CN101693130A - Method for ordered arrangement of magnetic induced multi-wall carbon nano tubes in chitosan basal body - Google Patents

Method for ordered arrangement of magnetic induced multi-wall carbon nano tubes in chitosan basal body Download PDF

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CN101693130A
CN101693130A CN 200910154049 CN200910154049A CN101693130A CN 101693130 A CN101693130 A CN 101693130A CN 200910154049 CN200910154049 CN 200910154049 CN 200910154049 A CN200910154049 A CN 200910154049A CN 101693130 A CN101693130 A CN 101693130A
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chitosan
carbon nano
tubes
magnetic
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CN101693130B (en
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王征科
赵辉
袁望章
胡巧玲
孙景志
唐本忠
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Zhejiang University ZJU
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Zhejiang University ZJU
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Abstract

The invention discloses a method for the ordered arrangement of magnetic induced multi-wall carbon nano tubes in a chitosan basal body, which comprises the following steps: protonizing poly(p-phenylene vinylene), adding FeC12*4H2O and FeC13*6H2O, stirring, regulating the pH value and enabling Fe2+ and Fe3+ to react so as to generate Fe3O4; then, regulating the pH value to be subacidity, adding the multi-wall carbon nano tubes, an acetate water solution and chitosan powder sequentially under stirring, obtaining a magnetic multi-wall carbon nano tube/chitosan mixed solution, standing and defoaming; injecting a little chitosan acetate solution into a mould for coating to form a film, then filling up the mould by the mixed solution, putting permanent magnets at both ends of the mould, soaking in an alkali solidifying liquid and forming a composite gel bar material; and washing the gel bar material by deionized water to be in a neutral state and drying. The invention realizes the parallel ordered arrangement and the uniform dispersion of the multi-wall carbon nano tubes in the polymer basal body, can be used for the magnetic therapy of orthopaedics and the internal fixation of fractures and has extensive application prospect in the field of biomedicine.

Description

The method of magnetic induced multi-wall carbon nano tubes ordered arrangement in chitosan basal body
Technical field
The present invention relates to the method for magnetic induced multi-wall carbon nano tubes ordered arrangement in chitosan basal body.
Background technology
Multi-walled carbon nano-tubes homodisperse and ordered arrangement in polymeric matrix are two key scientific problems of development of new composite, and the multi-walled carbon nano-tubes that is arranged in parallel can improve the mechanical property of composite effectively.But up to the present, also there is not method to realize CNT homodisperse, ordered arrangement in polymeric matrix.
Magnetic material is filled in the osseous tissue and can local magnetic therapy generates heat, and stimulates the osseous tissue growth.Static magnetic field long-time stimulus osseous tissue can prevent that the bone mineral density that is caused by surgical operation from descending.Therefore, adopt the method for magnetic induced orientation to realize multi-walled carbon nano-tubes parallel ordered arrangement in polymeric matrix, have a wide range of applications at biomedical sector.
Summary of the invention
The method that the purpose of this invention is to provide a kind of magnetic induced multi-wall carbon nano tubes ordered arrangement in chitosan basal body is to obtain to have the bone fracture internal fixation material of magnetic therapy functions.
The method of magnetic induced multi-wall carbon nano tubes of the present invention ordered arrangement in chitosan basal body comprises the steps:
1) stir down, it is in 3～5 the aqueous hydrochloric acid solution that 80～100mg poly-joined pH value to the amine phenylacetylene, forms polycation electrolyte, adds 100～140mg FeCl then 24H 2O and 220～280mgFeCl 36H 2O;
2) earlier regulate 1 with alkaline aqueous solution) more than the pH value to 12 of solution, make Fe 2+And Fe 3+Reaction generates Fe 3O 4PH value with the acidic aqueous solution regulator solution is 4～6 then;
3) stirring down, to 2) to add 16mg multi-walled carbon nano-tubes, volume fraction in the solution successively be 2% aqueous acetic acid, the cumulative volume that makes solution is 400ml;
4) adding 20g chitosan powder to 3) in the solution, stir, obtain magnetic multi-walled carbon nano-tubes/chitosan mixed solution, standing and defoaming;
5) be that 2% aqueous acetic acid preparation mass fraction is 5% chitosan solution with volume fraction, the chitosan solution that takes a morsel injects the mould coating filmform, again magnetic multi-walled carbon nano-tubes/chitosan mixed solution is filled with mould, place permanent magnet respectively in both mold ends, be immersed in mass fraction then and be in 5% the alkaline solidification liquid 6h at least, form magnetic orientation multi-walled carbon nano-tubes/chitosan three-dimensional pluralgel bar, be washed with distilled water to neutrality, drying.
Above-mentioned alkaline solidification liquid can be NaOH or KOH.Alkaline aqueous solution can be NaOH, KOH, NaHCO 3, KHCO 3Or ammonia.Acidic aqueous solution can be hydrochloric acid, acetic acid or sulphuric acid.
Beneficial effect of the present invention is:
The present invention adopts chemical precipitation method, by Fe 2+And Fe 3+Reaction generates ferroferric oxide nano granules, and magnetic-particle is coated on the multi-wall carbon nano-tube tube-surface with poly-to the amine phenylacetylene, puts on one deck water solublity, magnetic " overcoat " to multi-walled carbon nano-tubes.Adopt the method for original position precipitating, induced by magnetic field orientation to prepare magnetic orientation carbon pipe/chitosan nano composite bar, multi-walled carbon nano-tubes parallel ordered arrangement, homodisperse in polymeric matrix have been realized, the magnetic orientation multi-walled carbon nano-tubes can improve the mechanical property of composite bar, the magnetic therapy and the fracture internal fixation that are used for orthopaedics, stimulate new osteogenesis, have a wide range of applications at biomedical sector.
Description of drawings
Fig. 1 is the transmission electron microscope photo of composite bar behind ultrathin section of the inventive method preparation.
The specific embodiment
Further specify the present invention below in conjunction with specific embodiment.
Embodiment 1:
1) take by weighing the poly-of 80mg, join pH value and be in 3 the aqueous hydrochloric acid solution, stir 0.5h the amine phenylacetylene, poly-to the amine phenylacetylene by protonated, form polycation electrolyte;
2) to 1) add 100mg FeCl in the solution 24H 2O and 220mg FeCl 36H 2O stirs 0.5h;
3) regulate 2 with sodium bicarbonate aqueous solution) pH value to 12 of solution, make Fe 2+And Fe 3+Reaction generates Fe 3O 4
4) regulate 3 with aqueous hydrochloric acid solution) pH value of solution is 4;
5) the 16mg multi-walled carbon nano-tubes is joined 4) in the solution, stir 0.5h;
6) to 5) to add volume fraction in the solution be 2% aqueous acetic acid, the cumulative volume that makes solution is 400ml;
7) adding 20g chitosan powder to 6) in the solution, stir 0.5h, obtain magnetic multi-walled carbon nano-tubes/chitosan mixed solution, standing and defoaming;
8) be that 2% aqueous acetic acid preparation mass fraction is 5% chitosan solution with volume fraction, the chitosan solution that takes a morsel injects the mould coating filmform, again with 7) solution fills with mould, place permanent magnet respectively in both mold ends, be immersed in mass fraction then and be 6h in 5% the NaOH solidification liquid, form magnetic orientation multi-walled carbon nano-tubes/chitosan three-dimensional pluralgel bar; Be washed with distilled water to neutrality, be placed on temperature and be dry 72h in 60 ℃ the baking oven, obtain magnetic orientation multi-walled carbon nano-tubes/chitosan three-dimensional composite rod material.Composite bar adopts transmission electron microscope can observe multi-walled carbon nano-tubes parallel ordered arrangement, homodisperse (see figure 1) in chitosan basal body behind ultrathin section.
Embodiment 2:
1) take by weighing the poly-of 90mg, join pH value and be in 5 the aqueous hydrochloric acid solution, stir 0.5h the amine phenylacetylene, poly-to the amine phenylacetylene by protonated, form polycation electrolyte;
2) to 1) add 120mg FeCl in the solution 24H 2O and 240mg FeCl 36H 2O stirs 0.5h;
3) regulate 2 with potassium bicarbonate aqueous solution) pH value to 12.5 of solution, make Fe 2+And Fe 3+Reaction generates Fe 3O 4
4) regulate 3 with aqueous acetic acid) pH value of solution is 5;
5) the 16mg multi-walled carbon nano-tubes is joined 4) in the solution, stir 0.5h;
6) to 5) to add volume fraction in the solution be 2% aqueous acetic acid, the cumulative volume that makes solution is 400ml;
7) adding 20g chitosan powder to 6) in the solution, stir 0.5h, obtain magnetic multi-walled carbon nano-tubes/chitosan mixed solution, standing and defoaming;
8) be that 2% aqueous acetic acid preparation mass fraction is 5% chitosan solution with volume fraction, the chitosan solution that takes a morsel injects the mould coating filmform, again with 7) solution fills with mould, place permanent magnet respectively in both mold ends, be immersed in mass fraction then and be 12h in 5% the KOH solidification liquid, form magnetic orientation multi-walled carbon nano-tubes/chitosan three-dimensional pluralgel bar; Be washed with distilled water to neutrality, be placed on temperature and be dry 72h in 80 ℃ the baking oven, obtain magnetic orientation multi-walled carbon nano-tubes/chitosan three-dimensional composite rod material.
Embodiment 3:
1) take by weighing the poly-of 100mg, join pH value and be in 4 the aqueous hydrochloric acid solution, stir 1h the amine phenylacetylene, poly-to the amine phenylacetylene by protonated, form polycation electrolyte;
2) to 1) add 140mg FeCl in the solution 24H 2O and 280mg FeCl 36H 2O stirs 1h;
3) regulate 2 with ammonia spirit) pH value to 13 of solution, make Fe 2+And Fe 3+Reaction generates Fe 3O 4
4) regulate 3 with aqueous sulfuric acid) pH value of solution is 6;
5) the 16mg multi-walled carbon nano-tubes is joined 4) in the solution, stir 1h;
6) to 5) to add volume fraction in the solution be 2% aqueous acetic acid, the cumulative volume that makes solution is 400ml;
7) adding 20g chitosan powder to 6) in the solution, stir 1h, obtain magnetic multi-walled carbon nano-tubes/chitosan mixed solution, standing and defoaming;
8) be that 2% aqueous acetic acid preparation mass fraction is 5% chitosan solution with volume fraction, the chitosan solution that takes a morsel injects the mould coating filmform, again with 7) solution fills with mould, place permanent magnet respectively in both mold ends, be immersed in mass fraction then and be 24h in 5% the NaOH solidification liquid, form magnetic orientation multi-walled carbon nano-tubes/chitosan three-dimensional pluralgel bar; Be washed with distilled water to neutrality, be placed on temperature and be dry 72h in 65 ℃ the baking oven, obtain magnetic orientation multi-walled carbon nano-tubes/chitosan three-dimensional composite rod material.

Claims (4)

1. the method for magnetic induced multi-wall carbon nano tubes ordered arrangement in chitosan basal body comprises the steps:
1) stir down, it is in 3～5 the aqueous hydrochloric acid solution that 80～100mg poly-joined pH value to the amine phenylacetylene, forms polycation electrolyte, adds 100～140mg FeCl then 24H 2O and 220～280mgFeCl 36H 2O;
2) earlier regulate 1 with alkaline aqueous solution) more than the pH value to 12 of solution, make Fe 2+And Fe 3+Reaction generates Fe 3O 4PH value with the acidic aqueous solution regulator solution is 4～6 then;
3) stirring down, to 2) to add 16mg multi-walled carbon nano-tubes, volume fraction in the solution successively be 2% aqueous acetic acid, the cumulative volume that makes solution is 400ml;
4) adding 20g chitosan powder to 3) in the solution, stir, obtain magnetic multi-walled carbon nano-tubes/chitosan mixed solution, standing and defoaming;
5) be that 2% aqueous acetic acid preparation mass fraction is 5% chitosan solution with volume fraction, the chitosan solution that takes a morsel injects the mould coating filmform, again magnetic multi-walled carbon nano-tubes/chitosan mixed solution is filled with mould, place permanent magnet respectively in both mold ends, be immersed in mass fraction then and be in 5% the alkaline solidification liquid 6h at least, form magnetic orientation multi-walled carbon nano-tubes/chitosan three-dimensional pluralgel bar, be washed with distilled water to neutrality, drying.
2. the method for magnetic induced multi-wall carbon nano tubes according to claim 1 ordered arrangement in chitosan basal body is characterized in that alkaline solidification liquid is NaOH or KOH.
3. the method for magnetic induced multi-wall carbon nano tubes according to claim 1 ordered arrangement in chitosan basal body is characterized in that alkaline aqueous solution is NaOH, KOH, NaHCO 3, KHCO 3Or ammonia.
4. the method for magnetic induced multi-wall carbon nano tubes according to claim 1 ordered arrangement in chitosan basal body is characterized in that acidic aqueous solution is hydrochloric acid, acetic acid or sulphuric acid.
CN 200910154049 2009-10-22 2009-10-22 Method for ordered arrangement of magnetic induced multi-wall carbon nano tubes in chitosan basal body Expired - Fee Related CN101693130B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107010613A (en) * 2017-02-22 2017-08-04 延边大学 The preparation method of conductive magneto-conductive nano-functional material

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107010613A (en) * 2017-02-22 2017-08-04 延边大学 The preparation method of conductive magneto-conductive nano-functional material

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