CN100408115C - Biological material film with porous structure and its prepn - Google Patents
Biological material film with porous structure and its prepn Download PDFInfo
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- CN100408115C CN100408115C CNB2006100215085A CN200610021508A CN100408115C CN 100408115 C CN100408115 C CN 100408115C CN B2006100215085 A CNB2006100215085 A CN B2006100215085A CN 200610021508 A CN200610021508 A CN 200610021508A CN 100408115 C CN100408115 C CN 100408115C
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Abstract
The biological material film with porous structure is medical film of polyamide or composite polyamide/nanometer osteolith material with through pores in gradually changed sizes, and has one compact side with fine pores in diameters of 0.01-30 microns and the opposite loose side with large pores in diameters of 30-300 microns. During its preparation, solvent with high volatility is used as the dispersant, medical polyamide or composite polyamide/nanometer osteolith material is heated and stirred to form the filming liquid, and film is formed and washed with deionized water to obtain the biological film. The porous biological film has controllable porous structure, and excellent mechanical performance and biological performance, and may be used widely as medial separating film, medicine slow releasing film, tissue regeneration inducing film, etc.
Description
Technical field
The present invention relates to a kind ofly can in medicine and hygiene fields, be used to biological material film that uses and preparation method thereof.
Background technology
Since the nineties in last century, utilized artificial membrane vectoring aircraft soma healing by regeneration to become international popular research topic.Biological membrane technique (Barrier Membrane Technique is called for short BMT) is the clinical treatment new technique that causes the medical circle extensive concern in recent years.The principle of inducting osseous tissue regeneration art; be to utilize biomembranous physical barriers function that bone defective region and surrounding tissue are isolated; create the organizational environment of a relative closure; prevent the fiber sheath bone defective region of growing into; protection, obstruct, guiding or inducing action play in the district to wound; give full play to the reparation of organizing self, healing potentiality, finally make the injured tissues organ be regenerated and rebuild, thereby the regeneration function of osseous tissue is farthest brought into play.It is applied in treatment, tooth growing area bone quantity not sufficient for periodontal disease and other bone is damaged, the healing of the repairing and treating of bone does not connect, fracture etc. provides a new effective way.
The biological barrier film of research at present and utilization can be divided into absorbability and can not resorbable membrane two kinds.The biomembranous research that degradable absorbs mainly concentrates on collagem membrane, chitosan film, polylactic acid membrane, polyglycolic acid film and polylactic acid and polyglycolic acid co-polymer membrane etc. with application.This class degradability barrier film because hydration, hydrolysis or enzyme digestion reaction take place, can change its structure and mechanical property etc. in vivo, and degraded and absorbed speed is difficult to control, causes operative failure.The present collagem membranes (BIO-GIDE) of having obtained certain effect etc. are because of costing an arm and a leg, and the patient is difficult to accept.To study and use more at present be not expanded polytetrafluoroethylsealing film (E-PTFE), titanium film etc. to the absorbability biomembrane.Because it has stable physicochemical property, but with absorbing film mutually specific energy play better barrier action, help the hypertrophy of original bone surface, obtain more osteanagenesis.But also, need second operation to remove, as continue to be retained in original position, can produce complication such as bacterial infection, and cause easily that soft tissue flap splits, film exposes in early days, influence new osteogenesis amount just because it can not be degraded in vivo voluntarily.
The biomembranous common weak point of above-mentioned two classes also is to play mechanical stop and buffer action and does not possess and initiatively induce differentiation and promote the growth effect; usually also need with from body bone or other bone substitute couplings; and cause infection easily, thereby influence and limited its application.
So better biomembrane of urgent clinical needs searching; should be able to be by the fibroblast of barrier film prevention from surrounding soft tissue; play barrier, support, stable and protective effect; serve as bone guided or induced interstitial; allow bone wound surface osteoblast that time enough propagation, reconstruction of bone tissue are arranged, promote to form bone interface more closely, and have antibacterial ability; reduce and avoid causing operative failure, promote the application and the development of implantation body and orthopaedics clinical repair by bacterial infection.
Summary of the invention
At above-mentioned situation, the present invention at first will provide a kind of biological material film with loose structure, can satisfy above-mentioned clinical needs.On this basis, the present invention also will provide a kind of said this biomaterial film method with loose structure for preparing.
Biological material film with loose structure of the present invention, be at medical polyamide composition or be distributed with the pore structure of mutual perforation between by the both side surface of the membrane material body of medical polyamide/nano osteoid apatite composite parts with aperture gradual change form, promptly, one side at the membrane material body is that the aperture is the dense face of the tiny hole of 0.01～30 μ m, and the another side of film is that the aperture is the loose face of macropore of 30～300 μ m.The thickness of film generally can be 0.02～2mm, and wherein particularly preferred thickness can be 0.1～0.5mm.
Above-mentioned biological material film can only be medical polyamide-based composition, or is made by medical polyamide/nano osteoid apatite composite parts.Said medical polyamide-based composition can be medical polyamide 66 (PA66) commonly used at present, polyamide 6 (PA6), polyamide 46 (PA46), polyamide 10 (PA10), polyamide 11 (PA11), polyamide 12 (PA12), polyamide 6 10 (PA610), polyamide 6 12 (PA612), polyamide 1010 (PA1010), polyamide 1212 (PA1212), polyamide 5050 (PA5050), one or more in the polyamide 7030 (PA7030).Polyamide-based composition has good mechanical property and good filming performances such as high intensity, toughness, polar bond in the molecular structure makes its composite that not only can make stable homogeneous with other materials, and easily forms hydrogen bonded with the medicine that has polar group, somatomedin etc. and firmly adsorb.
Nanometer osteoid apatite composition in the said medical polyamide/nano osteoid apatite composite parts can also use the nanometer osteoid apatite composition that inorganic antibacterial components is arranged as load especially.When adopting medical polyamide/nano osteoid apatite (or load has the nanometer osteoid apatite of inorganic antibacterial components) composite parts, wherein the part by weight of nanometer osteoid apatite (or load has the nanometer osteoid apatite of inorganic antibacterial components) composition is 1%～70%, is preferably 40%～60%.The preparation of nanometer hydroxyapatite/polyamide series bio-medical composition can realize with reference to the method as existing report in the documents such as the patent No. 200310111033.5, application number 200510022326.5.Because the nanometer osteoid apatite crystal has good biological activity, with the common nano combined bioactive materials of forming of polyamide-based composition, can reach enhancings, benefit is tough, mechanics is compatible and characteristics such as raising biological activity.Can fit closely with repairing the position better after the biomembrane of this form of composite implants, produce biological bonding with the receptor bone district. can reach the purpose of biologic fusion and tissue reconstruction.
Matsurface with macropore helps sticking of osteoblast, osteocyte and grows, Zhi Mi micropore face plays buffer action relatively, prevent soft tissue and the connective tissue bone defective region of growing into, help the conveying of nutrition simultaneously, the sticking and grow of the migration of Interstitial cell, cell in the blood, thus ideal bone repairing effect obtained.Good barrier buffer action then can be played to implant site in the more fine and close surface that trickle aperture is only arranged.
On above-mentioned loose structure biological material film basis, can also be in said membrane material body further by means such as absorption and/or adhesions, the auxiliary activity composition of promising its gross weight 0.05%～20% of load is prepared the biological material film with corresponding bioactive functions, effect.These auxiliary elements can be respectively at least a in inorganic antibacterial composition, slow releasing pharmaceutical composition or the tissue growth factor.For example, can comprise have an antibacterial action comprise inorganic antibacterial compositions such as copper, zinc, silver, lanthanum, cerium, neodymium metal ion and corresponding copper sulfate thereof, copper chloride, zinc sulfate, zinc chloride, silver nitrate, Lanthanum (III) nitrate, cerous nitrate, neodymium nitrate salt compounds (preparation method can with reference to publication number CN1784975A Chinese patent literature), become membrane material with antibacterial functions effect.Experiment shows, compare with the nanometer osteoid apatite/polyamide compoiste material porous biomembrane that does not contain antimicrobial component, load the nanometer osteoid apatite/polyamide compoiste material porous biomembrane of inorganic antibacterial composition can have good antibacterial performance (as oral cavity bacterium etc.).The content of inorganic antibacterial composition generally can be 0.1～20% of film gross weight in the film, and particularly preferred scope is 0.1～8%.
In addition, said auxiliary activity composition can also include penicillin, gentamycin, tobramycin, vancomycin, antibiotic compositions such as berberine, and as the Radix Astragali, astragaloside, Radix Notoginseng, Radix Notoginseng total glycosides, Radix Salviae Miltiorrhizae, ingredients such as Herba Epimedii are particularly by its ingredient with slow-releasing that is prepared into; Can also comprise as bone morphogenetic protein (BMPs), transforming growth factor-beta (TGF-β), insulin like growth factor (IGF), fibroblast growth factor (FGFs), basic fibroblast growth factor (bFGF), vascular endothelial cell growth factor (VRGF), platelet-derived growth factor (PDGF), neoplasm necrosis somatomedin tissue growth factor compositions such as (TNF) becomes the membrane material with medicament slow release and/or guide tissue regeneration function.Experiment shows, selects medicine carrying for use or carries the somatomedin microsphere and can effectively protect the influence that is subject to external environment and lose the medicine of its effect or somatomedin (as BMP etc.), and can play slow releasing function.The medicine of institute's load or somatomedin amount in the film, general controlled 0.05～5% of the film gross weight that is made as.
Above-mentioned dissimilar auxiliary activity composition can be united use, thereby can be with the porous biomembrane of the multiple function of regeneration of medicament slow release, induced tissue and effect such as antibiotic.
Test shows, the above-mentioned biological material film of the present invention with loose structure, both can stop the soft tissue bone defective region of growing into effectively, can provide the carrier that adheres to for osteocyte again, defective region and surrounding tissue are isolated, the organizational environment of a relative closure is provided for freshman bone tissue, stop the other types cell to enter, the cell of Lin Jin bone stump with osteanagenesis potential enters this zone and the new bone of interference-free relatively formation simultaneously, playing the effect of selectivity tissue regeneration. the mesh-structured system that connects mutually in the film helps the conveying of nutrition, the migration of Interstitial cell in the blood, the sticking and grow of cell. particularly the porous of the form of composite osteoid apatite composition of giving birth in the membrane material also has the superior bioactive and the compatibility, when repairing barrier and support as bone, have bone conductibility and bone guided, helping new bone grows along the framework mesh. and nano-apatite crystals is uniformly distributed in the stake body, be beneficial to the multiple spot skeletonization, but accelerated bone defect repair not only, form synostosis with osseous tissue, and need not second operation, finally obtain good bone and integrate clinical efficacy.A large amount of polar groups in nano-apatite in the membrane material and/or the polyamide-based composition not only make film very easily with water molecules, deliquescing after the moisture absorption, make the film material be adsorbed on the bone defective region easily, and, make porous biomembrane have medicament slow release and guide tissue regeneration function easily by means carrying medicament and all kinds of somatomedin such as absorption and adhesions.Load has such regeneration membrane of antibiotic ion, antibacterial can also have stronger resistance infection, isolating, guiding outside regenerated two large effects, can also have antibacterial functions simultaneously, be particularly useful for the Oral Repair of a large amount of floras survivals, help reducing and infect, promote wound healing.Therefore but can solve the metabolite of absorbing film and the uncertain factor of degradation process influences new osteanagenesis problem, the defective of also having avoided absorbing film not to need second operation to take out need not with playing the inductive effect of barrier, support, bone conduction and bone with using from body bone or bone substitute.
The advantage of the porous biomembrane that the present invention is above-mentioned shows that also its application is convenient, can carry out cutting according to clinical needs.
The above-mentioned preparation of the present invention with biological material film of loose structure, can use the volatility good solvent to the medical polyamide composition in the selected filmogen earlier is dispersant, the medical polyamide composition that will be used for filmogen, or medical polyamide/nano osteoid apatite composite parts, or the nanometer osteoid apatite composition of medical polyamide/carrying inorganic antibacterial components, under 50 ℃～140 ℃ conditions, fully stir, being made for mass fraction is 5%～60%, after being preferably 10～30% no visible particle shape thing and having even thick film forming liquid, the mode of freely sprawling of pouring into currently reported and use, mode is sprawled in rotation, prolong stream mode, lift sophisticated system film modes such as mode, or other suitable thin film-forming method, be prepared into the membranaceous material bodies of said one-tenth, then in 20 ℃～90 ℃, dry under preferred 20 ℃～70 ℃ conditions, for example at room temperature natural air drying gets final product.Again through deionized water wash, remove desolvate and preparation process in other composition after drying of introducing get final product.Exsiccant mode can be just like natural air drying, oven dry, lyophilization or 20～60 ℃ of multiple modes such as vacuum drying.Can be cut into required specification size according to clinical use needs.
The above-mentioned preparation method of the present invention can adapt to the film for preparing various different used thicknesses.For example, when preparing thin perforated membrane, can adopt the little film forming liquid of mass fraction, on the contrary, prepare thicker perforated membrane and adopt the big film forming liquid of mass fraction.When adopting commonly used pouring into freely to sprawl, rotate modes such as sprawling, prolong stream, the unit are amount of pouring into generally can be 0.005～0.2ml/cm
2, preferred 0.01～0.1ml/cm
2. by the amount of pouring into of control unit are and the concentration of film forming liquid is the film forming thickness of may command, can adopt the bigger film unit are amount of pouring into during the preparation thick film.Lift number of times according to required film thickness when adopting pulling film forming, generally can be 1～20 time, when preparing thicker film, can increase and lift number of times.Simultaneously, adopt and freely sprawl, rotate the film isotropism of sprawling preparation, adopt the film that prolongs stream and method of pulling up preparation, then have orientation.
Test shows that the baking temperature after the film forming too high (for example greater than 90 ℃) will make the cracking that becomes fragile, the mechanical properties decrease of film.20～90 ℃ of dryings, can prepare porous biomembrane with excellent mechanical performances and gap structure.
The volatility good solvent of above-mentioned said medical polyamide composition, generally can select the most commonly used be easy to get as one or more the blended forms in the alcohols solvents such as methanol, ethanol, propanol.
For example, when only adopting medical polyamide-based composition as filmogen, the preparation of above-mentioned porous biomembrane, can be under the condition of 50 ℃～140 ℃ (preferred 60 ℃～80 ℃) and the existence of calcium class catalyst, mode by No. 200310111033.5 patent documentations is dissolved in the polyamide composition in its volatility good solvent, be prepared into the even thickness film forming liquid of the polyamide composition of said mass fraction, but (for example 20 ℃～50 ℃ of liquid cooling to be filmed, especially can be preferred 20 ℃～40 ℃) after, pour into or pulling film forming in said mode, dry under said temperature again, the labelling positive and negative (is distinguished dense face and loose face in easy to use.Gas phase contact surface when for example the front can refer to film forming, the dull and stereotyped contact surface when then reverse side promptly is film forming relatively), behind deionized water immersion, washing several, drying.
When adopting medical polyamide/nano osteoid apatite composite parts as filmogen, the preparation of above-mentioned porous biomembrane, be under stirring action, a certain amount of composite material sizing agent or powder to be scattered in the volatility good solvent of polyamide composition wherein equally, under 50 ℃～140 ℃ (preferred 80 ℃～120 ℃) heating conditions, fully stir, obtain even thickness and do not have the film forming liquid that the visible particle thing exists, cooling back the mode film forming such as pours into or lifts with above-mentioned, behind the dry down also labelling positive and negative of said temperature conditions, with the deionized water washing by soaking for several times, remove and to desolvate and composition such as catalyst, with natural air drying, oven dry, get final product after lyophilization or 20 ℃～60 ℃ mode dryings such as vacuum drying.
The formation of the membrane material body mesopore of the above-mentioned preparation method of the present invention, be because in its dry run, volatility good solvent (as ethanol) in the film forming liquid becomes gas phase by liquid phase and forms bubble and slowly grow up and formed the space, along with film is dry gradually, hole promptly is fixed, and has formed porous biomembrane.Dry under lower temperature, because the phase transfer speed of this volatile solvent is slower, the bubble that forms is grown up gradually, two sides at film all forms bigger hole, the relative closure phase transfer is slower but it is close to dull and stereotyped side, air bubble growth is bigger, and the hole of this face can be significantly greater than the hole (shown in Fig. 4,5) that contacts gas Interface; Temperature (as 50 ℃) during along with rising drying gradually, the transfer velocity of volatile solvent (as ethanol) is very fast, and air bubble growth is less, and the Kong Jun on film two sides reduces, and the hole of ingress of air face side reduces the most remarkable; When baking temperature is higher (as 90 ℃), because the phase transfer speed of solvent (as ethanol) is very fast, being close to bubble that platen surface forms expands rapidly and grows up and form big hole at this face, and ingress of air face side is because alcoholic acid evenly transfer fast only forms the relative dense face with tiny micropore.Thereby can prepare porous biomembrane (shown in Fig. 6,7) in the asymmetric pore structure that has shape distribution in gradient in the membrane material body.Therefore, the pore structure state in the porous biomembrane promptly can be controlled and regulate to the baking temperature when preparation of the present invention divides by the adjusting film forming.
On the basis of above-mentioned preparation method, going back load as hope in film has said auxiliary activity composition, can adopt preceding load of film forming and film forming back loading dual mode.
The mode of load is before the film forming, with the auxiliary activity composition of said proportional quantities or the microsphere (preparation method can with reference to currently reported pertinent literature) that is loaded with auxiliary activity composition (as medicine and somatomedin etc.) mix simultaneously be scattered in the said film forming liquid after, preparation becomes the film material body in the above described manner again, makes that load has corresponding auxiliary activity composition in the film material body.
For example, when mode of loading prepares carrying inorganic antimicrobial component film before with film forming, can prepare carrying inorganic antibacterial components nanometer osteoid apatite (preparation method can with reference to currently reported pertinent literature) earlier, and then prepare the film material body of the nanometer bone-like apatite stone material of medical polyamide/carrying inorganic antibacterial components according to above-mentioned method, corresponding auxiliary activity composition is carried in the film material body.
The mode of film forming back loading is, be in the aqueous solution of microsphere of 0.3～100 μ m or the organic solution after a period of time (different-thickness according to film got final product in general 1～24 hour) with said final dried membrane material body, can make that load has corresponding auxiliary activity composition in the film material body with the diameter that is soaked in the corresponding auxiliary active component that contains said proportional quantities or is loaded with corresponding auxiliary active component.
The concentration of auxiliary activity composition in its aqueous solution or organic solution such as above-mentioned said antimicrobial component, ingredient or somatomedin can be selected according to the character and/or the useful effect concentration of medicine.Wherein without limits to the organic solvent that is used to disperse these auxiliary activity compositions in the organic solution, can be according to the different in kind of medicine or somatomedin, the suitable solvent of selecting document to report for work and used is as acetone commonly used, chloroform etc.
The microsphere diameter of auxiliary activity compositions such as said carrying medicament or somatomedin is 0.3～100 μ m, can make microsphere enter the porous network structure of film and settles out.During application, microsphere suction swelling and degraded, medicine or somatomedin slowly discharge, and keep certain useful effect concentration in the long time.
Various said auxiliary activity composition is carried in the method in the membrane material body above-mentioned, as adhesive such as the gelatin that in the dispersion that contains these auxiliary activity compositions, is incorporated as its dispersion weight 0.05%～5% again, Polyethylene Glycol, collagen, chitosan, polyvinyl alcohol hydrogels, can more help sticking auxiliary activity compositions such as medicine or somatomedin.In exsiccant process, adhesive and medicine or somatomedin attach to the porous surface of film, along with the swelling and the degraded of adhesive, reach the slow release purpose during application.
In above-mentioned porous drug slow release and the biomembranous preparation method of guide tissue regeneration porous biomembrane, said drying mode and sterilization method, condition, all should select, with the influence that guarantees reason drying condition not and lost efficacy or reduce effect according to the character of auxiliary activity compositions such as employed medicine and/or somatomedin.For example, when load being had composition such as growth factor B MP, need to adopt lyophilization.
Because have the pore structure of distribution or asymmetrical distribution in the resulting membrane material body of above-mentioned preparation between the two sides, the mask of film is selective during application, as repairing bone defect, the matsurface in big space is close to osseous tissue, helps osteoblasticly sticking and growing.
Because polyamide has good mechanical property and good filming performances such as high intensity, toughness, polar bond in the molecular structure makes its composite that not only can make stable homogeneous with other materials, and easily forms hydrogen bonded with the medicine that has polar group, somatomedin etc. and firmly adsorb; The nanometer osteoid apatite crystal has good biological activity, with the synthetic nano combined bioactive materials of polyamide, reach enhancing, benefit is tough, mechanics is compatible and has improved characteristics such as biological activity, therefore after the biological material film of the above-mentioned loose structure of the present invention is implanted can with repair the position and fit closely, produce biological bonding with the receptor bone district, the purpose of biologic fusion and tissue reconstruction can be reached, pressing for of clinical tissue reparation can be satisfied.And its preparation method is very easy, and condition is easy to control, and does not use toxic reagent, does not have the residual of noxious substance, so the biological safety height.
Foregoing of the present invention is described in further detail again with the specific embodiment below in conjunction with accompanying drawing.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.
Description of drawings
Fig. 1 is the stereoscan photograph (S-450 type scanning electron microscope, FDAC) of the present invention with the porous biomembrane of single polyamide 66 material preparation.
Fig. 2 is the stereoscan photograph (S-450 type scanning electron microscope, FDAC) of the present invention with the porous biomembrane of polyamide 66/year silver and the preparation of nano titania apatite composite material.
Fig. 3 is the stereoscan photograph (S-450 type scanning electron microscope, FDAC) of big hole wall among Fig. 2.
Fig. 4 is the stereoscan photograph (baking temperature 20 ℃) (JSM-5900LV type, Jeol Ltd.) of the present invention with the porous biomembrane dense face of polyamide 66/nano-apatite Composite Preparation.
Fig. 5 is the stereoscan photograph (JSM-5900LV type, Jeol Ltd.) of the loose face of porous biomembrane under identical polyamide 66 with Fig. 4/nano-apatite composite and the preparation condition.
Fig. 6 is the stereoscan photograph (baking temperature 90 ℃) (JSM-5900LV type, Jeol Ltd.) of the present invention with the porous biomembrane dense face of polyamide 66/nano-apatite Composite Preparation
Fig. 7 is the stereoscan photograph (JSM-5900LV type, Jeol Ltd.) of the loose face of porous biomembrane under identical polyamide 66 with Fig. 6/nano-apatite composite and the preparation condition
The specific embodiment
Embodiment 1
At 70～80 ℃, under stirring and the effect of catalyst calcium chloride the 10g polyamide 66 is dissolved in the 100ml ethanol, make the film forming liquid of polyamide 66, liquid to be filmed is cooled to 30～40 ℃, about 1.5ml film forming liquid is poured on the glass plate that diameter is 12cm freely sprawls film forming, 70 ℃ of dryings, marking pen labelling positive and negative, with 200ml deionized water washing by soaking for several times, there is not chloride ion (each soak time was greater than 30 minutes) in the silver nitrate solution check eluent of 1M, 70 ℃ of oven dry promptly obtain polyamide 66 porous biomembrane of the present invention.
The polyamide 66 film of preparation is a loose structure, connects mutually between the Kong Yukong, and average pore size is about 60～70 μ m, and configuration as shown in Figure 1.Measure with slide gauge, the thickness of perforated membrane is 0.1mm.
Embodiment 2
At 70～80 ℃, under stirring and the effect of catalyst calcium chloride the 20g polyamide 66 is dissolved in the 100ml ethanol, make the film forming liquid of polyamide 66, liquid to be filmed is cooled to 30～40 ℃, about 2.5ml film forming liquid is poured on the glass plate that diameter is 12cm rotation sprawls film forming, 60 ℃ of dryings, marking pen labelling positive and negative, with 200ml deionized water washing by soaking for several times, there is not chloride ion (each soak time was greater than 30 minutes) in the silver nitrate solution check eluent of 1M, 70 ℃ of oven dry promptly obtain polyamide 66 porous biomembrane of the present invention.
The polyamide 66 film of preparation is a loose structure, connects mutually between the Kong Yukong, and average pore size is about 50～70 μ m.Measure with slide gauge, the thickness of perforated membrane is 0.2mm.
Embodiment 3
At 70～80 ℃, under stirring and the effect of catalyst calcium chloride the 10g polyamide 6 is dissolved in the 100ml ethanol, make the film forming liquid of polyamide 6, liquid to be filmed is cooled to 30～40 ℃, about 2ml film forming liquid is poured on the glass plate that diameter is 12cm freely sprawls film forming, 70 ℃ of dryings, marking pen labelling positive and negative, with 200ml deionized water washing by soaking for several times, there is not chloride ion (each soak time was greater than 30 minutes) in the silver nitrate solution check eluent of 1M, 70 ℃ of oven dry promptly obtain polyamide 6 porous biomembrane of the present invention.
The polyamide 6 film of preparation is a loose structure, connects mutually between the Kong Yukong, and average pore size is about 60～70 μ m.Measure with slide gauge, the thickness of perforated membrane is 0.12mm.
Embodiment 4
At 70～80 ℃, under stirring and the effect of catalyst calcium chloride 10g polyamide 46 is dissolved in the 100ml propanol, make the film forming liquid of polyamide 46, liquid to be filmed is cooled to 30～40 ℃, about 2.5ml film forming liquid is poured on the glass plate that diameter is 12cm freely sprawls film forming, 70 ℃ of dryings, marking pen labelling positive and negative, with 200ml deionized water washing by soaking for several times, there is not chloride ion (each soak time was greater than 30 minutes) in the silver nitrate solution check eluent of 1M, 70 ℃ of oven dry promptly obtain polyamide 46 porous biomembranes of the present invention.
Polyamide 46 films of preparation are loose structure, connect mutually between the Kong Yukong, and average pore size is about 60～70 μ m.Measure with slide gauge, the thickness of perforated membrane is 0.15mm.
Embodiment 5
At 70～80 ℃, under stirring and the effect of catalyst calcium chloride the 10g polyamide 66 is dissolved in the 100ml methanol, makes the film forming liquid of polyamide 66, liquid to be filmed is cooled to 30～40 ℃, pulling film forming, lifting number of times is 3 times, 30 ℃ of dryings, marking pen labelling positive and negative, with 200ml deionized water washing by soaking for several times, do not have chloride ion (each soak time was greater than 30 minutes) in the silver nitrate solution check eluent of 1M, 70 ℃ of oven dry promptly obtain polyamide 66 porous biomembrane of the present invention.
The polyamide 66 film of preparation is a loose structure, connects mutually between the Kong Yukong, and average pore size is about 90～110 μ m.Measure with slide gauge, the thickness of perforated membrane is 0.1mm.
Embodiment 6
At 70～80 ℃, under stirring and the effect of catalyst calcium chloride 10g polyamide 12 is dissolved in the 100ml ethanol, make the film forming liquid of polyamide 12, liquid to be filmed is cooled to 30～40 ℃, pulling film forming, lift number of times for for several times, there is not chloride ion in the silver nitrate solution check eluent of 1M, 50 ℃ of dryings, marking pen labelling positive and negative with 200ml deionized water washing by soaking for several times, does not have chloride ion (each soak time was greater than 30 minutes) in the silver nitrate solution of the 1M check eluent, 70 ℃ of oven dry promptly obtain polyamide 66 porous biomembrane of the present invention.
The polyamide 66 film of preparation is a loose structure, connects mutually between the Kong Yukong, and average pore size is about 60～90 μ m.Measure with slide gauge, the thickness of film is 0.1mm.
Embodiment 7
To contain in the slurry of polyamide 66/nano-apatite composite (wherein nano-apatite content is 40%) 10g and add ethanol, making gross mass is 100g, 100 ℃ of stirring conditions refluxed 60 minutes down, make composite become mass fraction and be about 10% homogeneous thickness film forming liquid, liquid to be filmed is cooled to 30～40 ℃, about 1.5ml film forming liquid is poured on the glass plate that diameter is 12cm freely sprawls film forming, 40 ℃ of dryings, marking pen is at the edge labelling positive and negative of film, with the deionized water washing by soaking for several times, there is not chloride ion (each soak time was greater than 60 minutes) in the silver nitrate solution check eluent of 1M, 70 ℃ of oven dry promptly make polyamide 66 of the present invention/nano-apatite composite porous biomembrane.
Polyamide 66/nano-apatite the composite material film of preparation is a loose structure, connects mutually between the Kong Yukong, and average pore size is about 50～60 μ m.Measure with slide gauge, the thickness of perforated membrane is 0.1mm.
Embodiment 8
To contain in the slurry of polyamide 66/nano-apatite composite (wherein nano-apatite content is 50%) 10g and add ethanol, making gross mass is 100g, 50 ℃ were stirred 100 minutes, make composite become mass fraction and be about 10% homogeneous thickness film forming liquid, liquid to be filmed is cooled to 30～40 ℃, about 1ml film forming liquid is poured on the glass plate that diameter is 12cm prolongs the stream film forming, 40 ℃ of dryings, marking pen is at the edge labelling positive and negative of film, with the deionized water washing by soaking for several times, there is not chloride ion (each soak time was greater than 60 minutes) in the silver nitrate solution check eluent of 1M, 70 ℃ of oven dry promptly make polyamide 66 of the present invention/nano-apatite composite porous biomembrane.
Polyamide 66/nano-apatite the composite material film of preparation is a loose structure, connects mutually between the Kong Yukong, and average pore size is about 50～60 μ m.Measure with slide gauge, the thickness of perforated membrane is 0.08mm.
Embodiment 9
To contain in the slurry of polyamide 6/nano-apatite composite (wherein nano-apatite content is 60%) 25g and add ethanol, making gross mass is 100g, 100 ℃ of stirring conditions refluxed 60 minutes down, make composite become mass fraction and be about 25% homogeneous thickness film forming liquid, liquid to be filmed is cooled to 30～40 ℃, about 2ml film forming liquid is poured on the glass plate that diameter is 12cm freely sprawls film forming, 40 ℃ of dryings, marking pen is at the edge labelling positive and negative of film, with the deionized water washing by soaking for several times, there is not chloride ion (each soak time was greater than 60 minutes) in the silver nitrate solution check eluent of 1M, 70 ℃ of oven dry promptly make polyamide 6 of the present invention/nano-apatite composite porous biomembrane.
Polyamide 6/nano-apatite the composite material film of preparation is a loose structure, connects mutually between the Kong Yukong, and average pore size is about 50～60 μ m.Measure with slide gauge, the thickness of the perforated membrane of preparation is 0.3mm.
Embodiment 10
To contain in the slurry of polyamide 46/ nano-apatite composite (wherein nano-apatite content is 68%) 30g and add ethanol, making gross mass is 100g, 100 ℃ of stirring conditions refluxed 80 minutes down, make composite become mass fraction and be about 30% homogeneous thickness film forming liquid, liquid to be filmed is cooled to 30～40 ℃, about 4ml film forming liquid is poured on the glass plate that diameter is 12cm freely sprawls film forming, 40 ℃ of dryings, marking pen is at the edge labelling positive and negative of film, with the deionized water washing by soaking for several times, there is not chloride ion (each soak time was greater than 60 minutes) in the silver nitrate solution check eluent of 1M, 70 ℃ of oven dry promptly make polyamide 46/ nano-apatite composite porous biomembrane of the present invention.
The polyamide 46/ nano-apatite composite material film of preparation is a loose structure, connects mutually between the Kong Yukong, and average pore size is about 50～60 μ m.Measure with slide gauge, the thickness of perforated membrane is 1mm.
Embodiment 11
To contain in the slurry of polyamide 66/carry silver (0.5%) and titanium dioxide (5.1%) nano-apatite composite (the nano-apatite content that wherein carries silver-colored and titanium dioxide is 40%) 40g and add ethanol, making gross mass is 100g, 100 ℃ of stirring conditions refluxed 60 minutes down, make composite become mass fraction and be about 40% homogeneous thickness film forming liquid, liquid to be filmed is cooled to 30～40 ℃, about 1ml film forming liquid is poured into the glass plate upper berth generate film that diameter is 12cm, 50 ℃ of dryings, marking pen is at the edge labelling positive and negative of film, with the deionized water washing by soaking for several times, there is not chloride ion (each soak time was greater than 60 minutes) in the silver nitrate solution check eluent of 1M, 60 ℃ of oven dry promptly make polyamide 66 of the present invention/antibiotic porous biomembrane of nano-apatite composite.
Polyamide 66/nano-apatite the composite material film of preparation is a loose structure, and average pore size is about 20～30 μ m, on the big hole wall aperture is arranged, and illustrates between the Kong Yukong to connect mutually that configuration is shown in Fig. 2,3.Measure with slide gauge, the thickness of perforated membrane is 0.28mm.
Embodiment 12
To contain in the slurry of polyamide 66/carry silver (0.5%) and titanium dioxide (5.1%) nano-apatite composite (the nano-apatite content that wherein carries silver-colored and titanium dioxide is 60%) 20g and add methanol, making gross mass is 100g, 90 ℃ of stirring conditions refluxed 60 minutes down, make composite become mass fraction and be about 20% homogeneous thickness film forming liquid, liquid to be filmed is cooled to 30～40 ℃, about 2ml film forming liquid is poured into the glass plate upper berth generate film that diameter is 12cm, 20 ℃ of dryings, marking pen is at the edge labelling positive and negative of film, with the deionized water washing by soaking for several times, do not have chloride ion (each soak time was greater than 60 minutes) in the silver nitrate solution check eluent of 1M, promptly make polyamide 66 of the present invention/antibiotic porous biomembrane of nano-apatite composite.
Polyamide 66/nano-apatite the composite material film of preparation is a loose structure, connects mutually between the Kong Yukong, and positive average pore size is about 10～20 μ m, and the reverse side average pore size is about 100～200 μ m, and configuration is shown in Fig. 4,5.Measure with slide gauge, the thickness of perforated membrane is 0.12mm.
Embodiment 13
To contain in the slurry of polyamide 66/carry silver (0.5%) and titanium dioxide (5.1%) nano-apatite composite (the nano-apatite content that wherein carries silver-colored and titanium dioxide is 60%) 20g and add ethanol, making gross mass is 100g, 120 ℃ of stirring conditions refluxed 60 minutes down, make composite become mass fraction and be about 20% homogeneous thickness film forming liquid, liquid to be filmed is cooled to 30～40 ℃, about 2ml film forming liquid is poured into the glass plate upper berth generate film that diameter is 12cm, 90 ℃ of dryings, marking pen is at the edge labelling positive and negative of film, with the deionized water washing by soaking for several times, there is not chloride ion (each soak time was greater than 60 minutes) in the silver nitrate solution check eluent of 1M, 60 ℃ of oven dry promptly make polyamide 66 of the present invention/antibiotic porous biomembrane of nano-apatite composite.
Measure with slide gauge, the thickness of the perforated membrane of preparation is 0.12mm.Polyamide 66/nano-apatite the composite material film of preparation is a loose structure, connects mutually between the Kong Yukong, and positive average pore size is about 0～1 μ m, and the reverse side average pore size is about 100～200 μ m, and configuration is shown in Fig. 6,7.
Embodiment 14
Composite porous biomembrane with embodiment 5 described method preparation oven dry, 15mg BMP somatomedin is dispersed in the 10ml distilled water, make and contain somatomedin liquid, getting 5 of films that are cut into 2 * 1cm specification puts into and contains somatomedin liquid, soaked 24 hours under 4 ℃ of conditions, lyophilization, 4 ℃ of preservations promptly obtain the porous biomembrane with induced tissue regeneration function of the present invention.
Embodiment 15
Composite porous biomembrane with embodiment 5 described method preparation oven dry, 25mg TGF somatomedin is dispersed in the 10ml distilled water, add 1% chitosan solution 0.5ml, make the somatomedin liquid that contains adhesive, get 5 of films that are cut into 2 * 1cm specification and put into the somatomedin liquid that contains adhesive, soaked 24 hours lyophilization under 4 ℃ of conditions, 4 ℃ of preservations promptly obtain the porous biomembrane with induced tissue regeneration function of the present invention.
Embodiment 16
Composite porous biomembrane with embodiment 5 described method preparation oven dry, the 20mg berberine is dispersed in the 10ml acetone, getting 5 of films that are cut into 2 * 1cm specification puts into this and contains antibiotic medicinal liquid, soaked 12 hours under 4 ℃ of conditions, lyophilization, 4 ℃ of preservations promptly obtain the porous biomembrane with medicament slow release function of the present invention.
Embodiment 17
Polyamide 66/year silver (0.5%) and titanium dioxide (5.1%) nano-apatite composite porous biomembrane with embodiment 11 described method preparation oven dry, the gelatine microsphere 50mg that carries the BMP somatomedin that diameter is about 10 μ m is dispersed in the 10ml distilled water, make and contain somatomedin liquid, getting 5 of films that are cut into 2 * 1cm specification puts into and contains somatomedin liquid, vibration 30min, soaked 2 hours under 4 ℃ of conditions, lyophilization, 4 ℃ of preservations promptly obtain the porous biomembrane with induced tissue regeneration function and antibacterial functions of the present invention.
Embodiment 18
Polyamide 66/year silver and nano titania apatite composite material porous biomembrane with embodiment 11 described method preparation oven dry, the 15mg Radix Astragali is dispersed in 10ml and heats up in a steamer in the water, make and contain medicinal liquid, getting 5 of films that are cut into 2 * 1cm specification puts into and contains medicinal liquid, vibration 30min, soaked 2 hours under 4 ℃ of conditions, lyophilization promptly obtains the porous biomembrane with induced tissue regeneration, medicament slow release and antibacterial functions of the present invention.
Embodiment 19
Polyamide 66/year silver and nano titania apatite composite material porous biomembrane with embodiment 11 described method preparation oven dry, 9.5ml adding concentration in the distilled water is 3% chitosan solution 0.5ml, add the 15mg Radix Astragali, disperse to make pastille liquid, get 5 of films that are cut into 2 * 1cm specification and put into and contain medicinal liquid, vibration 30min soaked 2 hours under 4 ℃ of conditions, lyophilization promptly obtains the porous biomembrane with medicament slow release and antibacterial functions of the present invention.
Embodiment 20
Polyamide 66/nano-apatite composite porous biomembrane with embodiment 8 described method preparation oven dry, 9.5ml adding concentration in the distilled water is 5% gelatin solution 0.5ml, add the 15mg Herba Epimedii extract, disperse to make pastille liquid, get 5 of films that are cut into 2 * 1cm specification and put into and contain medicinal liquid, vibration 30min soaked 2 hours under 4 ℃ of conditions, lyophilization promptly obtains the porous biomembrane with medicament slow release function of the present invention.
Embodiment 21
To contain in the slurry of polyamide 66/nano-apatite composite (wherein nano-apatite content is 40%) 4g and add ethanol, making gross mass is 30g, 100 ℃ of stirring conditions refluxed 60 minutes down, make composite become homogeneous thickness film forming liquid, liquid to be filmed is cooled to 30～40 ℃, adds diameter and is about the chitosan microball 200mg that carries berberine of 15 μ m and the BMP that carries that diameter is about 10 μ m
2Gelatine microsphere 100mg, stir 30min, about 2ml film forming liquid is poured into the glass plate upper berth generate film that diameter is 12cm, room temperature is air-dry, marking pen promptly obtains the porous biomembrane with induced tissue regeneration and medicament slow release function of the present invention at the edge labelling positive and negative of film.
Polyamide 66/nano-apatite composite material film is a loose structure, connects mutually between the Kong Yukong, and positive average pore size is about 10～20 μ m, and the reverse side average pore size is about 100～200 μ m.Measure with slide gauge, the thickness of perforated membrane is 0.12mm.
Embodiment 22
To contain in the slurry of polyamide 66/nano-apatite composite (wherein nano-apatite content is 40%) 60g and add ethanol, making gross mass is 100g, 140 ℃ of stirring conditions refluxed 60 minutes down, make composite become mass fraction and be about 60% homogeneous thickness film forming liquid, liquid to be filmed is cooled to 30～40 ℃, about 1.5ml film forming liquid is poured on the glass plate that diameter is 12cm freely sprawls film forming, 40 ℃ of dryings, marking pen is at the edge labelling positive and negative of film, with the deionized water washing by soaking for several times, there is not chloride ion (each soak time was greater than 60 minutes) in the silver nitrate solution check eluent of 1M, 70 ℃ of oven dry promptly make polyamide 66 of the present invention/nano-apatite composite porous biomembrane.
Polyamide 66/nano-apatite the composite material film of preparation is a loose structure, connects mutually between the Kong Yukong, and average pore size is about 60～80 μ m.Measure with slide gauge, the thickness of perforated membrane is 1.2mm.
Claims (10)
1. the biological material film that has loose structure, it is characterized in that being distributed with aperture gradual change form between by the both side surface of the membrane material body of medical polyamide/nano osteoid apatite composite parts the pore structure of mutual perforation, one side at the membrane material body is that the aperture is the dense face of the tiny hole of 0.01～30 μ m, and the another side of film is that the aperture is the loose face of macropore of 30～300 μ m.
2. the biological material film with loose structure as claimed in claim 1 is characterized in that said membrane material body is medical polyamide/nano osteoid apatite composite parts, and wherein the part by weight of nanometer osteoid apatite composition is 1%～70%.
3. the biological material film with loose structure as claimed in claim 2 is characterized in that said membrane material body is medical polyamide/nano osteoid apatite composite parts, and wherein the part by weight of nanometer osteoid apatite composition is 40%～60%.
4. as the described biological material film of one of claim 1 to 3 with loose structure, it is characterized in that the nanometer osteoid apatite composition in the said medical polyamide/nano osteoid apatite composite parts membrane material body is the nanometer osteoid apatite composition that load has inorganic antibacterial components, comprise copper, zinc, silver, lanthanum, cerium, neodymium metal ion and corresponding copper sulfate, copper chloride, zinc sulfate, zinc chloride, silver nitrate, Lanthanum (III) nitrate, cerous nitrate or neodymium nitrate salt compounds in the said inorganic antibacterial composition.
5. the biological material film with loose structure as claimed in claim 1, it is characterized in that going back in the said membrane material body auxiliary activity composition that load has gross weight 0.05%～20%, said auxiliary activity composition is at least a in slow releasing pharmaceutical composition or the tissue growth factor, wherein:
Include antibiotic in the slow releasing pharmaceutical composition, the Radix Astragali, astragaloside, Radix Notoginseng, Radix Notoginseng total glycosides, Radix Salviae Miltiorrhizae, or Herba Epimedii;
Comprise bone morphogenetic protein in the tissue growth factor, transforming growth factor-beta, insulin like growth factor, fibroblast growth factor, basic fibroblast growth factor, vascular endothelial cell growth factor, platelet-derived growth factor, or neoplasm necrosis somatomedin.
6. prepare the described method of claim 1 with loose structure biological material film, it is characterized in that the volatility good solvent with the medical polyamide composition in the selected filmogen is a dispersant, said medical polyamide/nano osteoid apatite composite parts is fully stirred in 50 ℃～140 ℃, after being made for mass fraction and being 5%～60% even thick film forming liquid, be prepared into the film material body, after 20 ℃～90 ℃ dryings, use the deionized water wash after drying.
7. preparation method as claimed in claim 6, the volatility good solvent that it is characterized in that said medical polyamide composition are at least a in methanol, ethanol, the propanol.
8. preparation method as claimed in claim 5, it is characterized in that said dried film material body to be soaked in the said auxiliary activity composition that contains membrane material body gross weight 005%～20%, or the diameter that is loaded with the auxiliary activity composition is in the solution of microsphere of 0.3～100 μ m, makes that load has corresponding auxiliary activity composition in the film material body.
9. preparation method as claimed in claim 5, it is characterized in that and to be scattered in for the auxiliary activity composition of said membrane material body gross weight 005%～20% or the microsphere that is loaded with the auxiliary activity composition mix simultaneously that the back refabrication becomes the film material body in the said film forming liquid, make that load has corresponding auxiliary activity composition in the film material body.
10. preparation method as claimed in claim 8 or 9, it is characterized in that said contain said auxiliary activity composition or be loaded with also contain at least a in the adhesive component that comprises gelatin, Polyethylene Glycol, collagen, chitosan, polyvinyl alcohol hydrogel in the solution of auxiliary activity composition microsphere, said adhesive component consumption is said auxiliary activity composition or is loaded with auxiliary activity composition microspheres solution system weight 0.05%～5%.
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