Phthalocyanine resin-based carbon nanospheres and preparation method thereof

Abstract

The invention discloses a phthalocyanine resin-based carbon nanosphere and a preparation method thereof, and relates to the field of carbon nanomaterials, the method comprises the following steps: adding a component A into a phthalocyanine resin monomer, and carrying out high-temperature stirring reaction to obtain a phthalocyanine resin prepolymer; the component A comprises a catalyst, organosilane and magnetic metal salt; adding the phthalocyanine resin prepolymer into the ionic liquid, adding an emulsifier, and stirring and curing at high temperature to obtain phthalocyanine resin nanospheres; placing the phthalocyanine resin nanospheres in a tubular furnace or a muffle furnace, heating to a carbonization temperature at a certain heating rate in an inert atmosphere, and performing high-temperature carbonization for a certain time to obtain the carbon nanospheres. The method is simple in preparation process and mild in condition, the element composition, the particle size, the specific surface area and the pore size distribution of the prepared carbon nanospheres can be regulated and controlled through the preparation process, and the carbon nanospheres can be widely applied to the fields of adsorption separation, energy storage, catalytic carriers, electromagnetic wave absorption and biomedicine.

Description

Technical Field

[0001] The invention belongs to the field of nano carbon materials, and in particular relates to a phthalocyanine resin-based nano carbon sphere and a preparation method thereof. Background Art

[0002] With the development of science and technology, nanocarbon materials such as carbon nanotubes and graphene have attracted much attention in the field of science and technology. As an important member of nanocarbon materials, nanocarbon balls have gradually become a research hotspot in the field of materials science due to their unique structure and excellent physical and chemical properties. They have increasingly wide applications in adsorption separation, energy storage, catalytic carriers, electromagnetic wave absorption, biomedicine, etc. Carbonization of organic precursors is one of the most commonly used methods for preparing nanocarbon balls. A large number of organic substances or polymers such as glucose, epoxy resin, phenolic resin, etc. have been used as precursors for preparing nanocarbon balls. However, nanocarbon balls prepared with these precursors usually have deficiencies such as imperfect carbon structure growth, poor process and performance controllability, and are limited in use in some application fields. Phthalocyanine resin is a new type of high-performance thermosetting resin, which is prepared by the addition polymerization reaction of nitrile groups of phthalonitrile monomers under heating conditions. It has excellent high-temperature mechanical properties and thermal oxidation stability. The system after curing of phthalocyanine resin has a highly cross-linked structure and a large number of aromatic ring structures, which are easier to form a regular and perfect structure during the carbonization process; in addition, the elemental composition and structure of phthalocyanine resin can be regulated by various conditions such as the type and ratio of polymerization monomers, the regulation of polymerization temperature, and the selection of curing agent. Therefore, phthalocyanine resin has broad application prospects in the field of preparing functional nanocarbon spheres with adjustable structure and properties. Summary of the invention

[0003] The purpose of the present invention is to solve the problems of imperfect carbon sphere structure growth, poor process and performance controllability existing in the preparation of nano-carbon spheres using existing raw materials and methods, and to provide a phthalocyanine resin-based nano-carbon sphere and a preparation method thereof.

[0004] To achieve the above purpose, the technical solution adopted by the present invention is as follows:

[0005] A method for preparing phthalocyanine resin-based nano-carbon spheres, the method comprising:

[0006] Step 1: Preparation of phthalocyanine resin prepolymer: adding component A to phthalocyanine resin monomer, stirring at high temperature to obtain phthalocyanine resin prepolymer; the component A includes a catalyst, an organic silane, and a magnetic metal salt;

[0007] Step 2: Preparation of phthalocyanine resin nanospheres: adding phthalocyanine resin prepolymer into ionic liquid and emulsifier, and then stirring and curing at high temperature to obtain phthalocyanine resin nanospheres;

[0008] Step 3: High-temperature carbonization of phthalocyanine resin nanospheres: Place the phthalocyanine resin nanospheres in a tubular furnace or a muffle furnace, and heat them to the carbonization temperature at a certain heating rate under an inert atmosphere. After a certain period of high-temperature carbonization, nano-carbon spheres are obtained.

[0009] Furthermore, in step 1, the phthalocyanine resin monomer is one of diether type, paraphenylene type, isophenyl type, biphenyl type, bisphenol A type, and bisphenol S type phthalocyanine monomers; the catalyst is one or more of transition metals, transition metal salts, organic amines, organic acid amine salts, organic acids, Lewis acids, and phenols; the organosilane is γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-[3-(trimethoxysilyl)propyl]ethylenediamine, N-aminoethyl-γ-aminopropyltrimethoxysilane , octaamino polyhedral oligomeric silsesquioxane, monoamino polyhedral oligomeric silsesquioxane, tetramethoxysilane, tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, methylphenyldimethoxysilane, diphenyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, hexadecyltrimethoxysilane; the magnetic metal salt is one or more of chlorides, nitrates, sulfates, and carbonates of iron, cobalt, and nickel.

[0010] Furthermore, in step 1, the mass ratio of the catalyst to the phthalocyanine resin monomer is 0.01-15:100, the mass ratio of the organosilane to the phthalocyanine resin monomer is 0-50:100, and the mass ratio of the magnetic metal salt to the phthalocyanine resin monomer is 0-50:100.

[0011] Furthermore, in step 1, the temperature of the high temperature stirring reaction is 150-250° C., and the time is 0.1-6 h.

[0012] Furthermore, in step 2, the ionic liquid is one of imidazole ionic liquid, pyridine ionic liquid, quaternary ammonium salt ionic liquid, quaternary phosphonium salt ionic liquid, pyrrolidine ionic liquid and piperidine ionic liquid. The function of the ionic liquid is to dissolve the phthalocyanine resin prepolymer and provide a liquid reaction environment for curing.

[0013] Furthermore, in step 2, the HLB value of the emulsifier is between 8 and 18; and the mass ratio of the emulsifier to the phthalocyanine resin prepolymer is 5-20:100.

[0014] Furthermore, in step 2, the curing temperature is 200-300° C. and the curing time is 1-10 h.

[0015] Furthermore, in step three, the inert atmosphere is one of nitrogen and argon.

[0016] Furthermore, in step three, the heating rate is 1-20°C / min, the carbonization temperature is 600-1500°C, and the time is 1-10h.

[0017] A phthalocyanine resin-based nanocarbon sphere prepared by the above preparation method, wherein the diameter of the nanocarbon sphere is 10-500nm and the specific surface area is 100-2500m 2 / g, the temperature T when the weight loss in air is 5% 5％ The temperature is 400-900°C, the carbon content in the carbon ball is 60-100%, the silicon content is 0-40%, and the magnetic metal content is 0-40%.

[0018] The beneficial effects of the present invention compared with the prior art are as follows: the preparation process of the method is simple and the conditions are mild; the elemental composition, particle size, specific surface area and pore size distribution of the prepared nano-carbon spheres can be regulated through the preparation process, and the method can be widely used in adsorption separation, energy storage, catalytic carrier, electromagnetic wave absorption and biomedical fields. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 This is a scanning electron microscope photo of the phthalocyanine resin-based nano-carbon spheres provided in Example 1;

[0020] Figure 2 The particle size distribution diagram of phthalocyanine resin-based nano-carbon spheres provided in Example 2;

[0021] Figure 3 This is a scanning electron microscope photo of the phthalocyanine resin-based nano-carbon spheres provided in Example 3;

[0022] Figure 4 The thermogravimetric curve of the phthalocyanine resin-based nano-carbon spheres in air provided in Example 4;

[0023] Figure 5 The thermogravimetric curve of the phthalocyanine resin-based nano-carbon spheres in air provided in Example 5;

[0024] Figure 6 This is a photo of the magnetic adsorption of phthalocyanine resin-based nano-carbon spheres provided in Example 6. DETAILED DESCRIPTION

[0025] The specific embodiments of the present invention are described in detail below, but it should be understood that the protection scope of the present invention is not limited by the specific embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work belong to the protection scope of the present invention. The experimental methods described in the embodiments of the present invention are conventional methods unless otherwise specified.

[0026] Example 1

[0027] Preparation of phthalocyanine resin prepolymer: 2% of catalyst 4,4'-diaminodiphenyl sulfone was added to the isophthalocyanine resin monomer, and the mixture was stirred at 220°C for 1 hour to obtain the phthalocyanine resin prepolymer.

[0028] Preparation of phthalocyanine resin nanospheres: phthalocyanine resin prepolymer is added into 1-butyl-3-methylimidazolium bromide ionic liquid, and 10% of emulsifier Tween 80 is added, and phthalocyanine resin nanospheres are obtained after high-speed stirring at 250° C. for 2 hours.

[0029] High-temperature carbonization of phthalocyanine resin nanospheres: The phthalocyanine resin nanospheres were placed in a tubular furnace, and the temperature was raised to 1000°C at 5°C / min under a nitrogen atmosphere. Nanocarbon spheres were obtained after carbonization for 1 hour.

[0030] The scanning electron microscope photo of the carbon nanospheres prepared in this example is shown in FIG. Figure 1 As shown in the figure, it can be seen that the diameter of the prepared nano-carbon spheres is 40-60nm, and the particle size distribution is relatively uniform.

[0031] Example 2

[0032] Preparation of phthalocyanine resin prepolymer: 2% of catalyst 1,4-bis(4-aminophenoxy)benzene was added to bisphenol A phthalocyanine resin monomer, and stirred at 230° C. for 0.5 h to obtain phthalocyanine resin prepolymer.

[0033] Preparation of phthalocyanine resin nanospheres: phthalocyanine resin prepolymer is added into 1-butyl-3-methylimidazolium bromide ionic liquid, and 20% of emulsifier Tween 80 is added, and phthalocyanine resin nanospheres are obtained after high-speed stirring at 260° C. for 4 hours.

[0034] High-temperature carbonization of phthalocyanine resin nanospheres: The phthalocyanine resin nanospheres were placed in a tubular furnace, and the temperature was raised to 1200°C at a rate of 10°C / min under an argon atmosphere. Nanocarbon spheres were obtained after carbonization for 1 hour.

[0035] The particle size distribution of the nano carbon spheres prepared in this example is as follows: Figure 2 As shown in the figure, it can be seen that the particle size distribution of the prepared nano-carbon spheres is concentrated between 70-300nm, among which more than 60% of the nano-carbon spheres have a particle size between 100-200nm.

[0036] Example 3

[0037] Preparation of phthalocyanine resin prepolymer: Add 1% catalyst 4,4'-diaminodiphenyl sulfone and 1% ZnCl2 to the isophthalocyanine resin monomer, then add 20% γ-aminopropyltrimethoxysilane, and stir at 210°C for 3h to obtain the phthalocyanine resin prepolymer.

[0038] Preparation of phthalocyanine resin nanospheres: phthalocyanine resin prepolymer is added into N-ethylpyridinium bromide ionic liquid, and 15% of emulsifier glyceryl monostearate is added, and phthalocyanine resin nanospheres are obtained after high-speed stirring at 240° C. for 3 hours.

[0039] High-temperature carbonization of phthalocyanine resin nanospheres: The phthalocyanine resin nanospheres were placed in a tubular furnace, and the temperature was raised to 800°C at a rate of 10°C / min under a nitrogen atmosphere. Nanocarbon spheres were obtained after carbonization for 2 hours.

[0040] The scanning electron microscope photo of the carbon nanospheres prepared in this example is shown in FIG. Figure 3 As shown in the figure, it can be seen that the diameter of the prepared nano-carbon spheres is 50-70nm, and the particle size distribution is relatively uniform.

[0041] Example 4

[0042] Preparation of phthalocyanine resin prepolymer: 2.5% of catalyst ZnCl2 was added to the biphenyl phthalocyanine resin monomer, and then 50% of octaamino polyhedral oligomeric silsesquioxane was added, and the mixture was stirred at 220°C for 1 hour to obtain the phthalocyanine resin prepolymer.

[0043] Preparation of phthalocyanine resin nanospheres: phthalocyanine resin prepolymer is added into 1-ethyl-3-methylimidazolium chloride ionic liquid, and 15% of emulsifier glyceryl monostearate is added, and phthalocyanine resin nanospheres are obtained after high-speed stirring at 300° C. for 4 hours.

[0044] High-temperature carbonization of phthalocyanine resin nanospheres: The phthalocyanine resin nanospheres were placed in a tubular furnace, and the temperature was raised to 800°C at a rate of 10°C / min under a nitrogen atmosphere. Nanocarbon spheres were obtained after carbonization for 4 hours.

[0045] The thermal weight loss curve of the carbon nanospheres prepared in this example in air is as follows: Figure 4 As shown in the figure, it can be seen that the prepared nanocarbon spheres have a T 5％ It has good thermal stability at 650℃.

[0046] Example 5

[0047] Preparation of phthalocyanine resin prepolymer: 2.5% of catalyst biphenyl diphenol was added to the isophthalocyanine resin monomer, and then 30% of tetramethoxysilane and 20% of ferric chloride were added, and the mixture was stirred at 230° C. for 2 hours to obtain the phthalocyanine resin prepolymer.

[0048] Preparation of phthalocyanine resin nanospheres: phthalocyanine resin prepolymer is added to 1-ethyl-3-methylimidazole chloride ionic liquid, and 10% of emulsifier fatty alcohol polyoxyethylene ether AEO-7 is added, and phthalocyanine resin nanospheres are obtained after high-speed stirring at 250°C for 4 hours.

[0049] High-temperature carbonization of phthalocyanine resin nanospheres: The phthalocyanine resin nanospheres were placed in a tubular furnace, and the temperature was raised to 800°C at a rate of 5°C / min under an argon atmosphere. Nanocarbon spheres were obtained after carbonization for 4 hours.

[0050] The thermal weight loss curve of the carbon nanospheres prepared in this example in air is as follows: Figure 5 As shown in the figure, it can be seen that the prepared nanocarbon spheres have a T 5％ It has good thermal stability at 600℃.

[0051] Example 6

[0052] Preparation of phthalocyanine resin prepolymer: Add 2% catalyst biphenyl and 2% CuCl2 to bisphenol S phthalocyanine resin monomer, then add 30% N-aminoethyl-γ-aminopropyltrimethoxysilane and 20% nickel nitrate, and stir at 220°C for 1 hour to obtain phthalocyanine resin prepolymer.

[0053] Preparation of phthalocyanine resin nanospheres: phthalocyanine resin prepolymer is added to 1-propyl-3-methylimidazolium bromide ionic liquid, and 15% of emulsifier polyoxyethylene monostearate is added, and phthalocyanine resin nanospheres are obtained after high-speed stirring at 280° C. for 5 hours.

[0054] High-temperature carbonization of phthalocyanine resin nanospheres: The phthalocyanine resin nanospheres were placed in a tubular furnace, and the temperature was raised to 1000°C at a rate of 10°C / min under a nitrogen atmosphere. Nanocarbon spheres were obtained after carbonization for 5 hours.

[0055] The magnetic adsorption photos of the nano carbon spheres prepared in this example are shown in Figure 6 As shown in the figure, it can be seen that the prepared nano-carbon spheres are magnetic due to being doped with nickel, and can be used in many functional application fields such as biomedicine and magnetic recording materials.

Claims

1. A method for preparing phthalocyanine resin-based nanocarbon spheres, characterized in that: The method is: Step 1: Preparation of phthalocyanine resin prepolymer: adding component A to phthalocyanine resin monomer, stirring at high temperature to obtain phthalocyanine resin prepolymer; the component A includes a catalyst, an organic silane, and a magnetic metal salt; Step 2: Preparation of phthalocyanine resin nanospheres: adding phthalocyanine resin prepolymer into ionic liquid and emulsifier, and then stirring and curing at high temperature to obtain phthalocyanine resin nanospheres; Step 3: High-temperature carbonization of phthalocyanine resin nanospheres: Place the phthalocyanine resin nanospheres in a tubular furnace or a muffle furnace, and heat them to the carbonization temperature at a certain heating rate under an inert atmosphere. After a certain period of high-temperature carbonization, nano-carbon spheres are obtained.

2. The method for preparing phthalocyanine resin-based nano-carbon spheres according to claim 1, characterized in that: In step 1, the phthalocyanine resin monomer is one of a diether type, a paraphenylene type, an isophenyl type, a biphenyl type, a bisphenol A type, and a bisphenol S type phthalocyanine monomer; the catalyst is one or more of a transition metal, a transition metal salt, an organic amine, an organic acid amine salt, an organic acid, a Lewis acid, and a phenol; the organosilane is γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-[3-(trimethoxysilyl)propyl]ethylenediamine, N-aminoethyl-γ-aminopropyltrimethoxysilane, octaamino One or more of polyhedral oligomeric silsesquioxane, monoamino polyhedral oligomeric silsesquioxane, tetramethoxysilane, tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, methylphenyldimethoxysilane, diphenyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, and hexadecyltrimethoxysilane; the magnetic metal salt is one or more of chlorides, nitrates, sulfates, and carbonates of iron, cobalt, and nickel.

3. A method for preparing phthalocyanine resin-based nano-carbon spheres according to claim 1 or 2, characterized in that: In step 1, the mass ratio of the catalyst to the phthalocyanine resin monomer is 0.01-15:100, the mass ratio of the organosilane to the phthalocyanine resin monomer is 0-50:100, and the mass ratio of the magnetic metal salt to the phthalocyanine resin monomer is 0-50:

100.

4. The method for preparing phthalocyanine resin-based nano-carbon spheres according to claim 1, characterized in that: In step 1, the temperature of the high temperature stirring reaction is 150-250° C., and the time is 0.1-6 h.

5. The method for preparing phthalocyanine resin-based nano-carbon spheres according to claim 1, characterized in that: In step 2, the ionic liquid is one of imidazole ionic liquids, pyridine ionic liquids, quaternary ammonium salt ionic liquids, quaternary phosphonium salt ionic liquids, pyrrolidine ionic liquids and piperidine ionic liquids.

6. The method for preparing phthalocyanine resin-based nano-carbon spheres according to claim 1, characterized in that: In step 2, the HLB value of the emulsifier is between 8 and 18; the mass ratio of the emulsifier to the phthalocyanine resin prepolymer is 5-20:

100.

7. The method for preparing phthalocyanine resin-based nano-carbon spheres according to claim 1, characterized in that: In step 2, the curing temperature is 200-300° C. and the curing time is 1-10 hours.

8. The method for preparing phthalocyanine resin-based nano-carbon spheres according to claim 1, characterized in that: In step 3, the inert atmosphere is one of nitrogen and argon.

9. The method for preparing phthalocyanine resin-based nano-carbon spheres according to claim 1, characterized in that: In step three, the heating rate is 1-20°C / min, the carbonization temperature is 600-1500°C, and the time is 1-10h.

10. A phthalocyanine resin-based nanocarbon sphere prepared by the preparation method according to any one of claims 1 to 9, characterized in that: The diameter of the nano carbon sphere is 10-500nm, and the specific surface area is 100-2500m 2 / g, the temperature T when the weight loss in air is 5% 5％ The temperature is 400-900°C, the carbon content in the carbon ball is 60-100%, the silicon content is 0-40%, and the magnetic metal content is 0-40%.

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