CN1254514C - Nano carbon tube grafted with super branched polymer synthesized in situ and preparation method - Google Patents
Nano carbon tube grafted with super branched polymer synthesized in situ and preparation method Download PDFInfo
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- CN1254514C CN1254514C CN 200410017695 CN200410017695A CN1254514C CN 1254514 C CN1254514 C CN 1254514C CN 200410017695 CN200410017695 CN 200410017695 CN 200410017695 A CN200410017695 A CN 200410017695A CN 1254514 C CN1254514 C CN 1254514C
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Abstract
The present invention provides a carbon nano tube grafted with a home position synthetized-superbranched polymer and a preparing method thereof. The carbon nano tube is acidified and acylated to react with a polyhydroxylated compound, and the surface of the carbon nano tube is provided with a large amount of hydroxyls. Then, the activity hydroxyls are used to initiate home position ring-opening polymerization to obtain the carbon nano tube grafted with the home position synthetized-superbranched polymer. Good solubility is represented in organic solvent for the carbon nano tube grafted with the home position synthetized-superbranched polymer. The carbon nano tube can be used as the special additive of high molecular material for preparing nano high-strength composite material and wave absorbing material. Meanwhile, the carbon nano tube can be used as a nano element with special functions due to the nano-grade size of the carbon nano tube and can also be used as a carrier for transferring substances between different systems. Consequently, the carbon nano tube has wide application prospects in various aspects of nano science, material science and biomedicine.
Description
Technical field: the present invention relates to a kind of novel method for preparing the carbon nanotube of polymer graft, particularly carbon nanotube of original position synthesis of super branched polymer graft 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, hyperbranched polymer is the research focus of polymkeric substance research field in recent years, owing to have particular structure and performance, very big application prospect must be arranged.And, obtain good grafted carbon nanotube than former grafting method is easier at carbon nano tube surface situ-formed graft hyperbranched polymer.Utilize original position synthetic method advantage, 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, the carbon nanotube of preparation original position synthesis of super branched polymer graft 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 home position polymerization reaction, thereby can cause the polymerization of specific monomer; In the presence of catalyzer, use home position polymerization reaction grafting hyperbranched polymer then, then obtain the carbon nanotube of original position synthesis of super branched polymer graft.
The concrete preparation method of the carbon nanotube of original position synthesis of super branched polymer graft 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, with 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 1～50 weight part, sealing, take out inflated with nitrogen repeatedly three times, behind 0～100kHz ultrasonication, 10～1000min, behind reaction 0.1～100hr under-20～200 ℃, suction filtration is behind the repetitive scrubbing, 0～180 ℃ of vacuum-drying obtains the carbon nanotube that the surface has hydroxyl;
Step (d): add carbon nanotube 1 weight part that step (c) gained surface has hydroxyl, sealing is taken out inflated with nitrogen three times repeatedly, adds catalyzer boron trifluoride diethyl etherate 0.1～10 weight part and solvent 1～50 weight part again, behind 0～100kHz ultrasonication, 10～1000min, drip monomer 0.1-50 down at-20～200 ℃) weight part, behind reaction 0.1～50hr, termination reaction, suction filtration, after the washing, 0～180 ℃ of vacuum-drying obtains the carbon nanotube of original position synthesis of super branched polymer graft.
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).
Used polyvalent alcohol comprises ethylene glycol, glycerol, 1,2-propylene glycol, 1, ammediol, 1,4-butyleneglycol, 1,2-butyleneglycol, 1,3 butylene glycol, trihydroxybutane or polyoxyethylene glycol in the inventive method step (c).
Used monomer comprises 3-ethyl-3-(methylol)-oxa-ring, 3-methyl-3-(methylol)-oxa-ring, 2-hydroxyethyl caprolactone, dehydration glycerine etc. in the inventive method step (d).Shown in the following chemical structural formula:
Solvent for use comprises methylene dichloride, chloroform, ethyl acetate, acetone in the inventive method step (d).
Preparation method provided by the invention is simple, and controllability is strong; The carbon nanotube of gained original position synthesis of super branched polymer graft 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: a kind of carbon nanotube transmission electron microscope picture of original position synthesis of super branched polymer graft
Fig. 2: a kind of carbon nanotube thermogravimetric analysis curve of original position synthesis of super branched polymer graft
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; after connecting ethylene glycol; in the presence of boron trifluoride diethyl etherate, cause 3-ethyl-3-methylol butylene oxide ring polymerization, then obtain the carbon nanotube of original position synthesis of super branched polymer graft.
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 0.1g of hydroxyl, sealing, take out inflated with nitrogen repeatedly three times, seal with the turned welt soft rubber ball, take out inflated with nitrogen repeatedly three times, add catalyzer boron trifluoride diethyl etherate 1g, behind 40kHz ultrasonication 30min, drip 3-ethyl-3-methylol butylene oxide ring 5g, after under ice-water bath, reacting 24hr, termination reaction, suction filtration are removed unreacted reactant and byproduct of reaction, repeatedly with behind the deionized water wash, 80 ℃ of vacuum-dryings obtain the carbon nanotube of original position synthesis of super branched polymer graft.
Fig. 1 has provided the carbon nanotube transmission electron microscope picture of original position synthesis of super branched polymer graft, and carbon nanotube is enclosed with the polymkeric substance of one deck light color as can be seen.
Can estimate the polymer graft amount from heat analysis data (Fig. 2) and probably account for 65% of total mass.
Embodiment 2: the multi-walled carbon nano-tubes with catalytic pyrolysis method preparation is initial raw material, and is acidified, after the acidylate, connect ethylene glycol after, in the presence of boron trifluoride diethyl etherate, cause the glycerol polymerization that dewaters, then obtain the carbon nanotube of original position synthesis of super branched polyether grafting.
Step (a) and (b), (c) are with embodiment 1; 3-ethyl in the step (d)-3-methylol butylene oxide ring is changed to dehydration glycerine, and other technical process is constant, obtains target product, and hot analytical results shows that polymer content is 70%.
Claims (7)
1. the preparation method of the carbon nanotube of original position synthesis of super branched polymer graft 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 0～100kHz 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;
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 1～50 weight part, sealing, take out inflated with nitrogen repeatedly three times, behind 0～100kHz ultrasonication, 10～1000min, behind reaction 0.1～100hr under-20～200 ℃, suction filtration is behind the repetitive scrubbing, 0～180 ℃ of vacuum-drying obtains the carbon nanotube that the surface has hydroxyl;
Step (d): add carbon nanotube 1 weight part that step (c) gained surface has hydroxyl, sealing is taken out inflated with nitrogen three times repeatedly, adds catalyzer boron trifluoride diethyl etherate 0.1～10 weight part and solvent 1～50 weight part again, behind 0～100kHz ultrasonication, 10～1000min, drip monomer 0.1-50 weight part down at-20～200 ℃, behind reaction 0.1～50hr, termination reaction, suction filtration, after the washing, 0～180 ℃ of vacuum-drying obtains the carbon nanotube of original position synthesis of super branched polymer graft; Used monomer is selected from a kind of in the chemical structural formula as follows:
2. the preparation method of the carbon nanotube of original position synthesis of super branched polymer graft 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 the carbon nanotube of original position synthesis of super branched polymer graft according to claim 1 is characterized in that the used acid with strong oxidizing property of step (a) is selected from 0.1～70wt% nitric acid, 0.1～100wt% 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 the carbon nanotube of original position synthesis of super branched polymer graft 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).
5. the preparation method of the carbon nanotube of original position synthesis of super branched polymer graft according to claim 1, it is characterized in that used polyvalent alcohol is selected from ethylene glycol, glycerol, 1 in the step (c), the 2-propylene glycol, 1, ammediol, 1,4-butyleneglycol, 1,2-butyleneglycol, 1,3 butylene glycol, trihydroxybutane or polyoxyethylene glycol.
6. the preparation method of the carbon nanotube of original position synthesis of super branched polymer graft according to claim 1 is characterized in that solvent for use is selected from methylene dichloride, chloroform, ethyl acetate or acetone in the step (d).
7. the carbon nanotube of original position synthesis of super branched polymer graft is characterized in that adopting the carbon nanotube of the original position synthesis of super branched polymer graft that each described preparation method of claim 1-6 obtains.
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| CN102730674B (en) * | 2012-07-08 | 2013-11-06 | 西北工业大学 | Hydrosilylation method for modifying graphene |
| CN103407999B (en) * | 2013-07-21 | 2015-05-13 | 西北工业大学 | Method for microwave-assisted preparation of hyperbranched polycyclophosphazene grafted graphene |
| CN106185861A (en) * | 2015-05-29 | 2016-12-07 | 天津工业大学 | A kind of new oxidation system method to multi-walled carbon nano-tubes functionalization |
| CN107857303B (en) * | 2017-11-07 | 2019-05-24 | 陕西科技大学 | The hydrophilic ferro-carbon composite nano particle and preparation method thereof modified based on hydrogen peroxide and PEG |
| CN109250963B (en) * | 2018-09-29 | 2021-07-16 | 福建省昊立建设工程有限公司 | Composite toughened concrete and preparation method thereof |
| CN111468071B (en) * | 2020-04-09 | 2022-09-20 | 中冶华天工程技术有限公司 | Rapid preparation method of magnetically separable composite adsorption material |
| CN112023894B (en) * | 2020-08-26 | 2023-05-16 | 扬州工业职业技术学院 | Sewage treatment additive and preparation method thereof |
| CN112811413B (en) * | 2021-03-30 | 2023-09-26 | 无锡零一未来新材料技术研究院有限公司 | Modification method of carbon nano tube, modified carbon nano tube and application thereof |
| 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 |
| CN113214638B (en) * | 2021-05-27 | 2022-04-22 | 湖南飞鸿达新材料有限公司 | Wave-absorbing heat-conducting flexible composite material and preparation method thereof |
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