoparticles and their dispersion disclosed herein may be applied on the window glass of houses, buildings, vehicles, ships, etc. There is provided an excellent function of infrared blocking with highly transparent, and to achieve sunlight controlling and thermal radiation controlling.

1 - 39 . (canceled) 
     
     
         40 . Tin-containing metal oxide nano-particles, said tin-containing metal oxide including tin element and a metallic element other than tin, wherein the tin-containing metal oxide nano-particles have a particle diameter distribution as defined with an index of dispersion degree of less than 7 and a steepness ratio of less than 3. 
     
     
         41 . The tin-containing metal oxide nano-particles according to  claim 40 , wherein said tin-containing metal oxide nano-particles are coated on surface with a surfactant, said surfactant is selected from a non-silane surface modifying agent, a silane coupling agent, a titanate coupling agent, or a mixture thereof, preferably the non-silane surface modifying agent is selected from sodium dodecyl sulphate, sodium lauryl sulphate, sodium laurate, sodium oleate, sodium naphthenate, sodium stearate, sodium abietate, sodium iso-octoate, sodium linoleate, sodium caproate, sodium ricinate, ethyl acetate, sodium acetate, dioctylsodium sulphosuccinate, polyoxyethylene sorbitan monooleate, sorbitan monooleate, sorbitan trioleate, PLURONIC®, polysorbate, N-polyvinyl pyrrolidone, polyethylene glycol, polyoxyethylene, bis-2 hydroxyethyl oleyl amine, hexadecyltrimethyl ammonium bromide, hydroxypropyl cellulose, hydroxypropylmethyl cellulose, maltose sugar, sucrose, citric acid, (ethylene)glycol, acrylic acid, methacrylic acid, β-hydroxyethyl acrylate, tetraethyl orthosilicate or a mixture thereof, the silane coupling agent is preferably selected from alkyl-trialkoxy-silane, (methyl)acryloxy-alkoxy-trialkoxy silane, acryloyloxy-alkoxy-trialkoxy silane, (methyl)acryloyloxy-alkyl-alkyl-dialkoxy silane, acryloyloxy-alkyl-alkyl-dialkoxy silane, (methyl)acryloyloxy-alkyl-dialkyl-alkoxy silane, acryloyloxy-alkyl-dialkyl-alkoxy silane, thiol-alkoxy-trialkoxy silane, γ-methacryloxypropyltrimethoxy silane, aryl-trialkoxy silane, vinyl silane, 3-glycidyloxypropyl-trialkoxy silane, polyether silane, γ-aminopropyl-triethoxy silane, γ-glycidyloxypropyltrimethoxy silane, γ-(methacryloyloxy) propyl-trimethoxy silane, γ-mercaptopropyltrimethoxy silane, γ-aminoethyl-aminopropyl-trimethoxy silane, bis-propyl-triethoxy silane, N-(β-aminoethyl)-γ-(aminopropyl)-methyldimethoxy silane, N-(β-aminoethyl)-γ-(aminopropyl)-trimethoxy silane, γ-aminoethyl-aminopropyl-trimethoxy silane, hexadecyltrimethoxy silane, or a mixture thereof. 
     
     
         42 . The tin-containing metal oxide nano-particles according to  claim 40 , wherein said metallic element other than tin is selected from antimony, indium, titanium, copper, zinc, zirconium, cerium, yttrium, lanthanum, niobium or a mixture thereof, preferably antimony, indium or a mixture thereof; and the molar ratio of said metallic element other than tin to tin is 1:0.01 to 1:100, or 1:0.05 to 1:50, or 1:0.05 to 1:20, or 1:0.05, or 1:0.1, or 1:0.15, or 1:0.2, or 1:5, or 1:10, or 1:15, or 1:20. 
     
     
         43 . The tin-containing metal oxide nano-particles according to  claim 40 , wherein said tin-containing metal oxide is an antimony-tin oxide or an indium-tin oxide. 
     
     
         44 . The tin-containing metal oxide nano-particles according to  claim 40 , wherein said tin-containing metal oxide nano-particles have a crystal structure, or a tetragonal cassiterite, bixbyite, tetragonal cassiterite-like or bixbyite-like structure. 
     
     
         45 . The tin-containing metal oxide nano-particles according to  claim 40 , wherein the index of dispersion degree is less than 5, or less than 4, or less than 3, or less than 2; and the steepness ratio is less than 2, or less than 1.8, or less than 1.5, or less than 1.3. 
     
     
         46 . The tin-containing metal oxide nano-particles according to  claim 40 , wherein said tin-containing metal oxide nano-particles have an initial average particle diameter of 2-50 nm, or 2-20 nm, or 2-10 nm. 
     
     
         47 . A method for preparing the tin-containing metal oxide nano-particles according to  claim 40 , the method comprises steps of:
 (1) reacting a solution containing tin ions and a solution containing ions of other metal with a precipitant solution to form tin-containing metal oxide precursor particles and a first by-product in ionic form;   (2) separating the tin-containing metal oxide precursor particles from the first by-product in ionic form to obtain tin-containing metal oxide precursor particles substantially free of ionic impurities;   (3) reacting the tin-containing metal oxide precursor particles substantially free of ionic impurities with an oxidizing agent or a reducing agent to obtain tin-containing metal oxide particles and a second by-product in ionic form;   (4) separating the tin-containing metal oxide particles from the second by-product in ionic form to obtain tin-containing metal oxide nano-particles substantially free of ionic impurities.   
     
     
         48 . The method according to  claim 47 , wherein in one or more of steps (2), (3) and (4), the tin-containing metal oxide precursor particles or the tin-containing metal oxide particles are coated with a surfactant, preferably a surfactant in an amount of 0.01% to 30% relative to the weight of tin-containing metal oxide precursor particles or tin-containing metal oxide particles is added in one or more of step (2), (3) and (4). 
     
     
         49 . The method according to  claim 47 , wherein the separating of step (2) or (4) is carried out by any one of methods of liquid-liquid phase transfer, liquid-liquid phase transfer after washing, centrifugation after washing, filtration after washing. 
     
     
         50 . The method according to  claim 47 , wherein the reacting of step (1) is carried out at a temperature of less than 100° C., or at a temperature range of 40-80° C., under non-acidic condition, or substantially alkaline condition, in an aqueous medium, the aqueous medium preferably comprising at least one of water, alcohols, amides, ketones, epoxides and mixtures thereof, and more preferably comprising one or more alcohols mixed with water, wherein the alcohols have a volume of 1% to 99% relative to water. 
     
     
         51 . The method according to  claim 47 , wherein the tin ions and/or ions of other metal in step (1) are derived from their acetate, halide, nitrate, phosphate, sulfate, perchlorate, borate, iodate, carbonate, perchlorate, tartrate, formate, gluconate, lactate, sulfamate, hydrates or mixtures of these salts. 
     
     
         52 . The method according to  claim 47 , wherein said precipitating agent in step (1) is a base, the base preferably being an oxygen-containing base, the oxygen-containing base preferably being selected from alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal carbonates, alkaline earth metal carbonates, alkali metal bicarbonates, ammonia, organic bases and mixtures thereof. 
     
     
         53 . The method according to  claim 47 , wherein step (3) is carried out at a temperature of greater than 100° C. and 1 to 20 atmospheres, preferably at a temperature of 150-400° C. and 5 to 10 atmospheres. 
     
     
         54 . The method according to  claim 47 , wherein said oxidizing agent in step (3) is a peroxide, preferably selected from Na 2 O 2 , K 2 O 2 , H 2 O 2  and peroxyacetic acid, and the reducing agent in step (3) is selected from hydrazine hydrate, ethylenediamine, oxalic acid, formaldehyde, acetaldehyde, metallic tin powder, sodium borohydride and a mixture thereof. 
     
     
         55 . The method according to  claim 47 , wherein said step (1) and/or step (3) is carried out under high shear condition. 
     
     
         56 . A dispersion of tin-containing metal oxide nano-particles, comprising a dispersion medium and the tin-containing metal oxide particles according to  claim 40 . 
     
     
         57 . The dispersion of tin-containing metal oxide nano-particles according to  claim 56 , wherein the tin-containing metal oxide nano-particles have a solid content of at least 5%, preferably at least 10%, or at least 25%, or at least 30%, or at least 40%, or at least 50%, relative to the weight of the dispersion, and the dispersion medium is selected from water, ethyl acetate, butyl acetate, alcohols, alkenes, ethers, ketones, aromatic solvents and mixtures thereof. 
     
     
         58 . The dispersion of tin-containing metal oxide nano-particles according to  claim 56 , further comprising metal oxide nano-particles for blocking UV light. 
     
     
         59 . The dispersion of tin-containing metal oxide nano-particles according to  claim 58 , wherein the metal oxide nano-particles for blocking UV light are selected from at least one of zinc oxide, titanium oxide and cerium oxide, and said metal oxide nano-particles for blocking UV light is in an amount of at least 5% relative to the weight of the dispersion. 
     
     
         60 . A sunlight control composite material, comprising the tin-containing metal oxide nano-particles according to  claim 40 . 
     
     
         61 . A material permeable to visible light, comprising the tin-containing metal oxide nano-particles according to  claim 40 .