CN101693131A - Method for reinforcing modified three-dimensional chitosan bar material by water soluble multi-wall carbon nano tubes - Google Patents
Method for reinforcing modified three-dimensional chitosan bar material by water soluble multi-wall carbon nano tubes Download PDFInfo
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- CN101693131A CN101693131A CN200910154050A CN200910154050A CN101693131A CN 101693131 A CN101693131 A CN 101693131A CN 200910154050 A CN200910154050 A CN 200910154050A CN 200910154050 A CN200910154050 A CN 200910154050A CN 101693131 A CN101693131 A CN 101693131A
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- 239000002048 multi walled nanotube Substances 0.000 title claims abstract description 60
- 229920001661 Chitosan Polymers 0.000 title claims abstract description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 title claims abstract description 10
- 239000000463 material Substances 0.000 title abstract description 11
- 230000003014 reinforcing effect Effects 0.000 title abstract 2
- 239000000243 solution Substances 0.000 claims abstract description 42
- 238000003756 stirring Methods 0.000 claims abstract description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 239000003792 electrolyte Substances 0.000 claims abstract description 7
- 239000012153 distilled water Substances 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 30
- UEXCJVNBTNXOEH-UHFFFAOYSA-N phenyl acethylene Natural products C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 claims description 16
- 238000005303 weighing Methods 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000007711 solidification Methods 0.000 claims description 7
- 230000008023 solidification Effects 0.000 claims description 7
- 230000002708 enhancing effect Effects 0.000 claims description 6
- 230000001186 cumulative effect Effects 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 abstract description 2
- -1 poly(p-phenylene vinylene) Polymers 0.000 abstract 2
- 229920000553 poly(phenylenevinylene) Polymers 0.000 abstract 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 abstract 1
- 239000003513 alkali Substances 0.000 abstract 1
- PAFYVDNYOJAWDX-UHFFFAOYSA-L calcium;2,2,2-trichloroacetate Chemical compound [Ca+2].[O-]C(=O)C(Cl)(Cl)Cl.[O-]C(=O)C(Cl)(Cl)Cl PAFYVDNYOJAWDX-UHFFFAOYSA-L 0.000 abstract 1
- 230000007935 neutral effect Effects 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 238000005452 bending Methods 0.000 description 8
- 239000011165 3D composite Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 241001597008 Nomeidae Species 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 208000010392 Bone Fractures Diseases 0.000 description 1
- 102000004316 Oxidoreductases Human genes 0.000 description 1
- 108090000854 Oxidoreductases Proteins 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009933 burial Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
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Abstract
The invention discloses a method for reinforcing a modified three-dimensional chitosan bar material by water soluble multi-wall carbon nano tubes, which comprises the following steps: adding poly(p-phenylene vinylene) into a dilute hydrochloric acid water solution, stirring, protonizing the poly(p-phenylene vinylene) to form polycationic electrolyte; adding multi-wall carbon nano tubes into the solution to form the water soluble multi-wall carbon nano tubes; afterwards, adding an acetate water solution; then, adding chitosan powder, stirring, forming a water soluble multi-wall carbon nano tube/chitosan mixed solution, standing and defoaming; and injecting the solution into a mould, infiltrating and dispersing by an alkali solidifying liquid to obtain a three-dimensional chitosan gel bar material modified by the water soluble multi-wall carbon nano tubes; and washing by distilled water to be in a neutral state and drying. The invention realizes the purpose of uniform dispersion of the multi-wall carbon nano tubes in the chitosan basal body, enhances the mechanical property of the chitosan bar material effectively and can be used as an internal fixation material of clinical fractures.
Description
Technical field
The present invention relates to method with water-soluble multi-wall carbon nanotube enhancing modified three-dimensional chitosan rod.
Background technology
Multi-walled carbon nano-tubes has excellent mechanical property and excellent biological compatibility, can be used for the bio-medical field, as: drug delivery system, biosensor and tissue engineering material etc.Simultaneously, multi-walled carbon nano-tubes can be used as reinforcing material, but they are insoluble to any solvent, and high temperature is not molten.Because the multi-wall carbon nano-tube tube-surface exists π-πGong Ezuoyong and Van der Waals force, they tend to be gathered into bulk, are difficult for disperseing, and cause reinforced effects not good.
Multi-walled carbon nano-tubes homodisperse in matrix is a key factor of improving reinforced effects, can improve its dispersibility by approach such as plasma functionalized, acid oxidases, but these methods can be destroyed the structure of multi-walled carbon nano-tubes.The dispersibility that utilizes polymeric coating layer to improve multi-walled carbon nano-tubes is a valid approach, as: utilize the macromolecule making coatings with conjugated chain, non-covalent functionalization multi-walled carbon nano-tubes can not damage its mechanical property.Polyacetylene and derivant thereof belong to the conjugated chain macromolecule, have the characteristic of many novelties, as: photoconduction, electroluminescent, liquid crystal characteristic, biocompatibility, cytotropism etc.Employing has high polar polyphenylacetylene derivant and coats multi-walled carbon nano-tubes, and it is dissolved in the aqueous medium.
Summary of the invention
The purpose of this invention is to provide a kind of method with water-soluble multi-wall carbon nanotube enhancing modified three-dimensional chitosan rod, this method can make high-intensity water-soluble multi-wall carbon nanotube/chitosan three-dimensional composite rod material, can be used as clinical bone fracture internal fixation material.
Method with water-soluble multi-wall carbon nanotube enhancing modified three-dimensional chitosan rod of the present invention, its concrete steps are as follows:
1) stir down, it is in 5 the aqueous hydrochloric acid solution that 20～40mg poly-joined pH value to the amine phenylacetylene, forms polycation electrolyte;
2) by multi-walled carbon nano-tubes with poly-be 1: 5 to amine phenylacetylene mass ratio, take by weighing multi-walled carbon nano-tubes and join 1) in the solution, stir, form water-soluble multi-wall carbon nanotube;
3) to 2) to add volume fraction in the solution be 2% aqueous acetic acid, the cumulative volume that makes solution is 200ml;
4) take by weighing 10g chitosan powder, join 3) in the solution, stir, form water-soluble multi-wall carbon nanotube/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 mould and forms one deck inner membrance earlier, then water-soluble multi-wall carbon nanotube/chitosan mixed solution is injected mould, again mould is put into mass fraction and is 5% alkaline solidification liquid, solidify 6h at least, the demoulding obtains water-soluble multi-wall carbon nanotube/chitosan three-dimensional pluralgel bar; Be washed with distilled water to neutrality, drying.
Above-mentioned alkaline solidification liquid can be NaOH or KOH.
Beneficial effect of the present invention is:
Chitosan all contains amino with poly-to the amine phenylacetylene, can be changed into polycation electrolyte by sour proton simultaneously.Poly-can closely be coated on the multi-wall carbon nano-tube tube-surface by π-πGong Ezuoyong and electron donor-receptor effect to the amine phenylacetylene, form core/shell structure, the outer field polyelectrolyte of multi-walled carbon nano-tubes can be dissolved in the aqueous medium it.With poly-the amine phenylacetylene is run into a large amount of OH by protonated chitosan
-During ion, neutralization reaction will take place in them, separate out again.Adopt coprecipitation with the multi-walled carbon nano-tubes emergency burial in chitosan basal body, thereby realized multi-walled carbon nano-tubes aim of even dispersion in polymeric matrix.When the multi-walled carbon nano-tubes when 0.08% joined in the chitosan basal body, the bending strength of composite bar and bending modulus reached 135.5MPa, 4.8GPa, compared with not composite modified chitosan bar and had improved 46.6%, 17.1% respectively.The content of homodisperse water-soluble multi-wall carbon nanotube in chitosan basal body seldom but can effectively be born load, thereby has improved the mechanical property of three-dimensional chitosan rod.
Description of drawings
Fig. 1 is that water-soluble multi-wall carbon nanotube is dispersed in the transmission electron microscope photo in the chitosan basal body.
The specific embodiment
Further specify the present invention below in conjunction with specific embodiment.
Embodiment 1:
1) take by weighing the poly-of 20mg, 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) by multi-walled carbon nano-tubes with poly-be 1: 5 to amine phenylacetylene mass ratio, take by weighing multi-walled carbon nano-tubes 4mg, and join 1) in the solution, stir, form water-soluble multi-wall carbon nanotube;
3) to 2) to add volume fraction in the solution be 2% aqueous acetic acid, the cumulative volume that makes solution is 200ml;
4) take by weighing 10g chitosan powder, join 3) in the solution, stir 0.5h, form water-soluble multi-wall carbon nanotube/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 mould and forms one deck inner membrance earlier, then with 4) solution injection mould, again mould is put into mass fraction and is 5% NaOH solidification liquid, solidify 6h, the demoulding obtains water-soluble multi-wall carbon nanotube/chitosan three-dimensional pluralgel bar; Be washed with distilled water to neutrality, dry 72h obtains water-soluble multi-wall carbon nanotube/chitosan three-dimensional composite rod material in 60 ℃ baking oven.
The Mechanics Performance Testing result:
Bending strength: 97.7MPa
Bending modulus: 4.1GPa
Embodiment 2:
1) take by weighing the poly-of 25mg, join pH value and be in 5 the aqueous hydrochloric acid solution, stir 1h the amine phenylacetylene, poly-to the amine phenylacetylene by protonated, form polycation electrolyte;
2) by multi-walled carbon nano-tubes with poly-be 1: 5 to amine phenylacetylene mass ratio, take by weighing multi-walled carbon nano-tubes 5mg, and join 1) in the solution, stir, form water-soluble multi-wall carbon nanotube;
3) to 2) to add volume fraction in the solution be 2% aqueous acetic acid, the cumulative volume that makes solution is 200ml;
4) take by weighing 10g chitosan powder, join 3) in the solution, stir 1h, form water-soluble multi-wall carbon nanotube/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 mould and forms one deck inner membrance earlier, then with 4) solution injection mould, again mould is put into mass fraction and is 5% KOH solidification liquid, solidify 24h, the demoulding obtains water-soluble multi-wall carbon nanotube/chitosan three-dimensional pluralgel bar; Be washed with distilled water to neutrality, dry 120h obtains water-soluble multi-wall carbon nanotube/chitosan three-dimensional composite rod material in 80 ℃ baking oven.
The Mechanics Performance Testing result:
Bending strength: 105.3MPa
Bending modulus: 4.2GPa
Embodiment 3:
1) take by weighing the poly-of 40mg, 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) by multi-walled carbon nano-tubes with poly-be 1: 5 to amine phenylacetylene mass ratio, take by weighing multi-walled carbon nano-tubes 8mg, and join 1) in the solution, stir, form water-soluble multi-wall carbon nanotube;
3) to 2) to add volume fraction in the solution be 2% aqueous acetic acid, the cumulative volume that makes solution is 200ml;
4) take by weighing 10g chitosan powder, join 3) in the solution, stir 0.5h, form water-soluble multi-wall carbon nanotube/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 mould and forms one deck inner membrance earlier, then with 4) solution injection mould, again mould is put into mass fraction and is 5% NaOH solidification liquid, solidify 12h, the demoulding obtains water-soluble multi-wall carbon nanotube/chitosan three-dimensional pluralgel bar; Be washed with distilled water to neutrality, dry 96h obtains water-soluble multi-wall carbon nanotube/chitosan three-dimensional composite rod material in 65 ℃ baking oven.Its transmission electron microscope photo as shown in Figure 1, as seen from the figure, multi-walled carbon nano-tubes is dispersed in the chitosan basal body.
The Mechanics Performance Testing result:
Bending strength: 135.5MPa
Bending modulus: 4.8GPa
Claims (2)
1. with the method for water-soluble multi-wall carbon nanotube enhancing modified three-dimensional chitosan rod, its concrete steps are as follows:
1) stir down, it is in 5 the aqueous hydrochloric acid solution that 20～40mg poly-joined pH value to the amine phenylacetylene, forms polycation electrolyte;
2) by multi-walled carbon nano-tubes with poly-be 1: 5 to amine phenylacetylene mass ratio, take by weighing multi-walled carbon nano-tubes and join 1) in the solution, stir, form water-soluble multi-wall carbon nanotube;
3) to 2) to add volume fraction in the solution be 2% aqueous acetic acid, the cumulative volume that makes solution is 200ml;
4) take by weighing 10g chitosan powder, join 3) in the solution, stir, form water-soluble multi-wall carbon nanotube/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 mould and forms one deck inner membrance earlier, then water-soluble multi-wall carbon nanotube/chitosan mixed solution is injected mould, again mould is put into mass fraction and is 5% alkaline solidification liquid, solidify 6h at least, the demoulding obtains water-soluble multi-wall carbon nanotube/chitosan three-dimensional pluralgel bar; Be washed with distilled water to neutrality, drying.
2. the method for water-soluble multi-wall carbon nanotube enhancing modified three-dimensional chitosan rod according to claim 1 is characterized in that alkaline solidification liquid is NaOH or KOH.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102120044A (en) * | 2011-03-10 | 2011-07-13 | 卢亢 | Chitosan and carbon nanometer tube compound surgical dressing and preparation method thereof |
| CN109266314A (en) * | 2018-11-16 | 2019-01-25 | 北京师范大学 | A kind of flexible compound phase-change material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101491695B (en) * | 2009-03-03 | 2012-06-27 | 陕西科技大学 | Preparation method of carbon nano-tube reinforced chitosan/silicon-containing hydroxylapatite composite material |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102120044A (en) * | 2011-03-10 | 2011-07-13 | 卢亢 | Chitosan and carbon nanometer tube compound surgical dressing and preparation method thereof |
| CN102120044B (en) * | 2011-03-10 | 2012-03-21 | 广东泰宝科技医疗用品有限公司 | Chitosan and carbon nanometer tube compound surgical dressing and preparation method thereof |
| CN109266314A (en) * | 2018-11-16 | 2019-01-25 | 北京师范大学 | A kind of flexible compound phase-change material and preparation method thereof |
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