CN101225192A - Method for preparing chitosan reinforced bars - Google Patents
Method for preparing chitosan reinforced bars Download PDFInfo
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- CN101225192A CN101225192A CNA2008100706067A CN200810070606A CN101225192A CN 101225192 A CN101225192 A CN 101225192A CN A2008100706067 A CNA2008100706067 A CN A2008100706067A CN 200810070606 A CN200810070606 A CN 200810070606A CN 101225192 A CN101225192 A CN 101225192A
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Abstract
The invention relates to a preparation method of a biological composite, in particular to a preparation method of chitosan reinforced rod, providing a preparation method of chitosan reinforced rod which has favorable mechanical property and is biodegradable, absorbable and can be taken as bone fracture internal fixation. The preparation method is characterized in that: chitosan powder is added into the acetic acid solution in which poly-lactic acid short fiber is dispersed, the solution is agitated to form a chitosan/acetic acid solution; the chitosan/acetic acid solution is smeared on the inner wall of a mould, the mould is immersed and precipitated into sodium hydroxide solution, and then chitosan membrane taken as a mould board for in situ precipitation is obtained; the mould is filled with the chitosan/acetic acid solution, and then the mould are taken off in the sodium hydroxide solution, while the chitosan/acetic acid solution is immersed into the sodium hydroxide solution until the whole chitosan gel rod is formed; the chitosan gel rod is immersed into distilled water till the water is neutral, and then the rod is dried, at last the poly-lactic acid short fiber reinforced transparent yellowish chitosan rod is obtained.
Description
Technical field
The present invention relates to a kind of preparation method of Biocomposite material, especially the method for the bone fracture internal fixation material that absorbs with a kind of good biocompatibility of Preparation of Chitosan, degradable.
Background technology
Use on the material market in traditional fracture, metallic substance such as stainless steel, cobalt base alloy, titanium alloy etc. are being obtained immense success as bone fracture internal fixation material aspect the treatment fracture, though the metal internal fixation material has some significant advantages, but the biocompatibility of this class material and osseous tissue is bad, can cause a series of untoward reaction, and maximum shortcoming is to degrade, and more can not be absorbed, and needs second operation to take out.Polymkeric substance as absorbable internal fixation material of fractures mainly is polylactic acid-based and the polyglycolic acid class at present, but this class synthetic macromolecule product price is more expensive, and in use all expose the problem that has non-infectious inflammation of later stage, there are the more external wound centers of report not re-use these devices.Chitosan has good biodegradability as a kind of alkaline polysaccharide in the unique a large amount of existence of occurring in nature, and its degraded product is a glucosamine, and is nontoxic, harmless to tissue, has excellent biocompatibility.But chitosan mainly concentrates on unidimensional wire rod such as self-absorption sutures at present in the research aspect the absorption-type embedded material; The internal fixation material of implanting bone directly with the chitosan three-dimensional moulding, is made in aspects such as the film material of two dimension such as artificial skin, also studies less at present both at home and abroad.Zhang Jianxiang etc. have reported a kind of preparation technology of chitosan bar, and chitosan bar has been carried out the biological experiment of a series of inside and outsides, the result shows that the chitosan rod has excellent biological compatibility and security, but its mechanical property awaits further to improve.
Summary of the invention
The object of the present invention is to provide a kind of mechanical property height, biodegradable, can absorb, the chitosan that can be used as bone fracture internal fixation material strengthens the preparation method of bar.
The present invention includes following steps:
1) getting the chitosan powder, to join the percent by volume that is dispersed with polylactic acid short-fiber in advance be in 0.5%～5% the acetic acid solution, dispersed with stirring evenly is mixed with the chitosan/acetic acid solution of concentration for (3～6) g/ml, and wherein the mass ratio of polylactic acid short-fiber and chitosan powder is (2～20): 100;
2) evenly smear chitosan/acetic acid solution that last layer step 1 is prepared at mould inner wall, in sodium hydroxide solution, soak precipitation then, form the template of chitosan film as the original position precipitating;
3) chitosan/acetic acid solution of step 1 preparation is filled with mould, in sodium hydroxide solution, slough mould, be dipped to and form chitosan gel rubber rod completely;
4) the chitosan gel rubber rod that step 3 is formed is dipped to neutrality in distilled water, and oven dry promptly obtains polylactic acid short-fiber enhanced chitosan transparent, little Huang and strengthens bar.
The length of polylactic acid short-fiber is preferably 2～23mm.
The concentration of sodium hydroxide solution is preferably (3～10) g/ml.
Chitosan/the acetic acid solution of step 1 preparation is filled with mould, preferably soak 8～20h after in sodium hydroxide solution, sloughing mould.
The chitosan gel rubber rod that step 3 is formed is dipped to neutrality in distilled water, be preferably in 30～100 ℃ of vacuum drying ovens and dry.
Acid fiber by polylactic be with starch materials such as corn, wheat through fermentation, polymerization, reel off raw silk from cocoons and make, its superior performance, mechanical strength is higher, and has good biological degradability, degraded product is harmless lactic acid and carbonic acid gas and water, can be absorbed by the body.The present invention is by the original position precipitation method, strengthen the mechanical property of chitosan with polylactic acid short-fiber, the mechanical property of prepared recombination chitosan bar is considerably beyond without the enhanced chitosan bar, its flexural strength far surpasses spongy bone, the flexural strength that is equivalent to Compact bone can better satisfy the mechanical property requirements as bone fracture internal fixation material.And material is complete Biodegradable material, and has good biocompatibility and biological activity with organism, can satisfy the medical performance requirement as bone fracture internal fixation material.
Embodiment
Following examples will the present invention is further illustrated.
Embodiment 1
Take by weighing 0.06g polylactic acid short-fiber (2mm) and join in 100mL2% (v/v) acetic acid solution to stir and make fiber dispersion, adding 3g chitosan powder in the solution stirs standing and defoaming.The chitosan solution that takes a morsel injects mould, forms one deck inner membrance in 3% (w/v) sodium hydroxide solidification liquid earlier, again mould is filled with solution, puts into sodium hydroxide solidification liquid and mold removal then.Behind the 20h chitosan gel rubber rod is put into distilled water and embathe, put into 30 ℃ of vacuum drying oven oven dry, promptly obtain polylactic acid short-fiber enhanced chitosan bar transparent, little Huang to neutrality.The flexural strength and the modulus in flexure of test chitosan bar the results are shown in Table 1.
Embodiment 2
Take by weighing 1.20g polylactic acid short-fiber (23mm) and join in 100mL2% (v/v) acetic acid solution to stir and make fiber dispersion, 6g chitosan powder in the solution stirs standing and defoaming.The chitosan solution that takes a morsel injects mould, forms one deck inner membrance in 10% (w/v) sodium hydroxide solidification liquid earlier, again mould is filled with solution, puts into sodium hydroxide solidification liquid and mold removal then.Behind the 8h chitosan gel rubber rod is put into distilled water and embathe, put into 80 ℃ of vacuum drying oven oven dry, promptly obtain polylactic acid short-fiber enhanced chitosan bar to neutrality.Its flexural strength and modulus in flexure see Table 1.
Embodiment 3
Take by weighing 0.12g polylactic acid short-fiber (2mm) and join in 100mL2% (v/v) acetic acid solution to stir and make fiber dispersion, 6g chitosan powder in the solution stirs standing and defoaming.The chitosan solution that takes a morsel injects mould, forms one deck inner membrance in 10% (w/v) sodium hydroxide solidification liquid earlier, again mould is filled with solution, puts into sodium hydroxide solidification liquid and mold removal then.Behind the 8h chitosan gel rubber rod is put into distilled water and embathe, put into 60 ℃ of vacuum drying oven oven dry, promptly obtain polylactic acid short-fiber enhanced chitosan bar to neutrality.Its flexural strength and modulus in flexure see Table 1.
Embodiment 4
Take by weighing 0.60g polylactic acid short-fiber (23mm) and join in 100mL2% (v/v) acetic acid solution to stir and make fiber dispersion, 6g chitosan powder in the solution stirs standing and defoaming.The chitosan solution that takes a morsel injects mould, forms one deck inner membrance in 3% (w/v) sodium hydroxide solidification liquid earlier, again mould is filled with solution, puts into sodium hydroxide solidification liquid and mold removal then.Behind the 20h chitosan gel rubber rod is put into distilled water and embathe, put into 60 ℃ of vacuum drying oven oven dry, promptly obtain polylactic acid short-fiber enhanced chitosan bar to neutrality.Its flexural strength and modulus in flexure see Table 1.
Embodiment 5
Take by weighing 0.50g polylactic acid short-fiber (14mm) and join in 100mL2% (v/v) acetic acid solution to stir and make fiber dispersion, 5g chitosan powder in the solution stirs standing and defoaming.The chitosan solution that takes a morsel injects mould, forms one deck inner membrance in 5% (w/v) sodium hydroxide solidification liquid earlier, again mould is filled with solution, puts into sodium hydroxide solidification liquid and mold removal then.Behind the 12h chitosan gel rubber rod is put into distilled water and embathe, put into 60 ℃ of vacuum drying oven oven dry, promptly obtain polylactic acid short-fiber enhanced chitosan bar to neutrality.Its flexural strength and modulus in flexure see Table 1.
Embodiment 6
Take by weighing 0.30g polylactic acid short-fiber (14mm) and join in 100mL2% (v/v) acetic acid solution to stir and make fiber dispersion, 3g chitosan powder in the solution stirs standing and defoaming.The chitosan solution that takes a morsel injects mould, forms one deck inner membrance in 3% (w/v) sodium hydroxide solidification liquid earlier, again mould is filled with solution, puts into sodium hydroxide solidification liquid and mold removal then.Behind the 20h chitosan gel rubber rod is put into distilled water and embathe, put into 60 ℃ of vacuum drying oven oven dry, promptly obtain polylactic acid short-fiber enhanced chitosan bar to neutrality.Its flexural strength and modulus in flexure see Table 1.
Embodiment 7
Take by weighing 0.60g polylactic acid short-fiber (14mm) and join in 100mL2% (v/v) acetic acid solution to stir and make fiber dispersion, 6g chitosan powder in the solution stirs standing and defoaming.The chitosan solution that takes a morsel injects mould, forms one deck inner membrance in 10% (w/v) sodium hydroxide solidification liquid earlier, again mould is filled with solution, puts into sodium hydroxide solidification liquid and mold removal then.Behind the 10h chitosan gel rubber rod is put into distilled water and embathe, put into 60 ℃ of vacuum drying oven oven dry, promptly obtain polylactic acid short-fiber enhanced chitosan bar to neutrality.Its flexural strength and modulus in flexure see Table 1.
Embodiment 8
Take by weighing 1.00g polylactic acid short-fiber (23mm) and join in 100mL2% (v/v) acetic acid solution to stir and make fiber dispersion, 5g chitosan powder in the solution stirs standing and defoaming.The chitosan solution that takes a morsel injects mould, forms one deck inner membrance in 5% (w/v) sodium hydroxide solidification liquid earlier, again mould is filled with solution, puts into sodium hydroxide solidification liquid and mold removal then.Behind the 20h chitosan gel rubber rod is put into distilled water and embathe, put into 60 ℃ of vacuum drying oven oven dry, promptly obtain polylactic acid short-fiber enhanced chitosan bar to neutrality.Its flexural strength and modulus in flexure see Table 1.
Comparative Examples
Take by weighing 5g chitosan powder, join 100mL2% (v/v) acetic acid solution, stir standing and defoaming.The chitosan solution that takes a morsel injects mould, forms one deck inner membrance in 5% (w/v) sodium hydroxide solidification liquid earlier, again mould is filled with solution, puts into sodium hydroxide solidification liquid and mold removal then.Behind the 20h chitosan gel rubber rod is put into distilled water and embathe, put into 60 ℃ of vacuum drying oven oven dry, promptly obtain chitosan bar to neutrality.Its flexural strength and modulus in flexure see Table 1.
As shown in table 1, the chitosan bar matrix material that the present invention obtains is compared with enhanced chitosan bar not, and the mechanical property of material is greatly improved, and mechanical strength is higher than spongy bone far away, near or surpass Compact bone.This matrix material and tissue good biocompatibility, degraded and absorbed can satisfy the mechanical property requirements as bone fracture internal fixation material again preferably fully, will have bigger application prospect.
Table 1 polylactic acid short-fiber strengthens chitosan bar flexural strength and modulus in flexure
| Embodiment | Flexural strength (MPa) | Modulus in flexure (GPa) |
| Comparative Examples embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 embodiment 6 embodiment 7 embodiment 8 spongy bones *Compact bone * | 86 88 120 102 133 145 142 138 125 2～13 126～150 | 4.8 5.2 6.2 5.3 6.2 5.8 5.6 5.9 6.3 1～2.4 13～18 |
Claims (5)
1. a chitosan strengthens the preparation method of bar, it is characterized in that may further comprise the steps:
1) getting the chitosan powder, to join the percent by volume that is dispersed with polylactic acid short-fiber in advance be in 0.5%～5% the acetic acid solution, dispersed with stirring evenly is mixed with chitosan/acetic acid solution that concentration is 3～6g/ml, and wherein the mass ratio of polylactic acid short-fiber and chitosan powder is 2～20: 100;
2) evenly smear chitosan/acetic acid solution that last layer step 1 is prepared at mould inner wall, in sodium hydroxide solution, soak precipitation then, form the template of chitosan film as the original position precipitating;
3) chitosan/acetic acid solution of step 1 preparation is filled with mould, in sodium hydroxide solution, slough mould, be dipped to and form chitosan gel rubber rod completely;
4) the chitosan gel rubber rod that step 3 is formed is dipped to neutrality in distilled water, and oven dry promptly obtains polylactic acid short-fiber enhanced chitosan transparent, little Huang and strengthens bar.
2. a kind of chitosan as claimed in claim 1 strengthens the preparation method of bar, and the length that it is characterized in that polylactic acid short-fiber is 2～23mm.
3. a kind of chitosan as claimed in claim 1 strengthens the preparation method of bar, and the concentration that it is characterized in that sodium hydroxide solution is 3～10g/ml.
4. a kind of chitosan as claimed in claim 1 strengthens the preparation method of bar, it is characterized in that the chitosan/acetic acid solution of step 1 preparation is filled with mould, soaks 8～20h slough mould in sodium hydroxide solution after.
5. a kind of chitosan as claimed in claim 1 strengthens the preparation method of bar, it is characterized in that the chitosan gel rubber rod that step 3 forms is dipped to neutrality in distilled water, dries in 30～100 ℃ of vacuum drying ovens.
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| CN200810070606A CN100582152C (en) | 2008-02-02 | 2008-02-02 | Method for preparing chitosan reinforced bars |
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| CN200810070606A CN100582152C (en) | 2008-02-02 | 2008-02-02 | Method for preparing chitosan reinforced bars |
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| CN101225192A true CN101225192A (en) | 2008-07-23 |
| CN100582152C CN100582152C (en) | 2010-01-20 |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101955640A (en) * | 2010-10-15 | 2011-01-26 | 华中科技大学 | Modified biopolymer fiber reinforced polylactic acid composite material and preparation method thereof |
| CN102604138A (en) * | 2012-03-12 | 2012-07-25 | 浙江大学 | Method for preparing chitosan substrate film by self-deposition of micron gel |
| CN101664569B (en) * | 2009-09-18 | 2012-10-03 | 浙江大学 | Preparation method of high strength sodium polyphosphate/chitosan hollow composite bar material |
| CN101664567B (en) * | 2009-09-18 | 2012-10-03 | 浙江大学 | Method for crosslinking, enhancing and modifying three-dimensional chitosan bar material by using epoxy chloropropane |
| CN101664566B (en) * | 2009-09-18 | 2012-10-03 | 浙江大学 | Method for modifying three-dimensional chitosan bars by Co60-gamma-ray radiation |
| CN101632844B (en) * | 2009-07-16 | 2012-10-03 | 浙江大学 | Method for preparing three-dimensional chitosan rod with high strength |
| CN101664568B (en) * | 2009-09-18 | 2012-10-03 | 浙江大学 | Method for enhancing and modifying three-dimensional chitosan bar material by using carboxyl chitosan |
| CN108295319A (en) * | 2018-03-08 | 2018-07-20 | 山东省药学科学院 | A kind of hydrophilic composite material and preparation method of medical nano fiber reinforcement type and purposes |
| CN108434534A (en) * | 2018-06-11 | 2018-08-24 | 浙江大学 | A kind of compound bone nail material of high-intensity graphene oxide/chitosan and preparation method thereof with imitative steel-concrete structures |
| CN112169020A (en) * | 2020-09-22 | 2021-01-05 | 福建吉特瑞生物科技有限公司 | Large chitosan material and preparation method thereof |
| CN116392639A (en) * | 2023-02-17 | 2023-07-07 | 无锡市中医医院 | Full-layer repair double-layer bracket and preparation method and application thereof |
Family Cites Families (2)
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| CN1362447A (en) * | 2001-01-05 | 2002-08-07 | 成都迪康中科生物医学材料有限公司 | Fiber reinforced polylactic acid composition |
| CN100515505C (en) * | 2006-04-30 | 2009-07-22 | 东华大学 | Method for preparing artificial breast wall and artificial bone material |
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- 2008-02-02 CN CN200810070606A patent/CN100582152C/en not_active Expired - Fee Related
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101632844B (en) * | 2009-07-16 | 2012-10-03 | 浙江大学 | Method for preparing three-dimensional chitosan rod with high strength |
| CN101664568B (en) * | 2009-09-18 | 2012-10-03 | 浙江大学 | Method for enhancing and modifying three-dimensional chitosan bar material by using carboxyl chitosan |
| CN101664569B (en) * | 2009-09-18 | 2012-10-03 | 浙江大学 | Preparation method of high strength sodium polyphosphate/chitosan hollow composite bar material |
| CN101664567B (en) * | 2009-09-18 | 2012-10-03 | 浙江大学 | Method for crosslinking, enhancing and modifying three-dimensional chitosan bar material by using epoxy chloropropane |
| CN101664566B (en) * | 2009-09-18 | 2012-10-03 | 浙江大学 | Method for modifying three-dimensional chitosan bars by Co60-gamma-ray radiation |
| CN101955640A (en) * | 2010-10-15 | 2011-01-26 | 华中科技大学 | Modified biopolymer fiber reinforced polylactic acid composite material and preparation method thereof |
| CN102604138A (en) * | 2012-03-12 | 2012-07-25 | 浙江大学 | Method for preparing chitosan substrate film by self-deposition of micron gel |
| CN102604138B (en) * | 2012-03-12 | 2013-09-11 | 浙江大学 | Method for preparing chitosan substrate film by self-deposition of micron gel |
| CN108295319A (en) * | 2018-03-08 | 2018-07-20 | 山东省药学科学院 | A kind of hydrophilic composite material and preparation method of medical nano fiber reinforcement type and purposes |
| CN108434534A (en) * | 2018-06-11 | 2018-08-24 | 浙江大学 | A kind of compound bone nail material of high-intensity graphene oxide/chitosan and preparation method thereof with imitative steel-concrete structures |
| CN108434534B (en) * | 2018-06-11 | 2020-05-19 | 浙江大学 | High-strength graphene oxide/chitosan composite bone screw material with steel bar-concrete-imitated structure and preparation method thereof |
| CN112169020A (en) * | 2020-09-22 | 2021-01-05 | 福建吉特瑞生物科技有限公司 | Large chitosan material and preparation method thereof |
| CN116392639A (en) * | 2023-02-17 | 2023-07-07 | 无锡市中医医院 | Full-layer repair double-layer bracket and preparation method and application thereof |
| CN116392639B (en) * | 2023-02-17 | 2024-02-13 | 无锡市中医医院 | Full-layer repair double-layer bracket and preparation method and application thereof |
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