CN102311621A - Method for preparing polylactic acid/inorganic particle composite material in compound force field - Google Patents
Method for preparing polylactic acid/inorganic particle composite material in compound force field Download PDFInfo
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- CN102311621A CN102311621A CN 201110192862 CN201110192862A CN102311621A CN 102311621 A CN102311621 A CN 102311621A CN 201110192862 CN201110192862 CN 201110192862 CN 201110192862 A CN201110192862 A CN 201110192862A CN 102311621 A CN102311621 A CN 102311621A
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Abstract
The invention discloses a method for preparing a polylactic acid/inorganic particle composite material in a compound force field, which comprises the following steps: 1) drying inorganic particles, weighing inorganic particles and polylactic acid powder according to a mass ratio of (0.05-0.2):1; 2) measuring an acetone solution with a ratio to the polylactic acid powder being 5 g/100 ml, adding the inorganic particles into the acetone solution, and placing the solution in a compound force field of vibration and mechanical stirring; adding the polylactic acid powder, fully dissolving and mixing the polylactic acid powder; 3) adding an ethanol solvent in the compound force field, coprecipitating the polylactic acid and the inorganic particles; 4) drying the precipitates in a vacuum drying oven to obtain a composite material; 5) pressing and molding the composite material. The invention performs solvent coprecipitation of the composite solution under the action of a compound force field of vibration in a vertical direction and mechanical stirring, reduces the apparent viscosity of the polymer solution, improves the dispersibility of the inorganic particles in the polymer matrix, and increases the mechanical properties of the composite material.
Description
Technical field
The present invention relates to a kind of method for preparing matrix material, relate in particular to a kind of method for preparing the polylactic acid/inorganic particle composite material.
Background technology
In the orthopaedics field, owing to the damaged ten minutes of bone due to the multiple reasons such as severe trauma, bone tumor, osteomyelitis is common, development ideal bio-medical material substitutes the autologous bone transplanting repairing bone defect, becomes the important topic in medical science and the biomaterial scientific domain.
In recent years, absorbable POLYACTIC ACID (PLA) type bone alternate material has become the emphasis of surgical reconstruction and the research of bone tissue engineer aspect.It has good biodegradability; Also have simultaneously excellent biological compatibility, Bioabsorbable; After degraded, can not leave over any environmental issue, and can exempt the misery of patient's second operation, be one type of implantable intravital biomaterial of FDA approval; Simultaneously; It also has physical strength, Young's modulus and hot formability preferably, can satisfy the requirement as cell growing carrier material basically in bone tissue engineer fields such as the regeneration of osseous tissue and cartilaginous tissue and reparations, is applied to medicament slow release material, material implanted, operating suture, orthopaedics immobilization material, tissue engineering material etc.
Although poly-lactic acid material has a lot of superior performances, when clinical independent use, still run into a large amount of problems.
The first, poly-lactic acid material is being used for separately when clinical, and its mechanical strength is not enough, is not enough to satisfy the requirement of part load bone.The second and since poly-lactic acid material in vivo in the environment with the interaction of body fluid, can decomposite acid product, make human body produce uncomfortable reaction.The 3rd, the degradation material POLYACTIC ACID lacks biological activity, can and not put with bone, the surface not can with bone generation bonding, can not type of formation bone material, promote bone growth.
And the adding of certain inorganic materials, Win 40350 for example, tricalcium phosphate and other phosphoric acid salt or silicate material not only can reduce cost significantly, can also effectively improve the mechanical strength of POLYACTIC ACID, enlarge its range of application; Simultaneously because the alkalescence of these inorganic materials itself, can in and the acid product that in degradation process, produces of POLYACTIC ACID; And the most important thing is that these inorganic ceramic materials can generate the inorganics class osteoplaque be rich in calcium phosphate with humoral response, and can form effective bonding with sclerous tissues or soft tissue through its cytoactive, the promotion bone growth.
Because there are very big difference in the physical properties of mineral filler and POLYACTIC ACID and chemical structure, thereby lack affinity between the two, consistency is bad; Bonding force is not strong, makes mixed system be difficult to reach the degree of mixing of expection, is difficult to realize homodisperse; Resulting product is very unstable; Demixing phenomenon might occur in the use, inorganic particulate is easy to from polymeric matrix, split away off, and causes physical strength sharply to descend at short notice; So be difficult to reach the ideal modified effect, received bigger restriction in the application of bearing position.Therefore, improve the dispersiveness between inorganic particles and the POLYACTIC ACID matrix, the interface of improving between the two just becomes the key that improves the mixture physical strength.
In the research in the past; The solvent coprecipitation method is a kind of important method of mixing POLYACTIC ACID and inorganic particulate and preparing composite materials, and this method is that POLYACTIC ACID is dissolved in its good solvent, then inorganic particulate is added solution; Under the effect of stirring, use the poor solvent of POLYACTIC ACID that POLYACTIC ACID and inorganic particulate coprecipitation are separated out; The subject matter of this method is: (1) polymer solution viscosity is bigger, and inorganic particulate is reunited in polymers soln easily, and is dispersed bad; (2) there are very big difference in physical properties and chemical structure between POLYACTIC ACID and the inorganic particulate, thereby lack affinity between the two, and consistency is bad, and bonding force is not strong, makes mixed system be difficult to reach the degree of mixing of expection, is difficult to realize homodisperse; (3) the big quantity research of inorganic particulate reinforced polymeric material all shows, the particle diameter that reduces inorganic particulate helps the mechanical property that improves polymer materials, and for example nanoparticle just improves clearly the mechanical property of polymer materials; But the inorganic particulate particle diameter is more little, and agglomeration is just obvious more, and the combination between pellet is poor more; Have tangible gap between pellet; Form defective, when composite materials receives external force, form stress concentration easily and ftracture; Mechanical property is difficult to effectively improved, even can descend; (4) because whipping appts is the mixing of leaning on two kinds of materials of turning effort realization of device; And in whole solution system, the suffered stress of the solution of different level is difference to some extent, makes to be difficult to realize uniform distribution on the vertical direction of inorganic particulate in solution; Simultaneously; Because inorganic particulate presents suspended state in polymers soln, because the effect of gravity can make that also inorganic particulate distribution of different level in polymers soln is different; Especially in coprecipitation process; The viscosity of polymers soln diminishes gradually, and is this because the ununiformity that the inorganic particulate that Stress Field Distribution is inhomogeneous and action of gravity causes distributes just seems more obvious, makes the composite materials component skewness that makes at last.(5) the composite materials dispersiveness is bad, has caused the mechanical property of composite materials not high, has limited its range of application in the orthopaedics field.
Summary of the invention
To weak point of the prior art; The invention provides a kind of AV that reduces polymers soln; Improve the dispersiveness of inorganic particulate in polymkeric substance, the compound force field that improves the composite materials mechanical property prepares the method for polylactic acid/inorganic particle composite material down.
Compound force field provided by the invention prepares the method for polylactic acid/inorganic particle composite material down, comprises the steps:
1) place 80 ℃ dry 24 hours of baking oven to remove the moisture of inorganic particulate inorganic particulate; Mass ratio by inorganic particulate and POLYACTIC ACID powder is (0.05～0.2): 1 takes by weighing inorganic particulate and POLYACTIC ACID powder, as subsequent use;
2) to measure acetone soln with the ratio of POLYACTIC ACID powder 5g/100ml, the inorganic particulate that drying is good is put in the acetone solvent, makes the acetone solvent that adds the inorganic particulate powder be in the vibration of a vertical direction and the effect of churned mechanically compound force field; And then in acetone solvent, slowly add subsequent use POLYACTIC ACID powder, and add continued and under the compound force field effect, mixed 3～5 hours, the POLYACTIC ACID powder is fully dissolved, and make inorganic particulate and POLYACTIC ACID powder thorough mixing;
3) under the effect of above-mentioned compound force field, slowly add alcohol solvent, POLYACTIC ACID and inorganic particulate co-precipitation are come out;
4) throw out after POLYACTIC ACID and the inorganic particulate co-precipitation is put into the vacuum drying oven inner drying 48 hours, remove remaining acetone and alcohol solvent, promptly make the polylactic acid/inorganic particle composite material;
5) with the compression moulding in vulcanizing press of polylactic acid/inorganic particle composite material, the vulcanizing press pressing pressure is 10MPa, and press temperature is 190 ℃.
Compound force field of the present invention prepares the method for polylactic acid/inorganic particle composite material down, compared with prior art, has following advantage:
1, the present invention is employed under the vibration of vertical direction and the compound force field effect that mechanical stirring combines complex solution is carried out the solvent co-precipitation, reduces the AV of polymers soln, improves the dispersiveness of inorganic particulate in polymers soln.
2, the mode of utilization vertical vibration makes the combination between pellet tightr, reduces the gap between pellet, eliminates effectively or overcomes one's shortcomings.
3, improve combination between phase and phase through vibration, improve the mixed of solvent coprecipitation method when the preparation composite materials.
4, to the stress on vertical direction of complex solution system, reduce the inorganic particulate dispersive ununiformity that stirring action and action of gravity cause in the different levels position, improve the homogeneity that the composite materials component distributes.
5, improve the dispersiveness of inorganic particulate in the POLYACTIC ACID matrix, improve combination situation between the two, improve the mechanical property of composite materials, enlarge its use range.
Embodiment
Compound force field prepares the method for polylactic acid/inorganic particle composite material down, comprises the steps:
1) place 80 ℃ dry 24 hours of baking oven to remove the moisture of inorganic particulate inorganic particulate; Mass ratio by inorganic particulate and POLYACTIC ACID powder is (0.05～0.2): 1 takes by weighing inorganic particulate and POLYACTIC ACID powder, as subsequent use.
2) to measure acetone soln with the ratio of POLYACTIC ACID powder 5g/100ml, the inorganic particulate that drying is good is put in the acetone solvent, makes the acetone solvent that adds the inorganic particulate powder be in the vibration of a vertical direction and the effect of churned mechanically compound force field; And then in acetone solvent, slowly add subsequent use POLYACTIC ACID powder, and add continued and under the compound force field effect, mixed 3～5 hours, the POLYACTIC ACID powder is fully dissolved, and make inorganic particulate and POLYACTIC ACID powder thorough mixing.
3) under the effect of above-mentioned compound force field, slowly add alcohol solvent, POLYACTIC ACID and inorganic particulate co-precipitation are come out.
4) solution after POLYACTIC ACID and the inorganic particulate co-precipitation is put into the vacuum drying oven inner drying 48 hours, remove remaining acetone and alcohol solvent, promptly make the polylactic acid/inorganic particle composite material.
5) with the compression moulding in vulcanizing press of polylactic acid/inorganic particle composite material, the vulcanizing press pressing pressure is 10MPa, and press temperature is 190 ℃.
Embodiment 1
Is example with the wollastonite particle as inorganic particulate:
1) with wollastonite particle (2500 orders, length-to-diameter ratio: 6～10; Particle diameter: 2-5 μ m) place 80 ℃ dry 24 hours of baking oven to remove the moisture of powder trace; And be that 0.05:1 takes by weighing wollastonite particle and POLYACTIC ACID powder by the mass ratio of wollastonite particle and POLYACTIC ACID powder, as subsequent use.
2) to measure amount of acetone with the ratio of POLYACTIC ACID 5g/100ml; The wollastonite particle that drying is good is put in the acetone solvent; Make its effect that is in mechanical vibration and churned mechanically compound force field, the POLYACTIC ACID powder that slow adding weighs up in advance in this field of force then adds the back and under the compound force field effect, continues to mix 3～5 hours; POLYACTIC ACID is fully dissolved, and make wollastonite particle and POLYACTIC ACID thorough mixing even.
3) under the effect of above-mentioned compound force field, slowly add alcohol solvent, POLYACTIC ACID and the co-precipitation of wollastonite particle are come out.
4) throw out of POLYACTIC ACID and the co-precipitation of wollastonite particle is put into vacuum drying oven and removed remaining ethanol and acetone solvent in dry 48 hours, promptly make POLYACTIC ACID/grammite composite material.
5) with the POLYACTIC ACID/grammite composite material for preparing compression moulding in vulcanizing press, preparation size is the dumbbell sheet batten of 25mm * 5mm * 2mm under the pressure of 10MPa, and the press temperature of POLYACTIC ACID/grammite composite material is 190 ℃.These battens are at room temperature placed the test that is used for mechanical property after 3 days.
Get identical POLYACTIC ACID and wollastonite particle in addition and prepare POLYACTIC ACID/grammite composite material with traditional solvent coprecipitation method.
The performance that adopts the composite materials that the solvent coprecipitation method under compound force field of the present invention makes compares with the performance of the composite materials that adopts traditional solvent coprecipitation method to make, and is as shown in the table:
| ? | Traditional solvent coprecipitation method | Solvent coprecipitation method under the compound force field |
| The wollastonite deployment conditions | Relatively poor | Better |
| Tensile strength | 44.8 | 49.5 |
| Flexural strength | 82.5 | 89.2 |
| Modulus in flexure | 2415 | 2548 |
Embodiment 2
Is example with the wollastonite particle as inorganic particulate:
1) with wollastonite particle (2500 orders, length-to-diameter ratio: 6～10; Particle diameter: 2-5 μ m) place 80 ℃ dry 24 hours of baking oven to remove the moisture of powder trace; And be that 0.1:1 takes by weighing wollastonite particle and POLYACTIC ACID powder by the mass ratio of wollastonite particle and POLYACTIC ACID powder, as subsequent use.
2) to measure amount of acetone with the ratio of POLYACTIC ACID 5g/100ml; The wollastonite particle that drying is good is put in the acetone solvent; Make its effect that is in mechanical vibration and churned mechanically compound force field, the POLYACTIC ACID powder that slow adding weighs up in advance in this field of force then adds the back and under the compound force field effect, continues to mix 3～5 hours; POLYACTIC ACID is fully dissolved, and make wollastonite particle and POLYACTIC ACID thorough mixing even.
3) under the effect of above-mentioned compound force field, slowly add alcohol solvent, POLYACTIC ACID and the co-precipitation of wollastonite particle are come out.
4) throw out of POLYACTIC ACID and the co-precipitation of wollastonite particle is put into vacuum drying oven and removed remaining ethanol and acetone solvent in dry 48 hours, promptly make POLYACTIC ACID/grammite composite material.
5) with the POLYACTIC ACID/grammite composite material for preparing compression moulding in vulcanizing press, preparation size is the dumbbell sheet batten of 25mm * 5mm * 2mm under the pressure of 10MPa, and the press temperature of POLYACTIC ACID/grammite composite material is 190 ℃.These battens are at room temperature placed the test that is used for mechanical property after 3 days.
Get identical POLYACTIC ACID and wollastonite particle in addition and prepare POLYACTIC ACID/grammite composite material with traditional solvent coprecipitation method.
The performance that adopts the composite materials that the solvent coprecipitation method under compound force field of the present invention makes compares with the performance of the composite materials that adopts traditional solvent coprecipitation method to make, and is as shown in the table:
| ? | Traditional solvent coprecipitation method | Solvent coprecipitation method under the compound force field |
| The wollastonite deployment conditions | Relatively poor | Better |
| Tensile strength | 58 | 62.6 |
| Flexural strength | 86．8 | 94.7 |
| Modulus in flexure | 2680 | 2812 |
Embodiment 3
Is example with the wollastonite particle as inorganic particulate:
1) with wollastonite particle (2500 orders, length-to-diameter ratio: 6～10; Particle diameter: 2-5 μ m) place 80 ℃ dry 24 hours of baking oven to remove the moisture of powder trace; And be that 0.2:1 takes by weighing wollastonite particle and POLYACTIC ACID powder by the mass ratio of wollastonite particle and POLYACTIC ACID powder, as subsequent use.
2) to measure amount of acetone with the ratio of POLYACTIC ACID 5g/100ml; The wollastonite particle that drying is good is put in the acetone solvent; Make its effect that is in mechanical vibration and churned mechanically compound force field, the POLYACTIC ACID powder that slow adding weighs up in advance in this field of force then adds the back and under the compound force field effect, continues to mix 3～5 hours; POLYACTIC ACID is fully dissolved, and make wollastonite particle and POLYACTIC ACID thorough mixing even.
3) under the effect of above-mentioned compound force field, slowly add alcohol solvent, POLYACTIC ACID and the co-precipitation of wollastonite particle are come out.
4) throw out after POLYACTIC ACID and the co-precipitation of wollastonite particle is put into vacuum drying oven and removed remaining ethanol and acetone solvent in dry 48 hours, promptly make POLYACTIC ACID/grammite composite material.
5) with the POLYACTIC ACID/grammite composite material for preparing compression moulding in vulcanizing press, preparation size is the dumbbell sheet batten of 25mm * 5mm * 2mm under the pressure of 10MPa, and the press temperature of POLYACTIC ACID/grammite composite material is 190 ℃.These battens are at room temperature placed the test that is used for mechanical property after 3 days.
Get identical POLYACTIC ACID and wollastonite particle in addition and prepare POLYACTIC ACID/grammite composite material with traditional solvent coprecipitation method.
The performance that adopts the composite materials that the solvent coprecipitation method under compound force field of the present invention makes compares with the performance of the composite materials that adopts traditional solvent coprecipitation method to make, and is as shown in the table:
| ? | Traditional solvent coprecipitation method | Solvent coprecipitation method under the compound force field |
| The wollastonite deployment conditions | Relatively poor | Better |
| Tensile strength | 41．3 | 46.9 |
| Flexural strength | 92.1 | 98.6 |
| Modulus in flexure | 3279 | 3491 |
Explanation is at last; Above embodiment is only unrestricted in order to technical scheme of the present invention to be described; Although with reference to preferred embodiment the present invention is specified, those of ordinary skill in the art should be appreciated that and can make amendment or be equal to replacement technical scheme of the present invention; And not breaking away from the aim and the scope of technical scheme of the present invention, it all should be encompassed in the middle of the claim scope of the present invention.
Claims (1)
1. the following method for preparing the polylactic acid/inorganic particle composite material of compound force field is characterized in that this method comprises the steps:
1) place 80 ℃ dry 24 hours of baking oven to remove the moisture of inorganic particulate inorganic particulate; Mass ratio by inorganic particulate and POLYACTIC ACID powder is (0.05～0.2): 1 takes by weighing inorganic particulate and POLYACTIC ACID powder, as subsequent use;
2) to measure acetone soln with the ratio of POLYACTIC ACID powder 5g/100ml, the inorganic particulate that drying is good is put in the acetone solvent, makes the acetone solvent that adds the inorganic particulate powder be in the vibration of a vertical direction and the effect of churned mechanically compound force field; And then in acetone solvent, slowly add subsequent use POLYACTIC ACID powder, and add continued and under the compound force field effect, mixed 3～5 hours, the POLYACTIC ACID powder is fully dissolved, and make inorganic particulate and POLYACTIC ACID powder thorough mixing;
3) under the effect of above-mentioned compound force field, slowly add alcohol solvent, POLYACTIC ACID and inorganic particulate co-precipitation are come out;
4) throw out after POLYACTIC ACID and the inorganic particulate co-precipitation is put into the vacuum drying oven inner drying 48 hours, remove remaining acetone and alcohol solvent, promptly make the polylactic acid/inorganic particle composite material;
5) with the compression moulding in vulcanizing press of polylactic acid/inorganic particle composite material, the vulcanizing press pressing pressure is 10MPa, and press temperature is 190 ℃.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022252982A1 (en) * | 2021-06-03 | 2022-12-08 | 青岛理工大学 | Preparation of polymer-coated inorganic particles using heterogeneous solution method, and application of polymer-coated inorganic particles |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201840994U (en) * | 2010-09-11 | 2011-05-25 | 安徽蓝柯复合材料有限公司 | Paint disperser |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201840994U (en) * | 2010-09-11 | 2011-05-25 | 安徽蓝柯复合材料有限公司 | Paint disperser |
Non-Patent Citations (1)
| Title |
|---|
| 《重庆工学院学报（自然科学）》 20090315 徐梁等 "聚乳酸/硅灰石生物医用复合材料的降解性能" 69-75 1 第23卷, 第3期 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022252982A1 (en) * | 2021-06-03 | 2022-12-08 | 青岛理工大学 | Preparation of polymer-coated inorganic particles using heterogeneous solution method, and application of polymer-coated inorganic particles |
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Application publication date: 20120111 |