CN103952795A - Lead core structure polyaniline/graphene composite nanometer fiber material preparation method - Google Patents

Abstract

Preparation method of polyaniline/graphene composite nanofiber material with lead core structure. Among organic polymer blue light materials, organic polyalkylfluorene is used as a device made of blue light material. The biggest defect is that the stability of the material decreases when the device works for a long time or is heated. The way to overcome this problem is to improve the material. Aging resistance, carrier transport and heat transfer performance, thereby improving the color purity retention time of the device. The method of the present invention comprises: the obtained soluble graphene is used as the core layer, polyaniline is used as the shell layer, and the polyaniline/graphene composite nanofiber material with lead core structure is prepared by high-voltage electrospinning technology by means of a sleeve type device, and the Composite nanofiber materials are used to make photoluminescent and electroluminescent devices. The invention is used for aniline monomer, polyaniline, graphene oxide and graphene nanofiber materials, manufacturing methods and applications.

Description

Preparation method of polyaniline/graphene composite nanofiber material with lead core structure

Technical field:

The invention relates to a triarylamine-fluorene copolymer and graphene composite nanofiber material with an aryl ether substituent in a lead core structure, a preparation method and an application.

Background technique:

In 1969, S.K. Deb first used amorphous WO ₃ Preparation of electrochromic devices, through gold electrodes to WO ₃ Film applied voltage, WO ₃ The film turns blue from the negative electrode, changing the voltage polarity, WO ₃ The film fades from the positive electrode. This pioneering work has aroused great interest in electrochromic research.

Electrochromism refers to the visible reversible color change that occurs when the color-changing material undergoes redox reaction ion doping under an applied electric field. Electrochromic devices have the characteristics of color tunability and low operating voltage, and have great application value in electrochromic displays, smart windows, and camouflage. Recent research has progressed from discoloration in the near-infrared to microwave range, developing applications in the fields of optical communications, data storage, and thermal control of buildings to increase or decrease heat.

Although the early electrochromic devices were mainly based on inorganic oxides, organic materials have attracted more and more attention because of their better color tunability, high color contrast, fast response time, and solution film-forming processing. Graphene shows certain application prospects in the fields of optoelectronic devices and electrode materials due to its unique two-dimensional plane and electronic structure and excellent performance. Graphene and its derivatives have the characteristics of large specific surface area and easy modification, which are suitable for the development of high-performance composite materials. The invention combines the graphene and the triarylamine polymer organically through the high-voltage electrospinning technology, and the introduction of the graphene further promotes the electron collection and transmission of the triarylamine polymer electroluminescent material.

Invention content:

The purpose of the present invention is to synthesize a triarylamine monomer with an aryl ether substituent, and utilize the monomer to copolymerize with fluorene to form a polyaniline; utilize high-voltage electrospinning technology to provide a lead-core structure polyaniline/graphene Preparation method of composite nanofiber material.

The purpose of the present invention is achieved like this:

A method for preparing a polyaniline/graphene composite nanofiber material with a lead core structure. The obtained soluble graphene is used as the core layer, and polyaniline is used as the shell layer. With the help of a sleeve-type device, a lead is prepared by high-voltage electrospinning technology. A polyaniline/graphene composite nanofiber material with a core structure, and making the composite nanofiber material into photoluminescent and electroluminescent devices.

The preparation method of the lead-core structure polyaniline/graphene composite nanofiber, the first step: dissolving the polyaniline in a solvent, and poly[2,7-(9,9-dioctylfluorene) -alternating-N-phenyl-N-(4-phenoxyphenyl)aniline] dissolved in toluene or tetrahydrofuran solvent, the content is 1.0～12.0% (wt.%); the second step: the soluble graphite The concentration of ethanol or aqueous solution of alkene is 0.5-6.0% (wt.%). With the help of a cannulated needle, use a micro-injection pump to control the flow rate ratio of the two solutions to 1:0.2-1:3.0, polyaniline: graphene, Among them, the polyaniline solution is used as the shell layer, and the graphene solution is used as the core or core layer; the third step: under the condition of 18-30°C, use high-voltage electrospinning technology to adjust the spinning voltage to 10-30kV, and the emitting electrode and receiving electrode The distance between the electrodes is 8-23 cm, and the lead-core structure polyaniline/graphene composite nanofiber material can be obtained on the receiving electrode.

The preparation method of the lead-core structure polyaniline/graphene composite nanofiber material, the polyaniline is polyaniline containing phenoxy triphenylamine structure, and its preparation method is to purify the obtained phenoxy-containing triphenylamine Monomer (Mon) and further polymerization to obtain poly[2,7-(9,9-dioctylfluorene)-alternating-N-phenyl-N-(4-phenoxyphenyl)aniline]; the specific steps are : With refined toluene as solvent, 1mmol triphenylamine monomer is added to toluene at a ratio of 10-25mL, using 9,9-dioctylfluorene-2,7-diboronic acid cis(1,3-propanediol) ester and phenoxy The triphenylamine is added according to the molar ratio of 1:1.0～1:1.05; the palladium catalyst Pd(PPh 3 ) 4 is added in a weight ratio of 1:25～1:30, and the palladium _catalyst Pd ₍ PPh ₃ ) ₄ and The ratio of 9,9-dioctylfluorene-2,7-diboronic acid cis(1,3-propanediol) ester is 1:25~1:30, add 2.5~3.0M sodium carbonate solution equal to the volume of toluene, Under the protection of high-purity argon or nitrogen, polyaniline containing phenoxytriphenylamine structure was prepared by Suzuki coupling reaction .

The preparation method of the lead-core structure polyaniline/graphene composite nanofiber material, the preparation process of the soluble graphene: prepare graphite oxide by weighing reagents such as flake graphite, concentrated sulfuric acid, phosphoric acid, potassium permanganate and hydrogen peroxide ene; use the above-mentioned graphene oxide to prepare a graphene oxide aqueous solution with a concentration of 8mg mL-1; take 26mL of the graphene oxide aqueous solution and add it to a three-necked bottle, and add 1mL of TGA under heating and stirring conditions for redox. The aqueous solution of graphene (T-RGO) can be obtained after 2-3 hours; add 200 μL of ammonia water dropwise into the above graphene aqueous solution, sonicate for more than 10 minutes, add 0.4 g of hydroxylamine hydrochloride under heating and stirring conditions, and react for 2 hours to obtain Graphene, cleaning standby; The ratio of the volume of described concentrated sulfuric acid and the mass of flake graphite is 4mL:1g～6mL:1g, the volume ratio of described concentrated sulfuric acid and phosphoric acid is 8:1～10:1, described The mass ratio of potassium permanganate and flake graphite is 7:1～8:1, the volume ratio of described deionized water and concentrated sulfuric acid is 4:1～6:1, the volume ratio of described concentrated sulfuric acid and hydrogen peroxide The ratio is 1:1-3:1, the mass concentration of hydrogen peroxide is 25-35%, the stirring speed is 200-300rpm, and the heating temperature is 80-85°C.

The preparation method of the described lead structure polyaniline/graphene composite nanofiber material, the chemical formula of the described phenoxy-containing polyaniline polymer is poly[2,7-(9,9-dioctylfluorene)- Alternate-N-phenyl-N-(4-phenoxyphenyl) aniline], the number average molecular weight of the polymer is 13,302-31,235 .

The device prepared by the preparation method of the lead-core structure polyaniline/graphene composite nanofiber material prepared by the lead-core structure polyaniline/graphene composite nanofiber, the diameter of the lead-core structure polyaniline/graphene composite nanofiber is 100～ 600nm, in which poly[2,7-(9,9-dioctylfluorene)-alternating-N-phenyl-N-(4-phenoxyphenyl)aniline] is used as the shell layer of the composite nanofiber material, thickness 20-100nm; graphene is used as the core or core layer of the composite nanofiber material with lead structure, and the diameter is 60-400nm; the lead structure poly[2,7-(9,9-dioctylfluorene)- Alternate-N-phenyl-N-(4-phenoxyphenyl) aniline]/graphene composite nanofiber material film has a thickness of 100nm-75μm and a fiber length of 15μm-15cm.

The device prepared by the lead core structure polyaniline/graphene composite nanofiber, the thickness of the light-emitting layer of the composite nanofiber material device is 100nm-75μm, the excitation voltage used is 30mV-50V, and the room temperature condition, the light-emitting wavelength can be tune, the wavelength range is 340-450nm, and the luminous efficiency is 5.5-25.0lm/W.

Application of the above-mentioned polyaniline/graphene composite nanofiber material with lead core structure in photoluminescence and electroluminescence devices.

Beneficial effect:

1. The present invention uses a chemical method to synthesize a phenoxy-containing triarylamine monomer with an aryl ether substituent, and utilizes the monomer to synthesize poly[2,7-(9,9-dioctylfluorene)-alternating-N- Phenyl-N-(4-phenoxyphenyl)aniline]. A lead-core structured poly[2,7-(9,9-dioctylfluorene)-alternating-N-phenyl-N-(4-phenoxyphenyl)aniline] was prepared by high-voltage electrospinning /Graphene nanofiber electroluminescent material, the thickness of the composite nanofiber film is adjustable from 100nm to 75μm, the average diameter of the fiber is 100～600nm, and the length of the fiber is 15μm～15cm; the introduction of graphene improves the polyaniline loading The carrier transport performance, and then improve the heat resistance of the material and the stability of electroluminescence, and improve the interchain aggregation of the triarylamine polymer.

The invention synthesizes a triphenylamine polymer with an aromatic ether substituent. This is based on the following points: ① The N atom on triphenylamine shows electronpositivity when forming cationic radicals (holes), while the oxygen of aryl ether has electron-donating properties, so it can improve the stability of N cationic radicals , thereby improving the stability of electroluminescence. ②Aromatic ethers have heat resistance, which can further improve the heat resistance of aniline polymer materials and prevent interchain aggregation. ③Graphene has good charge transport properties, which can further improve and enhance the charge transport properties of materials.

Description of drawings:

Accompanying drawing 1 is the chemical structure diagram of poly[2,7-(9,9-dioctylfluorene)-alternating-N-phenyl-N-(4-phenoxyphenyl)aniline] in the present invention.

Accompanying drawing 2 is the structural representation of lead core structure polyaniline/graphene composite nanofiber material among the present invention.

Accompanying drawing 3 is the structural representation of the electroluminescence device that the lead core structure polyaniline/graphene composite nanofiber material containing aryl ether substituent is formed among the present invention.

Accompanying drawing 4 is the infrared spectrogram of polyaniline P among the present invention.

Accompanying drawing 5 is the nuclear magnetic resonance spectrum 1H-NMR of polyaniline P in the present invention, wherein, solvent: deuterated chloroform (CDCl3).

Accompanying drawing 6 is the carbon nuclear magnetic resonance spectrum 13C-NMR of polyaniline P in the present invention.

Detailed ways:

Example 1:

A preparation method of polyaniline/graphene composite nanofiber material with lead core structure, the obtained soluble graphene is used as the core layer, polyaniline is used as the shell layer, and the lead core structure is prepared by using high-voltage electrospinning technology with the help of a sleeve device A polyaniline/graphene composite nanofiber material, and the lead core structure nanofiber material is made into photoluminescent and electroluminescent devices.

Example 2:

According to the preparation method of the lead-core structure polyaniline/graphene composite nanofiber described in Example 1, the first step: dissolve the polyaniline in a solvent, and use high-voltage electrospinning technology to prepare polyaniline/graphene composite The nanofiber material is poly[2,7-(9,9-dioctylfluorene)-alternating-N-phenyl-N-(4-phenoxyphenyl)aniline] dissolved in toluene (or tetrahydrofuran) solvent , the content is 1.0-12.0% (wt.%); the second step: the concentration of the ethanol (or water) solution of soluble graphene is 0.5-6.0% (wt.%), with the help of a cannulated needle, Use a micro-injection pump to control the flow rate ratio of the two solutions to 1:0.2 to 1:3.0 (polyaniline:graphene), wherein the polyaniline solution is used as the shell layer, and the graphene solution is used as the core (or core) layer; the third step : Under the condition of 18-30°C, using high-voltage electrospinning technology, the spinning voltage is adjusted to 10-30kV, and the distance between the transmitting electrode and the receiving electrode is 8-23cm. As shown in Figure 2, the polyaniline/graphene composite nanofiber material with lead core structure can be obtained on the receiving electrode. The average diameter of the composite nanofiber material is 100-600 nm; the fiber length is 15 μm-15 cm.

Example 3:

According to the preparation method of lead structure polyaniline/graphene composite nanofiber material described in embodiment 1 or 2, described polyaniline is the polyaniline containing phenoxytriphenylamine structure, and its structural representation is shown in Fig. 1, and its The preparation method is to purify the phenoxy-containing triphenylamine monomer (Mon) and further polymerize it to obtain poly[2,7-(9,9-dioctylfluorene)-alternating-N-phenyl-N-( 4-phenoxyphenyl)aniline]; the specific steps are: use refined toluene as solvent (1mmol triphenylamine monomer is added to toluene 10~25mL), use 9,9-dioctylfluorene-2,7-diboronic acid cis (1,3-propanediol) ester and phenoxy-containing triphenylamine are added in a molar ratio of 1:1.0 to 1:1.05; palladium catalyst Pd(PPh in a weight ratio of 1:25 to 1:30 ₃ ) ₄ , the palladium catalyst Pd(PPh ₃ ) ₄ The ratio of cis(1,3-propanediol) to 9,9-dioctylfluorene-2,7-diboronate is 1:25~1:30, add 2.5~3.0M sodium carbonate solution equal to the volume of toluene , under the protection of high-purity argon or nitrogen, polyaniline containing phenoxytriphenylamine structure was prepared by Suzuki coupling reaction.

Example 4:

According to the preparation method of lead structure polyaniline/graphene composite nanofiber material described in embodiment 1 or 2 or 3, (1) the preparation process of graphene oxide comprises: take flake graphite, concentrated sulfuric acid and phosphoric acid, add to Place the reaction vessel in an ice-salt bath, the temperature of the ice-salt bath is 2-4°C, stir for 15-20min, then add permanganate into the reaction vessel at a rate of 0.5-1.0g/min Potassium, stirred for 2.0-2.5 hours, removed the reaction vessel from the ice-salt bath, heated to a temperature of 35-40°C, stirred at a constant temperature for 23-24 hours, added deionized water to the reaction vessel, stirred evenly, added hydrogen peroxide, and Stir for 12 to 15 minutes to obtain graphite oxide; (2) The preparation process of graphene includes: using the above-mentioned graphene oxide to prepare a graphene oxide aqueous solution with a concentration of about 8mg mL-1; take 26mL of the graphene oxide aqueous solution and add it to In a three-neck flask, heat to 80-85°C, add 1mL of TGA under stirring conditions for redox, the time is 2.0-3.0h, and then the aqueous solution of graphene (T-RGO) is obtained; add 200μL ammonia water dropwise to the graphene In the aqueous solution, sonicate for 10-15 minutes, add 0.4 g of hydroxylamine hydrochloride under the condition of stirring at 80° C., and react for 2.0 hours to obtain graphene, which is washed for later use.

Example 5:

According to the preparation method of lead structure polyaniline/graphene composite nanofiber material described in embodiment 1 or 2 or 3 or 4, the ratio of the volume of described concentrated sulfuric acid and the mass of flake graphite is 4mL: 1g～6mL: 1g, the volume ratio of described concentrated sulfuric acid and phosphoric acid is 8:1～10:1, the mass ratio of described potassium permanganate and flake graphite is 7:1～8:1, described deionized water and The volume ratio of the concentrated sulfuric acid is 4:1～6:1, the volume ratio of the concentrated sulfuric acid and the hydrogen peroxide is 1:1～3:1, the mass concentration of the hydrogen peroxide is 25～35%, the stirring speed 200-300rpm; the heating temperature is 80-85°C.

Embodiment 6:

According to the preparation method of the lead structure polyaniline/graphene composite nanofiber material described in embodiment 1 or 2 or 3 or 4 or 5, as shown in Figure 1, the chemical formula of the described phenoxy-containing polyaniline polymer It is poly[2,7-(9,9-dioctylfluorene)-alternating-N-phenyl-N-(4-phenoxyphenyl)aniline], and the number-average molecular weight of the polymer is 13,302-31,235.

Embodiment 7:

According to the preparation method of lead structure polyaniline/graphene composite nanofiber material described in embodiment 1-6, the diameter of described lead structure polyaniline/graphene composite nanofiber is 100～600nm, wherein poly[2 ,7-(9,9-dioctylfluorene)-alternating-N-phenyl-N-(4-phenoxyphenyl)aniline] as the shell layer of composite nanofiber material, the thickness is 20-100nm; graphite Diene is used as the core (or core) layer of the lead-core structure composite nanofiber material, with a diameter of 60-400nm; the lead-core structure poly[2,7-(9,9-dioctylfluorene)-alternating-N- The thickness of the phenyl-N-(4-phenoxyphenyl)aniline]/graphene composite nanofiber material film is 100nm-75μm.

Example 8

According to the preparation method of the lead structure polyaniline/graphene composite nanofiber material described in Example 1-7, as shown in Figure 3, the thickness of the light-emitting layer of the composite nanofiber material device is 100nm～75μm, and the adopted The excitation voltage is 30mV-50V, the room temperature condition, the luminous wavelength is adjustable, the wavelength range is 340-450nm, and the luminous efficiency is 5.5-25.0lm/W.

Embodiment 9:

According to the manufacture method of lead structure polyaniline/graphene composite nanofiber material described in embodiment 1-8, the synthesis of polyaniline containing triarylamine structure is through purified 9,9-dioctylfluorene-2,7- cis (1,3-propanediol) diboronic acid ester and triphenylamine monomer, according to the molar ratio of 1:1.0 to 1:1.05, add palladium catalyst Pd(PPh3)4 with a weight ratio of 1:20 to 1:25 , and then add 2.5-3.0M sodium carbonate solution equal to the volume of the solvent (toluene), and under the protection of high-purity argon or nitrogen, obtain polyaniline containing aryl ether substituents through Suzuki coupling reaction, and the infrared spectrum of polyaniline 4. See Figures 5 and 6 for NMR spectra.

Example 10:

According to the manufacturing method of the lead-core structure polyaniline/graphene composite nanofiber material described in one of embodiments 1-9, the molecular weight characterization analysis of polyaniline containing aryl ether substituents is analyzed by gel permeation chromatography (GPC) Aniline polymers were characterized. Tetrahydrofuran was used as the mobile phase, and polystyrene standard samples were used for calibration. The number-average molecular weight Mn of the aniline polymer measured by gel permeation chromatography is 13,302-31,235, and the distribution index (D) is between 1.9523-2.3255.

Example 11:

According to the manufacturing method of the lead structure polyaniline/graphene composite nanofiber material described in one of the embodiments 1-10, it can be widely used as a blue light device material; other luminescent materials can also be doped in the electroluminescent material Light-emitting devices of other colors are obtained. It can be widely used in photoluminescence and electroluminescence devices.

Claims (8)

1. A method for preparing a lead-core structure polyaniline/graphene composite nanofiber material is characterized in that: the obtained soluble graphene is a core layer, polyaniline is a shell layer, and by means of a sleeve type device, utilizing high-voltage electrospinning A polyaniline/graphene composite nanofiber material with a lead core structure is prepared by silk technology, and the composite nanofiber material is made into a photoluminescent or electroluminescent device. 2. the preparation method of lead structure polyaniline/graphene composite nanofiber according to claim 1 is characterized in that: the first step: described polyaniline is dissolved in solvent, poly[2,7- (9,9-dioctylfluorene)-alternating-N-phenyl-N-(4-phenoxyphenyl)aniline] dissolved in toluene or tetrahydrofuran solvent, the content is 1.0～12.0%(wt.%) The second step: the concentration of the ethanol or aqueous solution of the soluble graphene is 0.5～6.0% (wt.%), with the help of a cannulated needle, the flow rate ratio of the two solutions controlled by a micro injection pump is 1:0.2～ 1:3.0, polyaniline: graphene, wherein, the polyaniline solution is used as the shell layer, and the graphene solution is used as the core or core layer; the third step: under the condition of 18-30°C, use high-voltage electrospinning technology to adjust the spinning The voltage is 10-30kV, the distance between the transmitting electrode and the receiving electrode is 8-23cm, and the polyaniline/graphene composite nanofiber material with lead core structure can be obtained on the receiving electrode. 3. according to the preparation method of the described lead structure polyaniline/graphene composite nanofiber material of claim 1 and 2, it is characterized in that: described polyaniline is the polyaniline containing phenoxytriphenylamine structure, and its preparation The method is to purify the obtained phenoxy-containing triphenylamine monomer (Mon) and further polymerize to obtain poly[2,7-(9,9-dioctylfluorene)-alternating-N-phenyl-N-(4- phenoxyphenyl) aniline]; the specific steps are: using refined toluene as a solvent, adding 1mmol triphenylamine monomer to a ratio of 10-25mL of toluene, using 9,9-dioctylfluorene-2,7-diboronic acid cis( 1,3-propanediol) ester and phenoxy-containing triphenylamine are added in a molar ratio of 1:1.0 to 1:1.05; palladium catalyst Pd(PPh ₃ ) ₄ is added in a weight ratio of 1:25 to 1:30, The ratio of the palladium catalyst Pd(PPh ₃ ) ₄ to 9,9-dioctylfluorene-2,7-diboronic acid cis(1,3-propanediol) ester is 1:25 to 1:30, and the addition of toluene Equal volume of 2.5-3.0M sodium carbonate solution, under the protection of high-purity argon or nitrogen, prepares polyaniline containing phenoxytriphenylamine structure through Suzuki coupling reaction. 4. according to the preparation method of claim 1 or 2 or 3 described lead structure polyaniline/graphene composite nanofiber material, it is characterized in that: the preparation process of described soluble graphene: take flake graphite, concentrated sulfuric acid , phosphoric acid, potassium permanganate and hydrogen peroxide and other reagents to prepare graphene oxide; use the above graphene oxide to modulate to obtain a graphene oxide aqueous solution with a concentration of 8mg mL-1; take 26mL of the graphene oxide aqueous solution and add it to a three-necked bottle. Under the condition of heating and stirring, add 1mL of TGA to carry out redox, the time is 2~3h, and the aqueous solution of graphene (T-RGO) is obtained; 200μL of ammonia water is added dropwise to the above graphene aqueous solution, ultrasonic for more than 10min, after heating, Add 0.4g of hydroxylamine hydrochloride under stirring conditions, react for 2h, and obtain graphene, wash for later use; the ratio of the volume of the concentrated sulfuric acid to the mass of the flake graphite is 4mL:1g～6mL:1g, the concentrated sulfuric acid and phosphoric acid The volume ratio is 8:1～10:1, the mass ratio of described potassium permanganate and flake graphite is 7:1～8:1, and the volume ratio of described deionized water and concentrated sulfuric acid is 4:1 ~6:1, the volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 1:1~3:1, the mass concentration of the hydrogen peroxide is 25~35%, the stirring speed is 200~300rpm; the heating The temperature is 80-85°C. 5. according to the preparation method of claim 1 or 2 or 3 or 4 described lead structure polyaniline/graphene composite nanofiber material, it is characterized in that: the chemical formula of described phenoxy-containing polyaniline polymer is poly [2,7-(9,9-dioctylfluorene)-alternating-N-phenyl-N-(4-phenoxyphenyl)aniline], the number average molecular weight of the polymer is 13,302-31,235. 6. a kind of lead structure polyaniline/graphene composite nanofiber prepared by the preparation method of the lead structure polyaniline/graphene composite nanofiber material described in one of claim 1 or 2 or 3 or 4 or 5 The device is characterized in that: lead core structure polyaniline/graphene composite nanofibers have a diameter of 100-600nm, in which poly[2,7-(9,9-dioctylfluorene)-alternating-N-phenyl-N- (4-phenoxyphenyl) aniline] as the shell layer of the composite nanofiber material, the thickness is 20～100nm; Graphene is used as the core or core layer of the lead core structure composite nanofiber material, and the diameter is 60～400nm; Lead core structure poly[2,7-(9,9-dioctylfluorene)-alternating-N-phenyl-N-(4-phenoxyphenyl)aniline]/graphene composite nanofiber material film The thickness is 100nm-75μm, and the fiber length is 15μm-15cm. 7. The device prepared by lead structure polyaniline/graphene composite nanofiber according to claim 6 is characterized in that: the thickness of the light-emitting layer of the composite nanofiber material device is 100nm～75 μm, and the excitation voltage adopted is 30mV～50V, room temperature condition, adjustable luminous wavelength, wavelength range is 340～450nm, luminous efficiency is 5.5～25.0lm/W. 8. the application of a lead structure polyaniline/graphene composite nanofiber material prepared by claim 6 or 7 in photoluminescence, electroluminescence devices.