• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
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    • 专利摘要:
    A method for making silver nanowires having a high aspect ratio is provided wherein the total glycol concentration is <0.001% by weight at all times.
    公开号:FR3027610A1
    申请号:FR1560274
    申请日:2015-10-28
    公开日:2016-04-29
    发明作者:Patrick T Mcgough；Janet M Goss；George J Frycek；George L Athens；Wei Wang；Jonathan D Lunn；Robin P Ziebarth；Richard A Patyk
    申请人:Dow Global Technologies LLC；
    IPC主号:
    专利说明:

    [0001] The present invention relates generally to the field of manufacturing silver nanowires. In particular, the present invention relates to a method for producing silver nanowires having a high aspect ratio for use in a variety of applications. [0002] High conductivity films with high transparency are of great value for use as electrodes or coatings in a wide range of electronic applications, including, for example, touchscreen displays and cells. PV. Current technology for these applications involves the use of films containing tin-doped indium oxide (ITO) that are deposited by physical vapor deposition processes. The high capital cost of physical vapor deposition processes has led to the desire to find other transparent conductive materials and other coating approaches. The use of dispersed silver nanowires in the form of a percolation network has emerged as a promising alternative to films containing ITO. The use of silver nanowires has the potential advantage that they can be implemented using roll-to-roll techniques. Thus, silver nanowires have the advantage of low cost manufacturing with the potential to provide higher transparency and conductivity than conventional ITO containing films. The "polyol process" has been disclosed for the manufacture of silver-based nanostructures. The polyol process utilizes ethylene glycol (or other glycol) both as a solvent and as a reducing agent in the production of silver nanowires. The use of glycols, however, has several inherent disadvantages. Specifically, the use of a glycol as both a reducing agent and a solvent leads to a decrease in the control of the reaction because the main species of reducing agent (glycolaldehyde) is produced in situ and its presence and concentration are dependent on the extent of exposure to oxygen. Also, the use of a glycol introduces the possibility of formation of combustible glycol / air mixtures in the free space of the reactor used to produce the silver nanowires. Finally, the use of large volumes of glycol creates waste problems, which increases the cost of marketing such operations. [0004] An approach constituting an alternative to the polyol process for making silver nanowires has been disclosed by Miyagishima, et al. in U.S. Patent Application Publication No. 20100078197. Miyagishima, et al. disclose a method for producing metal nanowires, comprising: adding a solution of a metal complex to an aqueous solvent containing at least one halide as a reducing agent, and heating the resulting mixture to 150 ° C or less, wherein the metal nanowires comprise metal nanowires having a diameter of 50 nm or less and a major axis length of 5 μm or more in an amount of 50 mass% or more in terms of the amount of metal relative to the total metal particles. [0005] An alternative approach to the polyol process for making silver nanowires has been disclosed by Lunn, et al. in U.S. Patent Application Publication No. 20130283974. Lunn, et al. disclose a method for making silver nanowires having a high aspect ratio, wherein the recovered silver nanowires have an average diameter of 25 to 80 nm and an average length of 10 to 100 μm; and where the total glycol concentration is <0.001 wt% at any time during the process. However, while producing silver nanowires having a desirable high aspect ratio, the manufacturing method described by Lunn, et al. also leads to the formation of silver nanowire populations having an extended diameter distribution which can lead to a lack of uniformity in the electrical properties of films produced with it. [0007] Thus, there remains a need for other methods for manufacturing silver nanowires. In particular, processes for manufacturing silver nanowires which do not involve the use of a glycol, wherein the produced silver nanowires have a high aspect ratio (preferably> 500) in combination with a narrow distribution of diameters of silver nanowires. The present invention provides a method for manufacturing silver nanowires having a high aspect ratio, comprising: providing a container; the supply of water; the supply of a reducing sugar; providing a polyvinylpyrrolidone (PVP), wherein the polyvinylpyrrolidone (PVP) provided can be divided into a first portion of the polyvinylpyrrolidone (PVP) and a second portion of the polyvinylpyrrolidone (PVP); providing a source of copper (II) ions; providing a source of halide ions; providing a source of silver ions, wherein the provided silver ion source can be divided into a first portion of the silver ion source and a second portion of the silver ion source; adding water, reducing sugar, copper ion source (II) and the halide ion source to the container to form a combination; heating the combination at 110 to 160 ° C; mixing the first portion of the polyvinylpyrrolidone (PVP) with the first portion of the silver ion source to form a polyvinylpyrrolidone / mixed silver ion source; adding the polyvinylpyrrolidone / silver ion source mixed with the combination into the vessel to form a creation mixture; then, following a delay period, adding to the vessel the second portion of the polyvinylpyrrolidone (PVP) and the second portion of the silver ion source to form a growth mixture; maintaining the growth mixture at 110 to 160 ° C for a holding period of 2 to 30 hours to provide a product mixture; and recovering a plurality of silver nanowires having a high aspect ratio from the product mixture; where the total glycol concentration in the container is <0.001% by weight.
    [0002] In a particular embodiment, the process of the present invention further comprises: maintaining the combination at 120 to 155 ° C during the addition of the polyvinylpyrrolidone / mixed silver ion source and during the delay period; and maintaining the growth mixture at 120 to 140 ° C during the holding period. According to a first variant, the second part of the polyvinylpyrrolidone (PVP) and the second part of the silver ion source are added to the container simultaneously after the delay period.
    [0003] According to a second variant, the second part of the polyvinylpyrrolidone (PVP) and the second part of the source of silver ions are mixed for a mixing time of 0.5 seconds to 1 hour before being added to the container after the period of delay. According to a particular feature, the first part of the polyvinylpyrrolidone (PVP) and the first part of the silver ion source are mixed for a mixing time of 0.5 seconds to 1 hour to form the polyvinylpyrrolidone / silver ion source mixed before being added to the container. According to another particular characteristic, the first part of the polyvinylpyrrolidone (PVP) represents 10 to 40% by weight of the polyvinylpyrrolidone (PVP) supplied, and the first part of the source of silver ions represents 10 to 40% by weight the silver ion source provided. In another particular embodiment, the method of the present invention further comprises: providing a pH adjusting agent; adding the pH adjusting agent to the combination prior to adding the polyvinylpyrrolidone / mixed silver ion source; wherein the combination has a pH of 2.0 to 4.0 prior to the addition of the polyvinylpyrrolidone / silver ion source mixed with the container. In yet another particular embodiment, the method of the present invention further comprises: providing a reducing agent; adding the reducing agent to the creation mixture.
    [0004] In yet another particular embodiment, the method of the present invention further comprises: purging a gas space from the container in contact with the combination in the container to provide a reduced oxygen gas concentration in the space of container gas; bubbling into the silver ion source provided with an inert gas to extract the entrained oxygen gas from the supplied silver ion source and to give a low concentration of oxygen gas in a silver ion gas space in contact with the silver ion source provided; purging a PVP gas gap in contact with the polyvinylpyrrolidone (PVP) provided to provide a dilute oxygen gas concentration in the PVP gas space; maintaining the low oxygen gas concentration in the silver ion gas space and the dilute oxygen gas concentration in the PVP gas space; and maintaining the reduced oxygen gas concentration in the container gas space during the addition of the polyvinylpyrrolidone / mixed silver ion source, during formation of the growth mixture, and during the holding period.
    [0005] The present invention also provides a method for manufacturing silver nanowires having a high aspect ratio, characterized in that it comprises: providing a container; the supply of water; the supply of a reducing sugar; provision of polyvinylpyrrolidone (PVP); providing a source of copper (II) ions; providing a source of halide ions; providing a source of silver ions; the division of water into five separate volumes; combining a first volume of water with the reducing sugar to form a sub-combination of reducing sugar; combining a second volume of water with the polyvinylpyrrolidone (PVP) provided to form a polyvinylpyrrolidone (PVP) sub-combination, wherein the polyvinylpyrrolidone (PVP) sub-combination can be divided into a first part of the sub-combination of polyvinylpyrrolidone (PVP); combination of polyvinylpyrrolidone (PVP) and a second part of the polyvinylpyrrolidone (PVP) sub-combination; combining a third volume of water with the copper (II) ion source to form a sub-combination of copper (II) ions; combining a fourth volume of water with the halide ion source to form a sub-combination of halide ions; combining a fifth volume of water with the supplied silver ion source to form a sub-combination of silver ions, where the silver ion sub-combination can be divided into a first part of the sub-combination silver ions and a second part of the silver ion sub-combination; Adding the reducing sugar sub-combination, the copper (II) ion sub-combination and the halide ion sub-combination to the container to form a combination; heating the combination at 110 to 160 ° C; Mixing the first part of the polyvinylpyrrolidone (PVP) sub-combination with the first part of the silver ion sub-combination to form a polyvinylpyrrolidone / mixed silver ion sub-combination; adding the polyvinylpyrrolidone / silver ion sub-combination mixed with the combination into the vessel to form a creation mixture; then, following a delay period, adding to the vessel the second part of the polyvinylpyrrolidone (PVP) sub-combination and the second part of the silver ion sub-combination to form a mixture growth; maintaining the growth mixture at 110 to 160 ° C for a holding period of 2 to 30 hours to provide a product mixture; and recovering a plurality of silver nanowires having a high aspect ratio from the product mixture; Wherein the total glycol concentration in the vessel is <0.001% by weight. The present invention provides a method for making silver nanowires having a high aspect ratio, comprising: providing a container; the supply of water; providing a reducing sugar; provision of polyvinylpyrrolidone (PVP); providing a source of copper (II) ions; providing a source of halide ions; providing a source of silver ions; the division of water into five separate volumes; combining a first volume of water with the reducing sugar to form a sub-combination of reducing sugar; combining a second volume of water with the polyvinylpyrrolidone (PVP) provided to form a polyvinylpyrrolidone (PVP) sub-combination, wherein the polyvinylpyrrolidone (PVP) sub-combination is divided into a first part of the sub-combination polyvinylpyrrolidone (PVP) and a second part of the polyvinylpyrrolidone (PVP) sub-combination; combining a third volume of water with the copper (II) ion source to form a sub-combination of copper (II) ions; combining a fourth volume of water with the halide ion source to form a sub-combination of halide ions; combining a fifth volume of water with the supplied silver ion source to form a sub-combination of silver ions, where the silver ion sub-combination is divided into a first part of the sub-combination of silver ions and a second part of the silver ion sub-combination; adding the reducing sugar sub-combination, the copper (II) ion sub-combination and the halide ion sub-combination to the container to form a combination; heating the combination at 110 to 160 ° C; mixing the first part of the polyvinylpyrrolidone (PVP) sub-combination with the first part of the silver ion sub-combination to form a polyvinylpyrrolidone / mixed silver ion sub-combination; adding the polyvinylpyrrolidone / silver ion mixed sub-combination to the combination into the vessel to form a creation mixture; then, following a delay period, adding to the vessel the second part of the polyvinylpyrrolidone (PVP) sub-combination and the second part of the silver ion sub-combination to form a mixture of growth; maintaining the growth mixture at 110 to 160 ° C for a holding period of 2 to 30 hours to provide a product mixture; and recovering a plurality of silver nanowires having a high aspect ratio from the product mixture; wherein the total glycol concentration in the vessel is <0.001% by weight. DETAILED DESCRIPTION [0010] A method for making silver nanowires having a high aspect ratio has been found which surprisingly provides nanowires of silver having an average diameter of 20 to 60 nm and an average length of 20 to 100 μm, while avoiding the inherent disadvantages that are associated with the use of glycols and while providing silver nanowires having a high degree of uniformity of diameters. Silver nanowire populations having a narrow diameter distribution as provided by the method of the present invention provide an advantage in the preparation of films having more uniform conductive properties and transparency in the film. The term "total glycol concentration" as used herein means the combined total of the concentration of all glycols (eg, ethylene glycol, propylene glycol, butylene glycol, poly (ethylene glycol), poly (propylene glycol)) present in the container. [0012] The term "high aspect ratio" as used herein with reference to the plurality of recovered silver nanowires means that the average aspect ratio of the plurality of recovered silver nanowires is> 500 The term "fraction of silver nanoparticles" or "NPF" used here is the fraction of silver nanoparticles of a sample of silver nanowires determined according to the following equation: NPF = N PA / TA Where TA is the total surface area of a substrate that is occluded by a given deposited sample of silver nanowires; and, NPA is the portion of the total occluded surface area attributable to silver nanoparticles having an aspect ratio <3 included in the deposited sample of silver nanowires. [0014] Preferably, the method for making silver nanowires having a high aspect ratio of the present invention comprises: providing a container; the supply of water; the supply of a reducing sugar; providing a polyvinylpyrrolidone (PVP), wherein the polyvinylpyrrolidone (PVP) provided can be divided into a first portion of the polyvinylpyrrolidone (PVP) and a second portion of the polyvinylpyrrolidone (PVP); providing a source of copper (II) ions; providing a source of halide ions; providing a source of silver ions, wherein the provided silver ion source can be divided into a first portion of the silver ion source and a second portion of the silver ion source; adding water, reducing sugar, copper ion source (II) and the halide ion source to the container to form a combination; heating the combination at 110 to 160 ° C (preferably at 120 to 155 ° C, more preferably at 130 to 155 ° C, particularly preferably at 150 ° C); mixing the first part of polyvinylpyrrolidone (PVP) with the first part of the silver ion source to form a polyvinylpyrrolidone / mixed silver ion source (preferably, where the first part of the polyvinylpyrrolidone (PVP) and the first part of the silver ion source are mixed during a premixing period of 0.5 seconds to 4 hours (preferably 0.5 seconds to 1 hour, more preferably 1 minute to 1 hour; preferably, 5 minutes to 1 hour) to form the polyvinylpyrrolidone / mixed silver ion source before being added to the combination in the container); adding the polyvinylpyrrolidone / silver ion source mixed with the combination into the container (preferably, with stirring, preferably, wherein the polyvinylpyrrolidone / mixed silver ion source is added to the combination under a surface of the combination in the container) to form a creation mixture (preferably, while maintaining the combination at 110 to 160 ° C (preferably at 120 to 155 ° C, more preferably at 130 to 155 ° C; preferably, at 150 ° C) during addition of polyvinylpyrrolidone / mixed silver ion source); then, following a delay period (preferably, where the delay period is 1 to 60 minutes (more preferably, 1 to 20 minutes, particularly preferably 5 to 15 minutes) (preferably, where the creation mixture is cooled to 100 to 150 ° C (preferably 110 to 140 ° C, more preferably 120 to 135 ° C, particularly preferably 125 to 135 ° C) during the delay), adding to the vessel the second portion of the polyvinylpyrrolidone (PVP) and the second portion of the silver ion source to form a growth mixture, maintaining the growth mixture at 100 to 150 ° C ( preferably at 110 to 140 ° C, more preferably at 120 to 140 ° C, particularly preferably at 125 to 135 ° C) for a holding period of 2 to 30 hours (preferably 4 to 20 hours, more preferably 6 to 18 hours, particularly preferably ble, from 7 to 10 hours) to provide a product mixture, and recovering a plurality of silver nanowires having a high aspect ratio from the product mixture; wherein the total glycol concentration in the vessel is <0.001 wt.% at any time during the process to make silver nanowires having a high aspect ratio; (Preferably, where the polyvinylpyrrolidone (PVP) supplied and the supplied silver ion source are added to the container at a ratio by weight of the silver ion polyvinylpyrrolidone (PVP) of 4: 1 to 10: 1, and where the source The supplied halide ion source and the supplied copper ion source (II) are added to the vessel at a weight ratio of the halide ions to copper (II) ions of 1: 1 to 5: 1, wherein the plurality of nanowires of silver having a high aspect ratio have an average diameter of 20 to 80 nm and an average length of 10 to 100 μm (preferably, where the plurality of recovered silver nanowires have an average aspect ratio of> 500)) . Preferably, in the process for producing silver nanowires having a high aspect ratio of the present invention, the polyvinylpyrrolidone (PVP) supplied is divided into a first part of the polyvinylpyrrolidone (PVP) and a second part polyvinylpyrrolidone (PVP); and the supplied silver ion source is divided into a first portion of the silver ion source and a second portion of the silver ion source; wherein the first portion of the polyvinylpyrrolidone (PVP) is mixed with the first portion of the silver ion source to form the polyvinylpyrrolidone / mixed silver ion source; where the remaining polyvinylpyrrolidone (PVP) is the second part of the polyvinylpyrrolidone (PVP); and where the remaining silver ion source is the second part of the silver ion source. Preferably, the first part of the polyvinylpyrrolidone (PVP) is 10 to 40% by weight (preferably 10 to 30% by weight, more preferably 15 to 25% by weight, particularly preferably 20% by weight). weight) of the polyvinylpyrrolidone (PVP) provided; and the first part of the silver ion source is 10 to 40% by weight (preferably 10 to 30% by weight, more preferably 15 to 25% by weight); particularly preferably 20% by weight) of the supplied silver ion source. Preferably, the polyvinylpyrrolidone / mixed silver ion source is added to the combination in the container for a charging time of 10 seconds to 10 minutes (more preferably 30 seconds to 5 minutes, particularly preferably 30 seconds to 5 minutes; at 90 seconds). Preferably, the second portion of the polyvinylpyrrolidone (PVP) and the second portion of the silver ion source are added to the container for a feed time of 1 to 60 minutes (more preferably 1 to 30 minutes; particularly preferably, from 1 to 15 minutes). Preferably, in the process for producing silver nanowires having a high aspect ratio of the present invention, the polyvinylpyrrolidone (PVP) provided is divided into a first portion and a second portion and the ion source. money provided is divided into a first part and a second part; wherein the first portion of the polyvinylpyrrolidone (PVP) and the first portion of the silver ion source are mixed to form the polyvinylpyrrolidone / mixed silver ion source. Preferably, the first part of the polyvinylpyrrolidone (PVP) and the first part of the silver ion source are mixed during a premixing period of 0.5 seconds to 4 hours (preferably 0.5 seconds to 1 hour). more preferably 1 minute to 1 hour, particularly preferably 5 minutes to 1 hour) to form the polyvinylpyrrolidone / mixed silver ion source.
    [0006] The first part of the polyvinylpyrrolidone (PVP) and the first part of the silver ion source are mixed during the premixing period with any method known to those of ordinary skill in the art. Preferably, the first part of the polyvinylpyrrolidone (PVP) and the first part of the silver ion source are mixed with at least one of the mixture of the first part of the polyvinylpyrrolidone (PVP) and the first part of the the source of silver ions in a closed container (preferably in an inert atmosphere such as nitrogen); and simultaneously transferring the first portion of the polyvinylpyrrolidone (PVP) and the first portion of the silver ion source through a conduit common to the combination in the container. When the residence time in the common conduit for the first part of the polyvinylpyrrolidone (PVP) and the first part of the silver ion source is equal to the premixing period, the premixing period is preferably from 2 to 30 seconds ; more preferably, from 2 to 15 seconds; particularly preferably from 2 to 10 seconds). [0017] Preferably, in the process for producing silver nanowires having a high aspect ratio of the present invention, the second part of the polyvinylpyrrolidone (PVP) and the second part of the silver ion source can to be added to the contents of the container successively, simultaneously in the form of separate feeds, simultaneously in the form of a mixed feed or a certain combination thereof (for example, some successively, some simultaneously as separate feeds and some simultaneously as a mixed feed). Preferably, at least one of the second portion of the polyvinylpyrrolidone (PVP) and the second portion of the silver ion source is added to the container at a point beneath a surface of the combination in the container. More preferably, at least the second portion of the silver ion source is added to the container at a point beneath a surface of the combination in the container. Preferably, the second part of the polyvinylpyrrolidone (PVP) and the second part of the silver ion source are added to the container simultaneously as separate feeds, simultaneously as a mixed feed or a combination thereof (for example, some simultaneously as separate power supplies and some simultaneously as a mixed feed). Particularly preferably, the second portion of the polyvinylpyrrolidone (PVP) and the second portion of the silver ion source are added to the container as a mixed feed. Preferably, the mixed feed is added to the combination at a point beneath a surface of the combination in the container. The mixed feed may be formed in the same manner as described for the formation of polyvinylpyrrolidone / mixed silver ion source, where the second part of the polyvinylpyrrolidone (PVP) and the second part of the silver ion source used are mixed for a mixing time of from 0.5 seconds to 4 hours (preferably from 0.5 seconds to 2 hours, more preferably from 5 minutes to 1.5 hours, particularly preferably from 5 minutes to 1 hour); hour) to form the mixed feed. Preferably, the mixing time is the premixing period. Preferably, the water supplied in the process for producing silver nanowires having a high aspect ratio of the present invention is at least one of deionized water and distilled water to limit impurities. accidental. More preferably, the water provided in the process for making silver nanowires having a high aspect ratio of the present invention is deionized and distilled. Most preferably, the water provided in the process for making silver nanowires having a high aspect ratio of the present invention is ultrapure water which meets or exceeds the requirements for Type 1 water according to ASTM D1193-99e1 (Standard Specification for "Standard Specification for Reagent Water"). Preferably, the reducing sugar provided in the process for making silver nanowires having a high aspect ratio of the present invention is selected from the group consisting of at least one of the aldoses (e.g. glucose, glyceraldehyde, galactose, mannose); disaccharides with a free hemiacetal unit (eg, lactose and maltose); and sugars carrying a ketone (eg, fructose). More preferably, the reducing sugar provided in the process for making silver nanowires having a high aspect ratio of the present invention is selected from the group consisting of at least one of an aldose, lactose, maltose and fructose. More preferably, the reducing sugar provided in the process for making silver nanowires having a high aspect ratio of the present invention is selected from the group consisting of at least one of glucose, glyceraldehyde, galactose , mannose, lactose, fructose and maltose. Most preferably, the reducing sugar provided in the process for making silver nanowires having a high aspect ratio of the present invention is D-glucose. [0020] Preferably, the polyvinylpyrrolidone (PVP) provided in the process for producing silver nanowires having a high aspect ratio of the present invention has a weight average molecular weight, Mw, of 20,000 to 300,000 Daltons. More preferably, the polyvinylpyrrolidone (PVP) provided in the process for making silver nanowires having a high aspect ratio of the present invention has a weight average molecular weight, Mw, of 30,000 to 200,000 Daltons. Particularly preferably, the polyvinylpyrrolidone (PVP) provided in the process for making silver nanowires having a high aspect ratio of the present invention has a weight average molecular weight, Mw, of 40,000 to 150,000 Daltons, of more preferably from 40,000 to 60,000 Daltons. [0021] Preferably, the copper (II) ion source provided in the process for producing silver nanowires having a high aspect ratio of the present invention is selected from the group consisting of at least one of CuCl2 and Cu (NO3) 2. More preferably, the copper (II) ion source provided in the process for making silver nanowires having a high aspect ratio of the present invention is selected from the group consisting of CuCl 2 and Cu (NO 3) 2 . Particularly preferably, the copper (II) ion source provided in the process for making silver nanowires having a high aspect ratio of the present invention is CuCl 2, where CuCl 2 is a copper (II) chloride. ) dihydrate. [0022] Preferably, the halide ion source provided in the process for making silver nanowires having a high aspect ratio of the present invention is selected from the group consisting of at least one of a source chloride ion source, fluoride ion source, bromide ion source and iodide ion source. More preferably, the halide ion source provided in the process for making silver nanowires having a high aspect ratio of the present invention is selected from the group consisting of at least one of a source of chloride ions and a source of fluoride ions. More preferably, the halide ion source provided in the process for making silver nanowires having a high aspect ratio of the present invention is a source of chloride ions. Particularly preferably, the halide ion source provided in the process for making silver nanowires having a high aspect ratio of the present invention is a source of chloride ions, where the source of chloride ions is a alkali metal chloride. Preferably, the alkali metal chloride is selected from the group consisting of at least one of sodium chloride, potassium chloride and lithium chloride. More preferably, the alkali metal chloride is selected from the group consisting of at least one of sodium chloride and potassium chloride. Particularly preferably, the alkali metal chloride is sodium chloride. [0023] Preferably, the silver ion source provided in the process for making silver nanowires having a high aspect ratio of the present invention is a silver complex. More preferably, the silver ion source provided in the process for making silver nanowires having a high aspect ratio of the present invention is a silver complex, wherein the silver complex is selected from the group consisting of at least one of silver nitrate (AgNO3) and silver acetate (AgC2H302). Most preferably, the silver ion source provided in the process for making silver nanowires having a high aspect ratio of the present invention is silver nitrate (AgNO 3). Preferably, the silver ion source provided in the process for producing silver nanowires having a high aspect ratio of the present invention has a silver concentration of 0.005 to 1 molar (M) (more preferably from 0.01 to 0.1 M, particularly preferably from 0.015 to 0.05 M). Preferably, the water, the reducing sugar, the source of copper (II) ions, the source of halide ions and the pH adjusting agent, if any, are added to the container in any order in an individual succession (ie, one at a time), simultaneously (ie, all at the same time), or semi-simultaneously (ie, some individually a at the same time, some simultaneously at the same time or in the form of sub-combinations). More preferably, at least two of the water, the reducing sugar, the copper ion source (II), the halide ion source and the pH adjusting agent are mixed together to form a sub-combination before adding to the container. [0025] Preferably, the water is divided into multiple volumes (preferably at least two volumes of water, more preferably at least three volumes of water, particularly preferably at least five volumes of water). ) which are then mixed with one or more of the reducing sugar, the copper ion source (II), the halide ion source, the pH adjusting agent, the polyvinylpyrrolidone (PVP) supplied and the silver ion source provided to form different subcombinations which include water prior to addition to the vessel. For example, the water is preferably divided into at least five volumes, wherein a first volume of water is combined with the reducing sugar to form a reducing sugar containing sub-combination, wherein a second volume of water is combined with the copper (II) ion source for forming a sub-combination containing copper (II) ions, wherein a third volume of water is combined with the halide ion source to form a sub-combination containing halide ions; wherein a fourth volume of water is combined with the supplied silver ion source to form a sub-combination containing silver ions (preferably, where the sub-combination containing silver ions is divided into a first part and a second part ); and a fifth volume of water is combined with the polyvinylpyrrolidone (PVP) provided to form a polyvinylpyrrolidone (PVP) containing sub-combination (preferably, the polyvinylpyrrolidone-containing sub-combination (PVP) is divided into two groups). 1 0 19 in a first part and a second part). These subcombinations are then processed in a manner similar to the individual components in the previous discussion of the process for making silver nanowires having a high aspect ratio of the present invention. [0026] The method for making high aspect ratio silver nanowires of the present invention preferably further comprises: providing a reducing agent; and adding the reducing agent to the creation mixture. [0027] Preferably, the reducing agent provided in the process for producing silver nanowires having a high aspect ratio of the present invention is selected from the group consisting of ascorbic acid, sodium borohydride ( NaBH4), hydrazine, hydrazine salts, hydroquinone, C1-5 alkylaldehydes and benzaldehyde. More preferably, the reducing agent provided in the process for making silver nanowires having a high aspect ratio of the present invention is selected from the group consisting of ascorbic acid, sodium borohydride (NaBH4) , hydrazine, hydrazine salts, hydroquinone, acetaldehyde, propionaldehyde and benzaldehyde. Most preferably, the reducing agent provided in the process for making silver nanowires having a high aspect ratio of the present invention is selected from the group consisting of ascorbic acid and sodium borohydride. [0028] The method for making silver nanowires having a high aspect ratio of the present invention preferably further comprises: providing a pH adjusting agent; and adding the pH adjusting agent to the container. The pH adjusting agent may be added to the container before the polyvinylpyrrolidone / mixed silver ion source is added to the container. Preferably, when the pH adjusting agent is added to the combination prior to addition of the polyvinylpyrrolidone / mixed silver ion source, wherein the combination has a pH of 2.0 to 4.0 (preferably from 2.0 to 3.5, more preferably from 2.4 to 3.3, particularly preferably from 2.4 to 2.6) prior to addition of the polyvinylpyrrolidone / silver ion source mixed with the container. The pH adjusting agent may be added to the container simultaneously with the polyvinylpyrrolidone / mixed silver ion source. Preferably, when the pH adjusting agent is added simultaneously with the polyvinylpyrrolidone / mixed silver ion source, the pH adjusting agent is added to the first part of the polyvinylpyrrolidone (PVP) prior to mixing with the first part of the silver ion source to form the polyvinylpyrrolidone / mixed silver ion source, where the first part of the polyvinylpyrrolidone (PVP) has a pH of 2.0 to 4.0 (preferably 2, 0 to 3.5, more preferably 2.3 to 3.3, more preferably 3.1 to 3.3). Preferably, when the pH adjusting agent is added simultaneously with the polyvinylpyrrolidone / mixed silver ion source, the pH adjusting agent is also added to the second part of the polyvinylpyrrolidone (PVP), where the second part of the polyvinylpyrrolidone (PVP) has a pH of 2.0 to 4.0 (preferably 2.0 to 3.5, more preferably 2.3 to 3.3, particularly preferably from 3.1 to 3.3). Preferably, the pH adjusting agent is added to the polyvinylpyrrolidone (PVP) supplied prior to the division of the polyvinylpyrrolidone (PVP) provided in a first portion and a second portion, wherein the polyvinylpyrrolidone (PVP) supplied at a pH of 2.0 to 4.0 (preferably 2.0 to 3.5, more preferably 2.3 to 3.3, particularly preferably 3.1 to 3.3). [0029] Preferably, the pH adjusting agent provided in the process for making high aspect ratio silver nanowires of the present invention is an acid. More preferably, the pH adjusting agent provided in the process for making silver nanowires having a high aspect ratio of the present invention is an acid, wherein the acid is selected from the group consisting of at least one of the inorganic acids (eg, nitric acid, sulfuric acid, hydrochloric acid, fluorosulfuric acid, phosphoric acid, fluoroantimonic acid) and the acids organic (e.g., methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, acetic acid, fluoroacetic acid, chloroacetic acid, citric acid, gluconic acid, lactic acid ). Preferably, the pH adjusting agent provided in the process for making silver nanowires having a high aspect ratio of the present invention has a pH <2.0. More preferably, the pH adjusting agent provided in the process for making silver nanowires having a high aspect ratio of the present invention includes nitric acid. Most preferably, the pH adjusting agent provided in the process for making silver nanowires having a high aspect ratio of the present invention is aqueous nitric acid. [0030] Preferably, the method for producing silver nanowires having a high aspect ratio of the present invention further comprises: purging a gas space of the container in contact with the combination in the container for give a reduced oxygen gas concentration in the gas space of the vessel. Preferably, the step of purging the gas space of the container in contact with the combination in the container to give the reduced oxygen gas concentration in the gas space of the container includes: (i) the isolation of 25 the gas space of the container of a surrounding atmosphere outside the container; (ii) then pressurizing the vessel gas space with an inert gas (preferably, wherein the inert gas is selected from the group consisting of argon, helium, methane, and nitrogen (more preferably argon, helium and nitrogen, more preferably argon and nitrogen, particularly preferably nitrogen); and, (iii) thereafter purging the gas space of the vessel to provide the reduced oxygen gas concentration in the gas space of the vessel. Preferably, the gas space of the vessel is vented to a pressure in the vessel which is> the atmospheric pressure of the surrounding atmosphere) to give the reduced oxygen gas concentration in the gas space of the vessel. Preferably, the reduced oxygen gas concentration is 2000 ppm (more preferably 400 ppm, particularly preferably 5. 20 ppm). More preferably, the step of purging the gas space of the container in contact with the combination in the container to give the reduced oxygen gas concentration in the gas space of the container, includes: (i) isolation the gas space of the container of a surrounding atmosphere outside the container; (ii) then pressurizing the vessel gas space with an inert gas (preferably, wherein the inert gas is selected from the group consisting of argon, helium, methane, and nitrogen (more preferably argon, helium and nitrogen, more preferably argon and nitrogen, particularly preferably nitrogen); and (iii) thereafter purging the gas space of the vessel to provide the reduced oxygen gas concentration in the gas space of the vessel (preferably, where the gas space of the vessel is vented to a pressure in the container which is> the atmospheric pressure of the surrounding atmosphere outside the container); and (iv) repeating steps (ii) and (iii) at least three times to give the reduced oxygen gas concentration in the container gas space (preferably, where the reduced oxygen gas concentration is 2000 ppm). (more preferably 5.400 ppm, particularly preferably 5. 20 ppm)). Preferably, the method for making silver nanowires having a high aspect ratio of the present invention further comprises: maintaining a reduced oxygen gas concentration in the container gas space during the addition of the polyvinylpyrrolidone / mixed silver ion source, during the formation of the growth mixture, and during the holding period. [0031] Preferably, the method for producing silver nanowires having a high aspect ratio of the present invention further comprises: bubbling into the silver ion source provided with an inert gas to extract the oxygen gas driven from the silver ion source and to give a low oxygen gas concentration in a silver ion gas space in contact with the silver ion source. Preferably, the bubbling step in the silver ion source provided with an inert gas comprises (preferably consists of): bubbling into the supplied silver ion source of an inert gas (preferably, where the inert gas is selected from the group consisting of argon, helium, methane, and nitrogen (more preferably argon, helium and nitrogen, more preferably argon and nitrogen, particularly preferably nitrogen) during a sparging time of 5 minutes (more preferably 5 minutes to 2 hours, particularly preferably 5 minutes to 1.5 hours) before adding to the vessel to extract entrained oxygen gas from the supplied silver ion source and to give a low concentration of oxygen gas in the silver ion gas space. Preferably, the low oxygen gas concentration in the silver ion gas space is 5000 ppm (preferably 5000 ppm, more preferably 5.400 ppm, particularly preferably 5 ppm). Preferably, the method for making silver nanowires having a high aspect ratio of the present invention further comprises: maintaining a low concentration of oxygen gas in the silver ion gas space up to the supplied silver ion source is added to the container. [0032] Preferably, the method for producing silver nanowires having a high aspect ratio of the present invention further comprises: purging a PVP gas gap in contact with the polyvinylpyrrolidone (PVP) supplied to give a dilute oxygen gas concentration in the PVP gas space. Preferably, the step of purging the PVP gas space to provide the concentration of oxygen gas diluted in the PVP gas space, includes: (i) isolating the polyvinylpyrrolidone (PVP) provided; (ii) then pressurizing the PVP gas space with an inert gas (preferably, wherein the inert gas is selected from the group consisting of argon, helium, methane, and nitrogen (more preferably argon, helium and nitrogen, more preferably argon and nitrogen, particularly preferably nitrogen); and (iii) thereafter purging the PVP gas space to give the dilute oxygen gas concentration in the PVP gas space. Preferably, the PVP gas space is purged to a pressure that is> atmospheric pressure of the surrounding atmosphere to give the dilute oxygen gas concentration in the PVP gas space. More preferably, the step of purging the PVP gas space to provide the concentration of oxygen gas diluted in the PVP gas space, includes: (i) isolating the polyvinylpyrrolidone (PVP) provided; (ii) then pressurizing the PVP gas space with an inert gas (preferably, wherein the inert gas is selected from the group consisting of argon, helium, methane, and nitrogen (more preferably argon, helium and nitrogen, more preferably argon and nitrogen, particularly preferably nitrogen); (iii) then purging the PVP gas space to give the concentration of dilute oxygen gas in the PVP gas space (preferably, where the PVP gas space is purged to a pressure of inert gas which is> atmospheric pressure); and, (iv) repeating steps (ii) and (iii) at least three times to give the dilute oxygen gas concentration in the PVP gas space. Preferably, the concentration of oxygen gas diluted in the PVP gas space is 10000 ppm (preferably 1000 ppm, more preferably 5.400 ppm, particularly preferably 5. 20 ppm). Preferably, the method for making silver nanowires having a high aspect ratio of the present invention further comprises: maintaining the dilute oxygen gas concentration in the PVP gas space until the polyvinylpyrrolidone (PVP) supplied is added to the container. Preferably, the method for producing silver nanowires having a high aspect ratio of the present invention further comprises: bleeding a gas space from the container in contact with the combination in the container to give a reduced oxygen gas concentration in the container gas space; bubbling into the silver ion source provided with an inert gas to extract the entrained oxygen gas from the supplied silver ion source and to give a low concentration of oxygen gas in a silver ion gas space in contact with the silver ion source provided; purging a PVP gas gap in contact with the polyvinylpyrrolidone (PVP) provided to provide a dilute oxygen gas concentration in the PVP gas space; maintaining a low oxygen gas concentration in the silver ion gas space and dilute oxygen gas concentration in the PVP gas space; and maintaining a reduced oxygen gas concentration in the container gas space during addition of the polyvinylpyrrolidone / mixed silver ion source, during formation of the growth mixture, and during the holding period. Preferably, in the process for making silver nanowires having a high aspect ratio of the present invention, the total glycol concentration in the container is <0.001 wt% at any time during the process. Preferably, in the process for producing silver nanowires having a high aspect ratio of the present invention, the polyvinylpyrrolidone (PVP) and the silver ion source are added to the container at a ratio by weight of silver ion polyvinylpyrrolidone (PVP) of 4: 1 to 10: 1 (more preferably 5: 1 to 8: 1, most preferably 6: 1 to 7: 1). Preferably, in the process for producing silver nanowires having a high aspect ratio of the present invention, the source of halide ions and the source of copper (II) ions are added to the container at a weight ratio of the halide ions to copper (II) ions of 1: 1 to 5: 1 (more preferably 2: 1 to 4: 1, particularly preferably 2.5: 1 to 3.5: 1). [0037] Preferably, in the process for manufacturing silver nanowires having a high aspect ratio of the present invention, the plurality of recovered silver nanowires have a mean diameter of 40 nm (preferably 20 to 20 nm). 40 nm, more preferably 20 to 35 nm, particularly preferably 20 to 30 nm). More preferably, in the process for producing silver nanowires having a high aspect ratio of the present invention, the plurality of recovered silver nanowires have a mean diameter of 40 nm (preferably 20 to 40 nm). more preferably 20 to 35 nm, particularly preferably 20 to 30 nm) and an average length of 10 to 100 μm. Preferably, the plurality of recovered silver nanowires have an average aspect ratio of> 500. [0038] Preferably, in the process for making silver nanowires having a high aspect ratio of the present invention, the The plurality of recovered silver nanowires have a standard deviation of diameter 26 nm (preferably 1 to 26 nm, more preferably 5 to 20 nm, particularly preferably 10 to 15 nm). More preferably, in the process for making silver nanowires having a high aspect ratio of the present invention, the plurality of recovered silver nanowires have a mean diameter of 5.40 nm (preferably 20 to 40 μm). more preferably 20 to 35 nm, more preferably 20 to 30 nm) with a standard deviation of diameter 26 nm (preferably 1 to 26 nm, more preferably at 20 nm, particularly preferably from 10 to 15 nm). Particularly preferably, in the process for producing silver nanowires having a high aspect ratio of the present invention, the plurality of recovered silver nanowires have a mean diameter of 40 nm (preferably 20 to 40 μm). more preferably 20 to 35 nm, more preferably 20 to 30 nm) with a standard deviation of 26 nm (preferably 1 to 26 nm, more preferably 5 to 25 nm). 20 nm, particularly preferably 10 to 15 nm) and an average length of 10 to 100 μm. Some embodiments of the present invention will now be described in detail in the following examples. The water used in the following examples was obtained by means of a Barnstead NANOPure TherrnoScientific purification system with a 0.2 μm pore size hollow fiber filter positioned downstream of the purification unit. some water. Example Si: halide ion sub-combination [0041] The halide ion sub-combination used herein in some examples was prepared by dissolving sodium chloride (0.2104 g, available from Sigma Aldrich) in the following manner: water (900 mL). Example S2: copper (II) ion sub-combination [0042] The copper (II) ion sub-combination used here in some examples was prepared by dissolving copper (II) chloride dihydrate (0.6137 g; available from Sigma Aldrich) in water (900 nL).
    [0007] Example S3: reducing sugar / copper ion (II) / halide ion sub-combination The reducing sugar / copper (II) ion / halide ion sub-combination used here in some examples was prepared by adding 13.5 g D-glucose to water (2159 mL) in a flask. Then 21.3 ml of the halide ion sub-combination prepared according to Example Si were added to the flask. Then 21.3 ml of the copper (II) ion sub-combination prepared according to Example S2 were added to the flask.
    [0008] Example S4: Polyvinylpyrrolidone (PVP) Sub-Combination The polyvinylpyrrolidone (PVP) sub-combination used here in some examples was prepared by addition of polyvinylpyrrolidone (52.2 g, weight average molecular weight of 50000 g / cm 2). mol Sokalan® K30 P available from BASF) to water (381 mL) in a flask and then flush the transfer equipment with water (203 mL) into the flask. Example 55: Sub-combination of silver ions The silver ion sub-combination used here in some examples was prepared by addition of AgNO 3 (12.7 g ACS reagent grade, 99.0% available from Sigma Aldrich) to water (152 mL) in a flask. Example S6: Polyvinylpyrrolidone / mixed silver ion sub-combination The polyvinylpyrrolidone / mixed silver ion sub-combination used here in some examples was prepared by adjusting the pH of a polyvinylpyrrolidone (PVP) sub-combination prepared according to US Pat. Example S4 at 3.1 to 3.3 with nitric acid followed by combination of the pH-adjusted polyvinylpyrrolidone (PVP) sub-combination with a silver ion sub-combination prepared according to Example S5 in a 1L conical bottom container and then successively rinsing the flask containing the polyvinylpyrrolidone (PVP) sub-combination and the flask containing the silver ion sub-combination with water (102 mL) into the conical bottom container. The polyvinylpyrrolidone / mixed silver ion sub-combination contained in the conical bottom vessel was then gently bubbled continuously with nitrogen until it was transferred to the reactor.
    [0009] Example S7: Reducing Sugar / Oolyvinylpyrrolidone (PVP) Sub-combination The reducing sugar / polyvinylpyrrolidone (PVP) sub-combination used here in some examples was prepared by addition of polyvinylpyrrolidone (52.2 g, weight average molecular weight). 50000 g / mol Sokalan® K30 P available from BASF) to water (1958 mL) in a flask. Then addition of D-glucose (13.5 g, 98% available from Sigma-Aldrich) to the flask. Example S8: silver ion sub-combination The silver ion sub-combination used herein in some examples was prepared by addition of AgNO 3 (12.7 g, ACS reagent grade, 99.0% available from Sigma Aldrich) to water (612 mL) in a flask. Then transfer the contents of the flask to an HPLC tank and flush the flask and transfer equipment with water (81 mL) into the HPLC tank. Preparation of silver nanowires Comparative Examples C1-C2 and Examples 1-27 In each of Comparative Examples C1-C2 and Examples 1-27, an 8-liter stainless steel pressure reactor equipped with a stirrer of Three-blade propeller type, a temperature control unit with an external resistive heating jacket and an internal cooling tube to facilitate temperature control was used. In each of Comparative Examples C1-C2 and Examples 1-27, a reducing sugar / copper ion (II) / halide ion sub-combination prepared according to Example S3 was added to the reactor. The transfer apparatus was then rinsed with water (152 mL) in the reactor. The reactor was then closed and the agitator was started at 200 rpm. The gas space in the reactor was then purged with> 620 x 103 Pa (90 psig) of nitrogen four times to a pressure> 414 x 103 Pa (60 psig) with holding under pressure for three minutes for each purge. The reactor was left with a nitrogen blanket at 111 x 103 Pa (16.1 psig) after the final purge. The set point for the temperature control unit was then set to 150 ° C. When the reactor contents reached a temperature of 150 ° C., the silver ion sub-combination prepared according to Example S5 and the polyvinylpyrrolidone (PVP) sub-combination prepared according to Example S4 were then transferred to the reaction vessel. reactor as noted below in each of Comparative Examples C1-C2 and Examples 1-27. Comparative Examples C1-C2 In each of Comparative Examples C1-C2, 1 / 5th of a sub-combination of silver ions prepared according to Example S5 and 1 / 5th of a sub-combination of polyvinylpyrrolidone (PVP ) prepared according to Example S4 were transferred to the reactor simultaneously, but separately for a charge time of 60 seconds to form a creation mixture. The silver ion sub-combination was added to the reactor at a point below the surface of the combination in the reactor. The polyvinylpyrrolidone (PVP) sub-combination was added to the reactor on the surface of the combination in the reactor. After a period of twenty minutes, the remaining 4/5 of the silver ion sub-combination and the remaining 4/5 of the polyvinylpyrrolidone (PVP) sub-combination were transferred to the reactor. similarly - simultaneously, but separately - during a feed time of 10 minutes to form a growth mixture. During the delay period, the set point for the temperature control device was lowered linearly from 150 ° C to 130 ° C, the lowering starting at 10 minutes in the delay period and ending with the period of time. time limit. The growth mixture was then stirred for a hold time of eight hours to form a product mixture. The product mixture was then cooled to room temperature. The agitator was stopped. The reactor was then vented to release any accumulated pressure in the vessel. The contents of the reactor were then collected. Examples 1-10 [0051] In each of Examples 1-10, 1 / 5th of a polyvinylpyrrolidone / mixed silver ion sub-combination prepared according to Example S6 following a premixing period after its preparation, as noted in Table 1, was transferred to the reactor for a 1 min charge time at a point below the surface of the combination in the reactor to form a creation mixture. After a period of twenty minutes, the remaining 45th of the polyvinylpyrrolidone / mixed silver ion sub-combination was then transferred to the reactor for a feed time of 10 minutes at a point below the surface of the mixture. of creation to form a growth mixture. During the delay period, the set point for the temperature control device was lowered linearly from 150 ° C to the temperature noted in Table 1, the lowering starting at 10 minutes in the delay period and ending with the delay period. The growth mixture was then stirred for a hold time as noted in Table 1 to form a product mixture. The product mixture was then cooled to room temperature. The agitator was stopped. The reactor was then vented to release any accumulated pressure in the vessel. The contents of the reactor were then collected.
    [0010] TABLE 1 Ex. Temp. Pre-mixing time IM of holding imil 01 n ° 1 <60 130 18 2 <60 130 8 3 120 130 8 4 240 130 8 960 130 8 6 10 130 8 7 <60 130 8 8 <60 130 18 9 <60 132 8 < Examples 11-25 [0052] In each of Examples 11-25, nitric acid was added to the combination in the reactor to adjust the pH of the combination to the pH noted in Table 2. Then, 1 / 5th of a polyvinylpyrrolidone / mixed silver ion sub-combination prepared according to Example S6 following a premixing period after its preparation, as noted in Table 2, was transferred to the reactor for a period of time. charge of 1 minute at a point below the surface of the suit in the reactor to form a creation mixture. Following a twenty-minute delay period, the remaining 45th of the polyvinylpyrrolidone / mixed silver ion sub-combination was then transferred to the reactor for a feed time of 10 minutes at a point below the surface of the mixture. of creation to form a growth mixture. During the delay period, the set point for the temperature control device was lowered linearly from 150 ° C to the temperature noted in Table 2, the lowering starting at 10 minutes in the delay period and ending with the delay period. The growth mixture was then stirred for a hold time as noted in Table 2 to form a product mixture. The product mixture was then cooled to room temperature. The agitator was stopped. The reactor was then vented to release any accumulated pressure in the vessel. The contents of the reactor were then collected. TABLE 2 Ex. Al Temp. Premixing time f ° C) for maintenance rIC 11 3.4 <60 130 8 12 3.4 <60 130 8 13 3.3 5 130 8 14 2.5 5 130 8 15 3.3 5 130 18 16 2 , 5 <60 130 8 17 2.5 <60 130 18 18 2.5 <60 130 12 19 2.5 <60 130 18 20 2.5 <60 130 8 21 2.5 <60 130 8 22 2.5 <60 130 8 23 2.5 <60 130 8 24 2.5 <60 130 8 25 2.5 <60 130 18 Example 26 [0053] During a charging time of 1 minute, 15th of a sub-combination of silver ions prepared according to Example S5 and 15th of a polyvinylpyrrolidone (PVP) sub-combination prepared according to Example S4, the pH of which was adjusted to 3.1 to 3.3 with nitric acid, were transferred to the reactor simultaneously through a mixing tee to form a mixed polyvinylpyrrolidone / silver ion source with a premix time of 2.7 seconds before entering the reactor at a point under the surface of the combination in the reactor to form a creation mixture. Following a 20-minute delay period, the remaining 4/5 of the silver ion sub-combination and the remaining 4/5 of the polyvinylpyrrolidone (PVP) sub-combination were mixed through the mixing with a mixing time of 6.8 seconds before entering the reactor at a point below the surface of the creating mixture for a feed time of 10 minutes to form a growth mixture. During the delay period, the set point for the temperature control device was lowered linearly from 150 ° C to 130 ° C, the lowering starting at 10 minutes in the delay period and ending with the period of time. time limit. The growth mixture was then stirred for a hold time of eight hours to form a product mixture. The product mixture was then cooled to room temperature.
    [0011] The agitator was stopped. The reactor was then vented to release any accumulated pressure in the vessel. The contents of the reactor were then collected. Example 27 [0054] During a 1 minute charging time, 1 / 5th of a polyvinylpyrrolidone / mixed silver ion sub-combination prepared according to Example S6 with a premix period <60 minutes was transferred to the reactor at a temperature of 1 minute. point under the surface of the suit in the reactor to form a creative mixture. After a period of twenty minutes, four-fifths of a silver ion sub-combination prepared according to Example S5 and four-fifths of a polyvinylpyrrolidone (PVP) sub-combination prepared according to US Pat. Example S4, whose pH was adjusted to 3.1 to 3.3 with nitric acid, was transferred simultaneously, but separately, to a point below the surface of the creation mixture in the reactor for a period of time. feed for 10 minutes to form a growth mixture. During the delay period, the set point for the temperature control device was lowered linearly from 150 ° C to 130 ° C, the lowering starting at 10 minutes in the delay period and ending with the period of time. time limit. The growth mixture was then stirred for a hold time of eight hours to form a product mixture. The product mixture was then cooled to room temperature. The agitator was stopped. The reactor was then vented to release any accumulated pressure in the vessel. The contents of the reactor were then collected. Comparative Example C3 [0055] An 8 L stainless steel pressure reactor equipped with a suspended mixer and a temperature control device was used. A halide ion sub-combination prepared according to Example S1 was added to a reducing sugar / PVP sub-combination prepared according to Example S7 in a flask. A sub-combination of copper (II) ions prepared according to Example S2 was then added to the flask. The beakers used in the preparation of the sub-combination containing halide ions and the sub-combination containing copper (II) ions were then rinsed with water (407 mL) in the flask. The pH of the flask contents was then adjusted from an initial pH of 3.73 to a pH of 3.14 with nitric acid (ACS reagent grade, 70%). The contents of the flask were then transferred to the reactor. The flask was then rinsed with water (191 mL) in the reactor. The stirrer was then started at a stirring speed of 200 rpm. A sample was taken from the reactor contents and the pH was measured at 3.19. A water rinse (20 mL) was added after the sample. The reactor was then closed and the gas space in the reactor was purged with> 620 x 103 Pa (90 psig) of nitrogen four times to a pressure of> 414 x 103 Pa (60 psig) with holding under pressure for three minutes for each purge. The reactor was left with a nitrogen blanket at 111 x 103 Pa (16.1 psig) after the final purge. The temperature control device was then set at 150 ° C. After the reactor contents reached 150 ° C, 20% by weight of a silver ion-containing sub-combination prepared according to Example S8 was added to the reactor in 1 minute. The reactor contents were then stirred for ten minutes while the set point of the temperature control device was maintained at 150 ° C. During the next ten minutes, the temperature set point was lowered linearly to 130 ° C. The remaining 80% by weight of the silver ion-containing sub-combination prepared according to Example S8 was then added to the reactor contents for the next ten minutes as well as an additional volume of water (102 mL). The reactor contents were then stirred for eighteen hours while the setting point of the temperature control device was maintained at 130 ° C. The reactor contents were then cooled to room temperature for the next thirty minutes. The reactor was then vented to release any accumulated pressure in the vessel. The mixer was stopped. The product was then collected. Analysis of the silver nanowires collected The silver nanowires produced in the comparative examples C1-C3 and Examples 1-27 were then analyzed with a FEI Nova field emitting gun (SEM) electron scanning microscope (SEM) Nano SEM using the Automated Image Acquisition (AIA) program from FEI. A drop of purified dispersion was taken from the UV / Vis cuvette and applied to a sample holder of SEM coated with a silica wafer before being dried under vacuum. The backscattering electronic images were collected with a FEI Nova Nano SEM Field Emission Scanning Electron Microscope. FEI's Automated Image Acquisition (AIA) program was used to move the deck, focus, and collect images. Eighteen images of each sample were acquired at a horizontal field width of 6 μm. Semi-automatic image analysis using the Image] software classified the objects as threads or particles based on an aspect ratio of 3. The yarn widths were measured automatically as well as the total area of wires in the pictures. Particles were classified with respect to the individual size and the total area of particles in the images. The Image] software was also used to determine the diameter of the silver nanowires in Table 3. It was observed that the average length of the silver nanowires exceeded 20 μm, based on the SEM images obtained for the analysis. diameters. The Image software was used to analyze the SEM images of the silver nanowires produced in each of the comparative examples C1-C3 and Examples 1-27 to give a relative measure of the silver nanoparticles having a ratio of appearance <3 in product samples. The statistic used for this measurement is the fraction of nanoparticles, NPF, determined according to the following expression: N Pr = N PA / TA; where TA is the total surface area of the substrate that is occluded by a given deposited sample of silver nanowires; and NPA is the portion of the total occluded surface area attributable to silver nanoparticles having an aspect ratio <3. UV / Vis spectral analysis of the silver nanowires produced in each of the examples Comparative C1-C3 and Examples 1-27 were performed using a Shimadzu UV 2401 spectrophotometer. The raw UV / Vis absorption spectra were normalized so that the local minimum near 320 nm and the local maximum in the vicinity of 375 nm cover the range from 0 to 1. The maximum absorption wavelength, λ max and the normalized absorption at 500 nm, Abs500, are shown in Table 3. TABLE 3 Ex. Diameter of NPF nanowires Analysis of silver (nm) spectral Median Avg. Avg-Amax Abs500 type (nm) enne Cl 45.4 54.5 29.5 0.29 381 0.4395 C2 45.6 55.6 33.3 0.27 380 0.4227 C3 42.0 60.0 46.0 0.24 377 0.2400 1 33.3 39.6 19.3 0.34 374 0.5367 2 35.5 41.1 19.1 0.29 374 0.4869 3 31.2 34.1 15.5 0.33 375 0.4731 4 32.6 39.7 22.7 0.38 375 0.5340 32.3 40.0 22.8 0.46 375 0.5653 6 33.0 37.4 19.0 0.28 375 0.4323 7 31.1 37.4 19.2 0.36 375 0.5706 8 30.6 35.2 15.1 0.38 374 0.5354 9 30.6 41.4 25.2 0.39 376 0.6619 30.2 37.1 20.1 0.47 375 0.8393 11 28.9 33.1 17.1 0.35 373 0.5365 12 27.6 31.3 14.9 0.38 374 0.5500 13 28.9 36.0 18.5 0.29 373 0.5944 14 30.9 37.5 21.2 0.44 374 0.4092 30.2 35.4 18.2 0.40 374 0.7268 16 32.2 33.9 12.6 0.25 373 0.3300 0.3729 17 31.6 34.0 16.3 0.28 374 18 31.6 34.5 15.1 0.21 375 0.4275 19 33.0 37.5 21.8 0, 23 374 0.3843 32.9 34.5 12.2 0.18 374 0.3353 21 33.0 35.2 13.8 0.27 374 0.4095 22 30.1 33.8 16.1 0, 18 374 0.3090 23 35.0 39.9 17.0 0.29 374 0.4005 24 37.7 39.9 12.1 0.18 373 0.3492 31.2 38.1 23.8 0, 44 374 0.3882 26 34.8 38.0 11.8 0.34 376 0.4162 27 32.4 39.9 24.5 0.29 375 0.3829
    权利要求:
    Claims (10)
    [0001]
    REVENDICATIONS1. A process for producing silver nanowires having a high aspect ratio, characterized by comprising: providing a container; the supply of water; the supply of a reducing sugar; providing a polyvinylpyrrolidone (PVP), wherein the polyvinylpyrrolidone (PVP) provided can be divided into a first portion of the polyvinylpyrrolidone (PVP) and a second portion of the polyvinylpyrrolidone (PVP); providing a source of copper (II) ions; providing a source of halide ions; providing a source of silver ions, wherein the provided silver ion source can be divided into a first portion of the silver ion source and a second portion of the silver ion source; adding water, reducing sugar, copper ion source (II) and the halide ion source to the container to form a combination; heating the combination at 110 to 160 ° C; mixing the first portion of the polyvinylpyrrolidone (PVP) with the first portion of the silver ion source to form a polyvinylpyrrolidone / mixed silver ion source; adding the polyvinylpyrrolidone / silver ion source mixed with the combination into the vessel to form a creation mixture; then, following a delay period, adding to the vessel the second portion of the polyvinylpyrrolidone (PVP) and the second portion of the silver ion source to form a growth mixture; growing at 110 to 160 ° C for a holding period of 2 to 30 hours to give a product mixture; and, recovering a plurality of silver nanowires having a high aspect ratio from the product mixture; where the total glycol concentration in the container is <0.001% by weight.
    [0002]
    The method of claim 1, further comprising: maintaining the combination at 120 to 155 ° C during the addition of the polyvinylpyrrolidone / mixed silver ion source and during the delay period; and maintaining the growth mixture at 120 to 140 ° C during the holding period.
    [0003]
    3. Method according to claim 1 or 2, characterized in that the second part of the polyvinylpyrrolidone (PVP) and the second part of the silver ion source are added to the container simultaneously after the delay period.
    [0004]
    4. Method according to claim 1 or 2, characterized in that the second part of the polyvinylpyrrolidone (PVP) and the second part of the silver ion source are mixed for a mixing time of 0.5 seconds to 1 hour before to be added to the container after the delay period.
    [0005]
    5. Method according to any one of the preceding claims, characterized in that the first part of the polyvinylpyrrolidone (PVP) and the first part of the silver ion source are mixed for a mixing time of 0.5 second to 1 hour. hour to form the polyvinylpyrrolidone / mixed silver ion source before being added to the container.
    [0006]
    6. Method according to any one of the preceding claims, characterized in that the first part of the polyvinylpyrrolidone (PVP) represents 10 to 40 ° by weight of the polyvinylpyrrolidone (PVP) supplied, and the first part of the source of Silver ions represent 10 to 40% by weight of the silver ion source supplied.
    [0007]
    The method of any of the preceding claims, further comprising: providing a pH adjusting agent; adding the pH adjusting agent to the combination prior to adding the polyvinylpyrrolidone / mixed silver ion source; wherein the combination has a pH of 2.0 to 4.0 prior to the addition of the polyvinylpyrrolidone / silver ion source mixed with the container.
    [0008]
    8. Method according to any one of the preceding claims, characterized in that it further comprises: providing a reducing agent; adding the reducing agent to the creation mixture.
    [0009]
    9. A method according to any one of the preceding claims, characterized in that it further comprises: purging a gas space of the container in contact with the combination in the container to give a reduced oxygen gas concentration in the container. gas space of the container; bubbling into the silver ion source provided with an inert gas to extract the entrained oxygen gas from the supplied silver ion source and to give a low concentration of oxygen gas in a gap of silver ion gas in contact with the silver ion source provided; purging a PVP gas gap in contact with the polyvinylpyrrolidone (PVP) provided to provide a dilute oxygen gas concentration in the PVP gas space; Maintaining the low concentration of oxygen gas in the silver ion gas space and the dilute oxygen gas concentration in the PVP gas space; and maintaining the reduced oxygen gas concentration in the container gas space during the addition of the polyvinylpyrrolidone / mixed silver ion source, during formation of the growth mixture, and during the holding period.
    [0010]
    10. A process for producing silver nanowires having a high aspect ratio, characterized in that it comprises: providing a container; the supply of water; the supply of a reducing sugar; provision of polyvinylpyrrolidone (PVP); providing a source of copper (II) ions; Providing a source of halide ions; providing a source of silver ions; the division of water into five separate volumes; combining a first volume of water with the reducing sugar to form a sub-combination of reducing sugar; Combining a second volume of water with the polyvinylpyrrolidone (PVP) provided to form a polyvinylpyrrolidone (PVP) sub-combination, wherein the polyvinylpyrrolidone (PVP) sub-combination can be divided into a first part of the sub-combination of polyvinylpyrrolidone (PVP); combination of polyvinylpyrrolidone (PVP) and a second part of the polyvinylpyrrolidone (PVP) sub-combination; combining a third volume of water with the copper (II) ion source to form a sub-combination of copper (II) ions; combining a fourth volume of water with the halide ion source to form a sub-combination of halide ions; combining a fifth volume of water with the silver ion source provided to form a sub-combination of halide ions; a combination of silver ions, wherein the silver ion sub-combination can be divided into a first part of the silver ion sub-combination and a second part of the silver ion sub-combination; adding the reducing sugar sub-combination, the copper (II) ion sub-combination and the halide ion sub-combination to the container to form a combination; heating the combination at 110 to 160 ° C; mixing the first part of the polyvinylpyrrolidone (PVP) sub-combination with the first part of the silver ion sub-combination to form a polyvinylpyrrolidone / mixed silver ion sub-combination; adding the polyvinylpyrrolidone / silver ion mixed sub-combination to the combination into the vessel to form a creation mixture; then, following a delay period, adding to the vessel the second part of the polyvinylpyrrolidone (PVP) sub-combination and the second part of the silver ion sub-combination to form a mixture of growth; maintaining the growth mixture at 110 to 160 ° C for a holding period of 2 to 30 hours to provide a product mixture; and recovering a plurality of silver nanowires having a high aspect ratio from the product mixture; where the total glycol concentration in the vessel is <0.001 wt%.
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    同族专利:
    公开号 | 公开日
    CN105537608B|2017-12-22|
    TW201615549A|2016-05-01|
    KR20160049982A|2016-05-10|
    US20160114393A1|2016-04-28|
    DE102015013239A1|2016-04-28|
    JP2016166403A|2016-09-15|
    CN105537608A|2016-05-04|
    US9999926B2|2018-06-19|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    EP1448725A4|2001-10-05|2008-07-23|Cabot Corp|Low viscosity precursor compositions and methods for the deposition of conductive electronic features|
    US7585349B2|2002-12-09|2009-09-08|The University Of Washington|Methods of nanostructure formation and shape selection|
    WO2006076612A2|2005-01-14|2006-07-20|Cabot Corporation|A process for manufacturing application specific printable circuits and other custom electronic devices|
    US7968008B2|2006-08-03|2011-06-28|Fry's Metals, Inc.|Particles and inks and films using them|
    US7922787B2|2008-02-02|2011-04-12|Seashell Technology, Llc|Methods for the production of silver nanowires|
    JP5203769B2|2008-03-31|2013-06-05|富士フイルム株式会社|Silver nanowire and method for producing the same, aqueous dispersion and transparent conductor|
    JP2009299162A|2008-06-16|2009-12-24|Fujifilm Corp|Silver nanowire, method for producing the same, water base dispersion product and transparent conductor|
    JP5306760B2|2008-09-30|2013-10-02|富士フイルム株式会社|Transparent conductor, touch panel, and solar cell panel|
    TWI372666B|2008-12-23|2012-09-21|Ind Tech Res Inst|Preparing composition of silver nanowire and method for forming silver nanowire|
    US20100242679A1|2009-03-29|2010-09-30|Yi-Hsiuan Yu|Method for continuously fabricating silver nanowire|
    US8512438B2|2009-08-25|2013-08-20|Cambrios Technologies Corporation|Methods for controlling metal nanostructures morphology|
    US9636746B2|2010-07-22|2017-05-02|Nanotech & Beyond Co., Ltd.|Method for manufacturing silver nanowires|
    US9630250B2|2010-12-17|2017-04-25|Seiko Pmc Corporation|Process for producing silver nanowires and agent for controlling growth of silver nanowires|
    CN102328095B|2011-10-14|2013-03-27|济南大学|Preparation method of metal silver nanowires with adjustable length and diameter|
    TWI476160B|2011-12-19|2015-03-11|Ind Tech Res Inst|Method for preparing silver nanowire|
    US9034075B2|2012-04-30|2015-05-19|Dow Global Technologies Llc|Methods of manufacturing high aspect ratio silver nanowires|
    CN104583114B|2012-06-18|2017-04-05|苏州诺菲纳米科技有限公司|The agglomerated thing of the nanowire suspended liquid being stored in container is reduced|
    US9148969B2|2012-07-30|2015-09-29|Rohm And Haas Electronic Materials Llc|Method of manufacturing high aspect ratio silver nanowires|
    WO2014138749A1|2013-03-08|2014-09-12|Innova Dynamics, Inc.|Production of nanostructures|
    CN103433503B|2013-08-19|2015-10-28|中国科学院合肥物质科学研究院|A kind of preparation method of ultra-long silver nanowire|
    US20150266096A1|2014-03-18|2015-09-24|Blue Nano Inc.|Silver nanowires with thin diameter and high aspect ratio and hydrothermal synthesis method for making the same|
    DE102015013219A1|2014-10-28|2016-04-28|Dow Global Technologies Llc|Process for the preparation of silver nanowires|DE102015013220A1|2014-10-28|2016-04-28|Dow Global Technologies Llc|Process for the preparation of silver nanowires|
    US10376898B2|2015-06-12|2019-08-13|Dow Global Technologies Llc|Method for manufacturing high aspect ratio silver nanowires|
    JP6526739B2|2016-06-02|2019-06-05|Ｄｏｗａエレクトロニクス株式会社|Silver nanowire, method for producing the same, silver nanowire ink and transparent conductive film|
    CN107639236B|2017-09-08|2020-08-18|中国乐凯集团有限公司|Preparation method of silver nanowires and product|
    CN110369732B|2018-04-12|2020-10-20|北京化工大学|Low-temperature preparation method of silver nanowires|
    CN110576193A|2019-10-29|2019-12-17|哈尔滨工业大学|method for preparing superfine silver nanowires by using citrate as reducing agent|
    法律状态:
    2016-09-19| PLFP| Fee payment|Year of fee payment: 2 |
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    2020-10-16| PLSC| Publication of the preliminary search report|Effective date: 20201016 |
    2021-10-22| RX| Complete rejection|Effective date: 20210914 |
    优先权:
    申请号 | 申请日 | 专利标题
    US201462069435P| true| 2014-10-28|2014-10-28|
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