CN100494275C - Method for preparing surface bionic mineralization coat carbon fiber enhancement polylactic acid material - Google Patents
Method for preparing surface bionic mineralization coat carbon fiber enhancement polylactic acid material Download PDFInfo
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- CN100494275C CN100494275C CNB200710068442XA CN200710068442A CN100494275C CN 100494275 C CN100494275 C CN 100494275C CN B200710068442X A CNB200710068442X A CN B200710068442XA CN 200710068442 A CN200710068442 A CN 200710068442A CN 100494275 C CN100494275 C CN 100494275C
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- carbon fiber
- polylactic acid
- hydroxyapatite
- hydroxyapatite coating
- coating layer
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Abstract
The invention discloses a producing method for surface bionic mineralizing coating carbon fiber enhanced polylactic acid material with the steps of: soaking the carbon fiber in the simulated body liquid with 5 times concentration, getting carbon fiber whose surface has hydroxyapatite coating; then putting the lactide, carbon fiber whose surface has hydroxyapatite coating and stannous octoate catalyst in the die, compacting, sealing, vacuumizing, reacting for 24-48 hours between 140-160 DEG C in vacuum and without water and oxygen. Preparing hydroxyapatite coating on the carbon fiber surface has two advantages, at one side it could improve the bio-activity and bio-compatibility of the carbon fiber, at the other side it also could avoid the uneven dispersion of hydroxyapatite in the carbon fiber enhanced polylactic acid/hydroxyapatite compound material and it adopts in-situ composite method to produce a material with a good mechanical performance and without any poisonous solvent.
Description
Technical field
The present invention relates to a kind of preparation method of surface bionic mineralization coat carbon fiber enhancement polylactic acid material.
Background technology
At present, carbon fiber (CF) enhanced poly(lactic acid) (PLA) matrix material of internal fixing of being used to fracture is to adopt solution blended process or the preparation of melting heat platen press, solution blended process adopts organic solvent, solvent is difficult for removing fully in the material that generates, in case the remaining solvent that implants can have very big side effect to human body.Adopt the melting heat platen press, PLA will pass through molten state, and temperature is near its pyrolysis temperature, and makes part material generation pyrolysis, causes the loss of molecular weight, influences the intensity of material.And the carbon fiber reinforced lactic acid composite material, degraded is acid in human body, easily causes intravital inflammation.Other a kind of carbon fiber (CF) enhanced poly(lactic acid) (PLA)/hydroxyapatite (HA) is arranged though matrix material in degradation process, HA can cushion the acidity that the PLA degraded produces, but mostly also adopt the method preparation of fusion hot pressing and solution blending, have the problem of residual harmful solvent equally; And the original position composite methods, after the rac-Lactide fusion, HA is deposited to the bottom of material easily in material, cause the skewness of HA in matrix material, though had now report to hydroxyapatite carry out finishing with polymkeric substance, improve the consistency of hydroxyapatite and polymkeric substance, and then the settling velocity of the HA that slows down, but percentage of grafting is not high, and effect is not clearly.
Summary of the invention
The objective of the invention is at the problems referred to above, a kind of preparation method of surface bionic mineralization coat carbon fiber enhancement polylactic acid material of the internal fixing that is used to fracture is provided.
The preparation method of surface bionic mineralization coat carbon fiber enhancement polylactic acid material of the present invention is characterized in that may further comprise the steps:
1) carbon fiber is placed the simulated body fluid (SBF) of 5 times of concentration soak, obtain the carbon fiber that the surface has hydroxyapatite coating layer;
2) rac-Lactide 65～75% by weight percentage, the surface has the carbon fiber 25～35% of hydroxyapatite (HA) coating, taking by weighing raw material, is catalyzer with the stannous octoate, and the weight of catalyzer is 4～6% of raw material gross weight, the carbon fiber and the catalyzer that rac-Lactide, surface are had hydroxyapatite coating layer are put into mould, compacting, sealing vacuumizes, under the condition of vacuum anhydrous and oxygen-free, react 24～48h between 140～160 ℃.
Above-mentioned simulated body fluid can be published in Biomaterials in 2006 by Tadashi Kokubo etc., inscribeed one's name to be: " How useful is SBF in predicting in vivo bone bioactivity " described method configuration obtains.
The weight of the hydroxyapatite coating layer of carbon fiber surface is determined that by soak time the time that carbon fiber soaks is long more in 5 times of SBF, the thickness of HA coating is thick more, so the content of HA is regulated by the soak time of carbon fiber in 5 times of SBF in the material.
In order to make matrix material have excellent mechanical property and HA the back lactic acid of degrading is had good shock absorption, the weight that generally makes hydroxyapatite coating layer is 5～8 times of carbon fiber weight.
The molecular weight of poly(lactic acid) can be regulated by the time and the catalyst consumption of conditioned reaction in the matrix material of the present invention.
The degradation time of matrix material of the present invention and the molecular weight of poly(lactic acid) have very big relation.The molecular weight of poly(lactic acid) is big more, and the time of composite degradation is just long more, and molecular weight is more little, and degradation time is short more, can adjust the size of molecular weight in the middle of using according to the required time of union of fracture.
Beneficial effect of the present invention is: preparation technology is simple, need not to add organic solvent, employing prepares the hydroxyapatite coating layer method of original position direct polymerization moulding again at the carbon fiber surface biomimetic mineralization, the biological activity and the biocompatibility of carbon fiber have been improved on the one hand, on the other hand, hydroxyapatite disperses uneven problem in again can carbon fiber reinforced polylactic acid/hydroxy apatite composite material.The material mechanical performance that generates is good, does not have any noxious solvent, and is harmless.
Embodiment
Embodiment 1
Place the simulated body fluid (SBF) of 5 times of concentration to soak for 4 weeks on the 0.4g carbon fiber, obtain the carbon fiber 3.5g that the surface has hydroxyapatite coating layer;
The carbon fiber and the 0.04g catalyzer that 6.5g rac-Lactide, 3.5g surface are had hydroxyapatite coating layer are put into mould, compacting, vacuumize, reacted 48 hours down at 160 ℃, after finishing, reaction records in the material polylactic acid molecule amount 130,000, the flexural strength of material is 380MPa, and modulus in flexure is 21.2GPa.In simulated body fluid, to degrade three months, the pH value of body fluid is constant substantially.
Embodiment 2
Place the simulated body fluid (SBF) of 5 times of concentration to soak for 2 weeks on the 0.3g carbon fiber, obtain the carbon fiber 2.5g that the surface has hydroxyapatite coating layer;
The carbon fiber and the 0.04g catalyzer that 7.5g rac-Lactide, 2.5g surface are had hydroxyapatite coating layer are put into mould, compacting, vacuumize, reacted 24 hours down at 140 ℃, after finishing, reaction records in the material polylactic acid molecule amount 50,000, the flexural strength of material is 297MPa, and modulus in flexure is 18GPa.In simulated body fluid, to degrade three months, the pH value of body fluid is constant substantially.
Claims (2)
1. the preparation method of a surface bionic mineralization coat carbon fiber enhancement polylactic acid material is characterized in that may further comprise the steps:
1) carbon fiber is placed the simulated body fluid of 5 times of concentration soak, obtain the carbon fiber that the surface has hydroxyapatite coating layer;
2) rac-Lactide 65～75% by weight percentage, the surface has the carbon fiber 25～35% of hydroxyapatite coating layer, taking by weighing raw material, is catalyzer with the stannous octoate, and the weight of catalyzer is 4～6% of raw material gross weight, the carbon fiber and the catalyzer that rac-Lactide, surface are had hydroxyapatite coating layer are put into mould, compacting, sealing vacuumizes, under the condition of vacuum anhydrous and oxygen-free, react 24～48h between 140～160 ℃.
2. the preparation method of surface bionic mineralization coat carbon fiber enhancement polylactic acid material according to claim 1, the weight that it is characterized in that the said hydroxyapatite coating layer of step 1) is 5～8 times of carbon fiber weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200710068442XA CN100494275C (en) | 2007-04-30 | 2007-04-30 | Method for preparing surface bionic mineralization coat carbon fiber enhancement polylactic acid material |
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|---|---|---|---|
| CNB200710068442XA CN100494275C (en) | 2007-04-30 | 2007-04-30 | Method for preparing surface bionic mineralization coat carbon fiber enhancement polylactic acid material |
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| CN101054464A CN101054464A (en) | 2007-10-17 |
| CN100494275C true CN100494275C (en) | 2009-06-03 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102850740B (en) * | 2012-09-04 | 2014-04-02 | 华南理工大学 | Preparation method for lactide grafted plant fiber reinforced poly lactic acid composite material |
| CN103387756B (en) * | 2013-07-30 | 2015-07-08 | 浙江微度医疗器械有限公司 | Modification method and application of hydroxyapatite |
| CN112375354A (en) * | 2020-11-17 | 2021-02-19 | 杨勇 | Carbon fiber polylactic acid filling master batch and preparation method thereof |
| CN114344545A (en) * | 2022-01-25 | 2022-04-15 | 大连大学 | Bacteriostatic hemostatic dressing and preparation method thereof |
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2007
- 2007-04-30 CN CNB200710068442XA patent/CN100494275C/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| 碳纤维增强羟基磷灰石/聚乳酸复合生物材料的制备和力学性能的研究. 张稚燕.浙江大学硕士学位论文. 2006 |
| 碳纤维增强羟基磷灰石/聚乳酸复合生物材料的制备和力学性能的研究. 张稚燕.浙江大学硕士学位论文. 2006 * |
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| CN101054464A (en) | 2007-10-17 |
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