CN103408931B - Preparation method of hybrid material compounded from fullerene micro-nano material and conjugated polymer - Google Patents

Abstract

The invention belongs to the technical field of material preparation, and relates to a method for preparing a hybrid material in which fullerene micro-nano materials and conjugated macromolecules are combined. After the fullerenes are ground in an agate mortar, take the good solvent to dissolve the fullerenes, then transfer them into a transparent glass bottle, disperse them with ultrasonic waves in an ice-water bath, and filter them at room temperature to obtain saturated fullerenes. solution, and then add isopropanol to cultivate to obtain a suspension containing fullerene-like micro-nano materials; dissolve the conjugated polymer in its good solvent, and filter to obtain a solution of the conjugated polymer; add the conjugated polymer solution to In the suspension liquid of the fullerene micro-nano material with a volume ratio of 1-10 times, after ultrasonic vibration and mixing treatment, the hybrid material composed of the fullerene micro-nano material and the conjugated macromolecule is cultivated. The overall process is simple, the principle is reliable, the production cycle is short, the performance of the prepared material is good, the application is wide, the reliability is strong, and the environment is friendly.

Description

Preparation method of a hybrid material composed of a fullerene-based micro-nano material and a conjugated polymer

Technical field:

The invention belongs to the technical field of material preparation, and relates to a composite modification technology of fullerene-based micro-nano materials, in particular to a method for preparing a hybrid material in which fullerene-based micro-nano materials are compounded with conjugated polymers.

Background technique:

Low-dimensional micro-nano carbonaceous materials are ideal systems for studying physical properties such as electron transport behavior, optical properties, and mechanical properties. They will play an important role in the research fields of integrated circuits and functional components such as micro-nano electronics and optoelectronic devices. Realizing the expansion of its application and diversification of functions, and the modification of low-dimensional nano-carbon structure materials have become a hot issue in the current scientific research of micro-nano materials. In 1985, Kroto and others discovered that fullerene C ₆₀ has a highly symmetric, spherically delocalized π-electron conjugated system, and has unique physical and chemical properties; fullerenes have unique photophysical properties, electrical conductivity, photoconductivity and optical limitation Sexual behavior has aroused great interest of scientists. After more than 20 years of research, there have been organic fullerene chemistry, fullerene supramolecular chemistry, metal fullerene clathrate, fullerene medicinal chemistry, fullerene New disciplines such as ene photoelectromagnetics, and are still developing; Prato et al. , 2002, 99, 5075) reported for the first time that an ionized derivative of C ₆₀ containing porphyrin units can form nanotubes, and it is believed that this is due to the π-π interaction between fullerene and porphyrin, through electrostatic due to interaction self-assembly. Chinese patents CN1195103 and CN1215973 disclose the use of electrochemical methods to electrophoresis aggregates of fullerenes into the nano-cavities of porous templates, thereby forming ordered micro-nanotubes and micro-nano whiskers; C ₆₀ one-dimensional polymer nanotubes connected by covalent bonds between C ₆₀ molecules obtained by controlled free radical polymerization. The free radical polymerization is to maintain the template adsorbed with monomer C ₆₀ molecules at 400-550°C under the protection of inert gas 2-4 hours, 0.5-1 hour under 1 kW UV light.

However, the above-mentioned methods have problems such as small aspect ratio of the obtained samples, poor control of purity, complicated preparation technology and the like. In recent years, Japanese Patent Laid-Open Patents 2005-254393A and 2006-124266A disclose the preparation of nanocrystals of fullerene C ₆₀ with a single crystal structure by the liquid-liquid interface precipitation method of saturated organic solution of C ₆₀ near room temperature and isopropanol Whiskers and nanotubes. The nanofibers synthesized by this method have a single crystal structure, high aspect ratio and high purity (99.9%). However, the problem with this method is that the nanotubes of fullerenes C ₆₀ and C ₇₀ are grown The cycle is long (more than one week), and the reproducibility is poor, so it is difficult to prepare on a large scale; in view of these problems, Chinese patent CN100581998C discloses a simple, easy to implement, good repeatability, suitable for mass production, single crystal structure, high aspect ratio and high A template-free preparation method of pure solid or hollow fullerene-based micro-nano fibers. At the same time, there are more and more studies on the preparation of fullerene micro-nano materials, such as Liu et al. A simple evaporation method prepares fullerene nano-micron materials of different dimensions by using different solvents and different evaporation temperatures, Jeong et al. (JYJeong, WSKim, SIPark, TSYoon, and BHChung, J.Phys.Chem.C, 2010, 114:12976) by adding anti-solvent to C ₆₀ -toluene solution to crystallize fullerene and prepare fullerene nanomaterials with different shapes.

At present, the liquid-liquid interface precipitation method has become the most simple and effective method for preparing fullerene-based micro-nanofibers and micro-nano-chips. However, the research on fullerenes cannot be limited to the preparation of fullerenes with different structures. On micro-nano materials (micro-nano whiskers/micro-nanotubes/micro-nano chips); studies have found that fullerenes, fullerene derivatives and fullerene-based nanostructures are good acceptors of electrons and can be used as acceptor systems Used in solar cells, however, compared with carbon nanotubes, the main disadvantage of fullerene-based micro-nanofibers is their low electrical conductivity, which limits their applications, but it is found that alkali metal-doped C ₆₀ fullerenes have Excellent superconductivity, compared with the original C ₆₀ powder, it has better conductivity; and the unique structure, size controllable and soluble in certain organic solvents of fullerene micro-nano fibers can also As a unique carrier and reaction field; therefore, the modification of fullerene micro-nano fibers conforms to the pace of the times.

Conductive polymers have been a hot research topic in the field of materials in recent years, but the conductivity of such conductive polymers is relatively low in the intrinsic state, and they must be doped to have good conductivity; fullerenes are good electron acceptors. body, and the conjugated polymer contains atoms with lone pairs of electrons, which are electron donors, so the conjugated polymer can be doped with fullerene molecules to increase its conductivity; about the preparation of the original fullerene powder and the conjugated Conjugated polymer hybrid materials have been reported endlessly, such as Wang et al. (Wang Q, Wang S, Li J, et al. J. Polym. ) using C ₆₀ powder and aniline as raw materials to prepare C ₆₀ / polyaniline composites by interfacial polymerization, under a certain ratio of C ₆₀ and polyaniline, the composite material has good conductivity; I.Sapurina et al. (I.Sapurina, M.Mokeev, V.Lavrentev, V.Zgonnik, et al.Eur.Polym.J,36,2000:2321-2326) By doping C ₆₀ into polyaniline, the thermal stability and electrical conductivity of polyaniline were increased The rate increases, but these methods only use the properties of fullerene electron acceptors, and use it to dope conjugated polymers to increase their conductivity. This kind of doping makes it more expensive. If the original fullerene can be used The hybridization of fullerene-based micro-nano materials prepared by powder and conjugated polymers can not only greatly change the morphology of fullerene-based micro-nano fibers/chips, but at the same time the conjugated polymers are doped with conductivity to obtain Improvement, such composites can obtain nano-hybrid materials with brand-new photoelectromagnetic and mechanical properties.

Invention content:

The purpose of the present invention is to overcome the shortcomings of the prior art, and seek to design a method for preparing a hybrid material composed of a fullerene-based micro-nano material and a conjugated polymer. Direct ultrasonic mixing for compounding not only modifies the shape of fullerene-based micro-nano materials, but also dopes conjugated polymers to form a new type of hybrid material with new opto-electromagnetic and mechanical properties.

In order to achieve the above object, the process method involved in the present invention comprises the following steps:

(1) Preparation of fullerene-based micro-nano materials: put fullerene-like substances in an agate mortar, grind them to a metallic luster, and take fullerene-like toluene, pyridine, xylene, benzene, carbon disulfide, and tetrachloride Add carbon, dichlorotoluene or dichloromethane good solvent or a mixed solvent of any proportion into the mortar to dissolve the fullerenes, then transfer it to a transparent glass bottle, and disperse it in an ice-water bath with a 50-500W ultrasonic wave for 10 minutes , filter at room temperature to obtain a fullerene-based saturated solution, then add isopropanol at a volume ratio of 1:1, put it in a constant temperature incubator at 4°C for 24 hours, and obtain a suspension containing fullerene-based micro-nano materials;

(2) Dissolving polyaniline, aniline, polypyrrole or polythiophene conjugated polymer in its good solvent, and filtering to obtain a solution of conjugated polymer;

(3) Add the conjugated polymer solution prepared in step (2) to the suspension prepared in step (1) with a volume ratio of 1-10 times, and after ultrasonic vibration and mixing, put it into a refrigerator at 4°C for cultivation. The hybrid material composed of fullerene micro-nano material and conjugated polymer completes the preparation of the hybrid material.

The fullerenes described in the present invention include C ₆₀ , C 70 fullerenes with a purity of 98-99.9%, mixtures of C ₆₀ and C ₇₀ and their derivatives ₍ such as C ₆₀ [C(OOC ₂ H ₅ ) ₂ ]) and high-carbon fullerenes (such as C ₈₂ , C ₈₄ , C ₁₀₀ , C ₁₁₀ ... C ₅₄₀ ); Micro-nano fibers and micro-nano chips interconnected by covalent bonds, ionic bonds or van der Waals forces between similar substances.

Compared with the prior art, the present invention innovatively prepares a hybrid material compounded with fullerene micro-nano materials and conjugated polymers with unique morphology, modifies the surface of fullerene micro-nano materials, increases the conjugated high The electrical conductivity of molecules; using the template-free preparation method of transparent colorless glass containers and constant temperature incubators, the hybrid materials of fullerene-like micro-nano materials and conjugated polymers are prepared by direct ultrasonic mixing; the hybrid materials with conjugated π electronic structure are used Fullerene-based micro-nanotubes, micro-nano whiskers and micro-nano-chips are new aggregate structures of fullerenes, which maintain the structure and properties of fullerene molecules and have the characteristics of quasi-one-dimensional nanostructures. Through hybridization with conjugated polymers, the morphology of fullerene-based micro-nano fibers and wafers can be changed, making them useful in micro-nano devices, field emission devices, fuel cell electrodes, confined chemical reaction fields, high-frequency filters and Photoelectric functional polymers and other fields have broad application prospects; the overall process is simple, the principle is reliable, the production cycle is short, the prepared material has good performance, wide application, strong reliability, and environmental friendliness.

Detailed ways:

Further illustrate the specific content of the present invention below by embodiment.

Example 1:

The preparation process steps of the present embodiment include:

(1) Weigh 14mg of C ₆₀ powder, grind it, dissolve it in 5ml of toluene, and ultrasonicate it for 10 minutes in an ice bath; after filtering the above solution, add 5ml of isopropanol to it at a volume ratio of 1:1, and put it in a constant temperature incubator Cultivate at a constant temperature of 4°C for 24 hours to prepare fullerene micro-nanofibers (FM/NFs) with a length of 10-20 μm;

(2) Measure 1.8ml of aniline (An) and add it to 100ml of HCl with a concentration of 1mol/L, mix and stir; then add 1.14g of ammonium persulfate (APS) to the above solution, stir for 1min, and put it in the refrigerator to control the temperature Refrigerate at -12°C for 12 hours, add 45ml of ammonia water with a concentration of 1.74mol/L and soak for 5 minutes after suction filtration, dry to obtain PANI-EB powder, grind it for use;

(3) Dissolve PANI-EB powder in N-methyl-2-pyrrolidone (N-methyl-2-pyrrolidone, NMP), sonicate for 5 minutes, filter to get PANI-EB/NMP colloid, take PANI-EB/NMP colloid Add it into the mother liquor bottle containing FM/NFs in different volume ratios, sonicate for 30 minutes in an ice bath, and put it in the refrigerator at 4°C for 48 hours to obtain the FM/NFs/PANI hybrid material;

(4) Characterization: The morphology and structure of the prepared FM/NFs/PANI hybrid materials were characterized by scanning electron microscopy (SEM).

Example 2:

This example is the same as Example 1. The liquid-liquid interface method is used to prepare fullerene micro-nano materials. The difference is that the good solvents are pyridine, pyridinone, benzene, carbon disulfide, aniline and ethanol. The prepared materials are Different body shapes, including flakes and pellets.

Example 3:

The difference between this example and Example 1 is that in the preparation of fullerene micro-nano materials, the methods of evaporating C ₆₀ -toluene saturated solution, C ₆₀ -benzene saturated solution and C ₆₀ -dichlorobenzene saturated solution are adopted. That is, evaporation method for preparation.

Example 4:

The difference between this example and Example 1 is that the fullerene micro-nano material is prepared by the electrochemical method in Chinese patents CN1195103 and CN1215973; or by the template method in Chinese patent 1267342C.

Example 5:

The steps of this embodiment are the same as those of Embodiment 1, except that the selected conjugated polymers are polypyrrole and polythiophene.

Embodiment 6:

The procedure of this embodiment is the same as that of Embodiment 1, except that the ultrasonic time selected for the ultrasonic mixing method is different and the aging time of the hybrid material after ultrasonic mixing is different.

Claims (2)

1. a hybrid material preparation method for fullerene micro Nano material and conjugated polymer compound, is characterized in that concrete steps comprise:

(1) fullerene material is placed in agate mortar, be ground to metalluster, get the toluene of fullerene, pyridine, dimethylbenzene, benzene, dithiocarbonic anhydride, tetracol phenixin, the mixed solvent of toluene dichloride or methylene dichloride good solvent or its any ratio adds in mortar and dissolves fullerene material, move into clear-glass bottle again, disperse 10 minutes with the ultrasonic echography of 50-500W in ice-water bath after, filtered at room temperature obtains fullerene saturated solution, then Virahol is added by the volume ratio of 1:1, put into 4 DEG C of constant incubators and carry out the suspension that cultivation obtains containing fullerene micro Nano material for 24 hours,

(2) polyaniline, polypyrrole or Polythiophene conjugated polymer are dissolved in its good solvent, obtain the solution of conjugated polymer after filtration;

(3) conjugated polymer solution prepared by step (2) being added volume ratio is in the suspension prepared of the step (1) of 1-10 times, after ultrasonic oscillation combination treatment, put into the hybrid material that 4 DEG C of refrigerators cultivate obtained fullerene micro Nano material and conjugated polymer compound, complete the preparation of hybrid material.

2. the hybrid material preparation method of fullerene micro Nano material according to claim 1 and conjugated polymer compound, it is characterized in that described fullerene material comprises purity is 98-99.9% soccerballene C ₆₀, C ₇₀, C ₆₀with C ₇₀mixture and derivative C ₆₀[C (OOC ₂h ₅) ₂] and high carbon number soccerballene, its medium high carbon number soccerballene comprises C ₈₂, C ₈₄, C ₁₀₀, C ₁₁₀and C ₅₄₀; Described fullerene micro Nano material comprises micro nanometer fiber and micro-nano wafer, is the micro nanometer fiber that is interconnected to by covalent linkage or ionic linkage or Van der Waals force between fullerene material and micro-nano wafer.