CN1209382C - Preparation method of block polymer grafted earbon nano-pipe - Google Patents
Preparation method of block polymer grafted earbon nano-pipe Download PDFInfo
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Abstract
The present invention provides a preparation method of carbon nanotubes in which block polymers are grafted. After being acidified and acylated, the carbon nanotubes react with polyol or polyamine so that hydroxyl or amino groups are attached to the surfaces of the carbon nanotubes. Then, the carbon nanotubes react with alpha-halogen acyl halide to obtain carbon nanotubes whose surfaces have initiation groups; then, monomers containing double bonds are initiated to be polymerized by atom transfer free radical polymerization reactions under the existence of catalysts and ligands to obtain carbon nanotubes in which single-segment macromolecules are grafted; the polymerization of another kind of monomers containing double bonds continues to be initiated by the carbon nanotubes in which single-segment macromolecules are grafted through the atom transfer free radical polymerization reactions to obtain the carbon nanotubes in which block polymers are grafted. Obtained products have good dissolubility, are capable of absorbing microparticles with different characteristics, are easy to be added to plastics, rubber, paint or fibers to prepare high-performance film materials, high-strength fiber materials, wave absorbing fiber materials, and have wide application prospect.
Description
Technical field: the present invention relates to a kind of preparation method of carbon nanotube of surface modification, particularly the preparation method of block polymer grafted carbon nanotube.
Background technology: the preparation method of carbon nanotube (Carbon Nanotube is called for short CNT) mainly contains catalyse pyrolysis, arc-over, template and laser evaporation etc.Prepared carbon nanotube be divided into Single Walled Carbon Nanotube (single-wall nanotube, SWNT) and multi-walled carbon nano-tubes (Multi-wall Nanotube, MWNT).Carbon nanotube/high molecule nano composite material obtains exploitation owing to having excellent performance.The preparation of carbon nanotube/high molecule nano composite material is divided into dual mode, a kind of be with the CNT (carbon nano-tube) mechanical dispersion in high molecular polymer, be called " blend "; Another kind of mode is after functional group is gone up in carbon nano tube surface processing connection, to carry out in-situ polymerization, thereby obtain connecting carbon nanotube/high molecule nano composite material by covalent linkage.A kind of mode in back can be improved the affinity and the solubility property of carbon nanotube greatly, thereby prepares high performance nano composite material.
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, people's success such as Masahito Sano is grafted to the tenth generation branch-shape polymer PAMAM (poly (amidoamine)) carbon nano tube surface (Angew.Chem.2001,113 (24): 4797-4799).Glucosamine (glucosamine) also successfully is grafted to carbon nano tube surface, has obtained water-soluble good carbon nanotube (Pompeo, F.; Resasco, D.E., Nano Letters, vol 0 no 0 A-E).People such as Ya-PingSun have done a lot of work in this respect, have successively realized PPEI-EI (poly (propionylethylenmine-co-ethylenmine), M
w≈ 200 000, EI molar fraction ≈ 15%) (J.Am.Chem.Soc.2000,122 (24), 5878-5880; J.Phys.Chem.B 2000,104 (30), 7071-7076; Nano Lett., 2001,1 (8), 423-427) and grafting (Nano Lett., 2001,1 (8), the 439-441 of some dendrimers; Chem.Mater.2001,13 (9): 2864-2869; J.Phys.Chem.B 2002,106 (6), 1294-1298), and studied the non-linear optical property of products therefrom.
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.Adopt the ATRP method, people such as Walt are grafted to gold surface with polymethylmethacrylate, have prepared core-shell type golden nanometer particle (Mandal, T.K.; Fleming, M.S.; Walt D.R.Nano Letters, Vol.2,3-7 (2002)).
Summary of the invention: the objective of the invention is to utilize atom transfer radical polymerization method by molecular designing, preparation block polymer grafted carbon nanotube satisfies the needs in different application field.
Content of the present invention is to be raw material with the carbon nanotube, has synthesized a series of block polymer grafted carbon nanotubes.Carbon nano tube surface of the present invention has number of polymers, polymkeric substance has different functional groups, the length of polymer molecular chain can be controlled effectively by changing initiation center and monomeric proportioning, the carbon nano tube surface graft(ing) degree can be controlled by the acidification degree to carbon nanotube, functional group's kind can be controlled by the monomer that adding contains different functional groups, can prepare the novel high polymer grafted carbon nanotube with multiple function thus.
The concrete preparation method of block polymer grafted carbon nanotube of the present invention is as follows:
Step (a): in flask, add 1～10g exsiccant carbon nanometer tube material and 5～50mL acid with strong oxidizing property, with 40～100kHz ultrasonication 30min～100hr post-heating to 20～200 ℃, reaction 0.5～100hr down stirs and refluxes, with the filter membrane suction filtration, repetitive scrubbing repeatedly to neutral, obtains the acidifying carbon nanotube behind 80～180 ℃ of vacuum-drying 10～30hr;
Step (b): in flask, add step (a) gained acidifying carbon nanotube 1～10g and acylating agent 1～100g, 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): in flask, add step (b) gained acidylate carbon nanotube 1～10g and polyalcohols or polynary amine 1～50g, 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, 80～180 ℃ of vacuum-dryings obtain the carbon nanotube that the surface has hydroxyl or amido;
Step (d): in flask, add carbon nanotube 1～10g and alpha-halogen carboxylic acid halides 1～50g 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, 80～180 ℃ of vacuum-dryings obtain the carbon nanotube that the surface has initiating group;
Step (e): add 0.6～5g catalyzer, 0.7～5g part in flask, the surface that adds step (d) gained again has the carbon nanotube 1～10g of initiating group, and solvent 10～50mL fills Ar or N after the sealing
21～100min, add and contain double bond monomer 10～80mL, continue inflated with nitrogen or argon gas 1～100min, react 20～1000hr down at 60～150 ℃, after viscosity is significantly increased, stopped reaction precipitates in methyl alcohol, and the gained precipitation heavily is dissolved in solvent, suction filtration, washing, 80～180 ℃ of vacuum-dryings obtain the macromolecular grafted carbon nanotube of single hop;
Step (f): add 0.4～5g catalyzer, 0.48～5g part in flask, add the macromolecular grafted carbon nanotube 2～10g of single hop that step (e) obtains again, solvent 10～50mL fills Ar or N after the sealing
21～100min, add another kind and contain double bond monomer 10～80mL, continue inflated with nitrogen or argon gas 1～100min, react 10～1000hr down at 50～150 ℃, after viscosity is significantly increased, stopped reaction precipitates in methyl alcohol, and the gained precipitation heavily is dissolved in solvent, suction filtration, washing, 80～180 ℃ of vacuum-dryings obtain block polymer grafted carbon nanotube.
Used carbon nanotube is the single wall or the multi-walled carbon nano-tubes of catalyse pyrolysis, arc-over, template and laser evaporation methods such as (CVD) preparation in the inventive method step (a).
The used acid with strong oxidizing property of the inventive method step (a) comprises 60～70% nitric acid, sulfuric acid, 1/100～100/1 ratio nitric acid/sulfuric acid mixing acid.
Used acylating agent comprises phosphorus trichloride, phosphorus pentachloride, thionyl chloride, phosphorus tribromide, phosphorus pentabromide, thionyl bromide in the inventive method step (b).
Polyalcohols or polynary amine substance used in the inventive method step (c) comprise ethylene glycol, glycerol, 1,2-propylene glycol, 1, ammediol, 1,4-butyleneglycol, 1,2-butyleneglycol, 1,3-butyleneglycol, trihydroxybutane, polyoxyethylene glycol, quadrol, third triamine, 1,2-propylene diamine, 1,3-propylene diamine, 1,4-butanediamine, 1,2-butanediamine, 1, all contain two and a plurality of hydroxyl and amino organism 3-butanediamine, fourth triamine, polyethyene diamine etc.
Do not use solvent among the inventive method step (c), (d) or with dimethyl sulfoxide (DMSO), N, dinethylformamide, N,N-dimethylacetamide, N-methyl-2-are that solvent or the mixed solvent that contains these solvents are reaction medium than pyrrolidone, chloroform, tetrahydrofuran (THF), ethyl acetate, acetone, acetonitrile, butanone, triethylamine, pyridine, dimethylamino pyridine.
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, alpha-chloro propionyl chloride in the inventive method step (d).
The inventive method step (e), (f) containing double bond monomer in is the monomer of free redical polymerization reaction, comprise Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, Rocryl 410, the vinylformic acid hydroxy butyl ester, the methacrylic acid hydroxy butyl ester, methyl acrylate, methyl methacrylate, vinylformic acid ammonia ethyl ester, aminoethyl methacrylate, N, N-dimethacrylate ammonia ethyl ester, N, N-dimethyl-aminoethyl methacrylate, vinylbenzene, p-chloromethyl styrene, between 1-chloro-4-methyl-benzene, acrylamide, N, the N-DMAA, Methacrylamide, N, N-dimethyl-Methacrylamide, the N-N-isopropylacrylamide, N-isopropyl-methyl acrylamide, N, N-diethyl acrylamide, N, N-diethyl-4-methyl-acrylamide, N, N-dihydroxy ethyl acrylamide, N-hydroxyethyl acrylamide, the N-hydroxyethyl methacrylamide, N-(trishydroxymethyl) methyl acrylamide, N-aminoethyl acrylamide, N-aminoethyl-Methacrylamide, N-(2-dimethylamino) ethyl acrylamide, Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, Rocryl 410, the vinylformic acid hydroxy butyl ester, the methacrylic acid hydroxy butyl ester, N, N-dihydroxy ethyl acrylamide, N-hydroxyethyl acrylamide, the N-hydroxyethyl methacrylamide, N-(trishydroxymethyl) methyl acrylamide.
Catalyst system therefor is the metallic compound that contains Cu (I), Fe (I), Mo (V), Re (V), Ru (II), Ni (I), Pb (II) such as cuprous chloride, cuprous bromide, iron protochloride, ferrous bromide, lithium molybdate, ReO in the inventive method step (e), (f)
2I (PPh
3)
2, RuCl
2, Ni (NCN) Br, Pd (OAc)
1Deng; Used part is 2-dipyridyl, Tetramethyl Ethylene Diamine, pentamethyl--diethyl triamine, hexamethyl-triethyl tetramine, oxalic acid, propanedioic acid, Succinic Acid, phthalic acid, triphenylphosphine, tri-n-butyl phosphine etc.; Solvent for use is dimethyl sulfoxide (DMSO), N, dinethylformamide, N,N-dimethylacetamide, N-methyl-2-are than pyrrolidone, chloroform, methylene dichloride, ethylene dichloride, tetrahydrofuran (THF), ethyl acetate, acetone, butanone, acetonitrile, propyl alcohol, ethanol, methyl alcohol or contain the mixture of these solvents.
Block polymer grafted carbon nanotube pattern is through the high power sem analysis, and internal structure is by high power TEM test, and in addition, block polymer grafted carbon nanotube also adopts nucleus magnetic resonance, infrared spectra, heat analysis etc. to characterize.
Block polymer grafted carbon nanotube prepared in accordance with the present invention, the polymer molecular chain that has the different affinities of two sections or multistage, have fabulous solvability, can in solution, adsorb, suitable biological medicine carrier, the special type function material done micropartical of different nature; Utilize different segmental character, can expand the application of carbon nanotube greatly in Jie's sight field; Meanwhile this carbon nanotube also has good assimilation effect to microwave, be easy to add in plastics, rubber, coating and the fiber, also film forming separately, the suitable body of doing the high-strength special type material or additive, high performance membrane material, high tensile strength fibrous material, absorption microwave filamentary material, prospect has a very wide range of applications.
Description of drawings:
The SEM contrast effect figure of Fig. 1: carbon nanotube single hop grafting PMMA (A) and block graft PMMA-PHEMA (B)
Fig. 2: carbon nanotube grafting PMMA-PHEMA's
1H NMR figure
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; with ATRP method grafting polymethylmethacrylate (PMMA), and then continue to connect poly hydroxy ethyl acrylate (PHEMA), obtain block polymer PMMA-PHEMA grafted carbon nanotube with the ATRP method.
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 20mL60% 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 methyl methacrylate MMA monomer 10mL, continues to fill N
210min reacts 20hr down at 60 ℃, after viscosity is significantly increased, and stopped reaction, in methyl alcohol, precipitate, the gained precipitation heavily is dissolved in chloroform, suction filtration, washing, remove unreacted monomer and catalyzer etc., 80 ℃ of vacuum-dryings obtain single hop PMMA grafted carbon nanotube, obtain material 3g;
Step (f): in the single neck round-bottomed flask of the 50mL that the magnetic agitation rotor is housed, add 0.4g CuBr, 0.48g part PMDETA, add the macromolecular grafted carbon nanotube 2g of single hop that step (e) obtains again, solvent DMF 10mL fills N after the sealing
210min adds hydroxyethyl methylacrylate HEMA monomer 10mL, continues to fill N
210min reacts 10hr down at 50 ℃, after viscosity is significantly increased, and stopped reaction, in methyl alcohol, precipitate, the gained precipitation heavily is dissolved in DMF, suction filtration, washing, remove unreacted monomer and catalyzer etc., 80 ℃ of vacuum-dryings obtain block PMMA-PHEMA grafted carbon nanotube.
The sem analysis result is as shown in Figure 1: left figure A is that carbon nanotube is at the later appearance of grafting PMMA, the skim polymkeric substance of surface coverage as can be seen, the mean diameter of carbon nanotube reaches more than the 30nm, (average 20～24nm) slightly increase, and the shape of carbon nanotube can distinguish than material carbon nanotube diameter.B is the exterior appearance of block PMMA-PHEMA in the grafting, and outward appearance changes to some extent as can be seen, and mean diameter reaches 40nm.This has proved the successful grafting of block polymer.
1H NMR result as shown in Figure 2, d is the characteristic peak of PMMA, b, c, e are the characteristic peak of PHEMA.
Claims (11)
1. the preparation method of block polymer grafted carbon nanotube is characterized in that concrete preparation method is as follows:
Step (a): in flask, add 1～10g exsiccant carbon nanometer tube material and 5～50mL acid with strong oxidizing property, with 40～100kHz ultrasonication 30min～100hr post-heating to 20～200 ℃, reaction 0.5～100hr down stirs and refluxes, with the filter membrane suction filtration, repetitive scrubbing repeatedly to neutral, obtains the acidifying carbon nanotube behind 80～180 ℃ of vacuum-drying 10～30hr;
Step (b): in flask, add step (a) gained acidifying carbon nanotube 1～10g and acylating agent 1～100g, 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): in flask, add step (b) gained acidylate carbon nanotube 1～10g and polyalcohols or polynary amine 1～50g, 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, 80～180 ℃ of vacuum-dryings obtain the carbon nanotube that the surface has hydroxyl or amido;
Step (d): in flask, add carbon nanotube 1～10g and alpha-halogen carboxylic acid halides 1～50g 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, 80～180 ℃ of vacuum-dryings obtain the carbon nanotube that the surface has initiating group;
Step (e): add 0.6～5g catalyzer, 0.7～5g part in flask, the surface that adds step (d) gained again has the carbon nanotube 1～10g of initiating group, and solvent 10～50mL fills Ar or N after the sealing
21～100min, add and contain double bond monomer 10～80mL, continue inflated with nitrogen or argon gas 1～100min, react 20～1000hr down at 60～150 ℃, after viscosity is significantly increased, stopped reaction precipitates in methyl alcohol, and the gained precipitation heavily is dissolved in solvent, suction filtration, washing, 80～180 ℃ of vacuum-dryings obtain the macromolecular grafted carbon nanotube of single hop;
Step (f): add 0.4～5g catalyzer, 0.48～5g part in flask, add the macromolecular grafted carbon nanotube 2～10g of single hop that step (e) obtains again, solvent 10～50mL fills Ar or N after the sealing
21～100min, add another kind and contain double bond monomer 10～80mL, continue inflated with nitrogen or argon gas 1～100min, react 10～1000hr down at 50～150 ℃, after viscosity is significantly increased, stopped reaction precipitates in methyl alcohol, and the gained precipitation heavily is dissolved in solvent, suction filtration, washing, 80～180 ℃ of vacuum-dryings obtain block polymer grafted carbon nanotube.
2. the preparation method of block polymer grafted carbon nanotube 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 and the preparation of laser evaporation method.
3. the preparation method of block polymer grafted carbon nanotube according to claim 1 is characterized in that the used acid with strong oxidizing property of step (a) comprises 60～70% nitric acid, sulfuric acid, 1/100～100/1 ratio nitric acid/sulfuric acid mixing acid.
4. the preparation method of block polymer grafted carbon nanotube according to claim 1 is characterized in that used acylating agent comprises phosphorus trichloride, phosphorus pentachloride, thionyl chloride, phosphorus tribromide, phosphorus pentabromide or thionyl bromide in the step (b).
5. the preparation method of block polymer grafted carbon nanotube according to claim 1, it is characterized in that polyalcohols used in the step (c) or polynary amine substance comprise ethylene glycol, glycerol, 1,2-propylene glycol, 1, ammediol, 1,4-butyleneglycol, 1,2-butyleneglycol, 1,3 butylene glycol, trihydroxybutane, polyoxyethylene glycol, quadrol, third triamine, 1,2-propylene diamine, 1,3-propylene diamine, 1,4-butanediamine, 1,2-butanediamine, 1,3-butanediamine, fourth triamine or polyethyene diamine.
6. the preparation method of block polymer 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, dimethylamino pyridine are that solvent or the mixed solvent that contains these solvents are reaction medium.
7. the preparation method of block polymer grafted carbon nanotube according to claim 1 is characterized in that 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 step (d).
8. the preparation method of block polymer grafted carbon nanotube according to claim 1, it is characterized in that step (e), (f) contain double bond monomer in for carrying out the monomer of Raolical polymerizable, comprise Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, Rocryl 410, the vinylformic acid hydroxy butyl ester, the methacrylic acid hydroxy butyl ester, methyl acrylate, methyl methacrylate, vinylformic acid ammonia ethyl ester, aminoethyl methacrylate, N, N-dimethacrylate ammonia ethyl ester, N, N-dimethyl-aminoethyl methacrylate, vinylbenzene, p-chloromethyl styrene, between 1-chloro-4-methyl-benzene, acrylamide, N, the N-DMAA, Methacrylamide, N, N-dimethyl-Methacrylamide, the N-N-isopropylacrylamide, N-isopropyl-methyl acrylamide, N, N-diethyl acrylamide, N, N-diethyl-4-methyl-acrylamide, N, N-dihydroxy ethyl acrylamide, N-hydroxyethyl acrylamide, the N-hydroxyethyl methacrylamide, N-(trishydroxymethyl) methyl acrylamide, N-aminoethyl acrylamide, N-aminoethyl-Methacrylamide, N-(2-dimethylamino) ethyl acrylamide, Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, Rocryl 410, the vinylformic acid hydroxy butyl ester, the methacrylic acid hydroxy butyl ester, N, N-dihydroxy ethyl acrylamide, N-hydroxyethyl acrylamide, N-hydroxyethyl methacrylamide or N-(trishydroxymethyl) methyl acrylamide.
9. the preparation method of block polymer grafted carbon nanotube according to claim 1 is characterized in that catalyst system therefor is for containing the metallic compound of Cu (I), Fe (I), Mo (V), Re (V), Ru (II), Ni (I), Pb (II) among step (e), (f); 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.
10. the preparation method of block polymer grafted carbon nanotube according to claim 9 is characterized in that catalyst system therefor is cuprous chloride, cuprous bromide, iron protochloride, ferrous bromide, lithium molybdate, ReO among step (e), (f)
2I (PPh
3)
2, RuCl
2, Ni (NCN) Br or Pd (OAc)
2
11. block polymer grafted carbon nanotube is characterized in that the block polymer grafted carbon nanotube that adopts preparation method as described below to obtain:
Step (a): in flask, add 1～10g exsiccant carbon nanometer tube material and 5～50mL acid with strong oxidizing property, with 40～100kHz ultrasonication 30min～100hr post-heating to 20～200 ℃, reaction 0.5～100hr down stirs and refluxes, with the filter membrane suction filtration, repetitive scrubbing repeatedly to neutral, obtains the acidifying carbon nanotube behind 80～180 ℃ of vacuum-drying 10～30hr;
Step (b): in flask, add step (a) gained acidifying carbon nanotube 1～10g and acylating agent 1～100g, 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): in flask, add step (b) gained acidylate carbon nanotube 1～10g and polyalcohols or polynary amine 1～50g, 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, 80～180 ℃ of vacuum-dryings obtain the carbon nanotube that the surface has hydroxyl or amido;
Step (d): in flask, add carbon nanotube 1～10g and alpha-halogen carboxylic acid halides 1～50g 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, 80～180 ℃ of vacuum-dryings obtain the carbon nanotube that the surface has initiating group;
Step (e): add 0.6～5g catalyzer, 0.7～5g part in flask, the surface that adds step (d) gained again has the carbon nanotube 1～10g of initiating group, and solvent 10～50mL fills Ar or N after the sealing
21～100min, add and contain double bond monomer 10～80mL, continue inflated with nitrogen or argon gas 1～100min, react 20～1000hr down at 60～150 ℃, after viscosity is significantly increased, stopped reaction precipitates in methyl alcohol, and the gained precipitation heavily is dissolved in solvent, suction filtration, washing, 80～180 ℃ of vacuum-dryings obtain the macromolecular grafted carbon nanotube of single hop;
Step (f): add 0.4～5g catalyzer, 0.48～5g part in flask, add the macromolecular grafted carbon nanotube 2～10g of single hop that step (e) obtains again, solvent 10～50mL fills Ar or N after the sealing
21～100min, add another kind and contain double bond monomer 10～80mL, continue inflated with nitrogen or argon gas 1～100min, react 10～1000hr down at 50～150 ℃, after viscosity is significantly increased, stopped reaction precipitates in methyl alcohol, and the gained precipitation heavily is dissolved in solvent, suction filtration, washing, 80～180 ℃ of vacuum-dryings obtain block polymer grafted carbon nanotube.
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| CN100355826C (en) * | 2005-12-15 | 2007-12-19 | 上海交通大学 | Preparation process for improving bonding capacity of carbon nanotube with rubber molecule |
| CN100410289C (en) * | 2006-03-14 | 2008-08-13 | 同济大学 | Process for in-situ synthesis of amphiphilic polymer modified carbon nanotube |
| CN101104668B (en) * | 2006-07-12 | 2010-12-01 | 同济大学 | Method for preparing functional carbon nano-tube and application thereof |
| CN100427667C (en) * | 2006-11-02 | 2008-10-22 | 上海交通大学 | Polymer grafted carbon nomo fibre and its preparing method |
| CN102442660B (en) * | 2011-10-14 | 2013-08-28 | 苏州大学 | Surface modified carbon nanotube and preparation method thereof |
| CN102557011A (en) * | 2012-03-09 | 2012-07-11 | 桂林理工大学 | Method for performing functionalization treatment to surface of multi-walled carbon nanotube by utilizing hydrogen peroxide |
| CA2901726C (en) * | 2013-02-20 | 2019-06-04 | Tesla Nanocoatings, Inc. | Functionalized graphitic materials |
| CN104558629B (en) * | 2013-10-17 | 2018-08-17 | 中国石油化工股份有限公司 | A kind of method of microwave radiation to carbon nanotube graft modification |
| CN108192137B (en) * | 2016-12-08 | 2020-08-07 | 中国石油天然气股份有限公司 | Preparation method of high-dispersion carbon nano tube used as rubber filler |
| CN108034040B (en) * | 2017-12-23 | 2020-09-04 | 广东互典缓冲材料技术有限公司 | Tear-resistant buffer material and preparation method and application thereof |
| CN108565386B (en) * | 2018-04-08 | 2021-06-25 | 珠海鹏辉能源有限公司 | Lithium-sulfur battery diaphragm and preparation method thereof, and lithium-sulfur battery and preparation method thereof |
| 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 |
| CN111500001B (en) * | 2020-06-12 | 2022-04-12 | 南京工业大学 | Preparation method and application of carbon nanotube nano composite material |
| CN113024747B (en) * | 2021-03-30 | 2022-04-19 | 西南石油大学 | Hyperbranched polymer based on carbon nano tube and preparation method thereof |
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