CN1233737C - Polyactate self-modified hydroxyapatite/polylactate composite material and method for making same - Google Patents
Polyactate self-modified hydroxyapatite/polylactate composite material and method for making same Download PDFInfo
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- CN1233737C CN1233737C CN 03119058 CN03119058A CN1233737C CN 1233737 C CN1233737 C CN 1233737C CN 03119058 CN03119058 CN 03119058 CN 03119058 A CN03119058 A CN 03119058A CN 1233737 C CN1233737 C CN 1233737C
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- hydroxyapatite
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Abstract
The present invention provides a polylactic acid self-modified hydroxyapatite/polylactic acid composite material and a preparation method thereof. Firstly, the method adopts a polylactic acid for modifying the hydroxyapatite, the molecular weight of the polylactic acid is low, and the structural unit of the polylactic acid is the same as that of a composite material basal body; then, the modified hydroxyapatite is combined with a polylactic acid basal body whose molecular weight is relatively high, and the composite material is prepared through adsorption, dryness, rolling, refining and compression moulding forming. The method has simple process and no other small toxic inorganic or organic molecule introduction, and the prepared composite material has high biocompatibility and high initial bending strength of 114 to 210.2MPa.
Description
Technical field
The invention belongs to field of biomedical materials.Specifically be the matrix material and the preparation method of the higher poly(lactic acid) of less polylactic acid modified hydroxyapatite of a kind of molecular weight and relative molecular weight.
Technical background
The compound internal fixation material of hydroxyapatite/polylactic acid can combine the synosteosis ability of hydroxyapatite excellence and the absorbability and the workability of poly(lactic acid), makes it both have the synosteosis ability, has biodegradable again, thereby receives much attention.But discovered in recent years when the hydroxyapatite/polylactic acid matrix material is exposed in the physiological environment, does not wait defect to repair fully and just lose its active strength prematurely, and inefficacy mainly betides hydroxyapatite and poly(lactic acid) two-phase interface.Further studies show that, this be since hydroxyapatite and poly(lactic acid) two-phase interface lack effectively bonding due to.Existing certain methods is used to improve the interface performance of hydroxyapatite/polylactic acid matrix material, comprises using zirconates, polyacid, isocyanic ester, silane coupling agent etc.These methods can solve problem in a certain respect, but complex process, and there is toxicity more or less in inorganic or organic new coupling agents of introducing, thereby need further research to improve the method for this class composite property.
Summary of the invention
The object of the present invention is to provide a kind of new modified hydroxylapatite/lactic acid composite material and preparation method.This matrix material should not introduced other toxic inorganic or organic molecule, good biocompatibility, and the active strength height should have characteristics such as preparation technology is simple.
The object of the invention is achieved through the following technical solutions: a kind of modified hydroxylapatite and lactic acid composite material, it is the matrix material of polylactic acid modified hydroxyapatite and poly(lactic acid).
Described matrix material, it is that poly(lactic acid) matrix and quality are the matrix material of the dry polylactic acid modified hydroxyapatite of poly(lactic acid) substrate quality 20%～45%
The preparation method of described matrix material is: at first adopt identical with the matrices of composite material structural unit and poly(lactic acid) that molecular weight is less is carried out modification to hydroxyapatite, to carry out compound by relative higher poly(lactic acid) matrix with molecular weight through the hydroxyapatite of modification then, by absorption, drying, roller refining, compression molding, finally obtain poly(lactic acid) from modifying the hydroxyapatite/polylactic acid matrix material.
This composite material preparation process process comprises (following as nothing is indicated and is massfraction):
1. at room temperature 100 parts of dry hydroxylapatite powders are joined in 2000 parts of acetone, stir, obtain the suspension of hydroxyapatite;
2. in hydroxyapatite suspension, add 400 parts under stirring and contain 1～5 part of M
v=3.0 * 10
4～M
v=7.0 * 10
4The acetone soln of poly(lactic acid) drips 2500 parts of deionized waters subsequently, continues to stir 0.5 hour;
3. leave standstill, suction filtration, vacuum-drying 48 hours gets polylactic acid modified hydroxyapatite;
4. taking by weighing quality is M
v=4.5 * 10
5The dry polylactic acid modified hydroxyapatite of matrix poly(lactic acid) quality 20%～45%, it is scattered in an amount of dehydrated alcohol, ultrasonic 2 minutes, then the poly(lactic acid) matrix is thrown in wherein in batches, dipping absorption, take out airing,, promptly get poly(lactic acid) from modifying the hydroxyapatite/polylactic acid matrix material through roller refining, compression molding.The initial bending strength of this matrix material can reach 114～210.2MPa.
The present invention adopts the less polylactic acid modified hydroxyapatite of molecular weight, then with this hydroxyapatite and the higher compound matrix material of making of poly(lactic acid) of relative molecular weight, the used decorating molecule of this matrix material is identical with poly(lactic acid) matrix statement of account unit and poly(lactic acid) that molecular weight is less, because of not introducing other toxic inorganic or organic molecule, so have characteristics such as biocompatibility is better, technology is simple.
Embodiment
Embodiment 1. at room temperature is that the dry hydroxylapatite powder of 15 μ m joins in 2000 parts of acetone with 100 parts of median sizes, stirs 0.5 hour (800rpm), obtains the suspension of hydroxyapatite.In hydroxyapatite suspension, add 400 parts under stirring and contain 1 part of poly(lactic acid) (M
v=3.0 * 10
4) acetone soln, drip 2500 parts of deionized waters subsequently, continue to stir 0.5 hour, leave standstill, suction filtration, vacuum-drying 48 hours, viscosity-average molecular weight be M
v=3.0 * 10
4Polylactic acid modified hydroxyapatite.
Taking by weighing quality is matrix poly(lactic acid) (M
v=4.5 * 10
5) the dry polylactic acid modified hydroxyapatite of quality 20%, it is scattered in an amount of dehydrated alcohol, ultrasonic 2 minutes, then the poly(lactic acid) matrix is thrown in wherein in batches, dipping absorption, take out airing,, obtain poly(lactic acid) from modifying the hydroxyapatite/polylactic acid matrix material through roller refining, compression molding.The initial bending strength 125.6MPa of this matrix material.
Embodiment 2. at room temperature is that the dry hydroxylapatite powder of 15 μ m joins in 2000 parts of acetone with 100 parts of median sizes, stirs 0.5 hour (800rpm), obtains the suspension of hydroxyapatite.In hydroxyapatite suspension, add 400 parts under stirring and contain 1 part of poly(lactic acid) (M
v=7.0 * 10
4) acetone soln, drip 2500 parts of deionized waters subsequently, continue to stir 0.5 hour, leave standstill, suction filtration, vacuum-drying 48 hours, viscosity-average molecular weight be M
v=7.0 * 10
4Polylactic acid modified hydroxyapatite.
Taking by weighing quality is matrix poly(lactic acid) (M
v=4.5 * 10
5) the dry polylactic acid modified hydroxyapatite of quality 30%, it is scattered in an amount of dehydrated alcohol, ultrasonic 2 minutes, then the poly(lactic acid) matrix is thrown in wherein in batches, dipping absorption, take out airing,, obtain poly(lactic acid) from modifying the hydroxyapatite/polylactic acid matrix material through roller refining, compression molding.The initial bending strength 134.1MPa of this matrix material.
Embodiment 3. at room temperature is that the dry hydroxylapatite powder of 15 μ m joins in 2000 parts of acetone with 100 parts of median sizes, stirs 0.5 hour (800rpm), obtains the suspension of hydroxyapatite.In hydroxyapatite suspension, add 400 parts under stirring and contain 3 parts of poly(lactic acid) (M
v=3.0 * 10
4) acetone soln, drip 2500 parts of deionized waters subsequently, continue to stir 0.5 hour, leave standstill, suction filtration, vacuum-drying 48 hours, viscosity-average molecular weight be M
v=3.0 * 10
4Polylactic acid modified hydroxyapatite.
Taking by weighing quality is matrix poly(lactic acid) (M
v=4.5 * 10
5) the dry polylactic acid modified hydroxyapatite of quality 45%, it is scattered in an amount of dehydrated alcohol, ultrasonic 2 minutes, then the poly(lactic acid) matrix is thrown in wherein in batches, dipping absorption, take out airing,, obtain poly(lactic acid) from modifying the hydroxyapatite/polylactic acid matrix material through roller refining, compression molding.The initial bending strength 114.6MPa of this matrix material.
Embodiment 4. at room temperature is that the dry hydroxylapatite powder of 15 μ m joins in 2000 parts of acetone with 100 parts of median sizes, stirs 0.5 hour (800rpm), obtains the suspension of hydroxyapatite.In hydroxyapatite suspension, add 400 parts under stirring and contain 3 parts of poly(lactic acid) (M
v=3.0 * 10
4) acetone soln, drip 2500 parts of deionized waters subsequently, continue to stir 0.5 hour, leave standstill, suction filtration, vacuum-drying 48 hours, viscosity-average molecular weight be M
v=3.0 * 10
4Polylactic acid modified hydroxyapatite.
Taking by weighing quality is matrix poly(lactic acid) (M
v=4.5 * 10
5) the dry polylactic acid modified hydroxyapatite of quality 30%, it is scattered in an amount of dehydrated alcohol, ultrasonic 2 minutes, then the poly(lactic acid) matrix is thrown in wherein in batches, dipping absorption, take out airing,, obtain poly(lactic acid) from modifying the hydroxyapatite/polylactic acid matrix material through roller refining, compression molding.The initial bending strength 123.3MPa of this matrix material.
Embodiment 5. at room temperature is that the dry hydroxylapatite powder of 15 μ m joins in 2000 parts of acetone with 100 parts of median sizes, stirs 0.5 hour (800rpm), obtains the suspension of hydroxyapatite.In hydroxyapatite suspension, add 400 parts under stirring and contain 3 parts of poly(lactic acid) (M
v=7.0 * 10
4) acetone soln, drip 2500 parts of deionized waters subsequently, continue to stir 0.5 hour, leave standstill, suction filtration, vacuum-drying 48 hours, viscosity-average molecular weight be M
v=7.0 * 10
4Polylactic acid modified hydroxyapatite.
Taking by weighing quality is matrix poly(lactic acid) (M
v=4.5 * 10
5) the dry polylactic acid modified hydroxyapatite of quality 30%, it is scattered in an amount of dehydrated alcohol, ultrasonic 2 minutes, then the poly(lactic acid) matrix is thrown in wherein in batches, dipping absorption, take out airing,, obtain poly(lactic acid) from modifying the hydroxyapatite/polylactic acid matrix material through roller refining, compression molding.The initial bending strength 178.0MPa of this matrix material.
Embodiment 6. at room temperature is that the dry hydroxylapatite powder of 15 μ m joins in 2000 parts of acetone with 100 parts of median sizes, stirs 0.5 hour (800rpm), obtains the suspension of hydroxyapatite.In hydroxyapatite suspension, add 400 parts under stirring and contain 5 parts of poly(lactic acid) (M
v=7.0 * 10
4) acetone soln, drip 2500 parts of deionized waters subsequently, continue to stir 0.5 hour, leave standstill, suction filtration, vacuum-drying 48 hours, viscosity-average molecular weight be M
v=7.0 * 10
4Polylactic acid modified hydroxyapatite.
Taking by weighing quality is matrix poly(lactic acid) (M
v=4.5 * 10
5) the dry polylactic acid modified hydroxyapatite of quality 30%, it is scattered in an amount of dehydrated alcohol, ultrasonic 2 minutes, then the poly(lactic acid) matrix is thrown in wherein in batches, dipping absorption, take out airing,, obtain poly(lactic acid) from modifying the hydroxyapatite/polylactic acid matrix material through roller refining, compression molding.The initial bending strength 147.1MPa of this matrix material.
Embodiment 7. at room temperature is that the dry hydroxylapatite powder of 15 μ m joins in 2000 parts of acetone with 100 parts of median sizes, stirs 0.5 hour (800rpm), obtains the suspension of hydroxyapatite.In hydroxyapatite suspension, add 400 parts under stirring and contain 5 parts of poly(lactic acid) (M
v=7.0 * 10
4) acetone soln, drip 2500 parts of deionized waters subsequently, continue to stir 0.5 hour, leave standstill, suction filtration, vacuum-drying 48 hours, viscosity-average molecular weight be M
v=7.0 * 10
4Polylactic acid modified hydroxyapatite.
Taking by weighing quality is matrix poly(lactic acid) (M
v=4.5 * 10
5) the dry polylactic acid modified hydroxyapatite of quality 20%, it is scattered in an amount of dehydrated alcohol, ultrasonic 2 minutes, then the poly(lactic acid) matrix is thrown in wherein in batches, dipping absorption, take out airing,, obtain poly(lactic acid) from modifying the hydroxyapatite/polylactic acid matrix material through roller refining, compression molding.The initial bending strength 127.6MPa of this matrix material.
Embodiment 8. at room temperature is that the dry hydroxylapatite powder of 15 μ m joins in 2000 parts of acetone with 100 parts of median sizes, stirs 0.5 hour (800rpm), obtains the suspension of hydroxyapatite.In hydroxyapatite suspension, add 400 parts under stirring and contain 5 parts of poly(lactic acid) (M
v=7.0 * 10
4) acetone soln, drip 2500 parts of deionized waters subsequently, continue to stir 0.5 hour, leave standstill, suction filtration, vacuum-drying 48 hours, viscosity-average molecular weight be M
v=7.0 * 10
4Polylactic acid modified hydroxyapatite.
Taking by weighing quality is matrix poly(lactic acid) (M
v=4.5 * 10
5) the dry polylactic acid modified hydroxyapatite of quality 45%, it is scattered in an amount of dehydrated alcohol, ultrasonic 2 minutes, then the poly(lactic acid) matrix is thrown in wherein in batches, dipping absorption, take out airing,, obtain poly(lactic acid) from modifying the hydroxyapatite/polylactic acid matrix material through roller refining, compression molding.The initial bending strength 137.0MPa of this matrix material.
Embodiment 9. at room temperature is that the dry hydroxylapatite powder of 15 μ m joins in 2000 parts of acetone with 100 parts of median sizes, stirs 0.5 hour (800rpm), obtains the suspension of hydroxyapatite.In hydroxyapatite suspension, add 400 parts under stirring and contain 5 parts of poly(lactic acid) (M
v=3.0 * 10
4) acetone soln, drip 2500 parts of deionized waters subsequently, continue to stir 0.5 hour, leave standstill, suction filtration, vacuum-drying 48 hours, viscosity-average molecular weight be M
v=3.0 * 10
4Polylactic acid modified hydroxyapatite.
Taking by weighing quality is matrix poly(lactic acid) (M
v=4.5 * 10
5) the dry polylactic acid modified hydroxyapatite of quality 20%, it is scattered in an amount of dehydrated alcohol, ultrasonic 2 minutes, then the poly(lactic acid) matrix is thrown in wherein in batches, dipping absorption, take out airing,, obtain poly(lactic acid) from modifying the hydroxyapatite/polylactic acid matrix material through roller refining, compression molding.The initial bending strength 119.1MPa of this matrix material.
Embodiment 10. at room temperature is that the dry hydroxylapatite powder of 15 μ m joins in 2000 parts of acetone with 100 parts of median sizes, stirs 0.5 hour (800rpm), obtains the suspension of hydroxyapatite.In hydroxyapatite suspension, add 400 parts under stirring and contain 5 parts of poly(lactic acid) (M
v=3.0 * 10
4) acetone soln, drip 2500 parts of deionized waters subsequently, continue to stir 0.5 hour, leave standstill, suction filtration, vacuum-drying 48 hours, viscosity-average molecular weight be M
v=3.0 * 10
4Polylactic acid modified hydroxyapatite.
Taking by weighing quality is matrix poly(lactic acid) (M
v=4.5 * 10
5) the dry polylactic acid modified hydroxyapatite of quality 45%, it is scattered in an amount of dehydrated alcohol, ultrasonic 2 minutes, then the poly(lactic acid) matrix is thrown in wherein in batches, dipping absorption, take out airing,, obtain poly(lactic acid) from modifying the hydroxyapatite/polylactic acid matrix material through roller refining, compression molding.The initial bending strength 120.9MPa of this matrix material.
Embodiment 11. at room temperature is that the dry hydroxylapatite powder of 15 μ m joins in 2000 parts of acetone with 100 parts of median sizes, stirs 0.5 hour (800rpm), obtains the suspension of hydroxyapatite.In hydroxyapatite suspension, add 400 parts under stirring and contain 3 parts of poly(lactic acid) (M
v=7.0 * 10
4) acetone soln, drip 2500 parts of deionized waters subsequently, continue to stir 0.5 hour, leave standstill, suction filtration, vacuum-drying 48 hours, viscosity-average molecular weight be M
v=7.0 * 10
4Polylactic acid modified hydroxyapatite.
Taking by weighing quality is matrix poly(lactic acid) (M
v=4.5 * 10
5) the dry polylactic acid modified hydroxyapatite of quality 45%, it is scattered in an amount of dehydrated alcohol, ultrasonic 2 minutes, then the poly(lactic acid) matrix is thrown in wherein in batches, dipping absorption, take out airing,, obtain poly(lactic acid) from modifying the hydroxyapatite/polylactic acid matrix material through roller refining, compression molding.The initial bending strength 144.0MPa of this matrix material.
Embodiment 12. at room temperature is that the dry hydroxy apatite powder of 15 μ m joins in 2000 parts of acetone with 100 parts of median sizes, stirs 0.5 hour (800rpm), obtains the suspension of hydroxyapatite.In hydroxyapatite suspension, add 400 parts under stirring and contain 3 parts of poly(lactic acid) (M
v=7.0 * 10
4) acetone soln, drip 2500 parts of deionized waters subsequently, continue to stir 0.5 hour, leave standstill, suction filtration, vacuum-drying 48 hours, polylactic acid modified hydroxyapatite.
Taking by weighing quality is matrix poly(lactic acid) (M
v=4.5 * 10
5) the dry polylactic acid modified hydroxyapatite of quality 33%, it is scattered in an amount of dehydrated alcohol, ultrasonic 2 minutes, then the poly(lactic acid) matrix is thrown in wherein in batches, dipping absorption, take out airing,, obtain poly(lactic acid) from modifying the hydroxyapatite/polylactic acid matrix material through roller refining, compression molding.The initial bending strength 210.2MPa of this matrix material.
Claims (4)
1, a kind of modified hydroxylapatite and lactic acid composite material is characterized in that the matrix material of polylactic acid modified hydroxyapatite and poly(lactic acid).
2, matrix material as claimed in claim 1 is characterized in that poly(lactic acid) matrix and quality are the matrix material of the dry polylactic acid modified hydroxyapatite of poly(lactic acid) substrate quality 20%～45%.
3, the preparation method of the described matrix material of claim 1 is characterized in that at first adopting identical with the matrices of composite material structural unit and molecular weight M
v=3.0 * 10
4～M
v=7.0 * 10
4Poly(lactic acid) hydroxyapatite is carried out modification, then will be through the hydroxyapatite and the molecular weight M of modification
v=4.5 * 10
5The poly(lactic acid) matrix carry out compoundly, by absorption, dry, roller refining, compression molding, promptly obtain poly(lactic acid) from modifying the hydroxyapatite/polylactic acid matrix material.
4, preparation method as claimed in claim 3, its feature process process comprises:
Below as do not have to indicate and not to be massfraction,
1) at room temperature 100 parts of dry hydroxylapatite powders is joined in 2000 parts of acetone, stir, obtain the suspension of hydroxyapatite;
2) stirring adds 400 parts down and contains 1～5 part of M in hydroxyapatite suspension
v=3.0 * 10
4～M
v=7.0 * 10
4The acetone soln of poly(lactic acid) drips 2500 parts of deionized waters subsequently, continues to stir 0.5 hour;
3) leave standstill, suction filtration, vacuum-drying 48 hours gets polylactic acid modified hydroxyapatite;
4) taking by weighing quality is M
v=4.5 * 10
5The dry polylactic acid modified hydroxyapatite of matrix poly(lactic acid) quality 20%～45%, it is scattered in an amount of dehydrated alcohol, ultrasonic 2 minutes, then the poly(lactic acid) matrix is thrown in wherein in batches, dipping absorption, take out airing,, promptly get poly(lactic acid) from modifying the hydroxyapatite/polylactic acid matrix material through roller refining, compression molding.
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| CN 03119058 CN1233737C (en) | 2003-05-13 | 2003-05-13 | Polyactate self-modified hydroxyapatite/polylactate composite material and method for making same |
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|---|---|---|---|
| CN 03119058 CN1233737C (en) | 2003-05-13 | 2003-05-13 | Polyactate self-modified hydroxyapatite/polylactate composite material and method for making same |
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| CN1233737C true CN1233737C (en) | 2005-12-28 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100427283C (en) * | 2004-10-09 | 2008-10-22 | 武汉理工大学 | Directly heating, pressing and forming method for polylactic acid and hydroxy apatite composite material |
| CN100531807C (en) * | 2006-09-14 | 2009-08-26 | 同济大学 | Polylactic acid base/nano hydroxyapatite biological material and preparation method thereof |
| CN102153058B (en) * | 2010-12-24 | 2013-03-06 | 长春圣博玛生物材料有限公司 | Method for modifying nano hydroxyapatite, nano hydroxyapatite/polylactic acid compound material and preparation method of nano hydroxyapatite/polylactic acid compound material |
| TWI421163B (en) * | 2011-07-28 | 2014-01-01 | Chung Shan Inst Of Science | Method for making a poly-lactate/silica composite |
| EP3656406B1 (en) * | 2017-07-15 | 2023-12-27 | Shenzhen Corliber Scientific Co., Ltd. | Absorbable biomedical composite material and preparation method therefor |
| CN107376026B (en) * | 2017-07-15 | 2019-03-19 | 深圳市立心科学有限公司 | Absorbable bio-medical composition and preparation method thereof |
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2003
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