CN104001210B - Acid fiber by polylactic strengthens polylactic acid/hydroxy apatite composite material and preparation method thereof - Google Patents
Acid fiber by polylactic strengthens polylactic acid/hydroxy apatite composite material and preparation method thereof Download PDFInfo
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Abstract
A kind of acid fiber by polylactic strengthens polylactic acid/hydroxy apatite composite material, it is characterized in that comprising the multiple polylactic acid-glycolic base apatite film layers arranged from top to bottom, be provided with acid fiber by polylactic layer between adjacent two polylactic acid-glycolic base apatite film layers, each polylactic acid-glycolic base apatite film layer is together with the hot pressing of each acid fiber by polylactic layer; Described polylactic acid-glycolic base apatite film layer is the polylactic acid-glycolic base apatite film adopting the material be made up 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.The present invention also provides a kind of preparation method of above-mentioned composite.Composite material preparation process of the present invention is simple, and cost is low, and the composite materials property obtained is good, there is good tensile strength and toughness, there is biological activity and degradability, and not containing organic solvent human body being had to side effect, can be used as high strength bone 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 the synthetic macromolecular material that research is more at present, have nontoxic, good with human compatibility, the advantage such as degradablely can to absorb in vivo, but, existing achievement in research shows that polylactic acid mechanical strength is lower, and shortage biological activity, the gathering of its acid degradation products 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 can inducing peripheral osseous tissue growth and form firmly chemical bonding with host bone, but the shortcoming of hydroxyapatite to be mechanical performance not good, easily crisp, become carrying property poor to load, 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 the need to adding organic solvent, and mechanical property is good, there is biological activity and degradability.The technical scheme adopted is as follows:
A kind of acid fiber by polylactic strengthens polylactic acid/hydroxy apatite composite material, it is characterized in that comprising the multiple polylactic acid-glycolic base apatite film layers arranged from top to bottom, be provided with acid fiber by polylactic layer between adjacent two polylactic acid-glycolic base apatite film layers, each polylactic acid-glycolic base apatite film layer is together with the hot pressing of each acid fiber by polylactic layer; Described polylactic acid-glycolic base apatite film layer is the polylactic acid-glycolic base apatite film adopting the material be made up 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.
Polylactic acid contained by the above-mentioned material for making polylactic acid-glycolic base apatite film can be poly (l-lactic acid) (PLLA), poly-D, 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, the composite fibre that is a kind of or wherein multiple composition in Pfansteihl fiber and poly (l-lactic acid)-co-glycolic acid fiber.Above-mentioned acid fiber by polylactic also can be by poly (l-lactic acid), poly-D, two kinds of core shell structure composite fibers made 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 layer, 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) dried is carried out to graininess polylactic acid, removing moisture wherein;
(2) polylactic acid step (1) obtained mixes with the ratio of hydroxyapatite in polylactic acid 70-95% (weight), hydroxyapatite 5-30% (weight), obtains mixed material;
(3) mixed material that step (2) obtains is added double screw extruder blended, extrude, and extrudate comminutor is made pellet;
(4) pellet that step (3) obtains is added thin film extrusion equipment, make the polylactic acid-glycolic base apatite film that thickness is 0.05-0.1mm;
(5) on a metal plate, place one deck polylactic acid-glycolic base apatite film, then on this polylactic acid-glycolic base apatite film, one deck acid fiber by polylactic is laid, one deck polylactic acid-glycolic base apatite film is placed again on this strata acid fiber, repetition like this, until complete all placements of each strata lactic acid-hydroxyapatite films and the laying of each strata acid fiber, obtain stacking material; Then in stacking material the superiors polylactic acid-glycolic base apatite film above press another metal plate;
(6) stacking material that step (5) obtains is placed in dull and stereotyped heat pressing forming machines together with two metal plates hot-forming, obtains acid fiber by polylactic after cooling, the demoulding and strengthen polylactic acid/hydroxy apatite composite material.
In preferred steps (1), graininess polylactic acid is put into vacuum drying oven, under 60-65 C, dry 24-48 hour, removing 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), the polylactic acid obtain step (1) and hydroxyapatite put into high-speed mixer in described ratio, under the condition of 50-60 ° of C, with the speed of 1000-2000 rev/min mixing 1-5 minute, obtain mixed material.
In preferred steps (3), the extrusion die that double screw extruder used is equipped with has multiple material discharging round hole, and the diameter of material discharging round hole is 2-3mm.The temperature of the barrel of double screw extruder controls usually between 120-190 DEG C.
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 controls usually between 120-190 DEG C.
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 become one to 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 layer, 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, the composite fibre that is a kind of or wherein multiple composition in Pfansteihl fiber and poly (l-lactic acid)-co-glycolic acid fiber; Acid fiber by polylactic used also can be by poly (l-lactic acid), poly-D, two kinds of core shell structure composite fibers made in Pfansteihl and poly (l-lactic acid)-co-glycolic acid.
In preferred steps (5), the gross weight of the acid fiber by polylactic laid 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 by acid fiber by polylactic end winding support 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.
The conveniently demoulding, in preferred steps (5), each placement one antiseize membrane on the lateral surface of outmost two the polylactic acid-glycolic base apatite films of stacking material.
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 above lower platen and liftable (pressing to stacking material when top board declines); Lower platen and top board are 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, chiller (as water cooling pipeline or oil circulation cooling line) can be equipped with on lower platen and top board.
In preferred steps (6), temperature be 150-160 ° of C, pressure be the condition of 1-3 ton under hot-forming 5-10 minute, be then cooled to 15-30 ° of C, the demoulding after release.
In the present invention, by polylactic acid and hydroxyapatite compound, both can improve the mechanical property of polylactic acid and guide osteogenic characteristics, control action can be had to the biodegradation of hydroxyapatite again, ensureing 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 far above common poly-lactic acid material, will strengthen complex with it as reinforce, can improve performance and the intensity of composite; In addition, acid fiber by polylactic has identical chemical constitution with polylactic acid matrix, completely compatible therebetween, not Presence of an interface problem, the two is conducted destructive stress by good interface fit and is disperseed, and can alleviate stress and concentrate destruction to material itself.Polylactic acid/hydroxy apatite composite material is strengthened with biodegradable acid fiber by polylactic, not only there is good hot strength and modulus, and each component of this composite in vivo can be degradable, catabolite excretes 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 the need to adding organic solvent, the composite materials property obtained is good, has the mechanical properties such as good tensile strength and toughness, there is biological activity and degradability, and not containing organic solvent human body being had to side effect, be a kind of high-performance composite materials with broad prospect of application, can be used as high strength bone material.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of the stacking material (together with two metal plates) that in the embodiment of the present invention 1, step (5) is formed;
Fig. 2 is the structural representation of the acid fiber by polylactic enhancing polylactic acid/hydroxy apatite composite material of the embodiment of the present invention 1.
Detailed description of the invention
Embodiment 1
The preparation method of the acid fiber by polylactic enhancing polylactic acid/hydroxy apatite composite material of the present embodiment in turn includes the following steps:
(1) graininess polylactic acid (being graininess poly (l-lactic acid)) is put into vacuum drying oven, dry 24 hours under 65 C, removing moisture wherein;
(2) polylactic acid step (1) obtained mixes with the ratio of hydroxyapatite in polylactic acid 95% (weight), hydroxyapatite 5% (weight), obtains mixed material;
In this step (2), the polylactic acid obtain step (1) and hydroxyapatite put into high-speed mixer in described ratio, under the condition of 55 ° of C, mix 3 minutes, obtain mixed material with the speed of 1500 revs/min.
(3) mixed material that step (2) obtains is added double screw extruder blended, extrude, and extrudate comminutor is made pellet;
In this step (3), the extrusion die that double screw extruder used is equipped with has multiple material discharging round hole, and the diameter of material discharging round hole is 2mm.The temperature of the barrel of double screw extruder controls between 120-190 DEG C.
(4) pellet that step (3) obtains is added thin film extrusion equipment, make the polylactic acid-glycolic base apatite film that thickness is 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 controls between 120-190 DEG C.
(5) with reference to figure 1, one deck polylactic acid-glycolic base apatite film is placed on a metal plate 4, then on this polylactic acid-glycolic base apatite film, one deck acid fiber by polylactic is laid, one deck polylactic acid-glycolic base apatite film is placed again on this strata acid fiber, 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 polylactic acid-glycolic base apatite film layer 1, acid fiber by polylactic layer 2, polylactic acid-glycolic base apatite film layer 1 from top to bottom); Then in stacking material the superiors polylactic acid-glycolic base apatite film above press another metal plate 5;
In this step (5), lay after acid fiber by polylactic, with adhesive tape by acid fiber by polylactic end winding support metal plate 4 below.
The gross weight of the acid fiber by polylactic laid 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, the conveniently demoulding, in stacking material two-layer polylactic acid-glycolic base apatite film lateral surface on each place an antiseize membrane 3.
(6) stacking material that step (5) obtains is placed in dull and stereotyped heat pressing forming machines together with two metal plates hot-forming, obtains acid fiber by polylactic after cooling, the demoulding and strengthen polylactic acid/hydroxy apatite composite material.
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 above lower platen and liftable (pressing to stacking material when top board declines); Lower platen and top board are equipped with heater (as electric heater unit or deep fat heating pipe line) and chiller (as water cooling pipeline or oil circulation cooling line).When carrying out hot-forming, metal plate 4 is on lower platen, and top board presses to metal plate 5 after declining.
In this step (6), be 160 ° of C, pressure under being the condition of 2 tons hot-forming 10 minutes in temperature, be then cooled to 30 ° of C, the demoulding after release.
With reference to figure 2, the acid fiber by polylactic obtained strengthens polylactic acid/hydroxy apatite composite material and comprises two the polylactic acid-glycolic base apatite film layers 1 arranged from top to bottom, acid fiber by polylactic layer 2 is provided with, polylactic acid-glycolic base apatite film layer 2 (i.e. acid fiber by polylactic strengthen polylactic acid/hydroxy apatite composite material be made up of coarctate two the polylactic acid-glycolic base apatite film layers 1 of heat and an acid fiber by polylactic layer 2) together with the hot pressing of two acid fiber by polylactic layers 1 between two polylactic acid-glycolic base apatite film layers 1.The gross weight of two polylactic acid-glycolic base apatite film layers 1 accounts for acid fiber by polylactic strengthens polylactic acid/hydroxy apatite composite material gross weight 90%, and the gross weight of acid fiber by polylactic layer 2 accounts for acid fiber by polylactic strengthens polylactic acid/hydroxy apatite composite material gross weight 10%.
It is as follows that the acid fiber by polylactic obtained strengthens polylactic acid/hydroxy apatite composite material performance indications: stretch modulus is 10Gpa, and hot strength is 65MPa.
Embodiment 2
The preparation method of the acid fiber by polylactic enhancing polylactic acid/hydroxy apatite composite material of the present embodiment in turn includes the following steps:
(1) graininess polylactic acid (being graininess poly (l-lactic acid)) is put into vacuum drying oven, dry 24 hours under 65 C, removing moisture wherein;
(2) polylactic acid step (1) obtained mixes with the ratio of hydroxyapatite in polylactic acid 80% (weight), hydroxyapatite 20% (weight), obtains mixed material;
In this step (2), the polylactic acid obtain step (1) and hydroxyapatite put into high-speed mixer in described ratio, under the condition of 60 ° of C, mix 5 minutes, obtain mixed material with the speed of 1000 revs/min.
(3) mixed material that step (2) obtains is added double screw extruder blended, extrude, and extrudate comminutor is made pellet;
In this step (3), the extrusion die that double screw extruder used is equipped with has multiple material discharging round hole, and the diameter of material discharging round hole is 3mm.The temperature of the barrel of double screw extruder controls between 120-190 DEG C.
(4) pellet that step (3) obtains is added thin film extrusion equipment, make the polylactic acid-glycolic base apatite film that thickness is 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 controls between 120-190 DEG C.
(5) on a metal plate, place one deck polylactic acid-glycolic base apatite film, then on this polylactic acid-glycolic base apatite film, one deck acid fiber by polylactic (being poly (l-lactic acid) fiber) is laid, one deck polylactic acid-glycolic base apatite film is placed again on this strata acid fiber, 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 polylactic acid-glycolic base apatite film layer, acid fiber by polylactic layer, polylactic acid-glycolic base apatite film layer from top to bottom); Then in stacking material the superiors polylactic acid-glycolic base apatite film above press another metal plate;
In this step (5), lay after acid fiber by polylactic, with adhesive tape by acid fiber by polylactic end winding support metal plate below.
The gross weight of the acid fiber by polylactic laid 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 lead of the laying direction of acid fiber by polylactic and the middle polylactic acid-glycolic base apatite film of step (4) is perpendicular.
The conveniently demoulding, in stacking material two-layer polylactic acid-glycolic base apatite film lateral surface on each place an antiseize membrane.
(6) stacking material that step (5) obtains is placed in dull and stereotyped heat pressing forming machines together with two metal plates hot-forming, obtains acid fiber by polylactic after cooling, the demoulding and strengthen polylactic acid/hydroxy apatite composite material.
Dull and stereotyped heat pressing forming machines structure used in this step (6) is identical with embodiment 1.
In this step (6), be 160 ° of C, pressure under being the condition of 2 tons hot-forming 10 minutes in temperature, be then cooled to 20 ° of C, the demoulding after release.
The acid fiber by polylactic obtained strengthens polylactic acid/hydroxy apatite composite material and comprises two the polylactic acid-glycolic base apatite film layers arranged from top to bottom, acid fiber by polylactic layer is provided with, polylactic acid-glycolic base apatite film layer (i.e. acid fiber by polylactic strengthen polylactic acid/hydroxy apatite composite material be made up 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 between two polylactic acid-glycolic base apatite film layers.The gross weight of two polylactic acid-glycolic base apatite film layers accounts for acid fiber by polylactic strengthens polylactic acid/hydroxy apatite composite material gross weight 90%, and the gross weight of acid fiber by polylactic layer accounts for acid fiber by polylactic strengthens polylactic acid/hydroxy apatite composite material gross weight 10%.
It is as follows that the acid fiber by polylactic obtained strengthens polylactic acid/hydroxy apatite composite material performance indications: stretch modulus is 9.2Gpa, and hot strength is 45MPa.
Embodiment 3
The preparation method of the acid fiber by polylactic enhancing polylactic acid/hydroxy apatite composite material of the present embodiment in turn includes the following steps:
(1) graininess polylactic acid (be graininess and gather D, Pfansteihl) is put into vacuum drying oven, dry 48 hours under 60 C, removing moisture wherein;
(2) polylactic acid step (1) obtained mixes with the ratio of hydroxyapatite in polylactic acid 75% (weight), hydroxyapatite 25% (weight), obtains mixed material;
In this step (2), the polylactic acid obtain step (1) and hydroxyapatite put into high-speed mixer in described ratio, under the condition of 50 ° of C, mix 2 minutes, obtain mixed material with the speed of 2000 revs/min.
(3) mixed material that step (2) obtains is added double screw extruder blended, extrude, and extrudate comminutor is made pellet;
In this step (3), the extrusion die that double screw extruder used is equipped with has multiple material discharging round hole, and the diameter of material discharging round hole is 2mm.The temperature of the barrel of double screw extruder controls between 120-190 DEG C.
(4) pellet that step (3) obtains is added thin film extrusion equipment, make the polylactic acid-glycolic base apatite film that thickness is 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 controls between 120-190 DEG C.
(5) on a metal plate, place one deck polylactic acid-glycolic base apatite film, then on this polylactic acid-glycolic base apatite film, lay one deck acid fiber by polylactic and (be poly-D, Pfansteihl fiber), one deck polylactic acid-glycolic base apatite film is placed again on this strata acid fiber, then on second layer polylactic acid-glycolic base apatite film, lay one deck acid fiber by polylactic and (be poly-D, Pfansteihl fiber), one deck polylactic acid-glycolic base apatite film is placed again on second layer acid fiber by polylactic, (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 polylactic acid-glycolic base apatite film layer from top to bottom, 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 the superiors polylactic acid-glycolic base apatite film above press another metal plate,
In this step (5), lay after acid fiber by polylactic, with adhesive tape by acid fiber by polylactic end winding support metal plate below.
The gross weight of the acid fiber by polylactic laid 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 the lead of the laying direction of upper strata acid fiber by polylactic and the middle polylactic acid-glycolic base apatite film of step (4) is perpendicular.
The conveniently demoulding, each placement one antiseize membrane on the lateral surface of outmost two the polylactic acid-glycolic base apatite films of stacking material.
(6) stacking material that step (5) obtains is placed in dull and stereotyped heat pressing forming machines together with two metal plates hot-forming, obtains acid fiber by polylactic after cooling, the demoulding and strengthen polylactic acid/hydroxy apatite composite material.
Dull and stereotyped heat pressing forming machines structure used in this step (6) is identical with embodiment 1.
In this step (6), be 150 ° of C, pressure under being the condition of 3 tons hot-forming 5 minutes in temperature, be then cooled to 15 ° of C, the demoulding after release.
The acid fiber by polylactic obtained strengthens polylactic acid/hydroxy apatite composite material and comprises three the polylactic acid-glycolic base apatite film layers arranged from top to bottom, acid fiber by polylactic layer is provided with, each polylactic acid-glycolic base apatite film layer (i.e. acid fiber by polylactic strengthen polylactic acid/hydroxy apatite composite material be made up of coarctate three the polylactic acid-glycolic base apatite film layers of heat and two acid fiber by polylactic layers) together with the hot pressing of each acid fiber by polylactic layer between adjacent two polylactic acid-glycolic base apatite film layers.The gross weight of each polylactic acid-glycolic base apatite film layer accounts for acid fiber by polylactic strengthens polylactic acid/hydroxy apatite composite material gross weight 85%, and the gross weight of each acid fiber by polylactic layer accounts for acid fiber by polylactic strengthens polylactic acid/hydroxy apatite composite material gross weight 15%.
It is as follows that the acid fiber by polylactic obtained strengthens polylactic acid/hydroxy apatite composite material performance indications: stretch modulus is 12Gpa, and hot strength is 58MPa.
Embodiment 4
The preparation method of the acid fiber by polylactic enhancing polylactic acid/hydroxy apatite composite material of the present embodiment 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, dry 30 hours under 62 C, removing moisture wherein.
(2) polylactic acid step (1) obtained mixes with the ratio of hydroxyapatite in polylactic acid 70% (weight), hydroxyapatite 30% (weight), obtains mixed material;
In this step (2), the polylactic acid obtain step (1) and hydroxyapatite put into high-speed mixer in described ratio, under the condition of 60 ° of C, mix 1 minute, obtain mixed material with the speed of 2000 revs/min.
(3) mixed material that step (2) obtains is added double screw extruder blended, extrude, and extrudate comminutor is made pellet;
In this step (3), the extrusion die that double screw extruder used is equipped with has multiple material discharging round hole, and the diameter of material discharging round hole is 2mm.The temperature of the barrel of double screw extruder controls between 120-190 DEG C.
(4) pellet that step (3) obtains is added thin film extrusion equipment, make the polylactic acid-glycolic base apatite film that thickness is 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 controls between 120-190 DEG C.
(5) on a metal plate, place one deck polylactic acid-glycolic base apatite film, then on this polylactic acid-glycolic base apatite film, one deck acid fiber by polylactic (being poly (l-lactic acid)-co-glycolic acid fiber) is laid, one deck polylactic acid-glycolic base apatite film is placed again on this strata acid fiber, 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 polylactic acid-glycolic base apatite film layer, acid fiber by polylactic layer, polylactic acid-glycolic base apatite film layer from top to bottom); Then in stacking material the superiors polylactic acid-glycolic base apatite film above press another metal plate;
In this step (5), lay after acid fiber by polylactic, with adhesive tape by acid fiber by polylactic end winding support metal plate below.
The gross weight of the acid fiber by polylactic laid 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).
The conveniently demoulding, in stacking material two polylactic acid-glycolic base apatite films lateral surface on each place an antiseize membrane.
(6) stacking material that step (5) obtains is placed in dull and stereotyped heat pressing forming machines together with two metal plates hot-forming, obtains acid fiber by polylactic after cooling, the demoulding and strengthen polylactic acid/hydroxy apatite composite material.
Dull and stereotyped heat pressing forming machines structure used in this step (6) is identical with embodiment 1.
In this step (6), be 160 ° of C, pressure under being the condition of 1 ton hot-forming 8 minutes in temperature, be then cooled to 25 ° of C, the demoulding after release.
The acid fiber by polylactic obtained strengthens polylactic acid/hydroxy apatite composite material and comprises the multiple polylactic acid-glycolic base apatite film layers arranged from top to bottom, acid fiber by polylactic layer is provided with, each polylactic acid-glycolic base apatite film layer (i.e. acid fiber by polylactic strengthen polylactic acid/hydroxy apatite composite material be made up of coarctate two the polylactic acid-glycolic base apatite film layers of heat and an acid fiber by polylactic layer) together with the hot pressing of each acid fiber by polylactic layer between adjacent two polylactic acid-glycolic base apatite film layers.The gross weight of each polylactic acid-glycolic base apatite film layer accounts for acid fiber by polylactic strengthens polylactic acid/hydroxy apatite composite material gross weight 95%, and the gross weight of each acid fiber by polylactic layer accounts for acid fiber by polylactic strengthens polylactic acid/hydroxy apatite composite material gross weight 5%.
It is as follows that the acid fiber by polylactic obtained strengthens polylactic acid/hydroxy apatite composite material performance indications: stretch modulus is 5Gpa, and hot strength is 31MPa.
Embodiment 5
The preparation method of the acid fiber by polylactic enhancing polylactic acid/hydroxy apatite composite material of the present embodiment in turn includes the following steps:
(1) graininess polylactic acid (being graininess poly (l-lactic acid)) is put into vacuum drying oven, dry 24 hours under 65 C, removing moisture wherein.
(2) polylactic acid step (1) obtained mixes with the ratio of hydroxyapatite in polylactic acid 85% (weight), hydroxyapatite 15% (weight), obtains mixed material;
In this step (2), the polylactic acid obtain step (1) and hydroxyapatite put into high-speed mixer in described ratio, under the condition of 55 ° of C, mix 4 minutes, obtain mixed material with the speed of 1800 revs/min.
(3) mixed material that step (2) obtains is added double screw extruder blended, extrude, and extrudate comminutor is made pellet;
In this step (3), the extrusion die that double screw extruder used is equipped with has multiple material discharging round hole, and the diameter of material discharging round hole is 3mm.The temperature of the barrel of double screw extruder controls between 120-190 DEG C.
(4) pellet that step (3) obtains is added thin film extrusion equipment, make the polylactic acid-glycolic base apatite film that thickness is 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 controls between 120-190 DEG C.
(5) on a metal plate, place one deck polylactic acid-glycolic base apatite film, then on this polylactic acid-glycolic base apatite film, one deck acid fiber by polylactic is laid (all for by poly (l-lactic acid) and poly-D, the core shell structure composite fiber that Pfansteihl is made), one deck polylactic acid-glycolic base apatite film is placed again on this strata acid fiber, then on second layer polylactic acid-glycolic base apatite film, one deck acid fiber by polylactic is laid (all for by poly (l-lactic acid) and poly-D, the core shell structure composite fiber that Pfansteihl is made), one deck polylactic acid-glycolic base apatite film is placed again on second layer acid fiber by polylactic, then on third layer polylactic acid-glycolic base apatite film, one deck acid fiber by polylactic is laid (all for by poly (l-lactic acid) and poly-D, the core shell structure composite fiber that Pfansteihl is made), one deck polylactic acid-glycolic base apatite film is placed again on third layer acid fiber by polylactic, (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 polylactic acid-glycolic base apatite film layer from top to bottom, 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 the superiors polylactic acid-glycolic base apatite film above press another metal plate,
In this step (5), lay after acid fiber by polylactic, with adhesive tape by acid fiber by polylactic end winding support metal plate below.
The gross weight of the acid fiber by polylactic laid 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 third layer acid fiber by polylactic parallels with the lead of polylactic acid-glycolic base apatite film in step (4), and the lead of the laying direction of second layer acid fiber by polylactic and the middle polylactic acid-glycolic base apatite film of step (4) is perpendicular.
The conveniently demoulding, each placement one antiseize membrane on the lateral surface of outmost two the polylactic acid-glycolic base apatite films of stacking material.
(6) stacking material that step (5) obtains is placed in dull and stereotyped heat pressing forming machines together with two metal plates hot-forming, obtains acid fiber by polylactic after cooling, the demoulding and strengthen polylactic acid/hydroxy apatite composite material.
Dull and stereotyped heat pressing forming machines structure used in this step (6) is identical with embodiment 1.
In this step (6), be 155 ° of C, pressure under being the condition of 2 tons hot-forming 10 minutes in temperature, be then cooled to 20 ° of C, the demoulding after release.
The acid fiber by polylactic obtained strengthens polylactic acid/hydroxy apatite composite material and comprises four the polylactic acid-glycolic base apatite film layers arranged from top to bottom, acid fiber by polylactic layer is provided with, each polylactic acid-glycolic base apatite film layer (i.e. acid fiber by polylactic strengthen polylactic acid/hydroxy apatite composite material be made up of coarctate four the polylactic acid-glycolic base apatite film layers of heat and three acid fiber by polylactic layers) together with the hot pressing of each acid fiber by polylactic layer between adjacent two polylactic acid-glycolic base apatite film layers.The gross weight of each polylactic acid-glycolic base apatite film layer accounts for acid fiber by polylactic strengthens polylactic acid/hydroxy apatite composite material gross weight 85%, and the gross weight of each acid fiber by polylactic layer accounts for acid fiber by polylactic strengthens polylactic acid/hydroxy apatite composite material gross weight 15%.
It is as follows that the acid fiber by polylactic obtained 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 the multiple polylactic acid-glycolic base apatite film layers arranged from top to bottom, be provided with acid fiber by polylactic layer between adjacent two polylactic acid-glycolic base apatite film layers, each polylactic acid-glycolic base apatite film layer is together with the hot pressing of each acid fiber by polylactic layer; Described polylactic acid-glycolic base apatite film layer is the polylactic acid-glycolic base apatite film adopting the material be made up 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: the polylactic acid contained by the described material for making polylactic acid-glycolic base apatite film is poly (l-lactic acid), poly-D, 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, composite fibre that is a kind of or wherein multiple composition in Pfansteihl fiber and poly (l-lactic acid)-co-glycolic acid fiber, or by poly (l-lactic acid), poly-D, two kinds of core shell structure composite fibers made 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 any one of claim 1-3 strengthens the preparation method of polylactic acid/hydroxy apatite composite material, it is characterized in that in turn including the following steps:
(1) dried is carried out to graininess polylactic acid, removing moisture wherein;
(2) polylactic acid step (1) obtained mixes with the ratio of hydroxyapatite in polylactic acid 70-95% (weight), hydroxyapatite 5-30% (weight), obtains mixed material;
(3) mixed material that step (2) obtains is added double screw extruder blended, extrude, and extrudate comminutor is made pellet;
(4) pellet that step (3) obtains is added thin film extrusion equipment, make the polylactic acid-glycolic base apatite film that thickness is 0.05-0.1mm;
(5) on a metal plate, place one deck polylactic acid-glycolic base apatite film, then on this polylactic acid-glycolic base apatite film, one deck acid fiber by polylactic is laid, one deck polylactic acid-glycolic base apatite film is placed again on this strata acid fiber, repetition like this, until complete all placements of each strata lactic acid-hydroxyapatite films and the laying of each strata acid fiber, obtain stacking material; Then in stacking material the superiors polylactic acid-glycolic base apatite film above press another metal plate;
(6) stacking material that step (5) obtains is placed in dull and stereotyped heat pressing forming machines together with two metal plates hot-forming, obtains acid fiber by polylactic after cooling, the demoulding and strengthen polylactic acid/hydroxy apatite composite material.
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), after laying acid fiber by polylactic, with adhesive tape by acid fiber by polylactic end winding support 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), the laying direction of acid fiber by polylactic parallel with the lead of polylactic acid-glycolic base apatite film in step (4), perpendicular or become one to 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 laid 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), temperature be 150-160 ° of C, pressure be the condition of 1-3 ton under hot-forming 5-10 minute, then 15-30 ° of C is cooled to, the demoulding after release.
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| CN1680487A (en) * | 2004-04-06 | 2005-10-12 | 石宗利 | Phosphate fibrous reinforced polylactic composite material with controllable degradable absorbing biological activity and preparation thereof |
| CN101462391A (en) * | 2007-12-21 | 2009-06-24 | 清华大学 | Method for preparing carbon nano-tube composite material |
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| CN1680487A (en) * | 2004-04-06 | 2005-10-12 | 石宗利 | Phosphate fibrous reinforced polylactic composite material with controllable degradable absorbing biological activity and preparation thereof |
| CN101462391A (en) * | 2007-12-21 | 2009-06-24 | 清华大学 | Method for preparing carbon nano-tube composite material |
| CN101507841A (en) * | 2009-03-30 | 2009-08-19 | 西南交通大学 | Preparation method of inorganic calcium phosphate salt/biodegradable polymer fiber film composite material |
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