CN100427152C - Method for preparing porous osteolith/polyamide compound material - Google Patents
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Abstract
The invention relates to a method for preparing porous bone agustite/polyamide composite, wherein it comprises that: mixing bone agustite/medical polyamide with foaming agent as 5-tetrazole radical uniformly; at the temperature over than decompose temperature of foaming agent, injects and foams into porous blank; the diameter of said bone agustite is nanometer or micrometer level; the mass ration between foaming agent and bone agustite/polyamide is 0.2-1. 5-100; then removes the dense face of blank or partly removes, to prepare porous materials.
Description
Technical field
The present invention relates to a kind of preparation method of medical porous osteoid apatite/polyamide compoiste material.
Background technology
Medical porous material is because the three-dimensional porous structure of the uniqueness that is had helps osteoblast adhesion, differentiation and growth, promote growing into of bone, strengthen being connected between implant and the bone, realize good synostosis, and help the eliminating of moisture and nutrient substance at transmission that implants and metabolic waste, promote osteanagenesis and reconstruction, accelerate the recovery from illness process, therefore become hot research in recent years.Ideal porous material should have higher porosity and even pore distribution, 100～800 microns of pore diameter ranges, and average pore size is 200～350 microns, is interconnected between hole, has aperture concurrently on the big hole wall, has excellent mechanical intensity and good biological and learns function.Porous ceramics, porous metals, porous polymer materials and composite porous etc. are arranged in the present employed porous material.Because composite porous can have the unexistent excellent properties of one-component, thereby receive concern more and more widely.
Osteoid apatite is widely used in the reparation of clinical sclerous tissues owing to its excellent biological activity and bone conductibility and substitutes.It can with the firm synostosis of people's bone formation.But its inherent shortcoming is that fragility is big, by itself and the compound osteoid apatite/polyamide compoiste material that obtains of medical polyamide macromolecule component with excellent toughness, because of having the advantage separately of osteoid apatite and polyamide simultaneously concurrently, it is existing good biology performance, excellent mechanical intensity and toughness and machinability are arranged, existing many research reports again.
To the preparation of porous osteolith stone/polyamide compoiste material, Chinese patent 03135261.8 has been reported a kind of ion percolation.It does not have plasticizing process in forming process, osteoid apatite/polyamide compoiste material and inorganic salt conduct heat difficult, and composite is inconsistent with the shrinkage factor after being heated as inorganic salts such as sodium chloride, cause being difficult to molding, easily produce half-cooked phenomenon, the top layer of material is oxidized, can not prepare large-sized porous material, a large amount of inorganic salts also can't thoroughly be removed, and cause composite property to change, and safety reduces.Even after the molding, the easy avalanche when the aqueous solution soaking desalination of its porous material.This method adopts inorganic salt as perforating agent, and the hole of resulting porous material is subjected to the restriction of inorganic salt particle particle diameter, be difficult to obtain bigger hole and high porosity (greater than 70%), and mechanical property is relatively poor.For example be about at 40% o'clock in porosity, comprcssive strength only is 8MPa.In addition, the preparation time of this method is longer, and soak time reaches a couple of days, is unfavorable for large-scale production.
Chinese patent 03135262.6 has been reported a kind of injection moulding preparation method, adopts trihydrazinotriazine or barium azodicarboxylate as foaming agent.Because decomposing the back in process of production, trihydrazinotriazine produces the harmful gas ammonia, and decomposition temperature higher (greater than 275 ℃), being unfavorable for foaming, the melamine residual that its partially decomposed product such as toxicity are big also is difficult to remove in composite.And the catabolite tripolycyanamide is easy and polyamide is had an effect, and at high temperature makes polyamide degraded variable color, and the composite of preparation and goods porosity are not high, mechanical properties decrease.When adopting barium azodicarboxylate as foaming agent, residue is carboxylic acid barium or brium carbonate, also has the very strong toxicity that can cause cell death or animal dead, thereby influences the biological safety of gained porous material.In addition, because the temperature of the foaming agent that adopts and the processing temperature of material do not match in these above-mentioned injection mouldings, also be difficult to realize good control to quality of item.For example, foaming agent trihydrazinotriazine too high because of decomposition temperature can postpone foaming, and foaming agent decomposes not exclusively, the gas forming amount instability, thus influence loose structure.The decomposition temperature of barium azodicarboxylate foaming agent is then low excessively, is difficult to process stay-in-grade foamed materials because of foaming agent decomposes in advance.
Summary of the invention
At above-mentioned situation, the present invention will provide a kind of new method for preparing porous osteolith stone/polyamide compoiste material in the injection moulding mode on this basis, it can be prepared have better mechanical strength and machinability, and the part or all of porous porous material of excellent loose structure.
The preparation method of porous osteolith stone/polyamide compoiste material of the present invention, be with behind osteoid apatite/medical polyamide compoiste material and the foaming agent 5-phenyltetrazole uniform mixing, be higher than under the condition of foaming agent decomposition temperature, through the injection moulding process foaming is the porous blank, and the part by weight of foaming agent and porous osteolith stone/polyamide compoiste material is 0.2～1.5: 100.The particle diameter of said osteoid apatite is nanometer～micron order.Said medical polyamide can be for comprising polyamide 66, at least a in interior medical polyamide composition of polyamide 6, polyamide 10, polyamide 11, polyamide 12, polyamide 6 10, polyamide 6 12, polyamide 1010, polyamide 1212.Said osteoid apatite/medical polyamide compoiste material, can with reference to as the patent No. be 200310111033.5, number of patent application be 200510022326.5 or the method for other pertinent literature obtain.
For example, generally speaking, be 230 ℃～275 ℃ in injection temperature, mold temperature is 60 ℃～120 ℃, and injection speed is 60%～90%, and injection pressure is under the condition of 40～100MPa, and above-mentioned injection foaming forming process all can be finished smoothly and satisfactorily.With injection molding goods, clean through modes such as ultrasound wave, promptly obtain corresponding porous material goods after the oven dry.
For helping the uniform mixing of above-mentioned osteoid apatite/medical polyamide compoiste material and foaming agent 5-phenyltetrazole, the optimal way that can adopt is, with said foaming agent its good solvent with boiling point≤100 ℃, after the nontoxic or low poison solvent dissolving of low boilings such as dehydrated alcohol commonly used that uses as special recommendation or acetone, again with osteoid apatite/polyamide compoiste material uniform mixing, be higher than the solvent for use boiling point and be lower than the solvent of removing under the condition of foaming agent decomposition temperature in the composite material then, when for example adopting said dehydrated alcohol or acetone equal solvent, can carry out said injection mo(u)lding afterwards again in 80 ℃～120 ℃ oven dry (as can in vacuum drying oven, carrying out).
The inanimate matter of natural bone mainly is made up of the nano-hydroxy osteoid apatite, but owing to have the phosphorus in the various ion pair hydroxy kind osteolith structures and the replacement of calcium, so its calcium, phosphorus atoms mol ratio and be not equal to calcium, the phosphorus atoms mol ratio 1.67 of stoichiometric osteoid apatite.Osteoid apatite calcium, the phosphorus atoms mol ratio of human body different parts sclerous tissues are also inequality, and the calcium of people's bone, phosphorus atoms mol ratio also change in all ages and classes section.Therefore based on bionical notion, the calcium of osteoid apatite of the present invention, the design of phosphorus atoms mol ratio are desirable in 1.3～2.0 scope.
The mass percent of osteoid apatite can be 10～70wt% in porous osteolith stone/polyamide compoiste material in above-mentioned used osteoid apatite/medical polyamide compoiste material.
Through above-mentioned injection foaming forming process of the present invention, resulting porous blank has the top layer of a densification more.According to different use needs, the dense skin of this porous blank can be removed, becoming the porous moulding material of a kind of each side and use, also can be the dense skin of the porous blank that obtains of the said injection mo(u)lding of reserve part, and the porous, shaped material that becomes the non-homogeneous of each side uses.
Test shows, the hole pore diameter range of the porous osteolith stone/polyamide compoiste material goods that obtain with method for preparing of the present invention is 5～1000 microns, average pore size is between 150～500 microns, porosity is 15～90%, even pore distribution, can have aperture concurrently on big hole wall, comprcssive strength is 0.1～70MPa.
In above-mentioned preparation method of the present invention, the decomposition temperature of the 5-phenyltetrazole foaming agent that adopts is 200～240 ℃, is complementary with the melt processing temperature (230～275 ℃) of osteoid apatite/polyamide compoiste material itself, thereby decomposes complete, consumption is few, and gas forming amount is big.Experimental result shows, change the ratio of foaming agent and composite, and/or injection temperature, injection speed, mold temperature during injection moulding, and the single mode feeding quantity etc., effective control of porosity, average pore size and mechanical property can be realized, the porous material of the loose structure of suitable needs can be obtained prepared porous material.For example, injection temperature is low excessively, can increase the viscosity of melt, makes the volume growth of bubble minimizing and bubble slow, but the too high jet phenomenon that then easily takes place of temperature.And for example, the height of injection speed can influence the size of goods pore and the uniformity of distribution.In addition, the temperature of mould can exert an influence to the thickness of the surface smoothness of goods, dense skin and production cycle etc.For example, when the use amount of foaming agent is 0.25wt%, the single mode feeding quantity is 28g, injection temperature is 272%, injection speed is 90% and mold temperature when being 80 ℃, can obtain porosity and be about 40%, about 200 microns of average pore size, comprcssive strength is the more dense porous material of porous osteolith stone/polyamide 66 composite material (osteoid apatite is 40wt%) of 33MPa, and comprcssive strength can reach 70MPa.This simple and effective control is the essential condition of accomplishing scale production.
What the used foaming agent 5-phenyltetrazole of the present invention decomposed the back generation is that nitrogen, carbon dioxide and three kinds of gas componants of water reach the calcium benzoate less than 5ppm, nontoxic, no burn into do not burn, the molding of goods and physics, chemical property are not had influence, and in composite, has good dispersibility, help guaranteeing the biocompatibility and the biological safety of porous material, the residual antisepsis that calcium benzoate had less than 5ppm in the material can also make porous material or goods have longer storage life.
The present invention adopts the 5-phenyltetrazole as foaming agent, and prepare porous osteolith stone/polyamide compoiste material by in injection moulding process, finishing foaming, half-cooked, oxidation, the residual shortcoming of foaming agent have been solved effectively, shortened the production time, and porosity, the mechanical property of porous material have been improved, especially do not influence the safety of porous material,, and can obtain the some or all of porous material of porous form that is in the structure of control hole yet.Below in conjunction with the specific embodiment of drawings and Examples, foregoing of the present invention is described in further detail again.But this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following example.Do not breaking away under the above-mentioned technological thought situation of the present invention, various replacements or change according to ordinary skill knowledge and customary means are made all should comprise within the scope of the invention.Osteoid apatite/polyamide compoiste material among each embodiment, all can with reference to the patent No. be 200310111033.5 or application number be that 200510022326.5 method prepares.
Description of drawings
Fig. 1 is that porosity is the SEM photo of 78% composite microstructure of the present invention.
Fig. 2 is the photo of a kind of block composite product of the present invention.
Fig. 3 is the photo of a kind of composite material surface pattern of the present invention.
The specific embodiment
Embodiment 1
10g is dissolved in the 2000ml dehydrated alcohol with 5-phenyltetrazole foaming agent, filter, with spray apparatus it evenly is sprayed at (the osteoid apatite mass content is 40%) on 2kg osteoid apatite/polyamide 66 composite material, 80 ℃ of oven dry in vacuum drying oven, injection moulding drilling then.Mold cavity is 40 * 30 * 30mm
3, injection machine is a Ningbo span B160/120C type.The parameter of injection moulding is: 110～120 ℃ of mold temperatures, 260～275 ℃ of injection temperatures, injection speed 90%, injection pressure 70MPa.Change the single mode feeding quantity, be respectively 10,12g, 14g, 17g, 20g, 24g, 28g, 34g.The first base that makes is removed dense skin and is promptly obtained porous material, and porosity is about 89%, 83%, 78%, 73%, 68%, 64%, 58% ,-53%, 43% respectively, and average pore size is about 220～480 microns.With the ultrasonic cleaning 5 times in dehydrated alcohol of the porous material of gained, each scavenging period 10 minutes can use.The comprcssive strength corresponding with its porosity is as shown in table 1.Wherein porosity be 78% composite porous microstructure electron scanning micrograph as shown in Figure 1.
Embodiment 2
With 5-phenyltetrazole foaming agent 5g, 10g, 20g, 30g, be dissolved in respectively in the 5000ml dehydrated alcohol, filter, 2kg osteoid apatite/polyamide 66 composite material (the osteoid apatite mass content is 40%) is added in the solution, fully mix, dehydrated alcohol is removed in volatilization, be in the vacuum drying oven 80 ℃ 10 hours.Injection mo(u)lding then.Mold cavity is 40 * 30 * 30mm
3, injection machine produces the B160/120C type for the Ningbo span.Injection parameters is: 120 ℃ of mold temperatures, and 260～275 ℃ of injection temperatures, injection speed 90%, injection pressure 80MPa, the single mode feeding quantity is 18g.The first base that makes is removed dense skin and is promptly obtained porous material, and porosity is about 68%, and average pore size is about 220 microns, 230 microns, 300 microns, 360 microns respectively.With the ultrasonic cleaning 5 times in dehydrated alcohol of the porous material of gained, each scavenging period 10 minutes can use.
The mechanical property of table 1 different porosities material
*Partially porous part dense material mechanical property: 50-70MPa
Embodiment 3
30g is dissolved in the 3000ml acetone with 5-phenyltetrazole foaming agent, filters, and with spray apparatus it evenly is sprayed at (the osteoid apatite mass content is 30%) on 2kg nanometer osteoid apatite/polyamide 66 composite material, 80 ℃ of oven dry in vacuum drying oven.Injection moulding drilling then.Mold cavity is 40 * 30 * 30mm
3, injection machine produces the B160/120C type for the Ningbo span.Injection parameters is: 110～120 ℃ of mold temperatures, and 260～275 ℃ of injection temperatures, injection speed 90%, injection pressure 70MPa, the single mode feeding quantity is 12g.The first base that makes is removed compacted zone and is promptly obtained porous material, and porosity is about 90%, and average pore size is about 500 microns.With the ultrasonic cleaning 5 times in dehydrated alcohol of the porous material of gained, each scavenging period 10 minutes can use.
Embodiment 4
10g is dissolved in the 2000ml dehydrated alcohol with 5-phenyltetrazole foaming agent, filter, with spray apparatus it evenly is sprayed at (the osteoid apatite mass content is 40%) on 2kg osteoid apatite/polyamide 6 composite material, 80 ℃ of oven dry in vacuum drying oven, injection moulding drilling then.Mold cavity is 40 * 30 * 30mm
3, injection machine produces the B160/120C type for the Ningbo span.The Shooting Technique parameter is: 80 ℃ of mold temperatures, and 230～255 ℃ of injection temperatures, injection speed 90%, injection pressure 70MPa, the single mode feeding quantity is 17g.The first base that makes is removed compacted zone and is promptly obtained porous material, and porosity is about 70%, and average pore size is about 370 microns.With the ultrasonic cleaning 5 times in dehydrated alcohol of the porous material of gained, each scavenging period 10 minutes can use.This bulk is as shown in Figure 2 composite porous, and the photo of its surface topography as shown in Figure 3.
10g is dissolved in the 2000ml dehydrated alcohol with 5-phenyltetrazole foaming agent, filters, and with spray apparatus it evenly is sprayed at (the osteoid apatite mass content is 65%) on 2kg nanometer osteoid apatite/polyamide 12 composites, 80 ℃ of oven dry in vacuum drying oven.Injection moulding drilling then.Mold cavity is 40 * 30 * 30mm
3, injection machine produces the B160/120C type for the Ningbo span.Injection parameters is: 80 ℃ of mold temperatures, and 240～255 ℃ of injection temperatures, injection speed 90%, injection pressure 70MPa, the single mode feeding quantity is 13g, 17g, 20g.The first base that makes is removed compacted zone and is promptly obtained porous material, and porosity is respectively 86%, 80%, 69%, and average pore size is about 270～330 microns.With the ultrasonic cleaning 5 times in dehydrated alcohol of the porous material of gained, each scavenging period 10 minutes.
Embodiment 6
30g is dissolved in the 5000ml acetone with 5-phenyltetrazole foaming agent, filters, and with spray apparatus it evenly is sprayed at (the osteoid apatite mass content is 40%) on 2kg osteoid apatite/polyamide 66 composite material, 80 ℃ of oven dry in the vacuum drying oven.Injection moulding drilling then.Mold cavity is a hollow cylinder shape, external diameter 28mm, internal diameter 8mm, length 130mm.Injection machine produces the B160/120C type for the Ningbo span.Injection parameters is: 120 ℃ of mold temperatures, and 260～275 ℃ of injection temperatures, injection speed 90%, injection pressure 70MPa, the single mode feeding quantity is 55g.The cylindric extexine compacted zone of base just that makes is removed, promptly obtained the inner surface densification and the cylindric porous material of porous outer surface.With the ultrasonic cleaning 5 times in dehydrated alcohol of the porous material of gained, each scavenging period 10 minutes.
Embodiment 7
5g is dissolved in the 2000ml dehydrated alcohol with 5-phenyltetrazole foaming agent, filters, and with spray apparatus it evenly is sprayed at (the osteoid apatite mass content is 40%) on 2kg osteoid apatite/polyamide 66 composite material, 80 ℃ of oven dry in the vacuum drying oven.Injection moulding drilling then.Mold cavity is 40 * 30 * 30mm
3Injection machine produces the B160/120C type for the Ningbo span.Injection parameters is: 120 ℃ of mold temperatures, 260～275 ℃ of injection temperatures, injection speed 90%, injection pressure 70MPa, single mode feeding quantity 30g.The first base that makes is removed the extexine compacted zone and is promptly obtained the inner surface densification and the porous material of porous outer surface, and porosity is about 40%, and average pore size is about 200 microns.With the ultrasonic cleaning 5 times in dehydrated alcohol of the porous material of gained, each scavenging period 10 minutes.
Comparative example 1:
As foaming agent, dehydrated alcohol is as the solvent of dissolving foaming agent with trihydrazinotriazine.By foaming agent: composite=0.5: 100 (weight) is prepared burden.Foaming agent is dissolved in the dehydrated alcohol, after the filtration, with spray apparatus it evenly is sprayed at (the osteoid apatite mass percent is 40% in the composite) on 2kg osteoid apatite/polyamide 66 composite material, and 80 ℃ are reclaimed the ethanol oven dry in vacuum drying oven.Injection moulding drilling then.Mold cavity is 40 * 30 * 30mm
3Injection machine produces the B160/120C type for the Ningbo span.The Shooting Technique parameter is: 120 ℃ of mold temperatures, 270～285 ℃ of injection temperatures, injection speed 90%, injection pressure 70MPa.The porous material colour-darkening that obtains, the pore lack of homogeneity.
Porous osteolith stone/polyamide compoiste material that the present invention is prepared because wherein osteoid apatite is the main inorganic composition of people's bone, thereby can with people's bone formation synostosis, have good biology performance.Simultaneously, owing to the potentiation of osteoid apatite to polyamide, it has mechanical property preferably.For example when the porosity of porous material reached 80%, its comprcssive strength was still greater than 1MPa, and this makes it can be used as a kind of favorable tissue engineering scaffold material.And when this material is made into the bone renovating material of partly porous part densification or porosity when low, its mechanical property can reach 50～70MPa, can be used as the partly repair materials of load bone.This porous material can also be used for somatomedin compound to quicken the growth of tissue, and perhaps the base material as slow releasing carrier of medication and repair of cartilage material uses.
Claims (9)
1. the preparation method of porous osteolith stone/polyamide compoiste material, it is characterized in that behind osteoid apatite/medical polyamide compoiste material and the foaming agent 5-phenyltetrazole uniform mixing, be higher than under the condition of foaming agent decomposition temperature, through the injection moulding process foaming is the porous blank, the particle diameter of said osteoid apatite is nanometer～micron order, the part by weight of foaming agent and porous osteolith stone/polyamide compoiste material is (0.2～1.5): 100, said foaming agent is with its good solvent dissolving back and osteoid apatite/polyamide compoiste material uniform mixing of boiling point≤100 ℃, after being higher than the solvent for use boiling point and being lower than the solvent of removing under the condition of foaming agent decomposition temperature in the composite material, carry out said injection mo(u)lding again.
2. preparation method as claimed in claim 1, the solvent that it is characterized in that said dissolving foaming agent is dehydrated alcohol or acetone.
3. preparation method as claimed in claim 1 is characterized in that the calcium in the said osteoid apatite: the phosphorus mol ratio is (1.3～2.0): 1.
4. preparation method as claimed in claim 1 is characterized in that said medical polyamide is for comprising polyamide 66, polyamide 6, polyamide 10, polyamide 11, polyamide 12, polyamide 6 10, at least a in interior medical polyamide composition of polyamide 6 12, polyamide 1010, polyamide 1212.
5. preparation method as claimed in claim 1, the mass percent that it is characterized in that osteoid apatite in said porous osteolith stone/polyamide compoiste material is 10～70wt%.
6. preparation method as claimed in claim 1, the injection temperature when it is characterized in that said injection mo(u)lding is 230 ℃～275 ℃, and mold temperature is 60 ℃～120 ℃, and injection speed is 60%～90%, and injection pressure is 40～100MPa.
7. preparation method as claimed in claim 1 is characterized in that the porous material of gained or goods hole aperture are 5～1000 microns, and average pore size is between 150～500 microns, and porosity is 15～90%, and comprcssive strength is 0.1～70MPa.
8. as the described preparation method of one of claim 1 to 7, it is characterized in that the dense skin of porous blank that said injection mo(u)lding is obtained is removed, become the porous moulding material of each face.
9. as the described preparation method of one of claim 1 to 7, it is characterized in that the dense skin of the porous blank that the said injection mo(u)lding of reserve part obtains, become the porous, shaped material of the non-homogeneous form of each face.
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| CN1493615A (en) * | 2003-06-20 | 2004-05-05 | 四川大学 | Inorganic/organic nano-composite bioactivity porous material and its preparation method |
| CN1493365A (en) * | 2003-06-20 | 2004-05-05 | 四川大学 | Preparation method of nano apatite crystal composite tissue engineering support material |
| EP1604693A1 (en) * | 2004-06-09 | 2005-12-14 | Scil Technology GmbH | In situ forming scaffold, its manufacturing and use |
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| CN1493615A (en) * | 2003-06-20 | 2004-05-05 | 四川大学 | Inorganic/organic nano-composite bioactivity porous material and its preparation method |
| CN1493365A (en) * | 2003-06-20 | 2004-05-05 | 四川大学 | Preparation method of nano apatite crystal composite tissue engineering support material |
| EP1604693A1 (en) * | 2004-06-09 | 2005-12-14 | Scil Technology GmbH | In situ forming scaffold, its manufacturing and use |
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