CN101108727A - Polymer inarching carbon nano-tube and method of manufacturing the same - Google Patents
Polymer inarching carbon nano-tube and method of manufacturing the same Download PDFInfo
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Abstract
The invention discloses carbon nanotubes and the preparation method of the polymer graft modification, which adopts the acyl groups on the surface of the carbon nanotubes to initiate the ring-shaped monomeric compound to carry out cationic ring-opening polymerization reaction and gain the carbon nanotubes of the polymer graft modification. The invention realizes the surface modification of the carbon nanotubes via simple steps and can regulate the hydrophile and lipophilicity of the surface of the carbon nanotubes. The carbon nanotubes of the gained polymer graft modification and the carbon nanotubes of the polymer salt graft modification in different solvent show good solubility and polymer compatibility, thereby can be used as functional additive to improve the performances such as the electricity, magnetics, heat and mechanics of the polymer.
Description
Technical field
The present invention relates to a kind of polymer grafted carbon nano tube and preparation method thereof.
Background technology
Since carbon nanotube invention in 1991, carbon nanotube is subjected to extensive concern with its unique physicochemical property.Carbon nanotube has high strength, high length-diameter ratio, high-specific surface area, high thermal stability, good electroconductibility, good thermal conductivity and unique one dimension tubular structure, thus in the material field particularly the polymer composites field wide application prospect is arranged.
Because the carbon nanotube apolar surfaces is hydrophobic but also oleophobic property not only, carbon nanotube is difficult to be dissolved in the solvent, and very poor with the polymer interface consistency, carbon nanotube is difficult in good dispersion in the polymkeric substance, can't reach enhancing polymkeric substance mechanics, the electricity of expection, the effect of thermal property.Seem particularly important by carbon nano tube surface being modified change carbon nano tube surface characteristic.
People adopt micromolecular compound that nanotube is carried out chemically modified more in the time of early stage; as employing acidifying carbon nanotube and thionyl chloride reactions such as Chen J; obtain the acidylate carbon nanotube; react with the alkyl stearylamine again; the modified carbon nano-tube that obtains can be dissolved in (Science in a lot of organic solvents; 1998,282,95-98).Can also react with carboxylic acidifying carbon nanotube and sodium hydroxide, generate the carboxylate salt of carbon nanotube, further under the phase-transfer catalyst effect, react, obtain carbon nanotube (the Chinese patent publication number: CN 1613755A) that corresponding alkylate is modified with haloalkane.
Compare with the micromolecular compound modified carbon nano-tube of short chain, the carbon nanotube behind long-chain polymer-modified often has better solvability.Therefore, in recent years, attracted people to note greatly by the chain modified carbon nanotube of polymer macromolecule.As by conventional radical polymerization, polystyrene graft can be arrived carbon nano tube surface (Chem.Comm., 2002,2074-2075), but often there is a problem that can not be ignored in this situation, and promptly because there is a large amount of homopolymer, makes that final grafting efficiency is lower.Utilize the hydroxy-acid group that carbon nano tube surface has after the acidification, vulcabond or polyisocyanates can be grafted to carbon nano tube surface, and in order to preparation polyurethanes matrix material (Chinese patent publication number: CN1590289A).In addition, the initiator that can cause atom transfer radical polymerization is grafted to carbon nano tube surface, in the presence of catalyzer and part, can further cause the atom transfer radical polymerization (J.Am.Chem.Soc.2004 of different monomers, 126,170-176), as polystyrene, polychlorostyrene vinyl toluene (Chinese patent publication number: CN 1556125A), hyperbranched polymer (Chinese patent publication number: CN 1486927A), the special butyl ester of polymethyl acrylic acid (the Chinese patent publication number: CN 1546577A), block polymer (the Chinese patent publication number: CN 1513757A), polymethylmethacrylate (Chinese patent publication number: CN 1486999A) etc.
Preparation time is long, more loaded down with trivial details, the more high shortcoming of cost of process but the preparation method of above-mentioned modified carbon nano-tube exists more or less, has certain limitation in the middle of practical application.
Summary of the invention
The purpose of this invention is to provide carbon nanotube of a kind of polymer graft modification and preparation method thereof.
The present invention utilizes the positively charged ion ring-opening polymerization method by molecular designing, and in-situ preparing polymkeric substance crosslinking technology changes the carbon nano tube surface characteristic, reaches the solvent dispersion that improves carbon nanotube and the purpose of polymer phase capacitive.
Technical scheme of the present invention is as follows: pass through molecular designing, carbon nano tube surface is handled, make it to have the active group that to cause cationoid polymerisation, and catalysis cyclic monomer compound carries out the original position cationic ring-opening polymerization in the presence of catalyzer, obtains the carbon nanotube of polymer graft modification.
Concrete; the preparation method of the carbon nanotube of polymer graft modification provided by the present invention; it is catalyst mix with the acidylate carbon nanotube and 0.01～10 weight part of 1 weight part; add 1～100 weight part epoxy monomer compound then and react, obtain the carbon nanotube of polymer graft modification.
Wherein, catalyzer is iron trichloride, aluminum chloride or silver perchlorate; Described epoxy monomer compound is epoxy chloropropane, R-GLYCIDOL, epoxy bromopropane, propylene oxide, 2-methyl chloride-2-methyl oxirane, 2-monobromomethane-2-methyl oxirane, Styrene oxide 98min., tetrahydrofuran (THF), 1,3-propylene oxide or 2-chloromethyl-1, the 3-propylene oxide, its structural formula is following listed respectively:
In order to promote reaction process, also be added with 0～100 weight part anhydrous organic solvent in the reaction system.Described organic solvent is selected from methylene dichloride, trichloromethane, N, one or more in dinethylformamide, N,N-dimethylacetamide and the toluene.
In above-mentioned graft polymerization reaction process, the temperature of reaction is 0～200 ℃, and the reaction times is 0.1～100 hour.
When used epoxy monomer compound contains halogen, the carbon nanotube of 1 weight part resulting polymers graft modification all right and the aminated compounds of 1～100 weight part and the solvent of 0～100 weight part, at 0～100 degree centigrade of reaction 0.5～72hr, obtain the hydrophilic carbon nano tube of polymer salt graft modification.
Wherein, aminated compounds is pyridine, 4-pyridone, Methylimidazole, 4-vinylpridine or triethylamine; Described solvent is selected from dehydrated alcohol, methyl alcohol, water, N, one or more in dinethylformamide, the N,N-dimethylacetamide.
The following anti-row of the structural formula of these aminated compoundss.
In the present invention, used acidylate carbon nanotube can prepare (Science, 1998,282,95-98 with reference to existing literature; CN 1486927A etc.), also can prepare according to the following procedure:
1) acid with strong oxidizing property of the carbon nanotube of 1 weight part and 5～100 weight parts is mixed, and handles 0.1-100hr under ultrasonic or reflux conditions, removes acid solution, is washed to neutral and drying, obtains the acidifying carbon nanotube;
2) add gained acidifying carbon nanotube 1 weight part and acylating agent 1～100 weight part, heat 20～100 degrees centigrade, react 0.5-72hr under the stirring and refluxing, acylating agent is removed in washing, obtains the acidylate carbon nanotube.
Wherein, acid with strong oxidizing property comprises nitric acid, sulfuric acid or their mixing acid; Used acylating agent comprises phosphorus trichloride, phosphorus pentachloride, thionyl chloride, phosphorus tribromide, phosphorus pentabromide or thionyl bromide.
Employed carbon nanotube comprises commercially available various single wall or multi-walled carbon nano-tubes.
More than the carbon nanotube of prepared polymer graft modification also belong to protection scope of the present invention.
The present invention utilizes the acidylate group initiation cyclic monomer compound of carbon nano tube surface to carry out cationic ring-opening polymerization, obtain the carbon nanotube of polymer graft modification, because the lipophilicity of graftomer, the carbon nanotube of the polymer graft modification that obtains by the ring-opening polymerization of original position positively charged ion has good dispersion stabilization in organic solvent, can be as the high molecular additive of lipophilicity; Obtained the polymer graft modification carbon nanotube for halogen-containing cyclic monomer compound through ring-opening polymerization, by further quaternary ammonium reaction, can also obtain the carbon nanotube of polymer salt graft modification, make carbon nanotube have good water-dispersion stability, can be as the additive of water-soluble polymer.
The present invention has realized surface modification of carbon nanotube by easy steps, and can regulate and control the hydrophilic and lipophilicity of carbon nano tube surface, the carbon nanotube of the carbon nanotube of resulting polymer graft modification and polymer salt graft modification shows good solubility and polymer phase capacitive in different solvents, can be used as functional additive with performances such as the electricity of improving polymkeric substance, magnetics, calorifics, mechanics.
Description of drawings
Fig. 1 is the transmission electron microscope photo of salt (b) grafted modified carbon nano tube of Hydrin (a) and Hydrin;
Fig. 2 is the thermogravimetric analysis curve of the carbon nanotube of Hydrin graft modification;
Fig. 3 is the dispersion effect figures of different carbon nanotubes in water-methylene dichloride system.
Embodiment
The carbon nanotube of embodiment 1, the graft modification of preparation polytetrahydrofuran
Step (a): 0.2g material carbon nanotube joins in the Erlenmeyer flask that the 40ml vitriol oil and concentrated nitric acid (volume ratio 3: 1) nitration mixture are housed, and is put into then in the ultrasonic apparatus ultrasonic 3 hours.After the ultrasonic end, pour the dilution of a large amount of deionized waters into, use the filter paper suction filtration in 220nm aperture then, above solid constantly wash with deionized water, be about neutrality up to taking out the water that gets off.Solid is dried in vacuum drying oven, obtain the acidifying carbon nanotube.
Step (b): step (a) gained acidifying carbon nanotube 0.2g was added in the new thionyl chloride of steaming of 50ml reflux 24 hours, makes the carboxyl of carbon nano tube surface change into acyl chlorides.After product is used the Mierocrystalline cellulose filter paper filtering of aperture 220nm, vacuum-drying under the room temperature.Obtain acylated carbon nano-tube.
Step (c): gained acylated carbon nano-tube 0.2g is joined in the 50ml single port bottle, and add the 0.2g iron trichloride, add the 10ml anhydrous tetrahydro furan then.Plug sealing nitrogen bubble was removed oxygen in 10 minutes.The induction stirring reaction is 24 hours under the room temperature, precipitates in the ethanol that adds small amount of hydrochloric acid.Precipitation is dissolved in a large amount of tetrahydrofuran (THF)s again.With the tetrafluoroethylene filter paper suction filtration graftomer and the monomer in 220nm aperture, and, obtain the carbon nanotube of polytetrahydrofuran graft modification constantly with a large amount of tetrahydrofuran (THF) washings.
The thermogravimetic analysis (TGA) result shows that the polymer graft amount is 20%.
Embodiment 2: the carbon nanotube of the carbon nanotube of preparation Hydrin graft modification and the methylimidazole salt graft modification of Hydrin
Step (a): the preparation of acidifying carbon nanotube is with embodiment 1 step (a).
Step (b): the preparation of acidylate carbon nanotube is with embodiment 1 step (b).
Step (c): tetrahydrofuran (THF) in embodiment 1 step (c) is changed to epoxy chloropropane, and other technical process are constant, obtain the carbon nanotube of Hydrin graft modification.
Its transmission electron microscope photo as shown in Figure 1a.
Its thermogravimetic analysis (TGA) figure as shown in Figure 2, the result shows that the polymer graft amount is 40%.
Step (d): 95% ethanol with the carbon nanotube 0.2g of step (c) gained Hydrin graft modification joins 30ml adds the 10ml Methylimidazole again.Added backflow, induction stirring 12 hours, filter membrane suction filtration unreacted reactant, and constantly wash with massive laundering, obtain the carbon nanotube of the methylimidazole salt graft modification of the stable Hydrin of water-dispersion.Its transmission electron microscope photo is shown in Fig. 1 b.
In water and methylene dichloride biphasic system, the upper strata is a water, lower floor is a methylene dichloride, the carbon nanotube of the methylimidazole salt graft modification of the carbon nanotube of acidifying carbon nanotube, Hydrin graft modification and Hydrin is joined in this system, the dispersion results of three in water and methylene dichloride biphasic system shown in a, b, c among Fig. 3, can demonstrate the hydrophilic and oil loving change of carbon nano tube surface under the different modified conditions from Fig. 3 respectively.
Embodiment 3: the carbon nanotube of preparation poly(propylene oxide) graft modification
Step (a): the preparation of acidifying carbon nanotube is with embodiment 1 step (a).
Step (b): the preparation of acidylate carbon nanotube is with embodiment 1 step (b).
Step (c): tetrahydrofuran (THF) in embodiment 1 step (c) is changed to propylene oxide, and other technical process are constant, obtain the carbon nanotube of target product poly(propylene oxide) graft modification.Show that from the thermogravimetic analysis (TGA) result polymer graft amount is about 45%.
Embodiment 4: the carbon nanotube of the carbon nanotube agent of the poly-epoxy bromopropane graft modification of preparation and the pyridinium salt graft modification of poly-epoxy bromopropane
Step (a): the preparation of acidifying carbon nanotube is with embodiment 1 step (a).
Step (b): the preparation of acidylate carbon nanotube is with embodiment 1 step (b).
Step (c): tetrahydrofuran (THF) in embodiment 1 step (c) is changed to epoxy bromopropane, and other technical process are constant, obtain the carbon nanotube of the poly-epoxy bromopropane graft modification of target product.Show that from the thermogravimetic analysis (TGA) result polymer graft amount is about 40%.
Step (d): 95% ethanol with the carbon nanotube 0.2g of the poly-epoxy bromopropane graft modification of step (c) gained joins 30ml adds the 10ml pyridine again.Added backflow, induction stirring 12 hours, filter membrane suction filtration unreacted reactant, and constantly wash with massive laundering, obtain the carbon nanotube of the pyridinium salt graft modification of the stable poly-epoxy bromopropane of water-dispersion.
Embodiment 5: preparation polyoxygenated styrene-grafted modified carbon nanotube
Step (a): the preparation of acidifying carbon nanotube is with embodiment 1 step (a).
Step (b): the preparation of acidylate carbon nanotube is with embodiment 1 step (b).
Step (c): will go on foot the middle tetrahydrofuran (THF) of embodiment 1 rapid (c) and be changed to Styrene oxide 98min., other technical process are constant, obtain target product polyoxygenated styrene-grafted modified carbon nanotube.Show that from the thermogravimetic analysis (TGA) result polymer graft amount is about 35%.
Embodiment 6: the carbon nanotube of the carbon nanotube of preparation Hydrin graft modification and the methylimidazole salt graft modification of Hydrin
Step (a): the preparation of acidifying carbon nanotube is with embodiment 1 step (a).
Step (b): the preparation of acidylate carbon nanotube is with embodiment 1 step (b).
Step (c): the catalyzer in embodiment 2 steps (c) is changed to silver perchlorate, and other technical process are constant, obtain the carbon nanotube of target product Hydrin graft modification.From thermogravimetic analysis (TGA) as a result surface aggregate thing grafting amount be about 30%.
Step (d): 95% ethanol with the carbon nanotube 0.2g of step (c) gained Hydrin graft modification joins 30ml adds the 10ml Methylimidazole again.Added backflow, induction stirring 12 hours, filter membrane suction filtration unreacted reactant, and constantly wash with massive laundering, obtain the carbon nanotube of the methylimidazole salt graft modification of the stable Hydrin of water-dispersion.
Embodiment 7: the carbon nanotube of the poly-2-methyl chloride of preparation-2-methyl oxirane graft modification
Step a), b according to embodiment 1) preparation acidylate carbon nanotube.
Gained acylated carbon nano-tube 0.2g is joined in the 50ml single port bottle, and add the 0.02g aluminum chloride, add 100ml methylene dichloride and 50ml 2-methyl chloride-2-methyl oxirane then.Plug sealing nitrogen bubble was removed oxygen in 10 minutes.50 ℃ of following induction stirring were reacted 10 hours, precipitated in the ethanol that adds small amount of hydrochloric acid.Obtain the carbon nanotube of poly-2-methyl chloride-2-methyl oxirane graft modification after the washing.
The thermogravimetic analysis (TGA) result shows that the polymer graft amount is about 32%.
Embodiment 8: the carbon nanotube of the poly-1 graft modification of preparation
Step a), b according to embodiment 1) preparation acidylate carbon nanotube.
Gained acylated carbon nano-tube 0.2g is joined in the 50ml single port bottle, and add the 1g iron trichloride, add 100ml N then, dinethylformamide and 20ml 1.Plug sealing nitrogen bubble was removed oxygen in 10 minutes.100 ℃ of following induction stirring were reacted 5 hours, precipitated in the ethanol that adds small amount of hydrochloric acid.Obtain the carbon nanotube of poly-1 graft modification after the washing.
The thermogravimetic analysis (TGA) result shows that the polymer graft amount is about 28%.
Other epoxy monomer, as R-GLYCIDOL, 2-monobromomethane-2-methyl oxirane, and 2-chloromethyl-1 adopts identical method to modify and is grafted on the carbon nanotube, obtains the carbon nanotube of polymer graft modification.
Claims (10)
1. the preparation method of the carbon nanotube of a polymer graft modification; it is catalyst mix with the acidylate carbon nanotube and 0.01～10 weight part of 1 weight part; add 1～100 weight part epoxy monomer compound then and react, obtain the carbon nanotube of polymer graft modification.
2. preparation method according to claim 1 is characterized in that: described catalyzer is iron trichloride, aluminum chloride or silver perchlorate; Described epoxy monomer compound is epoxy chloropropane, R-GLYCIDOL, epoxy bromopropane, propylene oxide, 2-methyl chloride-2-methyl oxirane, 2-monobromomethane-2-methyl oxirane, Styrene oxide 98min., tetrahydrofuran (THF), 1 or 2-chloromethyl-1.
3. preparation method according to claim 1 is characterized in that: also be added with 0～100 weight part anhydrous organic solvent in the reaction system.
4. preparation method according to claim 3 is characterized in that: described organic solvent is selected from methylene dichloride, trichloromethane, N, one or more in dinethylformamide, N,N-dimethylacetamide and the toluene.
5. preparation method according to claim 1 is characterized in that: the temperature of reaction is 0～200 ℃, and the reaction times is 0.1～100 hour.
6. preparation method according to claim 1, it is characterized in that: when used epoxy monomer compound contains halogen, the carbon nanotube of 1 weight part resulting polymers graft modification all right and the aminated compounds of 1～100 weight part and the solvent of 0～100 weight part, at 0～100 degree centigrade of reaction 0.5～72hr, obtain the hydrophilic carbon nano tube of polymer salt graft modification.
7. preparation method according to claim 6 is characterized in that: aminated compounds is pyridine, 4-pyridone, Methylimidazole, 4-vinylpridine or triethylamine; Described solvent is selected from dehydrated alcohol, methyl alcohol, water, N, one or more in dinethylformamide, the N,N-dimethylacetamide.
8. according to the arbitrary described preparation method of claim 1-7, it is characterized in that: described acidylate carbon nanotube prepares according to the following procedure:
1) acid with strong oxidizing property of the carbon nanotube of 1 weight part and 5～100 weight parts is mixed, and handles 0.1-100hr under ultrasonic or reflux conditions, removes acid solution, is washed to neutral and drying, obtains the acidifying carbon nanotube;
2) add gained acidifying carbon nanotube 1 weight part and acylating agent 1～100 weight part, heat 20～100 degrees centigrade, react 0.5-72hr under the stirring and refluxing, acylating agent is removed in washing, obtains the acidylate carbon nanotube.
9. preparation method according to claim 8 is characterized in that: described acid with strong oxidizing property comprises nitric acid, sulfuric acid or their mixing acid; Used acylating agent comprises phosphorus trichloride, phosphorus pentachloride, thionyl chloride, phosphorus tribromide, phosphorus pentabromide or thionyl bromide.
10. the carbon nanotube of the polymer graft modification of claim 1-9 gained.
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