Novel free radical monomer containing diphenylamine structure and preparation method and application of polymer thereof
阅读说明：本技术 一种含二苯胺结构的新型自由基单体及其聚合物制备方法和用途 (Novel free radical monomer containing diphenylamine structure and preparation method and application of polymer thereof ) 是由 董丽杰 熊宇风 袁野 欧颖 张扬 琚艳云 于 2019-11-21 设计创作，主要内容包括：本发明公开了一种含二苯胺结构的新型自由基单体及其聚合物制备方法和用途,以二苯胺为原料制备含二苯胺结构的新型自由基材料；本发明自由基单体的合成方法工艺简单,产率高,纯化容易,适于工业生产。将所得的自由基化合物单体溶于氯仿中,加入物质的量为单体2～5倍的无水三氯化铁作为氧化剂,在保护气氛下通过氧化聚合反应制备得到含有聚二苯胺骨架的自由基聚合物。聚合物主链拥有较好的导电性,相对于其他的自由基聚合物材料拥有较好的倍率性能及循环稳定性,该自由基聚合物电池的理论比容量相对于单电子反应的其他自由基聚合物有较大的提高。(The invention discloses a novel free radical monomer containing a diphenylamine structure, a preparation method of a polymer thereof and application thereof, wherein diphenylamine is used as a raw material to prepare a novel free radical material containing the diphenylamine structure; the synthesis method of the free radical monomer has the advantages of simple process, high yield and easy purification, and is suitable for industrial production. Dissolving the obtained free radical compound monomer in chloroform, adding anhydrous ferric trichloride of which the amount of the substance is 2-5 times of that of the monomer as an oxidant, and carrying out oxidative polymerization reaction under a protective atmosphere to obtain the free radical polymer containing the polydianiline skeleton. The polymer main chain has better conductivity, has better rate performance and cycle stability compared with other free radical polymer materials, and the theoretical specific capacity of the free radical polymer battery is greatly improved compared with other free radical polymers in single electron reaction.)
1. A novel free radical monomer and polymer containing diphenylamine structure is characterized in that,
the structural general formula of the free radical monomer is as follows:
the structural general formula of the free radical polymer is as follows:
wherein Ar is1Selected from any one of the following structural formulas:
wherein Ar is2Selected from any one of the following structural formulas:
wherein R is a free radical selected from any one of the following structural formulas:
2. a process for preparing a novel free radical monomer containing a diphenylamine structure as claimed in claim 1, wherein the reaction is carried out according to the following chemical equation:
comprises the following steps:
(A1) utilizing active hydrogen on N atom in diphenylamine monomer and containing a halogen atomAnd one nitro-substituted Ar1Carrying out Ullmann coupling reaction on the monomer to obtain a monomer 1;
(A2) reducing the monomer 1 in the step (A1) to obtain a monomer 2;
(A3) reacting the monomer 2 of step (A2) with Ar having a halogen atom and a nitro group2Carrying out Ullmann coupling reaction on the monomer to obtain a monomer 3;
(A4) reducing the monomer 3 in step (a3) to obtain monomer 4;
(A5) carrying out amidation reaction on the monomer in the step (A4) and a carboxyl compound corresponding to the free radical R to prepare a novel free radical monomer containing a diphenylamine structure, wherein the novel free radical monomer is shown in a structural general formula I;
wherein the content of the first and second substances,
3. the process for preparing a novel radical monomer containing a diphenylamine structure as claimed in claim 2, wherein: the step (A1) is carried out by substituting Ar with one halogen atom and one nitro group in N, N-dimethylformamide1And diphenylamine are used as raw materials, the reaction is carried out under the action of a sodium hydride or cesium fluoride hydrogen-removing reagent through hydrogen-removing reaction, and after the reaction is carried out for 10-15 hours, a product is separated and purified through column chromatography to obtain a monomer 1 compound.
4. The process for preparing a novel radical monomer containing a diphenylamine structure as claimed in claim 2, wherein: and (A2) taking the compound with the structural general formula of the monomer 1 as a raw material, taking reduced iron powder or hydrazine hydrate as a reducing agent, heating to 80 ℃ in a mixed solvent of water and ethanol in which ammonium chloride is dissolved in the mixed solvent under the atmosphere of nitrogen, carrying out reduction reaction on nitro groups for 10-15 hours, and recrystallizing, separating and purifying the product by using ethanol or acetonitrile to obtain the amino compound with the structural general formula of the monomer 2.
5. The process for preparing a novel radical monomer containing a diphenylamine structure as claimed in claim 2, wherein: and (A4) taking a compound with a structural general formula of a monomer 3 as a raw material, taking reduced iron powder or hydrazine hydrate as a reducing agent, heating to 80 ℃ in a mixed solvent of water and ethanol in which ammonium chloride is dissolved in a nitrogen atmosphere, carrying out reduction reaction on nitro groups for 10-15 hours, and recrystallizing the product with ethanol or acetonitrile to obtain the diamine compound with the structural general formula of a monomer 4.
6. The process for preparing a novel radical monomer containing a diphenylamine structure as claimed in claim 2, wherein: specifically, the diamine compound with the structural general formula of the initiating monomer 4 and the carboxyl compound corresponding to the free radical R are subjected to amidation reaction, a commonly used catalytic system selects DCC/DMAP, HOBT/DIEA and HATU/DIC, the mixture is stirred for 24-36 hours at normal temperature under a protective atmosphere, and the product is separated and purified by column chromatography to obtain a corresponding free radical compound monomer; the molar ratio of the diamine compound with the structural general formula of the monomer 4, the carboxyl compound corresponding to R, the dehydrating agent and the 4-dimethylamino pyridine compound is 1:1-2:1.2-2.4: 0.1-0.5; the solvent of the reaction is dichloromethane, and the novel free radical monomer containing the diphenylamine structure shown in the structural general formula I is obtained.
7. A process for the preparation of a novel radical polymer containing diphenylamine structures as claimed in claim 1, wherein the reaction has the general formula:
the method comprises the following steps of dissolving a free radical compound monomer I into chloroform, adding anhydrous ferric chloride with the amount of 3-4 times of that of the monomer as an oxidant, and carrying out oxidative polymerization for 12-24 hours at 30 ℃ under the protection of nitrogen to obtain the novel free radical polymer II containing the diphenylamine structure as claimed in claim 1.
8. Use of a novel radical polymer containing diphenylamine structures as claimed in claim 1, characterized in that: mixing the free radical polymer, a conductive agent and a binder in DMF to prepare anode slurry; wherein the mass content of the free radical polymer in the positive electrode slurry is 20-85%, preferably 50-70%; the mass content of the conductive agent is 20-85%, preferably 25-45%; the mass content of the binder is 5-25%, preferably 10%; and uniformly coating the anode slurry on an aluminum foil attached with conductive carbon black, then drying in vacuum, and assembling the cathode, the diaphragm and the organic electrolyte into the button lithium ion battery.
9. Use of a novel radical polymer containing diphenylamine structures as claimed in claim 8, characterized in that: the negative electrode material adopts a metal lithium sheet; the current collector of the negative electrode adopts foamed nickel; the diaphragm is a PP film or a PE film; the organic electrolyte is 1mol/L LiPF6EC/DMC, wherein the volume ratio of LiPF6EC to DMC is 1: 1.
Technical Field
The invention relates to the field of material science, in particular to a novel free radical monomer containing a diphenylamine structure and a preparation method of a polymer thereof. The monomer can be used for synthesizing functionalized polymers such as poly-diphenylamine and the like, and particularly relates to preparation and application of a free radical polymer battery material.
Background
Lithium ion batteries, as an important energy storage device, have been widely used in portable consumer electronics, electric vehicles, and hybrid electric vehicles, and the growing applications of electric storage not only require that electrochemical batteries have sufficient energy density, but also impose certain requirements on their price, material sustainability, and environmental hazards. The conventional positive active material of the lithium ion battery usually uses transition metal oxides such as LiCoO2, and has the disadvantages of low energy density (energy density) and discharge capacity (power capacity), difficulty in rapid charge and discharge, short cycle, high price, toxicity, easy combustion, explosion, poor battery safety and the like. Organic electrode materials have higher theoretical capacity, environmental friendliness, renewability, and abundant resources compared to these inorganic electrode materials, and in order to realize such new battery technologies, there has recently been a great interest in developing naturally abundant and redox-active organic materials for constructing all-organic rechargeable batteries.
Organic Radical Batteries (ORB) are a new type of rechargeable batteries using stable Organic Radical polymers as electrode active materials, and compared with lithium ion batteries which are widely used at present, Radical polymer batteries have the advantages of rapid charge and discharge, good stability, high power density and energy density, long cycle life, easy processing, designable structure, safety, environmental protection and the like. In addition, the organic radical polymer can be prepared into a thin film battery. Recently, some free radical polymers with pendant nitroxide groups have been found to have bipolar (p-and n-dopable) redox activity and have been successfully applied to all-organic rechargeable batteries. In principle, electroactive polymers can have a broad potential similar to inorganic electrode materials, and even have a higher redox capacity than inorganic electrode materials. There are several possible ways to develop an ORB with high energy density in the prior art: firstly, the specific capacity of the material is obviously improved by increasing the effective free radical density and reducing the molecular weight of a structural unit, so that a novel electrode material with high energy density is obtained; secondly, strong electron-attracting (repelling) groups are introduced near the free radical sites to remarkably adjust the oxidation-reduction potential, positive and negative electrode materials suitable for application requirements are designed, and a secondary battery system with higher working voltage can be constructed; thirdly, stable free radicals are grafted on the main chain of the conductive polymer to improve the high-rate charge and discharge capacity. Therefore, the conjugated polymer main chain structure with high electron transport capacity can be designed to effectively improve the electron transfer and generation speed of the materials and improve the density of effective free radicals to improve the specific capacity of the battery, which is of great significance for manufacturing novel all-organic batteries with higher energy density.
Disclosure of Invention
Based on the defects of the prior art, the technical problem solved by the invention is to provide a novel free radical monomer containing a diphenylamine structure, a preparation method and application of the polymer, and the novel free radical monomer containing the diphenylamine structure and the polymer thereof can be used for synthesizing polymers such as functionalized polydianiline and have very high energy density.
In order to solve the above technical problems, the present invention provides a novel radical monomer and polymer containing diphenylamine structure, characterized in that,
the structural general formula of the free radical monomer is as follows:
the structural general formula of the free radical polymer is as follows:
wherein Ar is1Selected from any one of the following structural formulas:
wherein Ar is2Selected from any one of the following structural formulas:
wherein R is a free radical selected from any one of the following structural formulas:
a process for preparing the novel free radical monomer containing diphenylamine structure as claimed in claim 1, by reacting according to the following chemical equation:
comprises the following steps:
(A1) utilizes active hydrogen on N atom in diphenylamine monomer and Ar substituted by halogen atom and nitro1Carrying out Ullmann coupling reaction on the monomer to obtain a monomer 1;
(A2) reducing the monomer 1 in the step (A1) to obtain a
(A3) reacting the
(A4) reducing the
(A5) carrying out amidation reaction on the monomer in the step (A4) and a carboxyl compound corresponding to the free radical R to prepare a novel free radical monomer containing a diphenylamine structure, wherein the novel free radical monomer is shown in a structural general formula I;
wherein the content of the first and second substances,
as the optimization of the technical proposal, the novel free radical monomer containing diphenylamine structure and the preparation method of the polymer thereof further comprise part or all of the following technical characteristics:
as an improvement of the above technical scheme, the step (A1) is that Ar substituted by one halogen atom and one nitro in N, N-Dimethylformamide (DMF)1And diphenylamine are used as raw materials, the reaction is carried out under the action of a sodium hydride or cesium fluoride hydrogen-removing reagent through hydrogen-removing reaction, and after the reaction is carried out for 10-15 hours, a product is separated and purified through column chromatography to obtain a monomer 1 compound. The column chromatography separation and purification product is purified by using a mixed solution of dichloromethane and normal hexane as a mobile phase and silica gel as a stationary phase as column chromatography.
In the step (a2), the compound of the structural general formula of the monomer 1 is used as a raw material, reduced iron powder or hydrazine hydrate is used as a reducing agent, the mixture is heated to 80 ℃ in a mixed solvent of water and ethanol in which ammonium chloride is dissolved under the nitrogen atmosphere, the reduction reaction of the nitro group is carried out for 10 to 15 hours, and the product is recrystallized, separated and purified by ethanol or acetonitrile to obtain the amino compound of the structural general formula of the
In the step (a4), a compound of the general structural formula of the
As an improvement of the above technical scheme, the step (a5) is specifically that diamine compounds of the structural general formula of the initiation monomer 4 are respectively subjected to amidation reaction with carboxyl compounds corresponding to the free radicals R, a commonly used catalytic system is selected from DCC/DMAP, HOBT/DIEA and HATU/DIC, the mixture is stirred at normal temperature for 24-36 hours under a protective atmosphere, and the product is separated and purified by column chromatography to obtain corresponding free radical compound monomers; the molar ratio of the diamine compound with the structural general formula of the monomer 4, the carboxyl compound corresponding to R, the dehydrating agent and the 4-dimethylamino pyridine compound is 1:1-2:1.2-2.4: 0.1-0.5; the solvent of the reaction is dichloromethane, and the novel free radical monomer containing the diphenylamine structure shown in the structural general formula I is obtained.
A process for preparing the novel radical polymers containing diphenylamine structure according to claim 1, of the general formula:
the method comprises the following steps of dissolving a free radical compound monomer I into chloroform, adding anhydrous ferric chloride with the amount of 3-4 times of that of the monomer as an oxidant, and carrying out oxidative polymerization for 12-24 hours at 30 ℃ under the protection of nitrogen to obtain the novel free radical polymer II containing the diphenylamine structure as claimed in claim 1.
The application of the novel free radical polymer containing the diphenylamine structure is characterized in that the free radical polymer, a conductive agent and a binder are mixed in DMF to prepare positive electrode slurry; wherein the mass content of the free radical polymer in the positive electrode slurry is 20-85%, preferably 50-70%; the mass content of the conductive agent is 20-85%, preferably 25-45%; the mass content of the binder is 5-25%, preferably 10%; and uniformly coating the anode slurry on an aluminum foil attached with conductive carbon black, then drying in vacuum, and assembling the cathode, the diaphragm and the organic electrolyte into the button lithium ion battery.
As the optimization of the technical proposal, the novel free radical monomer containing diphenylamine structure and the application of the polymer thereof further comprise part or all of the following technical characteristics:
as an improvement of the technical scheme, the negative electrode material adopts a metal lithium sheet; the current collector of the negative electrode adopts foamed nickel; the diaphragm is a PP film or a PE film; the organic electrolyte is 1mol/LLIPF6EC/DMC, wherein the volume ratio of LiPF6EC to DMC is 1: 1.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
the synthesis method of the novel free radical monomer containing the diphenylamine structure has the advantages of simple process, high yield and easy purification, thereby being suitable for industrial production. Dissolving the obtained free radical compound monomer in chloroform, adding anhydrous ferric trichloride of which the amount of the substance is 2-5 times of that of the monomer as an oxidant, and carrying out oxidative polymerization reaction under a protective atmosphere to obtain the free radical polymer containing the polydianiline skeleton. The designed and synthesized free radical polymer has four active sites, namely diphenylamine taking nitrogen as a center and nitroxide radicals in two R groups, so that the redox capability of the polymer is improved, and the theoretical specific capacity of the free radical polymer battery is greatly improved compared with other free radical polymers in single electron reaction.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical means of the present invention more clearly understood, the present invention may be implemented in accordance with the contents of the description, and in order to make the above and other objects, features, and advantages of the present invention more clearly understood, the following detailed description is given in conjunction with the preferred embodiments.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings of the embodiments will be briefly described below.
FIG. 1 shows the preparation of the radical monomer N1, N1-bis (4-aminophenyl) -N4, N4-diphenylbezene-1, 4-diamine-PROXYL of example 11H-NMR nuclear magnetic resonance spectrum;
FIG. 2 is a mass spectrum of the radical monomer N1, N1-bis (4-aminophenyl) -N4, N4-diphenylbenzene-1,4-diamine-PROXYL of example 1;
FIG. 3 is an SEM photograph of the poly-N1, N1-bis (4-aminophenyl) -N4, N4-diphenyl benzizene-1, 4-diamine-PROXYL synthesized in example 1 complexed with carbon nanotubes;
FIG. 4 is an initial charge/discharge curve of a half-cell in which poly-N1, N1-bis (4-aminophenyl) -N4, N4-diphenyl benzizene-1, 4-diamine-PROXYL synthesized in example 1 was used as a cathode and metallic lithium was used as an anode.
Detailed Description
Other aspects, features and advantages of the present invention will become apparent from the following detailed description, which, when taken in conjunction with the drawings, illustrate by way of example the principles of the invention.
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