CN101664568B - Method for enhancing and modifying three-dimensional chitosan bar material by using carboxyl chitosan - Google Patents
Method for enhancing and modifying three-dimensional chitosan bar material by using carboxyl chitosan Download PDFInfo
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- CN101664568B CN101664568B CN200910152873A CN200910152873A CN101664568B CN 101664568 B CN101664568 B CN 101664568B CN 200910152873 A CN200910152873 A CN 200910152873A CN 200910152873 A CN200910152873 A CN 200910152873A CN 101664568 B CN101664568 B CN 101664568B
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- chitosan
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- 229920001661 Chitosan Polymers 0.000 title claims abstract description 121
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 title claims abstract description 36
- 239000000463 material Substances 0.000 title claims abstract description 16
- 230000002708 enhancing effect Effects 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 title claims abstract description 11
- 239000000243 solution Substances 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 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 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- 229960000583 acetic acid Drugs 0.000 claims abstract description 6
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 239000012153 distilled water Substances 0.000 claims abstract description 6
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000007711 solidification Methods 0.000 claims description 12
- 230000008023 solidification Effects 0.000 claims description 12
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 7
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 7
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims description 7
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 239000000052 vinegar Substances 0.000 claims description 5
- 235000021419 vinegar Nutrition 0.000 claims description 5
- 239000012467 final product Substances 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract description 4
- 230000001112 coagulating effect Effects 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 230000007935 neutral effect Effects 0.000 abstract 1
- 239000012466 permeate Substances 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 238000005452 bending Methods 0.000 description 8
- 230000008014 freezing Effects 0.000 description 3
- 238000007710 freezing Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 208000010392 Bone Fractures Diseases 0.000 description 2
- 230000029663 wound healing Effects 0.000 description 2
- 239000011165 3D composite Substances 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 description 1
- 230000000680 avirulence Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000019305 fibroblast migration Effects 0.000 description 1
- 230000033001 locomotion Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
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- Cosmetics (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention discloses a method for enhancing and modifying three-dimensional chitosan bar material by using carboxyl chitosan. The method comprises the following steps: adding carboxyl chitosan in deionized water, then adding glacial acetic acid, adding chitosan powder, stirring to obtain carboxyl chitosan/chitosan mixed solution, standing for defoaming, injecting chitosan solution in moulds to form a layer of inner film, then injecting the carboxyl chitosan/chitosan mixed solution in moulds, using alkaline coagulating liquid to permeate and spread, self-assembling to obtain carboxyl chitosan/chitosan composite gel bar material, washing the gel bar material with distilled water to be neutral and drying. The carboxyl chitosan/chitosan composite gel bar material prepared by the method of the invention has good mechanical properties, thus meeting the clinical operating requirements of the fracture internal fixation.
Description
Technical field
The present invention relates to the method for enhancing and modifying three-dimensional chitosan bar material by using carboxyl chitosan.
Background technology
Using carboxyl chitosan is the derivant of chitosan, and water soluble has the performance of many excellences, as: moisture retention, avirulence, biodegradability, biocompatibility, antibiotic property etc.The wound healing experiment shows in the body, in the collagen matrix, adds using carboxyl chitosan and can significantly promote wound healing, possibly be because using carboxyl chitosan can stimulate the fibroblast migration.Using carboxyl chitosan can improve the mechanical property of collagem membrane as reinforcing agent.Using carboxyl chitosan when 0.1% joins in the paper, can significantly improve the mechanical strength of paper.Therefore, can adopt enhancing and modifying three-dimensional chitosan bar material by using carboxyl chitosan, to satisfy the requirement of the clinical use of orthopaedics.
Summary of the invention
The method that the purpose of this invention is to provide a kind of enhancing and modifying three-dimensional chitosan bar material by using carboxyl chitosan, the compound bone fracture internal fixation material of biodegradable to obtain, high-intensity using carboxyl chitosan/chitosan three-dimensional.
The method of enhancing and modifying three-dimensional chitosan bar material by using carboxyl chitosan of the present invention may further comprise the steps:
1) by per 1～4g using carboxyl chitosan, joins in the 392ml deionized water, stir 0.5～1h, add the 8ml glacial acetic acid then, stir 0.5～2h;
2) stir down, in step 1) solution, add 20g chitosan powder, obtain using carboxyl chitosan/chitosan mixed solution, standing and defoaming by per 1～4g using carboxyl chitosan;
3) the chitosan powder being dissolved in volume fraction is in 2% the spirit of vinegar, is mixed with mass fraction and is 4%～5% chitosan solution, standing and defoaming;
4) the take a morsel chitosan solution of step 3) injects mould and forms one deck inner membrance earlier; Then with step 2) solution inject mould; Again mould being put into mass fraction is 5% alkaline solidification liquid, solidifies 6～24h, the demoulding; Obtain using carboxyl chitosan chitosan modified gel bar, be washed with distilled water to neutrality;
5) using carboxyl chitosan/chitosan plural gel bar is dry under 60 ℃～80 ℃, get final product.
Above-mentioned using carboxyl chitosan is carboxymethyl chitosan, carboxylic butyl chitosan or N-carboxylic propionyl chitosan sodium; The alkalescence solidification liquid is NaOH or KOH.
Beneficial effect of the present invention is:
There is very strong electrostatic interaction between the carboxylate functional group on amino on the chitosan molecule chain, acetamido and the using carboxyl chitosan strand; Can limit the motion of macromolecular chain; Make material become tightr simultaneously, thereby improved the mechanical property of composite bar.When the using carboxyl chitosan that contains 15% in using carboxyl chitosan/chitosan three-dimensional composite rod material; The bending strength of composite bar and bending modulus can reach 156.0MPa, 5.3GPa; Compare with unmodified chitosan bar and to have improved 68.8%, 29.3% respectively, can satisfy the clinical instructions for use of fracture internal fixation.
The specific embodiment
Further specify the present invention below in conjunction with specific embodiment.
Embodiment 1:
1) takes by weighing the 1g carboxymethyl chitosan, join in the 392ml deionized water, stir 0.5h, add the 8ml glacial acetic acid then, stir 0.5h;
2) stir down, in step 1) solution, add 20g chitosan powder, obtain carboxymethyl chitosan/chitosan mixed solution, standing and defoaming;
3) the chitosan powder being dissolved in volume fraction is in 2% the spirit of vinegar, is mixed with mass fraction and is 4% chitosan solution, standing and defoaming;
4) the take a morsel chitosan solution of step 3) evenly is coated on die surface, and it is 5% NaOH solidification liquid that mould is placed mass fraction, chitosan freezing film under the room temperature, and the demoulding obtains chitosan film; Then with step 2) solution inject mould, again mould being put into mass fraction is 5% NaOH solidification liquid, solidifies 6h, the demoulding obtains carboxymethyl chitosan chitosan modified gel bar, is washed with distilled water to neutrality;
5) carboxymethyl chitosan/chitosan plural gel bar being placed on temperature is dry 72h in 60 ℃ the baking oven, promptly obtains the three-dimensional chitosan rod of carboxymethyl chitosan enhancing modified.The Mechanics Performance Testing result:
Bending strength: 145.9MPa
Bending modulus: 5.1GPa
Embodiment 2:
1) takes by weighing 3g N-carboxylic propionyl chitosan sodium, join in the 392ml deionized water, stir 1h, add the 8ml glacial acetic acid then, stir 2h;
2) stir down, in step 1) solution, add 20g chitosan powder, obtain N-carboxylic propionyl chitosan sodium/chitosan mixed solution, standing and defoaming;
3) the chitosan powder being dissolved in volume fraction is in 2% the spirit of vinegar, is mixed with mass fraction and is 5% chitosan solution, standing and defoaming;
4) the take a morsel chitosan solution of step 3) evenly is coated on die surface, and it is 5% NaOH solidification liquid that mould is placed mass fraction, chitosan freezing film under the room temperature, and the demoulding obtains chitosan film; Then with step 2) solution inject mould, again mould being put into mass fraction is 5% NaOH solidification liquid, solidifies 12h, the demoulding obtains N-carboxylic propionyl chitosan sodium chitosan modified gel bar, is washed with distilled water to neutrality;
5) N-carboxylic propionyl chitosan sodium/chitosan plural gel bar being placed on temperature is dry 96h in 65 ℃ the baking oven, promptly obtains the three-dimensional chitosan rod of N-carboxylic propionyl chitosan sodium enhancing modified.The Mechanics Performance Testing result:
Bending strength: 156.0MPa
Bending modulus: 5.3GPa
Embodiment 3:
1) takes by weighing 4g carboxylic butyl chitosan, join in the 392ml deionized water, stir 1h, add the 8ml glacial acetic acid then, stir 2h;
2) stir down, in step 1) solution, add 20g chitosan powder, obtain carboxylic butyl chitosan/chitosan mixed solution, standing and defoaming;
3) the chitosan powder being dissolved in volume fraction is in 2% the spirit of vinegar, is mixed with mass fraction and is 5% chitosan solution, standing and defoaming;
4) the take a morsel chitosan solution of step 3) evenly is coated on die surface, and it is 5% KOH solidification liquid that mould is placed mass fraction, chitosan freezing film under the room temperature, and the demoulding obtains chitosan film; Then with step 2) solution inject mould, again mould being put into mass fraction is 5% KOH solidification liquid, solidifies 24h, the demoulding obtains the chitin modified chitosan gel rubber bar of carboxylic butyl, is washed with distilled water to neutrality;
5) carboxylic butyl chitosan/chitosan plural gel bar being placed on temperature is dry 100h in 80 ℃ the baking oven, promptly obtains the three-dimensional chitosan rod of carboxylic butyl chitosan enhancing modified.The Mechanics Performance Testing result:
Bending strength: 125.2MPa
Bending modulus: 4.7GPa
Claims (3)
1. the method for enhancing and modifying three-dimensional chitosan bar material by using carboxyl chitosan may further comprise the steps:
1) by per 1～4g using carboxyl chitosan, joins in the 392ml deionized water, stir 0.5～1h, add the 8ml glacial acetic acid then, stir 0.5～2h;
2) stir down, in step 1) solution, add 20g chitosan powder, obtain using carboxyl chitosan/chitosan mixed solution, standing and defoaming by per 1～4g using carboxyl chitosan;
3) the chitosan powder being dissolved in volume fraction is in 2% the spirit of vinegar, is mixed with mass fraction and is 4%～5% chitosan solution, standing and defoaming;
4) the take a morsel chitosan solution of step 3) injects mould and forms one deck inner membrance earlier; Then with step 2) solution inject mould; Again mould being put into mass fraction is 5% alkaline solidification liquid, solidifies 6～24h, the demoulding; Obtain using carboxyl chitosan chitosan modified gel bar, be washed with distilled water to neutrality;
5) using carboxyl chitosan/chitosan plural gel bar is dry under 60 ℃～80 ℃, get final product.
2. the method for enhancing and modifying three-dimensional chitosan bar material by using carboxyl chitosan according to claim 1 is characterized in that using carboxyl chitosan is carboxymethyl chitosan, carboxylic butyl chitosan or N-carboxylic propionyl chitosan sodium.
3. the method for enhancing and modifying three-dimensional chitosan bar material by using carboxyl chitosan according to claim 1 is characterized in that alkaline solidification liquid is NaOH solidification liquid or KOH solidification liquid.
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| CN200910152873A CN101664568B (en) | 2009-09-18 | 2009-09-18 | Method for enhancing and modifying three-dimensional chitosan bar material by using carboxyl chitosan |
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| CN200910152873A CN101664568B (en) | 2009-09-18 | 2009-09-18 | Method for enhancing and modifying three-dimensional chitosan bar material by using carboxyl chitosan |
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| CN101664568B true CN101664568B (en) | 2012-10-03 |
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| CN110818917B (en) * | 2019-11-19 | 2020-09-15 | 浙江大学 | Chitosan-based pure physical crosslinking double-network hydrogel and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101225192A (en) * | 2008-02-02 | 2008-07-23 | 厦门大学 | Method for preparing chitosan reinforced bars |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101225192A (en) * | 2008-02-02 | 2008-07-23 | 厦门大学 | Method for preparing chitosan reinforced bars |
Non-Patent Citations (2)
| Title |
|---|
| 申丙星等."可吸收壳聚糖纤维增强壳聚糖棒材".《复合材料学报》.2008,第25卷(第6期),28-31. |
| 胡巧玲等."原位沉析法制备壳聚糖棒材的研究".《高等学校化学学报》.2003,第24卷(第3期),528-531. |
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