CN1284728C - Temperatur esensitire type water soluble carbon nano pipe and its preparation method - Google Patents
Temperatur esensitire type water soluble carbon nano pipe and its preparation method Download PDFInfo
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- CN1284728C CN1284728C CN 200310121617 CN200310121617A CN1284728C CN 1284728 C CN1284728 C CN 1284728C CN 200310121617 CN200310121617 CN 200310121617 CN 200310121617 A CN200310121617 A CN 200310121617A CN 1284728 C CN1284728 C CN 1284728C
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Abstract
The present invention provides a temperature sensitive type water soluble carbon nanometer pipe and a preparation method thereof. In the preparation method, after a carbon nanometer pipe is treated, the surface of the carbon nanometer pipe is provided with a specific triggering group; then, temperature sensitive type water soluble monomers containing double bond are polymerized by the reaction of atom transfer radical polymerization to obtain the temperature sensitive type water soluble carbon nanometer pipe. The preparation method is simple, is easy to perform, and has high controllability. The temperature sensitive type water soluble carbon nanometer pipe has water solubility which is sensitive to temperature, namely that the temperature sensitive type water soluble carbon nanometer pipe has good solubility in water under normal temperature and is separated out when temperature rises. Owing to the dimension of the nanometer level, the temperature sensitive type water soluble carbon nanometer pipe can be used as a nanometer device with a special function, such as a temperature control nanometer switch. Thus, the temperature sensitive type water soluble carbon nanometer pipe has a wide application prospect in nanometer science, material science and biomedicine.
Description
Technical field: the present invention relates to a kind of preparation method of water-soluble carbon nanometer tube, particularly responsive to temperature type water-soluble carbon nanometer tube 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 Matyiaszewski 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 temperature responsive type water-soluble carbon nanometer tube 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, contain two key responsive to temperature type polymerisation then, obtain responsive to temperature type water-soluble polymers grafted carbon nanotube, just the responsive to temperature type water-soluble carbon nanometer tube with the atom transition free radical polymerization reaction initiation.
The concrete preparation method of responsive to temperature type water-soluble carbon nanometer tube 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 40～100kHz 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 40～100kHz 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 40～100kHz 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 40～100kHz 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 0.01～50 weight part fills Ar or N after the sealing
21～100min, add and contain two key responsive to temperature type water-soluble monomer 0.01～80 weight parts, continue inflated with nitrogen or argon gas 1～100min, behind reaction 0.01～1000hr under 0～150 ℃, stopped reaction, water dilutes, suction filtration, washing, 0～180 ℃ of vacuum-drying obtains the responsive to temperature type water-soluble carbon nanometer tube; Wherein to be grafted on the polymer chain structure of carbon nano tube surface as follows for gained:
M is a number of repeat unit, and span is 5～5000.
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.
Used responsive to temperature type water-soluble monomer is N,N-DMAA, N-N-isopropylacrylamide, N,N-dimethylacetamide, 2-(dimethylamino) ethyl propylene acid esters or 2-(dimethylamino) propyl group acrylate in the inventive method step (e).
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 water, 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; Products obtained therefrom has thermally sensitive water-soluble, promptly shows good solubility under the normal temperature in water, separates out from water when temperature raises; Owing to its nano level size, can be used as the nano-device of specific function, as temperature control nanotube switch; Thereby wide application prospect is arranged at nano science, Materials science and biomedical aspects.
Description of drawings:
Fig. 1: responsive to temperature type water-soluble carbon nanometer tube
1H NMR spectrogram
Fig. 2: responsive to temperature type water-soluble carbon nanometer tube solvability and temperature relation
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 initial raw material, and is acidified, after the acidylate; connect ethylene glycol; with alpha-brominated isobutyryl bromine reaction,, then obtain the responsive to temperature type water-soluble carbon nanometer tube again with ATRP method grafting poly N-isopropyl acrylamide.
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 aqueous solvent 5mL fills N after the sealing
210min adds N-N-isopropylacrylamide monomer 5g, continues to fill N
210min, behind reaction 20hr under 20 ℃, stopped reaction is after the water dilution, suction filtration, unreacted monomer and catalyzer etc. are removed in washing, 80 ℃ of vacuum-dryings obtain poly N-isopropyl acrylamide grafted responsive to temperature type water-soluble carbon nanometer tube, obtain material 2.0g.
Fig. 1 has provided the responsive to temperature type water-soluble carbon nanometer tube
1H NMR spectrogram, main polymer chain (CH
2-: δ=1.1～1.6ppm;-CH-: δ=1.7～2.0ppm) and sec.-propyl hydrogen (CH: δ=3.7～3.8ppm; CH
3: the existence of δ=0.8～1.0ppm) has proved the poly N-isopropyl acrylamide structure, and 50 ℃ of following polymer moieties no longer dissolve, so characteristic peak disappears on the nuclear-magnetism figure.Fig. 2 has provided the responsive to temperature type water-soluble carbon nanometer tube, and the curve of decreased solubility has proved temperature sensitivity with the temperature rising in water.Can estimate the polymer graft amount from heat analysis data and probably account for 60% of total mass, be about 50 from the nuclear-magnetism resulting estimate polymerization degree.
Claims (6)
1. the preparation method of responsive to temperature type water-soluble carbon nanometer tube 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 40～100kHz ultrasonication, 0.1～100hr post-heating to 20～200 ℃, reaction 0.5～100hr, with the filter membrane suction filtration, repetitive scrubbing repeatedly to neutral, obtains the acidifying carbon nanotube behind 0～180 ℃ of vacuum-drying 10～30hr; Wherein acid with strong oxidizing property is selected from 0.1～70wt% nitric 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;
Step (b): add step (a) gained acidifying carbon nanotube 1 weight part and acylating agent 1～100 weight part, behind 40～100kHz 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 40～100kHz 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 40～100kHz 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 0.01～50 weight part fills Ar or N after the sealing
21～100min, add 0.01～80 weight part N, N-DMAA or N-N-isopropylacrylamide monomer continue inflated with nitrogen or argon gas 1～100min, behind reaction 0.01～1000hr under 0～150 ℃, stopped reaction, water dilutes, suction filtration, washing, 0～180 ℃ of vacuum-drying obtains the responsive to temperature type water-soluble carbon nanometer tube; Wherein catalyzer is selected from cuprous chloride, cuprous bromide, iron protochloride or ferrous bromide; Used part is selected from 2-dipyridyl, Tetramethyl Ethylene Diamine, pentamethyl--diethyl triamine or hexamethyl-triethyl tetramine; Solvent for use is selected from water, 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;
Wherein to be grafted on the polymer chain structure of carbon nano tube surface as follows for gained:
M is a number of repeat unit, and span is 5～5000.
2. the preparation method of responsive to temperature type water-soluble carbon nanometer tube according to claim 1 is characterized in that carbon nanotube used in the step (a) is the single wall or the multi-walled carbon nano-tubes of catalyse pyrolysis, arc-over, template or the preparation of laser evaporation method.
3. the preparation method of responsive to temperature type water-soluble carbon nanometer tube according to claim 1 is characterized in that used acylating agent is selected from phosphorus trichloride, phosphorus pentachloride, thionyl chloride, phosphorus tribromide, phosphorus pentabromide or thionyl bromide in the step (b).
4. the preparation method of responsive to temperature type water-soluble carbon nanometer tube according to claim 1 is characterized in that polyvalent alcohol used in the step (c) or polyamine are selected from ethylene glycol, quadrol, glycerol, third triamine, 1,2-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.
5. the preparation method of responsive to temperature type water-soluble carbon nanometer tube according to claim 1 is characterized in that used alpha-halogen carboxylic acid halides is selected from 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).
6. the responsive to temperature type water-soluble carbon nanometer tube is characterized in that the responsive to temperature type water-soluble carbon nanometer tube that adopts each described preparation method of claim 1-5 to obtain; Wherein to be grafted on the polymer chain structure of carbon nano tube surface as follows for gained:
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| CN1308230C (en) * | 2005-06-17 | 2007-04-04 | 吉林大学 | Highly water-soluble carbon nanometer tube preparation method |
| CN101805432A (en) * | 2010-03-26 | 2010-08-18 | 武汉工程大学 | Thermosensitive graphene/polymer composite material and preparation method thereof |
| CN106698395A (en) * | 2016-12-06 | 2017-05-24 | 袁洁 | Modified carbon nanotube for solar energy |
| CN113753879A (en) * | 2020-06-05 | 2021-12-07 | 重庆科技学院 | Temperature-sensitive polymer modified carbon nanotube composite material and preparation method thereof |
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