CN104001210A - Polylactic acid fiber reinforced polylactic acid/hydroxyapatite composite material and preparation method thereof - Google Patents
Polylactic acid fiber reinforced polylactic acid/hydroxyapatite composite material and preparation method thereof Download PDFInfo
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- CN104001210A CN104001210A CN201410254491.2A CN201410254491A CN104001210A CN 104001210 A CN104001210 A CN 104001210A CN 201410254491 A CN201410254491 A CN 201410254491A CN 104001210 A CN104001210 A CN 104001210A
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Abstract
The invention discloses a polylactic acid fiber reinforced polylactic acid/hydroxyapatite composite material which is characterized by comprising a plurality of polylactic acid-hydroxyapatite film layers arranged from top to bottom, wherein a polylactic acid fiber layer is arranged between every adjacent two polylactic acid-hydroxyapatite film layers; each polylactic acid-hydroxyapatite film layer and each polylactic acid fiber layer are hotly pressed together; the polylactic acid-hydroxyapatite film layers are made from materials composed of 70-95 percent (weight) of polylactic acid and 5-30 percent (weight) of hydroxyapatite; the polylactic acid fiber layers are formed by paving polylactic acid fiber. The invention further provides a preparation method of the composite material. The preparation process of the composite material is simple, the cost is low, the obtained composite material is good in mechanical property, has good resistance to tensile stress and toughness, has biological activity and degradability, does not contain organic solvents having side effects for human bodies, and can act as a high-strength material.
Description
Technical field
The present invention relates to medical material, be specifically related to the preparation method that a kind of acid fiber by polylactic strengthens polylactic acid/hydroxy apatite composite material.
Background technology
Polylactic acid (PLA) is to study at present more synthetic macromolecular material, have nontoxic, good with human compatibility, the advantage such as can degradablely absorb in vivo, but, existing achievement in research shows that polylactic acid mechanical strength is lower, and shortage biological activity, its acid degradation product gathering easily causes inflammatory reaction in body.Hydroxyapatite (HA) is a kind of bioactive ceramics, it is inorganic constituents main in skeleton, there is good biocompatibility, biological activity and bone conductibility, and the growth of energy inducing peripheral osseous tissue also forms firmly chemical bonding with host bone, it is not good that yet the shortcoming of hydroxyapatite is mechanical performance, easily crisp, poor to loading into carrying property, and be not suitable for directly as osseous tissue material.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of acid fiber by polylactic and strengthens polylactic acid/hydroxy apatite composite material and this composite material and preparation method thereof, this composite material preparation process is simple, cost is low, without adding organic solvent, and mechanical property is good, there is biological activity and degradability.The technical scheme adopting is as follows:
A kind of acid fiber by polylactic strengthens polylactic acid/hydroxy apatite composite material, it is characterized in that comprising a plurality of polylactic acid-glycolic base apatite film layers of arranging from top to bottom, between adjacent two polylactic acid-glycolic base apatite film layers, be provided with acid fiber by polylactic layer, each polylactic acid-glycolic base apatite film layer is together with each acid fiber by polylactic layer hot pressing; Described polylactic acid-glycolic base apatite film layer is the polylactic acid-glycolic base apatite film that adopts the material be comprised of the polylactic acid of 70-95% (weight) and the hydroxyapatite of 5-30% (weight) to make; Described acid fiber by polylactic layer adopts acid fiber by polylactic to lay and forms.
Above-mentioned can be poly (l-lactic acid) (PLLA), poly-D for making the contained polylactic acid of material of polylactic acid-glycolic base apatite film, Pfansteihl (PDLLA) or poly (l-lactic acid)-co-glycolic acid (PLGA).
The thickness of above-mentioned polylactic acid-glycolic base apatite film is generally 0.05-0.1mm.
Above-mentioned acid fiber by polylactic can be poly (l-lactic acid) fiber, poly-D, a kind of in Pfansteihl fiber and poly (l-lactic acid)-co-glycolic acid fiber or the wherein composite fibre of multiple composition.Above-mentioned acid fiber by polylactic can be also by poly (l-lactic acid), poly-D, two kinds of core shell structure composite fibers of making in Pfansteihl and poly (l-lactic acid)-co-glycolic acid.
In preferred version, the gross weight of above-mentioned each polylactic acid-glycolic base apatite film layer accounts for the 85-95% that acid fiber by polylactic strengthens polylactic acid/hydroxy apatite composite material gross weight, and the gross weight of each acid fiber by polylactic layer accounts for the 5-15% that acid fiber by polylactic strengthens polylactic acid/hydroxy apatite composite material gross weight.
In preferred same acid fiber by polylactic layer, acid fiber by polylactic laying direction is consistent.In different acid fiber by polylactic layers, acid fiber by polylactic laying direction can be consistent or different.
The present invention also provides above-mentioned acid fiber by polylactic to strengthen a kind of preparation method of polylactic acid/hydroxy apatite composite material, it is characterized in that in turn including the following steps:
(1) graininess polylactic acid is carried out to dried, remove moisture wherein;
(2) polylactic acid step (1) being obtained mixes in the ratio of polylactic acid 70-95% (weight), hydroxyapatite 5-30% (weight) with hydroxyapatite, obtains mixed material;
(3) mixed material step (2) being obtained adds double screw extruder blend, extrudes, and extrudate is made to pellet with comminutor;
(4) pellet step (3) being obtained adds thin film extrusion equipment, and making thickness is the polylactic acid-glycolic base apatite film of 0.05-0.1mm;
(5) on a metal plate, place one deck polylactic acid-glycolic base apatite film, then at this, above polylactic acid-glycolic base apatite film, lay one deck acid fiber by polylactic, at this, above strata acid fiber, place again one deck polylactic acid-glycolic base apatite film, so repeat, until complete the placement of all each strata lactic acid-hydroxyapatite films and the laying of each strata acid fiber, obtain stacking material; Then in stacking material, above the polylactic acid-glycolic base apatite film of the superiors, press another metal plate;
(6) to be placed in dull and stereotyped heat pressing forming machines hot-forming, cooling, obtain acid fiber by polylactic after the demoulding strengthens polylactic acid/hydroxy apatite composite material together with two metal plates for stacking material step (5) being obtained.
In preferred steps (1), graininess polylactic acid is put into vacuum drying oven, under 60-65 C, dry 24-48 hour, remove moisture wherein.
In preferred steps (1), polylactic acid used is poly (l-lactic acid) (PLLA), poly-D, Pfansteihl (PDLLA) or poly (l-lactic acid)-co-glycolic acid (PLGA).
In preferred steps (2), polylactic acid and hydroxyapatite that step (1) is obtained are put into high-speed mixer in described ratio, under the condition of 50-60 ° of C, with the speed of 1000-2000 rev/min, mix 1-5 minute, obtain mixed material.
In preferred steps (3), the extrusion die that double screw extruder used is equipped with has a plurality of material discharging round holes, and the diameter of material discharging round hole is 2-3mm.The temperature of the barrel of double screw extruder is controlled between 120-190 ℃ conventionally.
In preferred steps (4), thin film extrusion equipment used comprises single screw extrusion machine and former, and the extrusion die of single screw extrusion machine has bar shaped discharging opening, and former used is flow casting molding equipment or calendering formation equipment.The temperature of the barrel of single screw extrusion machine is controlled between 120-190 ℃ conventionally.
In step (5), acid fiber by polylactic is laid in a certain direction, and the laying direction of acid fiber by polylactic can parallel with the lead of polylactic acid-glycolic base apatite film in step (4), perpendicular or becomes one be greater than zero and be less than the angle of 90 °.In preferred same acid fiber by polylactic layer, acid fiber by polylactic laying direction is consistent.In different acid fiber by polylactic layers, acid fiber by polylactic laying direction can be consistent or different.
In step (5), acid fiber by polylactic used can be poly (l-lactic acid) fiber, poly-D, a kind of in Pfansteihl fiber and poly (l-lactic acid)-co-glycolic acid fiber or the wherein composite fibre of multiple composition; Acid fiber by polylactic used can be also by poly (l-lactic acid), poly-D, two kinds of core shell structure composite fibers of making in Pfansteihl and poly (l-lactic acid)-co-glycolic acid.
In preferred steps (5), the gross weight of the acid fiber by polylactic of laying accounts for the 5-15% of stacking material gross weight, and the gross weight of each strata lactic acid-hydroxyapatite films accounts for the 85-95% of stacking material gross weight.
In preferred steps (5), lay after acid fiber by polylactic, with adhesive tape, acid fiber by polylactic end is fixed on metal plate below, to prevent acid fiber by polylactic thermal contraction in hot-forming process.
In step (5), two metal plates form heat pressing and molding mold; Metal plate used can adopt smooth aluminium alloy plate or steel plate.
For conveniently stripped, in preferred steps (5), on the lateral surface of outmost two the polylactic acid-glycolic base apatite films of stacking material, respectively place an antiseize membrane.
In step (6), dull and stereotyped heat pressing forming machines used generally includes lower platen and top board, and lower platen is fixed in frame, and top board is in lower platen top and liftable (top board presses to stacking material while declining); On lower platen and top board, be equipped with heater (as electric heater unit or deep fat heating pipe line); Described stacking material is placed in above the lower platen of dull and stereotyped heat pressing forming machines.In addition, in order to accelerate the rate of cooling after molding, can on lower platen and top board, be equipped with chiller (as water cooling pipeline or oil circulation cooling line).
In preferred steps (6), in temperature, be that 150-160 ° of C, pressure are hot-forming 5-10 minute under the condition of 1-3 ton, be then cooled to 15-30 ° of C, the demoulding after release.
In the present invention, polylactic acid and hydroxyapatite is compound, both can improve the mechanical property of polylactic acid and guide osteogenic characteristics, can there is control action to the biodegradation of hydroxyapatite again, guarantee that osseous tissue resume speed is consistent with material degradation speed.Acid fiber by polylactic has good crystallinity, stretched orientation process in machine-shaping process, and its mechanical property will strengthen complex with it as reinforce far above common poly-lactic acid material, can improve performance and the intensity of composite; In addition, acid fiber by polylactic has identical chemical constitution with polylactic acid matrix, completely compatible between the two, Presence of an interface problem not, the two is conducted and disperses destructive stress by good interface fit, can alleviate the destruction of stress concentration to material itself.With biodegradable acid fiber by polylactic, strengthen polylactic acid/hydroxy apatite composite material, not only there is good hot strength and modulus, and each component of this composite in vivo can be degradable, catabolite can excrete by function of human body, and centre does not produce rejection or other untoward reaction; Meanwhile, the biologically inert reaction that this fiber-inorganic/organic composite material can avoid metal material to produce, has biological activity.In brief, composite material preparation process of the present invention is simple, cost is low, without adding organic solvent, the composite materials property obtaining is good, has the mechanical properties such as good tensile strength and toughness, there is biological activity and degradability, and, containing human body being had to the organic solvent of side effect, not a kind of high-performance composite materials with broad prospect of application, can be used as high strength orthopaedics material.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of the stacking material (together with two metal plates) of step in the embodiment of the present invention 1 (5) formation;
Fig. 2 is the structural representation that the acid fiber by polylactic of the embodiment of the present invention 1 strengthens polylactic acid/hydroxy apatite composite material.
The specific embodiment
Embodiment 1
The preparation method that the acid fiber by polylactic of the present embodiment strengthens polylactic acid/hydroxy apatite composite material in turn includes the following steps:
(1) graininess polylactic acid (being graininess poly (l-lactic acid)) is put into vacuum drying oven, under 65 C, dry 24 hours, remove moisture wherein;
(2) polylactic acid step (1) being obtained mixes in the ratio of polylactic acid 95% (weight), hydroxyapatite 5% (weight) with hydroxyapatite, obtains mixed material;
In this step (2), polylactic acid and hydroxyapatite that step (1) is obtained are put into high-speed mixer in described ratio, under the condition of 55 ° of C, with the speed of 1500 revs/min, mix 3 minutes, obtain mixed material.
(3) mixed material step (2) being obtained adds double screw extruder blend, extrudes, and extrudate is made to pellet with comminutor;
In this step (3), the extrusion die that double screw extruder used is equipped with has a plurality of material discharging round holes, and the diameter of material discharging round hole is 2mm.The temperature of the barrel of double screw extruder is controlled between 120-190 ℃.
(4) pellet step (3) being obtained adds thin film extrusion equipment, and making thickness is the polylactic acid-glycolic base apatite film of 0.1mm;
In this step (4), thin film extrusion equipment used comprises single screw extrusion machine and former, and the extrusion die of single screw extrusion machine has bar shaped discharging opening, and former used is flow casting molding equipment or calendering formation equipment.The temperature of the barrel of single screw extrusion machine is controlled between 120-190 ℃.
(5) with reference to figure 1, on a metal plate 4, place one deck polylactic acid-glycolic base apatite film, then at this, above polylactic acid-glycolic base apatite film, lay one deck acid fiber by polylactic, at this, above strata acid fiber, place again one deck polylactic acid-glycolic base apatite film, obtain stacking material (this stacking material comprises two polylactic acid-glycolic base apatite film layers 1 and an acid fiber by polylactic layer 2, is followed successively by from top to bottom polylactic acid-glycolic base apatite film layer 1, acid fiber by polylactic layer 2, polylactic acid-glycolic base apatite film layer 1); Then in stacking material, above the polylactic acid-glycolic base apatite film of the superiors, press another metal plate 5;
In this step (5), lay after acid fiber by polylactic, with adhesive tape, acid fiber by polylactic end is fixed on metal plate 4 below.
The gross weight of the acid fiber by polylactic of laying accounts for 10% of stacking material gross weight, and the gross weight of each strata lactic acid-hydroxyapatite films accounts for 90% of stacking material gross weight.
The laying direction of acid fiber by polylactic parallels with the lead of polylactic acid-glycolic base apatite film in step (4).
With reference to figure 1, for conveniently stripped, in stacking material, on the lateral surface of two-layer polylactic acid-glycolic base apatite film, respectively place an antiseize membrane 3.
(6) to be placed in dull and stereotyped heat pressing forming machines hot-forming, cooling, obtain acid fiber by polylactic after the demoulding strengthens polylactic acid/hydroxy apatite composite material together with two metal plates for stacking material step (5) being obtained.
In this step (6), dull and stereotyped heat pressing forming machines used comprises lower platen and top board, and lower platen is fixed in frame, and top board is in lower platen top and liftable (top board presses to stacking material while declining); On lower platen and top board, be equipped with heater (as electric heater unit or deep fat heating pipe line) and chiller (as water cooling pipeline or oil circulation cooling line).Carry out when hot-forming, metal plate 4 is on lower platen, and top board presses to metal plate 5 after declining.
In this step (6), in temperature, be that 160 ° of C, pressure are under the condition of 2 tons hot-forming 10 minutes, be then cooled to 30 ° of C, the demoulding after release.
With reference to figure 2, the acid fiber by polylactic obtaining strengthens polylactic acid/hydroxy apatite composite material and comprises two polylactic acid-glycolic base apatite film layers 1 arranging from top to bottom, between two polylactic acid-glycolic base apatite film layers 1, be provided with acid fiber by polylactic layer 2, polylactic acid-glycolic base apatite film layer 2 is (being that acid fiber by polylactic enhancing polylactic acid/hydroxy apatite composite material is comprised of coarctate two the polylactic acid-glycolic base apatite film layers 1 of heat and an acid fiber by polylactic layer 2) together with two acid fiber by polylactic layer 1 hot pressing.The gross weight of two polylactic acid-glycolic base apatite film layers 1 accounts for acid fiber by polylactic and strengthens 90% of polylactic acid/hydroxy apatite composite material gross weight, and the gross weight of acid fiber by polylactic layer 2 accounts for acid fiber by polylactic and strengthens 10% of polylactic acid/hydroxy apatite composite material gross weight.
It is as follows that the acid fiber by polylactic obtaining strengthens polylactic acid/hydroxy apatite composite material performance indications: stretch modulus is 10Gpa, and hot strength is 65MPa.
Embodiment 2
The preparation method that the acid fiber by polylactic of the present embodiment strengthens polylactic acid/hydroxy apatite composite material in turn includes the following steps:
(1) graininess polylactic acid (being graininess poly (l-lactic acid)) is put into vacuum drying oven, under 65 C, dry 24 hours, remove moisture wherein;
(2) polylactic acid step (1) being obtained mixes in the ratio of polylactic acid 80% (weight), hydroxyapatite 20% (weight) with hydroxyapatite, obtains mixed material;
In this step (2), polylactic acid and hydroxyapatite that step (1) is obtained are put into high-speed mixer in described ratio, under the condition of 60 ° of C, with the speed of 1000 revs/min, mix 5 minutes, obtain mixed material.
(3) mixed material step (2) being obtained adds double screw extruder blend, extrudes, and extrudate is made to pellet with comminutor;
In this step (3), the extrusion die that double screw extruder used is equipped with has a plurality of material discharging round holes, and the diameter of material discharging round hole is 3mm.The temperature of the barrel of double screw extruder is controlled between 120-190 ℃.
(4) pellet step (3) being obtained adds thin film extrusion equipment, and making thickness is the polylactic acid-glycolic base apatite film of 0.1mm;
In this step (4), thin film extrusion equipment used comprises single screw extrusion machine and former, and the extrusion die of single screw extrusion machine has bar shaped discharging opening, and former used is flow casting molding equipment or calendering formation equipment.The temperature of the barrel of single screw extrusion machine is controlled between 120-190 ℃.
(5) on a metal plate, place one deck polylactic acid-glycolic base apatite film, then at this, above polylactic acid-glycolic base apatite film, lay one deck acid fiber by polylactic (being poly (l-lactic acid) fiber), at this, above strata acid fiber, place again one deck polylactic acid-glycolic base apatite film, obtain stacking material (this stacking material comprises two polylactic acid-glycolic base apatite film layers and an acid fiber by polylactic layer, is followed successively by from top to bottom polylactic acid-glycolic base apatite film layer, acid fiber by polylactic layer, polylactic acid-glycolic base apatite film layer); Then in stacking material, above the polylactic acid-glycolic base apatite film of the superiors, press another metal plate;
In this step (5), lay after acid fiber by polylactic, with adhesive tape, acid fiber by polylactic end is fixed on metal plate below.
The gross weight of the acid fiber by polylactic of laying accounts for 10% of stacking material gross weight, and the gross weight of each strata lactic acid-hydroxyapatite films accounts for 90% of stacking material gross weight.
In the laying direction of acid fiber by polylactic and step (4), the lead of polylactic acid-glycolic base apatite film is perpendicular.
For conveniently stripped, in stacking material, on the lateral surface of two-layer polylactic acid-glycolic base apatite film, respectively place an antiseize membrane.
(6) to be placed in dull and stereotyped heat pressing forming machines hot-forming, cooling, obtain acid fiber by polylactic after the demoulding strengthens polylactic acid/hydroxy apatite composite material together with two metal plates for stacking material step (5) being obtained.
Dull and stereotyped heat pressing forming machines structure used in this step (6) is identical with embodiment 1.
In this step (6), in temperature, be that 160 ° of C, pressure are under the condition of 2 tons hot-forming 10 minutes, be then cooled to 20 ° of C, the demoulding after release.
The acid fiber by polylactic obtaining strengthens polylactic acid/hydroxy apatite composite material and comprises two polylactic acid-glycolic base apatite film layers arranging from top to bottom, between two polylactic acid-glycolic base apatite film layers, be provided with acid fiber by polylactic layer, polylactic acid-glycolic base apatite film layer is (being that acid fiber by polylactic enhancing polylactic acid/hydroxy apatite composite material is comprised of coarctate two the polylactic acid-glycolic base apatite film layers of heat and an acid fiber by polylactic layer) together with two acid fiber by polylactic layer hot pressing.The gross weight of two polylactic acid-glycolic base apatite film layers accounts for acid fiber by polylactic and strengthens 90% of polylactic acid/hydroxy apatite composite material gross weight, and the gross weight of acid fiber by polylactic layer accounts for acid fiber by polylactic and strengthens 10% of polylactic acid/hydroxy apatite composite material gross weight.
It is as follows that the acid fiber by polylactic obtaining strengthens polylactic acid/hydroxy apatite composite material performance indications: stretch modulus is 9.2Gpa, and hot strength is 45MPa.
Embodiment 3
The preparation method that the acid fiber by polylactic of the present embodiment strengthens polylactic acid/hydroxy apatite composite material in turn includes the following steps:
(1) graininess polylactic acid (being the poly-D of graininess, Pfansteihl) is put into vacuum drying oven, under 60 C, dry 48 hours, remove moisture wherein;
(2) polylactic acid step (1) being obtained mixes in the ratio of polylactic acid 75% (weight), hydroxyapatite 25% (weight) with hydroxyapatite, obtains mixed material;
In this step (2), polylactic acid and hydroxyapatite that step (1) is obtained are put into high-speed mixer in described ratio, under the condition of 50 ° of C, with the speed of 2000 revs/min, mix 2 minutes, obtain mixed material.
(3) mixed material step (2) being obtained adds double screw extruder blend, extrudes, and extrudate is made to pellet with comminutor;
In this step (3), the extrusion die that double screw extruder used is equipped with has a plurality of material discharging round holes, and the diameter of material discharging round hole is 2mm.The temperature of the barrel of double screw extruder is controlled between 120-190 ℃.
(4) pellet step (3) being obtained adds thin film extrusion equipment, and making thickness is the polylactic acid-glycolic base apatite film of 0.05mm;
In this step (4), thin film extrusion equipment used comprises single screw extrusion machine and former, and the extrusion die of single screw extrusion machine has bar shaped discharging opening, and former used is flow casting molding equipment or calendering formation equipment.The temperature of the barrel of single screw extrusion machine is controlled between 120-190 ℃.
(5) on a metal plate, place one deck polylactic acid-glycolic base apatite film, then at this, above polylactic acid-glycolic base apatite film, lay one deck acid fiber by polylactic and (be poly-D, Pfansteihl fiber), at this, above strata acid fiber, place again one deck polylactic acid-glycolic base apatite film, then on second layer polylactic acid-glycolic base apatite film, lay one deck acid fiber by polylactic and (be poly-D, Pfansteihl fiber), on second layer acid fiber by polylactic, place again one deck polylactic acid-glycolic base apatite film, (this stacking material comprises three polylactic acid-glycolic base apatite film layers and two acid fiber by polylactic layers to obtain stacking material, be followed successively by from top to bottom polylactic acid-glycolic base apatite film layer, acid fiber by polylactic layer, polylactic acid-glycolic base apatite film layer, acid fiber by polylactic layer, polylactic acid-glycolic base apatite film layer), then in stacking material, above the polylactic acid-glycolic base apatite film of the superiors, press another metal plate,
In this step (5), lay after acid fiber by polylactic, with adhesive tape, acid fiber by polylactic end is fixed on metal plate below.
The gross weight of the acid fiber by polylactic of laying accounts for 15% of stacking material gross weight, and the gross weight of each strata lactic acid-hydroxyapatite films accounts for 85% of stacking material gross weight.
The laying direction of lower floor's acid fiber by polylactic parallels with the lead of polylactic acid-glycolic base apatite film in step (4), and in the laying direction of upper strata acid fiber by polylactic and step (4), the lead of polylactic acid-glycolic base apatite film is perpendicular.
For conveniently stripped, on the lateral surface of outmost two the polylactic acid-glycolic base apatite films of stacking material, respectively place an antiseize membrane.
(6) to be placed in dull and stereotyped heat pressing forming machines hot-forming, cooling, obtain acid fiber by polylactic after the demoulding strengthens polylactic acid/hydroxy apatite composite material together with two metal plates for stacking material step (5) being obtained.
Dull and stereotyped heat pressing forming machines structure used in this step (6) is identical with embodiment 1.
In this step (6), in temperature, be that 150 ° of C, pressure are under the condition of 3 tons hot-forming 5 minutes, be then cooled to 15 ° of C, the demoulding after release.
The acid fiber by polylactic obtaining strengthens polylactic acid/hydroxy apatite composite material and comprises three polylactic acid-glycolic base apatite film layers arranging from top to bottom, between adjacent two polylactic acid-glycolic base apatite film layers, be provided with acid fiber by polylactic layer, each polylactic acid-glycolic base apatite film layer is (being that acid fiber by polylactic enhancing polylactic acid/hydroxy apatite composite material is comprised of coarctate three the polylactic acid-glycolic base apatite film layers of heat and two acid fiber by polylactic layers) together with each acid fiber by polylactic layer hot pressing.The gross weight of each polylactic acid-glycolic base apatite film layer accounts for acid fiber by polylactic and strengthens 85% of polylactic acid/hydroxy apatite composite material gross weight, and the gross weight of each acid fiber by polylactic layer accounts for acid fiber by polylactic and strengthens 15% of polylactic acid/hydroxy apatite composite material gross weight.
It is as follows that the acid fiber by polylactic obtaining strengthens polylactic acid/hydroxy apatite composite material performance indications: stretch modulus is 12Gpa, and hot strength is 58MPa.
Embodiment 4
The preparation method that the acid fiber by polylactic of the present embodiment strengthens polylactic acid/hydroxy apatite composite material in turn includes the following steps:
(1) graininess polylactic acid (being graininess poly (l-lactic acid)-co-glycolic acid) is put into vacuum drying oven, under 62 C, dry 30 hours, remove moisture wherein.
(2) polylactic acid step (1) being obtained mixes in the ratio of polylactic acid 70% (weight), hydroxyapatite 30% (weight) with hydroxyapatite, obtains mixed material;
In this step (2), polylactic acid and hydroxyapatite that step (1) is obtained are put into high-speed mixer in described ratio, under the condition of 60 ° of C, with the speed of 2000 revs/min, mix 1 minute, obtain mixed material.
(3) mixed material step (2) being obtained adds double screw extruder blend, extrudes, and extrudate is made to pellet with comminutor;
In this step (3), the extrusion die that double screw extruder used is equipped with has a plurality of material discharging round holes, and the diameter of material discharging round hole is 2mm.The temperature of the barrel of double screw extruder is controlled between 120-190 ℃.
(4) pellet step (3) being obtained adds thin film extrusion equipment, and making thickness is the polylactic acid-glycolic base apatite film of 0.08mm;
In this step (4), thin film extrusion equipment used comprises single screw extrusion machine and former, and the extrusion die of single screw extrusion machine has bar shaped discharging opening, and former used is flow casting molding equipment or calendering formation equipment.The temperature of the barrel of single screw extrusion machine is controlled between 120-190 ℃.
(5) on a metal plate, place one deck polylactic acid-glycolic base apatite film, then at this, above polylactic acid-glycolic base apatite film, lay one deck acid fiber by polylactic (being poly (l-lactic acid)-co-glycolic acid fiber), at this, above strata acid fiber, place again one deck polylactic acid-glycolic base apatite film, obtain stacking material (this stacking material comprises two polylactic acid-glycolic base apatite film layers and an acid fiber by polylactic layer, is followed successively by from top to bottom polylactic acid-glycolic base apatite film layer, acid fiber by polylactic layer, polylactic acid-glycolic base apatite film layer); Then in stacking material, above the polylactic acid-glycolic base apatite film of the superiors, press another metal plate;
In this step (5), lay after acid fiber by polylactic, with adhesive tape, acid fiber by polylactic end is fixed on metal plate below.
The gross weight of the acid fiber by polylactic of laying accounts for 5% of stacking material gross weight, and the gross weight of each strata lactic acid-hydroxyapatite films accounts for 95% of stacking material gross weight.
The laying direction of acid fiber by polylactic parallels with the lead of polylactic acid-glycolic base apatite film in step (4).
For conveniently stripped, in stacking material, on the lateral surface of two polylactic acid-glycolic base apatite films, respectively place an antiseize membrane.
(6) to be placed in dull and stereotyped heat pressing forming machines hot-forming, cooling, obtain acid fiber by polylactic after the demoulding strengthens polylactic acid/hydroxy apatite composite material together with two metal plates for stacking material step (5) being obtained.
Dull and stereotyped heat pressing forming machines structure used in this step (6) is identical with embodiment 1.
In this step (6), in temperature, be that 160 ° of C, pressure are under the condition of 1 ton hot-forming 8 minutes, be then cooled to 25 ° of C, the demoulding after release.
The acid fiber by polylactic obtaining strengthens polylactic acid/hydroxy apatite composite material and comprises a plurality of polylactic acid-glycolic base apatite film layers of arranging from top to bottom, between adjacent two polylactic acid-glycolic base apatite film layers, be provided with acid fiber by polylactic layer, each polylactic acid-glycolic base apatite film layer is (being that acid fiber by polylactic enhancing polylactic acid/hydroxy apatite composite material is comprised of coarctate two the polylactic acid-glycolic base apatite film layers of heat and an acid fiber by polylactic layer) together with each acid fiber by polylactic layer hot pressing.The gross weight of each polylactic acid-glycolic base apatite film layer accounts for acid fiber by polylactic and strengthens 95% of polylactic acid/hydroxy apatite composite material gross weight, and the gross weight of each acid fiber by polylactic layer accounts for acid fiber by polylactic and strengthens 5% of polylactic acid/hydroxy apatite composite material gross weight.
It is as follows that the acid fiber by polylactic obtaining strengthens polylactic acid/hydroxy apatite composite material performance indications: stretch modulus is 5Gpa, and hot strength is 31MPa.
Embodiment 5
The preparation method that the acid fiber by polylactic of the present embodiment strengthens polylactic acid/hydroxy apatite composite material in turn includes the following steps:
(1) graininess polylactic acid (being graininess poly (l-lactic acid)) is put into vacuum drying oven, under 65 C, dry 24 hours, remove moisture wherein.
(2) polylactic acid step (1) being obtained mixes in the ratio of polylactic acid 85% (weight), hydroxyapatite 15% (weight) with hydroxyapatite, obtains mixed material;
In this step (2), polylactic acid and hydroxyapatite that step (1) is obtained are put into high-speed mixer in described ratio, under the condition of 55 ° of C, with the speed of 1800 revs/min, mix 4 minutes, obtain mixed material.
(3) mixed material step (2) being obtained adds double screw extruder blend, extrudes, and extrudate is made to pellet with comminutor;
In this step (3), the extrusion die that double screw extruder used is equipped with has a plurality of material discharging round holes, and the diameter of material discharging round hole is 3mm.The temperature of the barrel of double screw extruder is controlled between 120-190 ℃.
(4) pellet step (3) being obtained adds thin film extrusion equipment, and making thickness is the polylactic acid-glycolic base apatite film of 0.06mm;
In this step (4), thin film extrusion equipment used comprises single screw extrusion machine and former, and the extrusion die of single screw extrusion machine has bar shaped discharging opening, and former used is flow casting molding equipment or calendering formation equipment.The temperature of the barrel of single screw extrusion machine is controlled between 120-190 ℃.
(5) on a metal plate, place one deck polylactic acid-glycolic base apatite film, then at this, above polylactic acid-glycolic base apatite film, lay one deck acid fiber by polylactic (all for by poly (l-lactic acid) and poly-D, the core shell structure composite fiber that Pfansteihl is made), at this, above strata acid fiber, place again one deck polylactic acid-glycolic base apatite film, then on second layer polylactic acid-glycolic base apatite film, lay one deck acid fiber by polylactic (all for by poly (l-lactic acid) and poly-D, the core shell structure composite fiber that Pfansteihl is made), on second layer acid fiber by polylactic, place again one deck polylactic acid-glycolic base apatite film, then on the 3rd strata lactic acid-hydroxyapatite films, lay one deck acid fiber by polylactic (all for by poly (l-lactic acid) and poly-D, the core shell structure composite fiber that Pfansteihl is made), on the 3rd strata acid fiber, place again one deck polylactic acid-glycolic base apatite film, (this stacking material comprises four polylactic acid-glycolic base apatite film layers and three acid fiber by polylactic layers to obtain stacking material, be followed successively by from top to bottom polylactic acid-glycolic base apatite film layer, acid fiber by polylactic layer, polylactic acid-glycolic base apatite film layer, acid fiber by polylactic layer, polylactic acid-glycolic base apatite film layer, acid fiber by polylactic layer, polylactic acid-glycolic base apatite film layer), then in stacking material, above the polylactic acid-glycolic base apatite film of the superiors, press another metal plate,
In this step (5), lay after acid fiber by polylactic, with adhesive tape, acid fiber by polylactic end is fixed on metal plate below.
The gross weight of the acid fiber by polylactic of laying accounts for 15% of stacking material gross weight, and the gross weight of each strata lactic acid-hydroxyapatite films accounts for 85% of stacking material gross weight.
The laying direction of ground floor and the 3rd strata acid fiber parallels with the lead of polylactic acid-glycolic base apatite film in step (4), and in the laying direction of second layer acid fiber by polylactic and step (4), the lead of polylactic acid-glycolic base apatite film is perpendicular.
For conveniently stripped, on the lateral surface of outmost two the polylactic acid-glycolic base apatite films of stacking material, respectively place an antiseize membrane.
(6) to be placed in dull and stereotyped heat pressing forming machines hot-forming, cooling, obtain acid fiber by polylactic after the demoulding strengthens polylactic acid/hydroxy apatite composite material together with two metal plates for stacking material step (5) being obtained.
Dull and stereotyped heat pressing forming machines structure used in this step (6) is identical with embodiment 1.
In this step (6), in temperature, be that 155 ° of C, pressure are under the condition of 2 tons hot-forming 10 minutes, be then cooled to 20 ° of C, the demoulding after release.
The acid fiber by polylactic obtaining strengthens polylactic acid/hydroxy apatite composite material and comprises four polylactic acid-glycolic base apatite film layers arranging from top to bottom, between adjacent two polylactic acid-glycolic base apatite film layers, be provided with acid fiber by polylactic layer, each polylactic acid-glycolic base apatite film layer is (being that acid fiber by polylactic enhancing polylactic acid/hydroxy apatite composite material is comprised of coarctate four the polylactic acid-glycolic base apatite film layers of heat and three acid fiber by polylactic layers) together with each acid fiber by polylactic layer hot pressing.The gross weight of each polylactic acid-glycolic base apatite film layer accounts for acid fiber by polylactic and strengthens 85% of polylactic acid/hydroxy apatite composite material gross weight, and the gross weight of each acid fiber by polylactic layer accounts for acid fiber by polylactic and strengthens 15% of polylactic acid/hydroxy apatite composite material gross weight.
It is as follows that the acid fiber by polylactic obtaining strengthens polylactic acid/hydroxy apatite composite material performance indications: stretch modulus is 7.1Gpa, hot strength: 43MPa.
Claims (10)
1. an acid fiber by polylactic strengthens polylactic acid/hydroxy apatite composite material, it is characterized in that comprising a plurality of polylactic acid-glycolic base apatite film layers of arranging from top to bottom, between adjacent two polylactic acid-glycolic base apatite film layers, be provided with acid fiber by polylactic layer, each polylactic acid-glycolic base apatite film layer is together with each acid fiber by polylactic layer hot pressing; Described polylactic acid-glycolic base apatite film layer is the polylactic acid-glycolic base apatite film that adopts the material be comprised of the polylactic acid of 70-95% (weight) and the hydroxyapatite of 5-30% (weight) to make; Described acid fiber by polylactic layer adopts acid fiber by polylactic to lay and forms.
2. acid fiber by polylactic according to claim 1 strengthens polylactic acid/hydroxy apatite composite material, it is characterized in that: described is poly (l-lactic acid), poly-D for making the contained polylactic acid of material of polylactic acid-glycolic base apatite film, Pfansteihl or poly (l-lactic acid)-co-glycolic acid.
3. acid fiber by polylactic according to claim 1 strengthens polylactic acid/hydroxy apatite composite material, it is characterized in that: described acid fiber by polylactic is poly (l-lactic acid) fiber, poly-D, a kind of in Pfansteihl fiber and poly (l-lactic acid)-co-glycolic acid fiber or the wherein composite fibre of multiple composition, or by poly (l-lactic acid), poly-D, two kinds of core shell structure composite fibers of making in Pfansteihl and poly (l-lactic acid)-co-glycolic acid.
4. acid fiber by polylactic according to claim 1 strengthens polylactic acid/hydroxy apatite composite material, it is characterized in that: the gross weight of described each polylactic acid-glycolic base apatite film layer accounts for the 85-95% that acid fiber by polylactic strengthens polylactic acid/hydroxy apatite composite material gross weight, the gross weight of each acid fiber by polylactic layer accounts for the 5-15% that acid fiber by polylactic strengthens polylactic acid/hydroxy apatite composite material gross weight.
5. acid fiber by polylactic according to claim 1 strengthens polylactic acid/hydroxy apatite composite material, it is characterized in that: in same acid fiber by polylactic layer, acid fiber by polylactic laying direction is consistent.
6. the acid fiber by polylactic described in claim 1-3 any one strengthens the preparation method of polylactic acid/hydroxy apatite composite material, it is characterized in that in turn including the following steps:
(1) graininess polylactic acid is carried out to dried, remove moisture wherein;
(2) polylactic acid step (1) being obtained mixes in the ratio of polylactic acid 70-95% (weight), hydroxyapatite 5-30% (weight) with hydroxyapatite, obtains mixed material;
(3) mixed material step (2) being obtained adds double screw extruder blend, extrudes, and extrudate is made to pellet with comminutor;
(4) pellet step (3) being obtained adds thin film extrusion equipment, and making thickness is the polylactic acid-glycolic base apatite film of 0.05-0.1mm;
(5) on a metal plate, place one deck polylactic acid-glycolic base apatite film, then at this, above polylactic acid-glycolic base apatite film, lay one deck acid fiber by polylactic, at this, above strata acid fiber, place again one deck polylactic acid-glycolic base apatite film, so repeat, until complete the placement of all each strata lactic acid-hydroxyapatite films and the laying of each strata acid fiber, obtain stacking material; Then in stacking material, above the polylactic acid-glycolic base apatite film of the superiors, press another metal plate;
(6) to be placed in dull and stereotyped heat pressing forming machines hot-forming, cooling, obtain acid fiber by polylactic after the demoulding strengthens polylactic acid/hydroxy apatite composite material together with two metal plates for stacking material step (5) being obtained.
7. acid fiber by polylactic according to claim 6 strengthens the preparation method of polylactic acid/hydroxy apatite composite material, it is characterized in that: in step (5), lay after acid fiber by polylactic, with adhesive tape, acid fiber by polylactic end is fixed on metal plate below.
8. acid fiber by polylactic according to claim 6 strengthens the preparation method of polylactic acid/hydroxy apatite composite material, it is characterized in that: in step (5), in the laying direction of acid fiber by polylactic and step (4) lead of polylactic acid-glycolic base apatite film parallel, perpendicular or becomes one be greater than zero and be less than the angle of 90 °; In same acid fiber by polylactic layer, acid fiber by polylactic laying direction is consistent.
9. acid fiber by polylactic according to claim 6 strengthens the preparation method of polylactic acid/hydroxy apatite composite material, it is characterized in that: in step (5), the gross weight of the acid fiber by polylactic of laying accounts for the 5-15% of stacking material gross weight, and the gross weight of each strata lactic acid-hydroxyapatite films accounts for the 85-95% of stacking material gross weight.
10. acid fiber by polylactic according to claim 6 strengthens the preparation method of polylactic acid/hydroxy apatite composite material, it is characterized in that: in step (6), in temperature, be that 150-160 ° of C, pressure are hot-forming 5-10 minute under the condition of 1-3 ton, then be cooled to 15-30 ° of C, the demoulding after release.
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| CN107118526A (en) * | 2017-04-17 | 2017-09-01 | 宁波诺丁汉大学 | Glass fibre nanometer hydroxyapatite PLA trielement composite material and preparation method thereof |
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