CN116622039B - Vinyl pyrrolidone segmented copolymer and preparation method and application thereof - Google Patents

Vinyl pyrrolidone segmented copolymer and preparation method and application thereof Download PDF

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CN116622039B
CN116622039B CN202310920216.9A CN202310920216A CN116622039B CN 116622039 B CN116622039 B CN 116622039B CN 202310920216 A CN202310920216 A CN 202310920216A CN 116622039 B CN116622039 B CN 116622039B
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vinyl pyrrolidone
solvent
chain transfer
transfer agent
block copolymer
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CN116622039A (en
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王宇
朱广东
陈占
夏阳
熊俊超
乐文伟
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SHANGHAI YUKING WATER SOLUBLE MATERIAL Tech CO Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2438/00—Living radical polymerisation
    • C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Abstract

The invention provides a vinyl pyrrolidone segmented copolymer, a preparation method and application thereof, wherein the preparation raw materials of the vinyl pyrrolidone segmented copolymer comprise vinyl pyrrolidone, a chain transfer agent, an initiator and a solvent, the preparation raw materials of the chain transfer agent comprise conductive monomers, and the RAFT chain extension reaction is carried out by adopting the preparation raw materials, so that the obtained vinyl pyrrolidone segmented copolymer has amphipathy, excellent conductive property and good self-assembly property, further the problem of contact resistance increase caused when silver nanowires prepared by the vinyl pyrrolidone segmented copolymer are coated into transparent electrodes can be avoided, the preparation process of the silver nanowires can be effectively regulated and controlled, and the silver nanowires with narrow diameters, high length-diameter ratios and monodispersion properties can be obtained more easily.

Description

Vinyl pyrrolidone segmented copolymer and preparation method and application thereof
Technical Field
The invention belongs to the technical field of silver nanowires, and particularly relates to a vinyl pyrrolidone segmented copolymer and a preparation method and application thereof.
Background
Transparent electrodes are widely used in the fields of displays, solar cells, organic electroluminescent devices and the like. In recent years, with the development of flexible technology, products such as flexible displays, flexible solar cells, flexible sensors, and the like have been brought from laboratories to the market. While the conventional transparent electrode material Indium Tin Oxide (ITO) cannot meet the development of flexible electronic devices due to its brittleness, silver nanowire (AgNWs) flexible transparent electrodes have electrical and optical characteristics comparable to those of ITO, and have excellent mechanical flexibility, and are considered as novel flexible electrode materials most likely to replace ITO.
The preparation process of the silver nanowire flexible transparent electrode mainly comprises the steps of coating silver nanowire dispersion liquid on a substrate, and drying to obtain a silver nanowire transparent conductive film; while silver nanowire films are intended to conduct electricity, firstly good contact between nanowires is ensured. Research shows that the contact resistance between nanowires is far greater than the resistance of the nanowires themselves, so reducing the contact resistance and reducing the contact is an important factor in improving the conductivity of the transparent electrode.
The silver nanowire is generally produced and prepared by adopting a liquid-phase polyalcohol method, wherein polyalcohol is used as a solvent and a reducing agent, polyvinylpyrrolidone (PVP) is used as a blocking agent, halogen is used as an inducer, and a silver precursor is reduced into five-twin crystal particles at high temperature and gradually grown into a nano silver wire; the capping agent PVP plays an important role in the growth process of the silver nanowire, and anisotropic growth is obtained through the high-surface energy crystal face adsorbed on the silver nanowire, so that the silver nanowire which grows in one dimension along the axial direction is obtained, the surface of the obtained silver nanowire is obviously adsorbed by PVP, and the adsorption is very beneficial to dispersion of the silver nanowire. CN111032256a discloses a method for producing silver nanowires, a silver nanowire ink, and a transparent conductive film, comprising a step of reducing and precipitating silver into a linear form in an alcohol solvent in which a silver compound and an organic protective agent are dissolved, wherein a polymer having a vinylpyrrolidone structural unit is used as the organic protective agent, and the reduction and precipitation is performed in the liquid in a state in which an organic acid ester is dissolved in the alcohol solvent at a concentration of 0.1 to 20 mmol/L. However, PVP as a non-conductive polymer also greatly interferes with the conductivity of the silver nanowire film, particularly causing an increase in contact resistance.
Therefore, in order to overcome the above technical problems, development of a polyvinylpyrrolidone block copolymer with conductive properties is a technical problem which is urgently needed to be solved at present.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a vinyl pyrrolidone segmented copolymer, a preparation method and application thereof, wherein the vinyl pyrrolidone segmented copolymer is prepared by selecting vinyl pyrrolidone, a chain transfer agent, an initiator and a solvent as preparation raw materials to carry out a RAFT chain extension reaction, and the preparation raw materials of the chain transfer agent are limited to comprise conductive monomers, so that the obtained vinyl pyrrolidone segmented copolymer has amphipathy, excellent conductive property and good self-assembly property, further the problem of contact resistance increase caused when silver nanowires prepared by adopting the vinyl pyrrolidone segmented copolymer as a blocking agent are coated into transparent electrodes can be avoided, the preparation process of the silver nanowires can be effectively regulated, and the silver nanowires with narrow diameter, high length-diameter ratio and monodisperse property can be obtained more easily.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a vinyl pyrrolidone block copolymer, wherein the vinyl pyrrolidone block copolymer is prepared from vinyl pyrrolidone, a chain transfer agent, an initiator and a solvent;
and the preparation raw materials of the chain transfer agent comprise conductive monomers.
The preparation raw materials of the vinyl pyrrolidone segmented copolymer comprise vinyl pyrrolidone, a chain transfer agent, an initiator and a solvent, and the preparation raw materials of the chain transfer agent comprise conductive monomers, and the vinyl pyrrolidone segmented copolymer obtained by carrying out RAFT chain extension reaction by adopting the preparation raw materials has amphipathy, excellent conductive property and good self-assembly property; firstly, due to the excellent conductive property, when the polyvinylpyrrolidone segmented copolymer is used as a capping agent for preparing silver nanowires, the surface of the silver nanowires has good conductive property, the defect that the conventional polyvinylpyrrolidone (PVP) is not conductive as the capping agent is effectively overcome, the contact resistance of a transparent electrode prepared by further adopting the silver nanowires is obviously reduced, and the process treatment necessity of annealing or high pressure and the like after the transparent electrode of the silver nanowires is coated is greatly reduced; secondly, by utilizing the good self-assembly characteristic of the polyvinylpyrrolidone segmented copolymer, the conductive polymer chain segment can form micelle microcapsules which are used as nucleation points for silver ion reduction deposition, and the nucleation growth is positioned, so that the diameter and the length of the silver nanowire are effectively regulated and controlled, and the silver nanowire with a narrow diameter and a high length-diameter ratio is more easily obtained; finally, because the polyvinylpyrrolidone segmented copolymer has amphiphilic property, compared with single PVP, the polyvinylpyrrolidone segmented copolymer is more beneficial to the dispersion uniformity of the silver nanowires in the dispersion liquid and the good dispersion wettability with the base material during coating, the aggregation can be reduced, and the silver nanowires in the prepared silver nanowire transparent electrode have proper nano size, excellent transparency and good conductive property.
Preferably, the initiator comprises an azo-type initiator.
Preferably, the azo initiator comprises any one or a combination of at least two of azobisisobutyronitrile, azobisisovaleronitrile, azobisisoheptonitrile or azobisisobutyrate.
Preferably, the solvent is a RAFT polymerisation solvent.
Preferably, the RAFT polymerization solvent comprises any one or a combination of at least two of dioxane, N-dimethylamide, dimethylsulfoxide or N-methylpyrrolidone.
Preferably, the chain transfer agent is prepared by a process comprising the steps of:
(1) Reacting a conductive monomer with a first Grignard reagent in a solvent, adding a catalytic initiator to react, adding a second Grignard reagent to react, and quenching to obtain a vinyl-terminated conductive polymer;
(2) Reacting the vinyl-terminated conductive polymer obtained in the step (1) with a borohydride reagent in a solvent, adding a sodium hydroxide solution for mixing, and then adding hydrogen peroxide for reaction to obtain a hydroxyl-terminated conductive polymer;
(3) Mixing the hydroxyl-terminated conductive polymer obtained in the step (2) with sodium hydroxide solution in a solvent, adding carbon disulfide for reaction, and adding bromoalkane for reaction to obtain the chain transfer agent.
In the invention, the chain transfer agent is prepared by adopting the GRIM method.
Preferably, the conductive monomer in step (1) comprises pyrrole monomer and/or thiophene monomer.
Preferably, the pyrrole monomer has the structural general formula ofWherein R is 1 Selected from H or C3-C15 alkyl (e.g., C4, C6, C8, C10, C12 or C14 alkyl).
Preferably, the thiophene monomer has the structural general formula ofOr->Wherein R is 2 ~R 4 Each independently selected from H or C3-C12 alkyl (e.g., C4, C6, C8, C10 or C12 alkyl).
Preferably, the first grignard reagent in step (1) comprises R-MgX, wherein R is an alkyl group, X is a halogen, and further preferably any one or a combination of at least two of methyl magnesium chloride, phenyl magnesium bromide, tert-butyl magnesium bromide, isopropyl magnesium bromide or isopropyl magnesium chloride.
Preferably, the molar ratio of the first formative reagent to the conductive monomer in step (1) is 1:1.
Preferably, the solvent of step (1) comprises any one or a combination of at least two of tetrahydrofuran, benzene, toluene or n-hexane.
Preferably, the mass to volume ratio of the conductive monomer in the step (1) to the solvent in the step (1) is 1:5-15 (for example, 1:7, 1:9, 1:11 or 1:13, etc.), and the unit is g: mL.
Preferably, the catalytic initiator in step (1) is a metal nickel complex.
Preferably, the metal nickel complex comprises 1, 3-bis (diphenylpropane) nickel dichloride (Ni (dppe) Cl 2 ) And/or 1, 3-bis (diphenylpropane) nickel dibromide (Ni (dppe) Br) 2 ）。
Preferably, the molar ratio of the catalytic initiator to the conductive monomer in step (1) is 1 (30-55), such as 1:32, 1:34, 1:36, 1:38, 1:40, 1:42, 1:44, 1:46, 1:48, 1:50, 1:52, or 1:54, etc.
Preferably, the second grignard reagent of step (1) is a vinyl grignard reagent.
Preferably, the vinyl grignard reagent comprises vinyl magnesium bromide and/or vinyl magnesium chloride.
Preferably, the molar ratio of the second grignard reagent to the catalytic initiator in step (1) is (3-5): 1, for example 3.2:1, 3.4:1, 3.6:1, 3.8:1, 4:1, 4.2:1, 4.4:1, 4.6:1 or 4.8:1, etc.
Preferably, the temperature of the reaction in step (1) is room temperature.
Preferably, the reactions of step (1) are all carried out under nitrogen atmosphere.
Preferably, the step (1) specifically includes: under nitrogen atmosphere, adding a conductive monomer and a first Grignard reagent into a solvent, reacting for 3-5 h (such as 3.2 h, 3.4 h, 3.6 h, 3.8 h, 4 h, 4.2 h, 4.4 h, 4.6 h or 4.8 h, etc.) at room temperature, adding a catalytic initiator, continuing to react for 10-30 min (such as 12 min, 14 min, 16 min, 18 min, 20 min, 22 min, 24 min, 26 min or 28 min, etc.), adding a second Grignard reagent, continuing to react for 15-25 min (such as 16 min, 17 min, 18 min, 19 min, 20 min, 21 min, 22 min, 23 min or 24 min, etc.), adding methanol for quenching reaction after the reaction is completed, filtering and precipitating, adopting the solvent to dissolve, continuing to add methanol precipitation, circulating the operation for several times, and drying in a vacuum drying box to obtain the vinyl-terminated conductive polymer.
Preferably, the hydroboration agent of step (2) comprises 9-borobicyclo [3, 1 ]]-nonane (9-BBN), bis (3-methyl-2-butyl) boronAlkane (Sia) 2 BH), catechol Borane (CBH) or (1, 2-trimethylpropyl) borane (ThexylBH) 2 ) Any one or a combination of at least two of these.
Preferably, the molar ratio of the borohydride reagent to the vinyl-terminated conductive polymer in step (2) is (1.5-2.5): 1, for example, 1.7:1, 1.9:1, 2.1:1, or 2.3:1, etc.
Preferably, the solvent of step (2) comprises an ether solvent.
Preferably, the ether solvent comprises any one or a combination of at least two of tetrahydrofuran, diethylene glycol dimethyl ether, diethyl ether and dimethyl sulfide, and further preferably tetrahydrofuran.
Preferably, the volume to mass ratio of the solvent to the vinyl-terminated conductive polymer in the step (2) is (20-80): 1, for example, 30:1, 40:1, 50:1, 60:1 or 70:1, etc., with the unit of mL: g.
Preferably, the molar concentration of the sodium hydroxide solution in the step (2) is 3-8 mol/L, for example 4 mol/L, 5 mol/L, 6 mol/L or 7 mol/L, etc.
Preferably, the molar ratio of the sodium hydroxide solution to the borohydride reagent in the step (2) is (5-15): 1, for example, 7:1, 9:1, 11:1 or 13:1.
Preferably, the concentration of the hydrogen peroxide in the step (2) is 30%.
Preferably, the volume ratio of the sodium hydroxide solution to the hydrogen peroxide in the step (2) is 1:1.
Preferably, the reactions of step (2) are all carried out under nitrogen atmosphere.
Preferably, the step (2) specifically includes: dissolving the vinyl-terminated conductive polymer obtained in the step (1) in a solvent under a nitrogen atmosphere, adding a borohydride reagent, reacting for 12-24 hours (such as 14 h, 16 h, 18 h, 20 h or 22 h and the like) at 30-60 ℃ (such as 35 ℃, 40 ℃, 45 ℃, 50 ℃ or 55 ℃, and the like), adding a sodium hydroxide solution, stirring uniformly, cooling to room temperature, adding hydrogen peroxide, reacting for 6-12 hours at constant temperature (such as 7 h, 8 h, 9 h, 10 h or 11 h and the like) at 30-50 ℃ (such as 32 ℃, 34 ℃, 36 ℃, 38 ℃, 40 ℃, 42 ℃, 44 ℃, 46 ℃ or 48 ℃, and the like), precipitating the product in a mixed solvent of water and methanol, filtering, washing and filtering for multiple times by using methanol, and vacuum drying to obtain the hydroxyl-terminated conductive polymer.
Preferably, the molar concentration of the sodium hydroxide solution in the step (3) is 3-8 mol/L, for example 4 mol/L, 5 mol/L, 6 mol/L or 7 mol/L, etc.
Preferably, the molar ratio of the sodium hydroxide solution to the hydroxyl-terminated conductive polymer in the step (3) is (1-1.3): 1, for example, 1.05:1, 1.1:1, 1.15:1, 1.2:1, or 1.25:1, etc.
Preferably, the solvent of step (3) comprises an ether solvent.
Preferably, the ether solvent comprises any one or a combination of at least two of tetrahydrofuran, such as tetrahydrofuran, diethylene glycol dimethyl ether, diethyl ether or dimethyl sulfide.
Preferably, the volume to mass ratio of the solvent to the hydroxyl-terminated conductive polymer in the step (3) is (20-50): 1, for example, 25:1, 30:1, 35:1, 40:1 or 45:1, etc., with the unit of mL: g.
Preferably, the molar ratio of carbon disulfide to hydroxyl-terminated conductive polymer in step (3) is (1.2-1.5): 1, for example, 1.25:1, 1.3:1, 1.35:1, 1.4:1, or 1.45:1, etc.
Preferably, the bromoalkane of step (3) comprises any one or a combination of at least two of ethyl 2-bromopropionate, 2-bromopropionic acid, 2-bromobutyric acid, 2-bromoisobutyric acid, methyl 2-bromopropionate, methyl 2-bromobutyrate, ethyl 3-bromobutyrate, isopropyl 2-bromoisobutyrate or benzyl bromide.
Preferably, the molar ratio of bromoalkane to carbon disulfide in the step (3) is (1-1.5): 1, for example, 1.2:1, 1.3:1 or 1.4:1.
Preferably, the step (3) specifically includes: dissolving the hydroxyl-terminated polymer obtained in the step (2) in a solvent, adding a sodium hydroxide solution, stirring uniformly, recovering the room temperature, adding carbon disulfide, reacting for 2-5 hours (2.5 h, 3 h, 3.5 h, 4 h or 4.5 h, and the like) at 30-50 ℃ (for example, 32 ℃, 34 ℃, 36 ℃, 38 ℃, 40 ℃, 42 ℃, 44 ℃, 46 ℃ or 48 ℃ and the like), adding bromoalkane, reacting for 12-24 hours (for example, 14 h, 16 h, 18 h, 20 h or 22 h, and the like) at room temperature, precipitating by adopting a mixed solvent of water and methanol, washing and purifying for a plurality of times by using frozen methanol, and vacuum drying to obtain the chain transfer agent.
As a preferred technical scheme of the invention, the preparation method of the chain transfer agent comprises the following steps:
(1) Adding a conductive monomer and a first Grignard reagent into a solvent under a nitrogen atmosphere, reacting for 3-5 hours at room temperature, adding a catalytic initiator, continuously reacting for 10-30 minutes at room temperature, adding a second Grignard reagent, continuously reacting for 15-25 minutes at room temperature, adding methanol for quenching reaction after the reaction is completed, filtering and precipitating, dissolving by adopting the solvent, continuously adding methanol for precipitating, recycling the operation for several times, and drying in a vacuum drying box to obtain a vinyl-terminated conductive polymer;
(2) Dissolving the vinyl-terminated conductive polymer obtained in the step (1) in a solvent under the nitrogen atmosphere, adding a borohydride reagent, reacting for 12-24 hours at 30-60 ℃, adding a sodium hydroxide solution, stirring uniformly, cooling to room temperature, adding hydrogen peroxide, reacting for 6-12 hours at constant temperature of 30-50 ℃, precipitating the product in a mixed solvent of water and methanol after the reaction is finished, filtering, washing and filtering for many times by using methanol, and drying in vacuum to obtain the hydroxyl-terminated conductive polymer;
(3) And (3) dissolving the hydroxyl-terminated conductive polymer obtained in the step (2) in a solvent, adding a sodium hydroxide solution, stirring uniformly, recovering the normal temperature, adding carbon disulfide, reacting for 2-5 hours at 30-50 ℃, adding bromoalkane, reacting for 12-24 hours at room temperature, precipitating by adopting a mixed solvent of water and methanol, washing and purifying for several times by using frozen methanol, and vacuum drying to obtain the chain transfer agent.
Preferably, the molar ratio of chain transfer agent to vinyl pyrrolidone is 1 (80-250), such as 1:90, 1:100, 1:120, 1:140, 1:160, 1:180, 1:200, 1:220, or 1:240, etc.
As a preferable technical scheme of the invention, the mol ratio of the chain transfer agent to the vinyl pyrrolidone is defined as 1 (80-250), and the aim is to control the chain segment ratio of the chain transfer agent to the polyvinyl pyrrolidone, so as to regulate the hydrophilic and hydrophobic characteristics of the vinyl pyrrolidone segmented copolymer, and to obtain an effective self-assembled micelle effect in a solvent; if the molar ratio of the two is not within the above-defined range, the obtained vinyl pyrrolidone segmented copolymer cannot form effective self-assembled micelle in a solvent system, which is not beneficial to the subsequent growth regulation and control of silver nanowires.
Preferably, the mass ratio of the chain transfer agent to the solvent to the initiator is 1 (3-6): 0.01-0.05.
Wherein the mass ratio of the chain transfer agent to the solvent is 1:3.5, 1:4, 1:4.5, 1:5 or 1:5.5, etc.
The mass ratio of the chain transfer agent to the initiator is 1:0.015, 1:0.02, 1:0.025, 1:0.03, 1:0.035, 1:0.04 or 1:0.045, etc.
In a second aspect, the present invention provides a process for the preparation of a vinylpyrrolidone block copolymer according to the first aspect, the process comprising: and (3) reacting the vinyl pyrrolidone, a chain transfer agent, an initiator and a solvent to obtain the vinyl pyrrolidone block copolymer.
Preferably, the reaction time is 6-15 hours, such as 7 h, 8 h, 9 h, 10 h, 11 h, 12 h, 13 h or 14 h, etc.
Preferably, the temperature of the reaction is 60 to 90 ℃, for example 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, or the like.
As a preferred technical scheme of the invention, the preparation method of the vinyl pyrrolidone segmented copolymer comprises the following steps: and (3) after circularly vacuumizing and introducing nitrogen, reacting the vinyl pyrrolidone, a chain transfer agent, an initiator and a solvent for 6-15 hours at 60-90 ℃, precipitating by adopting a mixed solvent of acetone and n-hexane, washing and purifying for several times, and drying to obtain the vinyl pyrrolidone segmented copolymer.
In a third aspect, the present invention provides the use of a vinylpyrrolidone block copolymer as described in the first aspect as a capping agent.
In a fourth aspect, the present invention provides a silver nanowire, the silver nanowire being prepared from a starting material comprising a vinylpyrrolidone block copolymer according to the first aspect.
In the present invention, other preparation raw materials and preparation methods of the silver nanowires are not particularly limited, and may be prepared, for example, as follows:
(A1) Adding lithium chloride, potassium bromide and the vinyl pyrrolidone segmented copolymer according to the first aspect into ethylene glycol at normal temperature, stirring and dissolving to prepare a solution A;
dissolving silver nitrate in glycol, and stirring at room temperature to dissolve the silver nitrate to obtain a silver-containing solution B;
(A2) And (3) heating the solution A obtained in the step (A1) to 160-180 ℃ under the protection of proper nitrogen, dropwise adding the solution B obtained in the step (A1) into the solution A, controlling the dropwise adding time, naturally cooling and settling after the dropwise adding is completed for a period of time, centrifugally separating sediment, washing with ethanol and centrifuging for several times, and obtaining the silver nanowire.
In a fifth aspect, the present invention provides a silver nanowire transparent electrode, the material of which comprises silver nanowires as described in the third aspect.
Preferably, the silver nanowire transparent electrode is prepared by a method comprising: dispersing silver nanowires in solvents such as methanol or ethanol to prepare dispersion liquid, coating the dispersion liquid on the surface of a substrate, and drying to obtain the silver nanowire transparent electrode.
Compared with the prior art, the invention has the following beneficial effects:
the preparation raw materials of the vinyl pyrrolidone segmented copolymer comprise vinyl pyrrolidone, a chain transfer agent, an initiator and a solvent, the preparation raw materials of the chain transfer agent comprise conductive monomers, and the vinyl pyrrolidone segmented copolymer has excellent conductive characteristics by selecting the preparation raw materials to carry out RAFT chain extension reaction, so that the problem that contact resistance is increased when a conventional PVP (polyvinyl pyrrolidone) nanowire is coated into a transparent electrode can be effectively solved; meanwhile, the vinyl pyrrolidone segmented copolymer is an amphiphilic segmented copolymer and has good self-assembly characteristic, so that the preparation process of the silver nanowire can be effectively regulated and controlled when the vinyl pyrrolidone segmented copolymer is applied to preparation of the silver nanowire, and the silver nanowire with narrow diameter, high length-diameter ratio and uniform monodispersion characteristic can be obtained more easily.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Preparation example 1
A chain transfer agent, the method of preparation comprising the steps of:
(1) 50. 50 g (0.22 mol) are stirred under nitrogenAnd 0.22 mol of t-butylmagnesium bromide was added to 250 mL tetrahydrofuran, reacted at room temperature for 3 h, and 0.0044 mol of Ni (dppe) Cl was added 2 Catalytic initiator, continuously reacting for 10 min at room temperature, adding 0.0132 mol of ethylene magnesium bromide, continuously reacting for 15 min at room temperature, adding methanol for quenching reaction after the reaction is completed, filtering the precipitate, dissolving with tetrahydrofuran, continuously adding methanol for precipitation, recycling the operation for 3 times, and drying in a vacuum drying oven to obtain vinyl-terminated conductive polymer with the number of 3100 and the molecular weight distribution of 1.24;
(2) Adding 0.019 mol of 9-BBN into 0.8L tetrahydrofuran of the terminal vinyl conductive polymer obtained in the step (1) in the atmosphere of nitrogen, reacting 18 h at 30 ℃, adding 32 mL of 3M sodium hydroxide solution, uniformly stirring, cooling to room temperature, adding 32 mL of 30% hydrogen peroxide, reacting 8 h at the constant temperature of 40 ℃, precipitating the product in a mixed solvent of water and methanol after the reaction is finished, filtering, washing and filtering for multiple times by using methanol, and drying in vacuum to obtain the terminal hydroxyl conductive polymer;
(3) 30 g (0.0097 mol) of the hydroxyl-terminated conductive polymer obtained in the step (2) is dissolved in 0.6L tetrahydrofuran, 3.2 mL of 3M sodium hydroxide solution is added to be stirred uniformly, after the room temperature is restored, 0.013 mol of carbon disulfide is added, 5 h is reacted at 30 ℃, 0.013 mol of ethyl 2-bromopropionate is added to be reacted at room temperature, 12 h is reacted at room temperature, a mixed solvent of water and methanol is adopted for precipitation, the mixture is washed and purified for a plurality of times by using frozen methanol, and the chain transfer agent is obtained by vacuum drying.
Preparation example 2
A chain transfer agent, the method of preparation comprising the steps of:
(1) 50. 50 g (0.127 mol) are stirred under nitrogenAnd 0.127 mol of isopropyl magnesium bromide was added to 500 mL toluene, reacted at room temperature for 5 h, and 0.0042 mol of Ni (dppe) Br was added 2 Catalytic initiator, continuously reacting for 20 min at room temperature, adding 0.17 mol of ethylene magnesium chloride, continuously reacting for 20 min at room temperature, adding methanol for quenching reaction after the reaction is completed, filtering the precipitate, dissolving with toluene, continuously adding methanol for precipitation, recycling the operation for 3 times, and drying in a vacuum drying oven to obtain vinyl-terminated conductive polymer with the number of 6300 and the molecular weight distribution of 1.33;
(2) Under the nitrogen atmosphere, 40. 40 g (0.00064 mol) of the terminal vinyl conductive polymer obtained in the step (1) is added into 1.6L diethylene glycol dimethyl ether, and 0.013 mol of Sia is added 2 BH (basic oxygen furnace) is reacted at 50 ℃ for 15 h, 26 mL of 5M sodium hydroxide solution is added for stirring uniformly, cooling is carried out to room temperature, then 26 mL of 30% hydrogen peroxide is added for reacting at the constant temperature of 30 ℃ for 12 h, after the reaction is finished, the product is precipitated in a mixed solvent of water and methanol, and after filtration, methanol is used for washing and filtration for many times, and vacuum drying is carried out, so that hydroxyl-terminated conductive polymer is obtained;
(3) 30 g (0.0048 mol) of the hydroxyl-terminated conductive polymer obtained in the step (2) is dissolved in 1.2L diethylene glycol dimethyl ether, 0.9 mL of 6M sodium hydroxide solution is added to stir uniformly, after the temperature is restored to normal temperature, 0.0062 mol of carbon disulfide is added to react at 40 ℃ with 4 h, 0.0074 mol of ethyl 2-bromobutyrate is added to react at room temperature with 20 h, precipitation is carried out by adopting a mixed solvent of water and methanol, the mixture is washed and purified for a plurality of times by using refrigerated methanol, and vacuum drying is carried out, so that the chain transfer agent is obtained.
Preparation example 3
A chain transfer agent, the method of preparation comprising the steps of:
(1) 50. 50 g (0.167 mol) are reacted under nitrogenAnd 0.167 mol of t-butylmagnesium bromide was added to 500 mL tetrahydrofuran, reacted at room temperature for 4 h, and 0.0042 mol of Ni (dppe) Cl was added 2 As a catalytic initiator, continuing to react for 25 min at room temperature, adding 0.021 mol of ethylene magnesium bromide, continuing to react for 20 min at room temperature, adding methanol for quenching reaction after the reaction is finished, filtering the precipitate, dissolving with tetrahydrofuran, continuing to add methanol for precipitation, recycling the operation for 4 times, and drying in a vacuum drying oven to obtain the terminal vinyl conductive polymer with the number average molecular weight of 5200 and the molecular weight distribution of 1.28;
(2) Adding 0.019 mol of CBH into 2.4L tetrahydrofuran of the terminal vinyl conductive polymer obtained in the step (1) in the atmosphere of nitrogen, reacting 24. h at 40 ℃, adding 57 mL of 5M sodium hydroxide solution, uniformly stirring, cooling to room temperature, adding 57 mL of 30% hydrogen peroxide, reacting at the constant temperature of 40 ℃ for 10 h, precipitating the product in a mixed solvent of water and methanol after the reaction is finished, filtering, washing and filtering for multiple times by using methanol, and vacuum drying to obtain the terminal hydroxyl conductive polymer;
(3) 30 g (0.0058 mol) of the hydroxyl-terminated conductive polymer obtained in the step (2) is dissolved in 1.5L tetrahydrofuran, 1.4 mL of 5M sodium hydroxide solution is added to be stirred uniformly, after the room temperature is restored, 0.0081 mol of carbon disulfide is added to react at 50 ℃ for 3 h, 0.011 mol of 2-bromobutyric acid is added to react at room temperature for 24 h, a mixed solvent of water and methanol is adopted for precipitation, the mixture is used for washing and purification for a plurality of times by using frozen methanol, and the chain transfer agent is obtained by vacuum drying.
Preparation example 4
A chain transfer agent, the method of preparation comprising the steps of:
(1) 50. 50 g (0.15 mol) are reacted under nitrogenAnd 0.15 mol of t-butylmagnesium bromide was added to 750 mL tetrahydrofuran, reacted at room temperature for 4 h, and 0.0028 mol of Ni (dppe) Br was added 2 As a catalytic initiator, continuing to react for 30 min at room temperature, adding 0.0112 mol of ethylene magnesium bromide, continuing to react for 25 min at room temperature, adding methanol for quenching reaction after the reaction is finished, filtering the precipitate, dissolving with tetrahydrofuran, continuing to add methanol for precipitation, recycling the operation for 4 times, and drying in a vacuum drying oven to obtain the vinyl-terminated conductive polymer with the number average molecular weight of 8300 and the molecular weight distribution of 1.31;
(2) Adding 0.0097mol of 9-BBN into the vinyl-terminated conductive polymer 3.2L dimethyl sulfide obtained in the step (1) in the presence of nitrogen, reacting at 60 ℃ for 12 h, adding 12 mL of 8M sodium hydroxide solution, stirring uniformly, cooling to room temperature, adding 12 mL of 30% hydrogen peroxide, reacting at 50 ℃ for 6 h at constant temperature, precipitating the product in a mixed solvent of water and methanol after the reaction is finished, filtering, washing and filtering for multiple times by using methanol, and drying in vacuum to obtain the hydroxyl-terminated conductive polymer;
(3) 30 g (0.0036 mol) of the hydroxyl-terminated conductive polymer obtained in the step (2) is dissolved in 0.9L tetrahydrofuran, 0.6 mL of 6M sodium hydroxide solution is added to be stirred uniformly, after the room temperature is restored, 0.0054 mol of carbon disulfide is added to react at 60 ℃ with 2 h, 0.0081 mol of 2-bromobutyric acid is added to react at room temperature with 18 h, a mixed solvent of water and methanol is adopted to precipitate, the mixture is washed and purified for a plurality of times by using frozen methanol, and the chain transfer agent is obtained by vacuum drying.
Example 1
A vinyl pyrrolidone block copolymer, which is prepared by a process comprising: 60 g of N, N-dimethylamide, 20. 20 g (0.0065 mol) of a chain transfer agent (preparation example 1), 57.7 g (0.52 mol) of vinylpyrrolidone (NVP) and 0.2 g of azobisisobutyronitrile were added to a flask, the flask was evacuated and circulated three times by nitrogen gas and then sealed, reacted at 60℃for 12 h, precipitated with a mixed solvent of acetone and n-hexane, washed and purified several times, and dried to obtain the vinylpyrrolidone block copolymer.
Example 2
A vinyl pyrrolidone block copolymer, which is prepared by a process comprising: 100 g dimethyl sulfoxide, 20 g (0.0032 mol) of chain transfer agent (preparation 2), 53.3 g (0.48 mol) of vinylpyrrolidone (NVP) and 0.4 g azodiisovaleronitrile are added into a flask, the flask is vacuumized and sealed after being circulated by nitrogen for three times, the mixture is reacted at 70 ℃ for 15 h, the mixture is precipitated by adopting a mixed solvent of acetone and normal hexane, and the mixture is washed and purified for a plurality of times and dried, so that the vinylpyrrolidone segmented copolymer is obtained.
Example 3
A vinyl pyrrolidone block copolymer, which is prepared by a process comprising: 60 g of N-methylpyrrolidone, 20. 20 g (0.0038 mol) of a chain transfer agent (preparation example 3), 84.4 g (0.76 mol) of vinylpyrrolidone (NVP) and 1 g of dimethyl azodiisobutyrate were added to a flask, the flask was evacuated and circulated three times by nitrogen, then sealed, reacted at 80℃for 10 h, precipitated with a mixed solvent of acetone and N-hexane, washed and purified several times, and dried to obtain the vinylpyrrolidone block copolymer.
Example 4
A vinyl pyrrolidone block copolymer, which is prepared by a process comprising: 120 g of N, N-dimethylamide, 20. 20 g (0.0024 mol) of a chain transfer agent (preparation example 4), 66.6 g (0.6 mol) of vinylpyrrolidone (NVP) and 0.5. 0.5 g of azobisisobutyronitrile were added to a flask, the flask was evacuated and circulated three times with nitrogen gas and then sealed, 6 h was reversed at 90℃and precipitation was carried out with a mixed solvent of acetone and n-hexane, and washing and purification were carried out several times, and drying was carried out to obtain the vinylpyrrolidone block copolymer.
Example 5
A vinylpyrrolidone block copolymer differing from example 1 only in that the amount of vinylpyrrolidone added was 1 mol, and the other components, amounts and preparation methods were the same as in example 1.
Example 6
A vinylpyrrolidone block copolymer differing from example 1 only in that the addition amount of vinylpyrrolidone was 0.2 mol, and the other components, amounts and preparation methods were the same as in example 1.
Comparative example 1
Polyvinylpyrrolidone (PVP) from Shanghai Geon, brand PVP-K30.
Application example 1
A silver nanowire, the preparation method comprising the steps of:
(1) At normal temperature, adding 0.1 g lithium chloride, 0.015 g potassium bromide and 15 g vinyl pyrrolidone block copolymer (example 1) into 500 g glycol, stirring and dissolving to prepare a solution A;
dissolving 8.5. 8.5 g silver nitrate in 50 g ethylene glycol, and stirring at room temperature to obtain silver-containing solution B;
(2) And (3) heating the solution A obtained in the step (1) to 170 ℃ under the protection of proper nitrogen, dropwise adding the solution B obtained in the step (1) for 30 min, naturally cooling and settling after the dropwise adding is completed and the reaction is continued for 60 min, centrifugally separating sediment, washing with ethanol, centrifuging for several times, and storing the obtained silver nanowires in ethanol.
Application examples 2 to 6
The silver nanowires are different from application example 1 only in that the vinylpyrrolidone block copolymers obtained in examples 2 to 6 are respectively used for replacing the vinylpyrrolidone block copolymer obtained in example 1, and other components, amounts and preparation methods are the same as application example 1.
Comparative application example 1
A silver nanowire differing from application example 1 only in that PVP obtained in comparative example 1 was used instead of the vinylpyrrolidone block copolymer obtained in example 1, and other components, amounts and preparation methods were the same as those of application example 1.
Performance test:
1. test for preparation example:
(1) Number average molecular weight and dispersion index: the molecular weight and the dispersion index of a chain transfer agent product are detected by using a Shimadzu gel permeation chromatography GPC, DMF with 0.1 mmol LiBr as a mobile phase, the flow rate is 1.0 mL/min, the column temperature is 50 ℃, a polymer matrix filler water-soluble chromatographic column and PEG/PEO are used as standard substances.
The vinyl-terminated conductive polymer obtained in the step (1) of preparation examples 1-4 is tested by the test method (1), and the test results are shown in table 1:
TABLE 1
The hydroxyl-terminated conductive polymer obtained in the step (2) and the chain transfer agent finally obtained in the preparation example of the present invention are treated with the terminal groups of the ethyl-terminated conductive polymer, and thus, the three have little change in molecular weight.
2. Test for application example:
(2) Diameter, length and aspect ratio: the diameter and length of the silver nanowires were tested by SEM (korea COXEM EM-30 Plus), and the measurement average value of 100 silver nanowires was taken;
(3) Yield: ratio of actual product mass to theoretical yield.
The silver nanowires obtained in application examples 1 to 6 and comparative application example 1 were tested according to the above test methods (2) to (3), and the test results are shown in table 2:
TABLE 2
As can be seen from the data in table 2:
the average diameter of the silver nanowires provided in application examples 1-4 is 23.11-27.89 nm, the length is 28.11-31.55 mu m, the length-diameter ratio is 1099-1224, and the yield is 83.2-86.9%; and the silver nanowire prepared by adopting PVP to replace the vinyl pyrrolidone segmented copolymer as the end capping agent in the comparative application example 1 has the advantages of thicker diameter, shorter length, lower length-diameter ratio and very low yield.
As can be seen from comparing the data of application examples 1 and 5-6, the vinyl pyrrolidone block copolymer prepared by using vinyl pyrrolidone and chain transfer agent in different molar ratios can also affect the length, diameter and yield of silver nanowires.
3. Respectively precipitating and dispersing the silver nanowires obtained in application examples 1-6 and comparative application example 1 in an ethanol solvent to prepare a dispersion liquid of 2.5 mg/mL, respectively coating the obtained dispersion liquid on the surface of a substrate formed by a PET film of 10X 5 cm by adopting a cold-pressing linear Meyer rod, and drying at 120 ℃ for 1 min to obtain a transparent electrode film sample of the silver nanowires to be detected;
(4) Haze: under the irradiation of a standard c light source, adopting a Shanghai Shen Guang instrument and meter WGT-S type transmissivity/haze meter to measure the haze of the silver nanowire transparent electrode film
(5) Sheet resistance: and testing the square resistance of the electrode film by adopting four probes.
Tests were performed according to the above test methods (4) and (5), and the test results are shown in table 3:
TABLE 3 Table 3
From the data in table 3, it can be seen that:
the haze of the transparent electrode film of the silver nanowire prepared by the silver nanowire provided in application examples 1-4 is 0.22-0.3%, the sheet resistance is 18.5-21.3 omega/sq, and the haze of the transparent electrode film of the silver nanowire prepared by the silver nanowire provided in comparative application example 1 is as high as 1.85%, and the sheet resistance is as high as 385 omega/sq.
Further comparing the data of application examples 1 and application examples 5 to 6, it can be seen that the haze and sheet resistance of the transparent electrode film of silver nanowire prepared from the silver nanowire obtained in application examples 5 to 6 are also increased, which indicates that the vinyl pyrrolidone and chain transfer agent with different molar ratios affect the performance of the final transparent electrode film of silver nanowire.
The applicant states that the present invention is illustrated by the above examples as a vinylpyrrolidone block copolymer and a process for its preparation and use, but the present invention is not limited to the above examples, i.e. it is not meant that the present invention must be practiced by relying on the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.

Claims (9)

1. The vinyl pyrrolidone block copolymer is characterized in that the raw materials for preparing the vinyl pyrrolidone block copolymer comprise vinyl pyrrolidone, a chain transfer agent, an initiator and a solvent;
the preparation raw materials of the chain transfer agent comprise conductive monomers;
the chain transfer agent is prepared by a method comprising the steps of:
(1) Reacting a conductive monomer with a first Grignard reagent in a solvent, adding a catalytic initiator to react, adding a second Grignard reagent to react, and quenching to obtain a vinyl-terminated conductive polymer;
(2) Reacting the vinyl-terminated conductive polymer obtained in the step (1) with a borohydride reagent in a solvent, adding a sodium hydroxide solution for mixing, and then adding hydrogen peroxide for reaction to obtain a hydroxyl-terminated conductive polymer;
(3) Mixing the hydroxyl-terminated conductive polymer obtained in the step (2) with a sodium hydroxide solution in a solvent, adding carbon disulfide to react, and then adding any one or a combination of at least two of ethyl 2-bromopropionate, 2-bromopropionic acid, 2-bromobutyric acid, 2-bromoisobutyric acid, methyl 2-bromopropionate, methyl 2-bromobutyrate, ethyl 3-bromobutyrate, isopropyl 2-bromoisobutyrate or benzyl bromide to react to obtain the chain transfer agent;
the conductive monomer in the step (1) comprises pyrrole monomer and/or thiophene monomer;
the first Grignard reagent in the step (1) comprises R-MgX, wherein R is alkyl, and X is halogen;
the second grignard reagent in the step (1) is a vinyl grignard reagent;
the structural general formula of the pyrrole monomer isWherein R is 1 Selected from H or C3-C15 alkyl;
the structural general formula of the thiophene monomer isOr->Wherein R is 2 ~R 4 Each independently selected from H or C3-C12 alkyl.
2. The vinylpyrrolidone block copolymer of claim 1, wherein the initiator comprises an azo-based initiator, and the solvent is a RAFT polymerization solvent.
3. The vinyl pyrrolidone block copolymer of claim 1, wherein the molar ratio of chain transfer agent to vinyl pyrrolidone is 1 (80-250).
4. The vinyl pyrrolidone block copolymer according to claim 1, wherein the mass ratio of the chain transfer agent, the solvent and the initiator is 1 (3-6): 0.01-0.05.
5. A method for preparing a vinylpyrrolidone block copolymer according to any one of claims 1 to 4, comprising: and (3) reacting the vinyl pyrrolidone, a chain transfer agent, an initiator and a solvent to obtain the vinyl pyrrolidone block copolymer.
6. The preparation method according to claim 5, wherein the reaction time is 6-15 hours and the temperature is 60-90 ℃.
7. Use of a vinylpyrrolidone block copolymer according to any one of claims 1 to 4 as a capping agent.
8. A silver nanowire, characterized in that a preparation raw material of the silver nanowire comprises the vinyl pyrrolidone block copolymer according to any one of claims 1 to 4.
9. A silver nanowire transparent electrode, characterized in that the material of the silver nanowire transparent electrode comprises the silver nanowire according to claim 8.
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