CN1218979C - Ultrabranching poly parachloro methyl benzene etthylene grafted carbon nano pipe and its preparation method - Google Patents
Ultrabranching poly parachloro methyl benzene etthylene grafted carbon nano pipe and its preparation method Download PDFInfo
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- CN1218979C CN1218979C CN 200310121620 CN200310121620A CN1218979C CN 1218979 C CN1218979 C CN 1218979C CN 200310121620 CN200310121620 CN 200310121620 CN 200310121620 A CN200310121620 A CN 200310121620A CN 1218979 C CN1218979 C CN 1218979C
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Abstract
The present invention provides a hyper branched poly(p-chloromethyl stryrene) grafted carbon nano-tube and a preparation method thereof. In the method, a carbon nano-tube is processed for causing the surface to be provided with specific initiating groups; atom transfer radical polymerization reaction is used for initiating the polymerization of p-chloromethyl styrene monomers for obtaining the super branched poly-p-chloromethyl styrene grafted carbon nano-tube . The preparation method is simple and easy and has strong controllability; obtained products in organic solvents show good solubility, and the obtained products can be used as special type additive agents of high molecular materials; simultaneously, because of the nanometer grade size, the products can be used as nanometer devices with special functions and can also be used as carriers of mass transmission and transition between different systems; and thereby, the products have a large application prospect at nanometer science aspect, material science aspect biomedicine science aspect, etc.
Description
Technical field: the present invention relates to a kind of carbon nanotube of polymer graft, particularly hyperbranched poly p-chloromethyl styrene grafted carbon nanotube and preparation method thereof.
Background technology: carbon nanotube (Cabon Nanotube is called for short CNT) is just found a kind of novel carbon structure in 1991, is the body that is rolled into by the Graphene lamella that carbon atom forms.Carbon nanotube be divided into Single Walled Carbon Nanotube (Single-wall Nanotube, SWNT) and multi-walled carbon nano-tubes (Multi-wall Nanotube, MWNT).Its preparation method mainly contains catalyse pyrolysis, arc-over, template and laser evaporation etc.
Because diameter is very little, length-to-diameter ratio is big, carbon nanotube is regarded as quasi-one-dimensional nanometer material.Confirmed now that carbon nanotube has peculiar electric property, superpower mechanical property, good adsorption property, thereby caused very big attention in the material field.The transistor and the indicating meter that have now had carbon nanotube to make come out.
Along with the development of nano science and technology, various carbon nanotubes with specified property cause people's interest gradually.The acid treatment that people such as Richard E.Smalley scrutinized carbon nanotube in 1998, obtained the products distribution situation under the different treatment condition, this has laid good basis (Science, 1998,280 (22): 1253-1255) for further studying later on.Afterwards, various modified carbon nano-tubes and composite structure thereof are produced out.Such as carbon nanotube with solvent solubility, have carbon nano tube device of molecular detection function or the like.
On the other hand, Sawamoto and Matyjaszewski have almost simultaneously found that independently transition metal-catalyzed " activity " controllable free-radical polymerisation of a kind of usefulness is atom transfer radical polymerization (ATRP).This method becomes the research focus of polymer chemistry in the world soon, and is described as " the recent studies on method of 21 century ".This method is to the control of target product with keep and be better than traditional polymerization greatly aspect the lower molecular weight distributing index, also avoided in the traditional method the harsh requirement to the polymerization environment.Simultaneously, because the popularity of initiator, especially, can in product, introduce functional group easily, also can synthesize multiple block polymer with the participation of the initiator of functional group.
Along with science and technology development, have the nanostructure of unique texture and function and the attention that nano-device has obtained people gradually, the annual report that a large amount of this respects are all arranged.Utilize the advantage of ATRP method, the combined carbon nanotube just can synthesize various carbon nano tube devices with ad hoc structure, and the application that this can expand above method and material greatly promotes the development of this science and technical field.
Summary of the invention: the objective of the invention is to utilize methods such as atom transfer radical polymerization by molecular designing, preparation hyperbranched poly p-chloromethyl styrene grafted carbon nanotube satisfies the needs in different application field.
Technical scheme of the present invention is as follows:
By molecular designing, carbon nano tube surface is handled, make it to have the required active group of ATRP polyreaction, thereby can cause the polymerization that contains double bond monomer; In the presence of catalyzer and part, cause the p-chloromethyl styrene polymerization then, then obtain hyperbranched poly p-chloromethyl styrene grafted carbon nanotube with atom transition free radical polymerization reaction.
The concrete preparation method of hyperbranched poly p-chloromethyl styrene grafted carbon nanotube of the present invention is as follows:
Step (a): 1 weight part exsiccant carbon nanometer tube material and 0.1～100 weight part acid with strong oxidizing property, with 0～100kHz ultrasonication, 0.1～100hr post-heating to 20～200 ℃, reaction 0.5～100hr, use the filter membrane suction filtration, repetitive scrubbing repeatedly to neutral, obtains the acidifying carbon nanotube behind 0～180 ℃ of vacuum-drying 10～30hr;
Step (b): add step (a) gained acidifying carbon nanotube 1 weight part and acylating agent 1～100 weight part, behind 0～100kHz ultrasonication, 10～1000min, be heated to 20～200 ℃, reaction 0.5～100hr down stirs and refluxes, suction filtration and repetitive scrubbing are removed acylating agent, obtain acylated carbon nano-tube;
Step (c): add step (b) gained acidylate carbon nanotube 1 weight part and polyvalent alcohol or polyamine 1～50 weight part, sealing, take out inflated with nitrogen repeatedly three times, behind 0～100kHz ultrasonication, 10～1000min, react 1～20hr down at 20～200 ℃, suction filtration is behind the repetitive scrubbing, 0～180 ℃ of vacuum-drying obtains the carbon nanotube that the surface has hydroxyl or amido;
Step (d): add carbon nanotube 1 weight part and alpha-halogen carboxylic acid halides 1～50 weight part that step (c) gained surface has hydroxyl or amido, sealing, take out inflated with nitrogen repeatedly three times, behind 0～100kHz ultrasonication, 10～1000min, react 1～20hr down at 20～200 ℃, suction filtration is after the washing, 0～180 ℃ of vacuum-drying obtains the carbon nanotube that the surface has initiating group;
Step (e): add 0.01～1 weight part catalyzer, 0.01～5 weight part part, the surface that adds step (d) gained again has carbon nanotube 1 weight part of initiating group, and solvent 0～50 weight part fills Ar or N after the sealing
21～100min, add p-chloromethyl styrene monomer 0.01～80 weight part, continue inflated with nitrogen or argon gas 1～100min, react 0.01～1000hr, stopped reaction down at 0～150 ℃, in solvent, dilute, suction filtration, washing, 0～180 ℃ of vacuum-drying, obtain the polymerization degree and be 5～1000 hyperbranched poly p-chloromethyl styrene grafted carbon nanotube, polymer architecture is as shown below:
Used carbon nanotube is the single wall or the multi-walled carbon nano-tubes of catalyse pyrolysis, arc-over, template and the preparation of laser evaporation method in the inventive method step (a).
The used acid with strong oxidizing property of the inventive method step (a) comprises 0.1～70% weight acid concentration nitric acid, 0.1～100% weight acid concentration sulfuric acid, 1/100～100/1 mol ratio nitric acid and sulfuric acid mixed solution, 1/100～100/1 mol ratio potassium permanganate and sulfuric acid mixed solution, 1/100～100/1 mol ratio potassium permanganate and hydrochloric acid mixed solution, 1/100～100/1 mol ratio potassium permanganate and nitric acid mixing solutions, 1/100～100/1 mol ratio H
2O
2With sulfuric acid mixed solution, 1/100～100/1 mol ratio H
2O
2With hydrochloric acid mixed solution or 1/100～100/1 mol ratio H
2O
2With the nitric acid mixing solutions.
Used acylating agent comprises phosphorus trichloride, phosphorus pentachloride, thionyl chloride, phosphorus tribromide, phosphorus pentabromide or thionyl bromide in the inventive method step (b).
Polyvalent alcohol or polyamine material used in the inventive method step (c) comprise ethylene glycol, quadrol, glycerol, third triamine, 1, the 2-propylene glycol, 1,2-propylene diamine, 1, ammediol, 1,3-propylene diamine, 1,4-butyleneglycol, 1,4-butanediamine, 1,2-butyleneglycol, 1,2-butanediamine, 1,3 butylene glycol, 1,3-butanediamine, trihydroxybutane, fourth triamine, polyoxyethylene glycol or polyethyene diamine.
Used alpha-halogen carboxylic acid halides comprises alpha-brominated butyryl bromide, alpha-brominated isobutyl acylbromide, alpha-brominated propionyl bromide, alpha-chloro butyryl chloride, alpha-chloro isobutyryl chloride or alpha-chloro propionyl chloride in the inventive method step (d).
Do not use solvent among the inventive method step (c), (d) or with dimethyl sulfoxide (DMSO), N, dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-, chloroform, tetrahydrofuran (THF), ethyl acetate, acetone, acetonitrile, butanone, triethylamine, pyridine or dimethylamino pyridine are that solvent or the mixed solvent that contains these solvents are reaction medium.
Catalyst system therefor is the metallic compound that contains Cu (I), Fe (II), Mo (V), Re (V), Ru (II), Ni (I) or Pb (II) such as cuprous chloride, cuprous bromide, iron protochloride, ferrous bromide, lithium molybdate, ReO in the inventive method step (e)
2I (PPh
3)
2, RuCl
2, Ni (NCN) Br or Pd (OAc)
2Used part is 2-dipyridyl, Tetramethyl Ethylene Diamine, pentamethyl--diethyl triamine, hexamethyl-triethyl tetramine, oxalic acid, propanedioic acid, Succinic Acid, phthalic acid, triphenylphosphine or tri-n-butyl phosphine; Solvent for use is dimethyl sulfoxide (DMSO), N, dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-, chloroform, methylene dichloride, ethylene dichloride, tetrahydrofuran (THF), ethyl acetate, acetone, butanone, acetonitrile, propyl alcohol, ethanol, methyl alcohol or contain the mixture of these solvents.
Preparation method provided by the invention is simple, and controllability is strong; Gained hyperbranched poly p-chloromethyl styrene grafted carbon nanotube shows good solubility owing to have a large amount of wetting ability carboxylic groups in water; This solvability has been improved the workability of carbon nanotube greatly, can be used as the specialist additive of water-soluble high-molecular material; Owing to its nano level size, can be used as the nano-device of specific function simultaneously, construct specific quantum structure; Also can be used as the carrier of material transfer and transfer between different system, realize specific purpose; Thereby have purposes widely at nano science, Materials science and biomedical aspects, wide application prospect is arranged.
Description of drawings:
Fig. 1: hyperbranched poly p-chloromethyl styrene grafted carbon nanotube
1H NMR spectrogram
Fig. 2: hyperbranched poly p-chloromethyl styrene grafted carbon nanotube infrared spectrum
Embodiment: the following examples are to further specify of the present invention, rather than limit the scope of the invention.
Embodiment 1: the multi-walled carbon nano-tubes with the catalytic pyrolysis method preparation is an initial raw material; acidified; after the acidylate; connect ethylene glycol; again with alpha-brominated isobutyryl bromine reaction; cause the monomeric polymerization of p-chloromethyl styrene with ATRP method original position, because monomeric characteristic own then obtains hyperbranched poly p-chloromethyl styrene grafted carbon nanotube.
Step (a): in the single neck round-bottomed flask of the 100mL that the magnetic agitation rotor is housed, add 2g exsiccant carbon nanometer tube material and 20mL 60% weight ratio concentration concentrated nitric acid, with 40kHz ultrasonication 30min post-heating to 120 ℃, reaction 24hr down stirs and refluxes, with φ 0.22 μ m tetrafluoroethylene millipore filtration suction filtration, repeatedly to neutral, obtain acidifying carbon nanotube behind 80 ℃ of vacuum-drying 24hr with the deionized water repetitive scrubbing;
Step (b): in the single neck round-bottomed flask of the 100mL that the magnetic agitation rotor is housed, add step (a) gained acidifying carbon nanotube 1.5g and thionyl chloride 8g, behind 40kHz ultrasonication 30min, be heated to 60 ℃, reaction 24hr down stirs and refluxes, suction filtration and repetitive scrubbing are removed thionyl chloride, obtain acylated carbon nano-tube;
Step (c): in the single neck round-bottomed flask of the 100mL that the magnetic agitation rotor is housed, add step (b) gained acidylate carbon nanotube 1.3g and ethylene glycol 25g, seal with the turned welt soft rubber ball, take out inflated with nitrogen repeatedly three times, behind 40kHz ultrasonication 30min, react 24hr down at 100 ℃, suction filtration is removed unreacted reactant and byproduct of reaction, with behind the deionized water wash, 80 ℃ of vacuum-dryings obtain the carbon nanotube that the surface has hydroxyl repeatedly;
Step (d): in the single neck round-bottomed flask of the 100mL that the magnetic agitation rotor is housed, adding step (c) gained surface has the carbon nanotube 1.1g and the alpha-brominated isobutyl acylbromide 1g of hydroxyl, seal with the turned welt soft rubber ball, take out inflated with nitrogen repeatedly three times, behind 40kHz ultrasonication 30min, at 20 times reaction 1～20hr, suction filtration is removed unreacted reactant and byproduct of reaction, with behind the deionized water wash, 80 ℃ of vacuum-dryings obtain the carbon nanotube that the surface has initiating group repeatedly;
Step (e): in the single neck round-bottomed flask of the 50mL that the magnetic agitation rotor is housed, add 0.6g CuBr, 0.7g part PMDETA (pentamethyl--diethyl triamine), the surface that adds step (d) gained again has the carbon nanotube 1g of initiating group, and solvent DMF 10mL fills N after the sealing
210min adds the special butyl ester monomer of vinylformic acid 10mL, continues to fill N
210min, behind reaction 20hr under 100 ℃, stopped reaction, after the chloroform dilution, suction filtration, unreacted monomer and catalyzer etc. are removed in washing, and 80 ℃ of vacuum-dryings obtain hyperbranched poly p-chloromethyl styrene grafted carbon nanotube 1.7g.
Fig. 1 has provided hyperbranched poly p-chloromethyl styrene grafted carbon nanotube
1H NMR spectrogram, main polymer chain (CH
2-: δ=1.2～1.4ppm;-CH-: δ=3.0～3.5ppm) and phenyl ring (proof of δ=7.1～7.6ppm) structure of poly-p-chloromethyl styrene.Infrared spectrum (Fig. 2) has clearly proved phenyl ring (～1040cm
-1) and methylene radical (～1660cm
-1).
Can estimate the polymer graft amount from heat analysis data and probably account for 50% of total mass, the polymerization degree is between 10～50.
Claims (9)
1. the preparation method of hyperbranched poly p-chloromethyl styrene grafted carbon nanotube is characterized in that concrete preparation method is as follows:
Step (a): 1 weight part exsiccant carbon nanometer tube material and 0.1～100 weight part acid with strong oxidizing property, with 0.1～100 hour post-heating to 20～200 of 40～100kHz ultrasonication ℃, reacted 0.5～100 hour, with the filter membrane suction filtration, repeatedly to neutral, 0～180 ℃ of vacuum-drying obtains the acidifying carbon nanotube to repetitive scrubbing after 10～30 hours;
Step (b): add step (a) gained acidifying carbon nanotube 1 weight part and acylating agent 1～100 weight part, with 40～100kHz ultrasonication after 10～1000 minutes, be heated to 20～200 ℃, the stirring and the reaction down 0.5～100 hour that refluxes, suction filtration and repetitive scrubbing are removed acylating agent, obtain acylated carbon nano-tube;
Step (c): add step (b) gained acidylate carbon nanotube 1 weight part and polyvalent alcohol or polyamine 1～50 weight part, sealing, take out inflated with nitrogen repeatedly three times, with 40～100kHz ultrasonication after 10～1000 minutes, reacted 1～20 hour down at 20～200 ℃, suction filtration is behind the repetitive scrubbing, 0～180 ℃ of vacuum-drying obtains the carbon nanotube that the surface has hydroxyl or amido;
Step (d): add carbon nanotube 1 weight part and alpha-halogen carboxylic acid halides 1～50 weight part that step (c) gained surface has hydroxyl or amido, sealing, take out inflated with nitrogen repeatedly three times, with 40～100kHz ultrasonication after 10～1000 minutes, reacted 1～20 hour down at 20～200 ℃, suction filtration is after the washing, 0～180 ℃ of vacuum-drying obtains the carbon nanotube that the surface has initiating group;
Step (e): add 0.01～1 weight part catalyzer, 0.01～5 weight part part, the surface that adds step (d) gained again has carbon nanotube 1 weight part of initiating group, and solvent 10～50 weight parts fill Ar or N after the sealing
21～100 minute, add p-chloromethyl styrene monomer 0.01～80 weight part, continue inflated with nitrogen or argon gas 1～100 minute, and reacted 0.01～1000 hour stopped reaction at 0～150 ℃ down, add solvent cut, suction filtration, washing, 0～180 ℃ of vacuum-drying, obtain the polymerization degree and be 5～1000 hyperbranched poly p-chloromethyl styrene grafted carbon nanotube, polymer architecture such as figure below:
2. the preparation method of hyperbranched poly p-chloromethyl styrene grafted carbon nanotube according to claim 1 is characterized in that used carbon nanotube has catalyse pyrolysis, arc-over, template or laser evaporation method to prepare in the step (a) single wall or multi-walled carbon nano-tubes.
3. the preparation method of hyperbranched poly p-chloromethyl styrene grafted carbon nanotube according to claim 1 is characterized in that the used acid with strong oxidizing property of step (a) has 0.1～70% weight acid concentration nitric acid, 0.1～100% weight acid concentration sulfuric acid, 1/100～100/1 mol ratio nitric acid and sulfuric acid mixed solution, 1/100～100/1 mol ratio potassium permanganate and sulfuric acid mixed solution, 1/100～100/1 mol ratio potassium permanganate and hydrochloric acid mixed solution, 1/100～100/1 mol ratio potassium permanganate and nitric acid mixing solutions, 1/100～100/1 mol ratio H
2O
2With sulfuric acid mixed solution, 1/100～100/1 mol ratio H
2O
2With hydrochloric acid mixed solution or 1/100～100/1 mol ratio H
2O
2With the nitric acid mixing solutions.
4. the preparation method of hyperbranched poly p-chloromethyl styrene grafted carbon nanotube according to claim 1 is characterized in that used acylating agent has phosphorus trichloride, phosphorus pentachloride, thionyl chloride, phosphorus tribromide, phosphorus pentabromide or thionyl bromide in the step (b).
5. the preparation method of hyperbranched poly p-chloromethyl styrene grafted carbon nanotube according to claim 1, it is characterized in that polyvalent alcohol used in the step (c) or polyamine material have ethylene glycol, quadrol, glycerol, third triamine, 1, the 2-propylene glycol, 1,2-propylene diamine, 1, ammediol, 1,3-propylene diamine, 1,4-butyleneglycol, 1,4-butanediamine, 1,2-butyleneglycol, 1,2-butanediamine, 1,3-butyleneglycol, 1,3-butanediamine, trihydroxybutane, fourth triamine, polyoxyethylene glycol or polyethyene diamine.
6. the preparation method of hyperbranched poly p-chloromethyl styrene grafted carbon nanotube according to claim 1 is characterized in that used alpha-halogen carboxylic acid halides has alpha-brominated butyryl bromide, alpha-brominated isobutyl acylbromide, alpha-brominated propionyl bromide, alpha-chloro butyryl chloride, alpha-chloro isobutyryl chloride or alpha-chloro propionyl chloride in the step (d).
7. the preparation method of hyperbranched poly p-chloromethyl styrene grafted carbon nanotube according to claim 1, it is characterized in that not using among step (c), (d) solvent or with dimethyl sulfoxide (DMSO), N, dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-, chloroform, tetrahydrofuran (THF), ethyl acetate, acetone, acetonitrile, butanone, triethylamine, pyridine or dimethylamino pyridine are that solvent or the mixed solvent that contains these solvents are reaction medium.
8. the preparation method of hyperbranched poly p-chloromethyl styrene grafted carbon nanotube according to claim 1, it is characterized in that catalyst system therefor wherein has cuprous chloride, cuprous bromide, iron protochloride, ferrous bromide, lithium molybdate, iodate oxidation two (triphenyl phosphorus base) rhenium, protochloride ruthenium, bromination nitrogen cyanogen nickel or plumbic acetate for containing the metallic compound of Cu (I), Fe (II), Mo (V), Re (V), Ru (II), Ni (I) or Pb (II) in the step (e); Used part is 2-dipyridyl, Tetramethyl Ethylene Diamine, pentamethyl--diethyl triamine, hexamethyl-triethyl tetramine, oxalic acid, propanedioic acid, Succinic Acid, phthalic acid, triphenylphosphine or tri-n-butyl phosphine; Solvent for use is dimethyl sulfoxide (DMSO), N, dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-, chloroform, methylene dichloride, ethylene dichloride, tetrahydrofuran (THF), ethyl acetate, acetone, butanone, acetonitrile, propyl alcohol, ethanol, methyl alcohol or contain the mixture of these solvents.
9. hyperbranched poly p-chloromethyl styrene grafted carbon nanotube is characterized in that the hyperbranched poly p-chloromethyl styrene grafted carbon nanotube that adopts the described preparation method of claim 1-8 to obtain.
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