CN102008751A - Biodegradable stent composite material and preparation method thereof - Google Patents
Biodegradable stent composite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a biodegradable stent composite material and a preparation method thereof. The degradable material has a multi-gradient composite structure, and comprises a matrix made of a medical metal or an alloy thereof, a chemical coupling layer attached to the surface of the matrix, a high polymer transition layer attached to the surface of the chemical coupling layer and a degradable high polymer functional layer fixed on the surface of the high polymer transition layer. The stent composite material has high mechanical property, degradation property and biocompatibility, also can absorb and carry needed therapeutic medicaments, and meets the requirement on clinical treatment. The degradable composite material can be used as stent materials of esophagi, biliary ducts, intestinal tracts, urethrae, tracheae and other non-vessel lumens and blood vessels, and also can be used for manufacturing artificial bones, bone nails, bone connectors, bone sutures, anchors for suture, intervertebral discs, hemostatic clamps, hemostatic forceps, hemostatic plates, hemostatic screws, tissue adhesives, sealants and other medical devices and products.
Description
Technical field
The invention belongs to the medical function material field, relate to a kind of biodegradation prop composite and preparation method thereof.
Background technology
For good/malignant strictures of esophagus, bile duct, intestinal, urethra, trachea etc. and block, traditional Drug therapy and surgical effect are limited, and implant frame becomes a kind of effective minimally-invasive treatment technology in development in recent years, be a kind of fast,, but as retaining intravital " permanent stents ", the medical procedure that the problem that shows is also very effective and comparatively safe, do not control or the disease of refractory has been opened up new treatment approach for traditional operation, improved the existence time limit of tumor patient and cured probability.The widely used support of clinical medicine mainly is Ni/Ti alloy bracket, stainless steel stent, plastic rubber bracket etc. at present.These supports really get involved played aspect the clinical treatment positive remarkably productive: such as implanting long term complications such as back constant pain, foreign body inflammatory reaction, neointimal hyperplasia, advanced thrombus.
Biodegradable stent supports at the mechanics that provides in early days of clinical treatment, finishes the back degradation in vivo in specific treatment cycle, has overcome shortcoming and many complication of permanent stents, becomes the research focus of recent medical profession and materialogy.The research of degraded support at present mainly concentrates on the high-molecular organic material aspect.Li Wentao, thank to build in and reported among the patent ZL 200510104766.5 " preparation method of biodegradable medicine-carrying polymer stock support " with polylactic acid and polycaprolactone and mix by a certain percentage and prepare a kind of carried stent through melt extruding molding.Labinaz M, Stack RS etc. are at J.Interv.Cardiol. (1995,8:395-405) publish an article " Biodegradable stents:the future of interventional cardiology " reported with Poly-L-lactic acid (PLLA) but the macromolecular material preparation self discharge support, in order to the restenosis of treatment percutaneous coronary sacculus postoperative.
The depolymerization support also exists a lot of not enough in clinical practice, the subject matter that exposes has: (1) mechanical support undercapacity, at the support that is inferior to metal material aspect the restriction tube chamber retraction, certain application is mainly arranged aspect angiocarpy bracket at present, but non-vessel lumen such as esophagus, bile duct, intestinal, urethra, trachea need bigger radial support power usually, and pure polymeric material is difficult to meet the demands; (2) in degraded poor controllability, the machine-shaping process thermal degradation takes place easily, along with macromolecular material degraded in vivo, the mechanical property of support obviously descends, and does not satisfy the support requirement, causes taking place displacement and slippage accident; (3) local heat production too much in the polymer degradation in vivo process, the acid degradation product gathers, and causes taking place problems such as tissue inflammation reaction.
In known metal material, magnesium, ferrum and alloy thereof are the materials that can degrade in human body fluid, have good mechanical performance and minimum degraded side effect, be verified and can be used for medical material, and magnesium and ferrum all are indispensable important nutrients in the human body.Peuster M etc. are at periodical Heart (2001,86:563-569) publish an article " A novel approach to temporary stenting:degradable cardiovascular stents produced from corrodible metal-results 6-18 months after implantation into New Zealand white rabbits ", reported the test situation of a kind of retort stand (iron content＞99.8%) in the New Zealand white rabbit descending aorta.Heublein B etc. are at periodical Heart (2003,89:651-656) publish an article " Biocorrosion of magnesium alloys:a new principle in cardiovascular implant technology ", reported a kind of making of magnesium alloy bracket and the pig tremulous pulse of being in result of the test.
Above magnesium, ferrum and alloy thereof are to cause the international degradable medical metal material of paying attention in recent years, and present research is only limited to the arteries support, but also seldom relates at aspects such as esophagus, bile duct, intestinal, urethra, tracheas.And digestion, urinary system, all kinds of tube chambers of respiratory system narrow, block in addition the sickness rate of canceration at the clinical more vast scale that occupies, therefore research is applicable to that the practical biodegradable stent in these fields has very big urgency and clinical meaning.
But magnesium, ferrum and alloy thereof are used alone as biomedical material and also have some problems, mainly are:
(1) chemical property is too active in electrolyte environment, and decay resistance is relatively poor, and degradation rate is too fast, therefore must can have use value by suitable surface treatment;
(2) surface of metal material does not have organo-functional group, is difficult to absorb and the appendix curative drug, so be necessary to introduce the organic polymer functional layer on its surface.
Summary of the invention
The objective of the invention is to overcome the deficiency that existing timbering material exists, propose the compound degraded timbering material of a kind of many gradients.Described prop composite has excellent mechanical property, degradation property and bio-compatible performance, can also absorb the curative drug required with appendix simultaneously, satisfies the needs of clinical treatment.Described prop composite is preferably used as the timbering material of non-vessel lumen such as esophagus, bile duct, intestinal, urethra, trachea.
Another object of the present invention is the preparation method that proposes above-mentioned degraded prop composite.
The invention provides following technical scheme:
A kind of biodegradation prop composite, the composite construction with many gradients comprises: the matrix that is made of medical metal or its alloy; Invest the chemical coupling layer of described matrix surface; Invest the polymeric transition layer of described chemical coupling laminar surface; Be fixed in the degradable macromolecule functional layer of described polymeric transition laminar surface.
Wherein, described medical metal or its alloy, preferably magnesium, ferrous metal or its alloy.Described magnesium metal or its alloy, the preferably magnesium alloy that becomes greater than one or more system combinations of 50% magnalium series alloy, magnesium manganese series alloy, magnesium zinc series alloy, magnesium zirconium series alloy, magnesium rare earth metal alloy, magnesium lithium series alloy, magnesium calcium series alloy or magnesium silver series alloy from: pure magnesium (99.9%), content of magnesium.Described ferrous metal or its alloy, preferably certainly: pure iron or iron content the alloy 50% or more of iron-holder more than 99.9%.
Wherein, the described chemical coupling layer that invests matrix surface, the silane that preferably has organo-functional group, in its molecular structure, have simultaneously: (1) can with inorganic material chemically combined reactive group, described group is preferably from chloro, methoxyl group, ethyoxyl, methoxy ethoxy or acetoxyl group; And (2) can with organic material chemically combined reactive group, described group is preferably from vinyl, amino, epoxy radicals, methacryloxy, sulfydryl or urea groups.
Be applicable to silane coupler of the present invention, preferably certainly: VTES, vinyl silane tri-butyl peroxy, aminoethyl aminopropyl trimethoxysilane, 3-methacryloxypropyl trimethoxy silane, aminopropyl triethoxysilane, 3-glycidyl ether oxygen propyl trimethoxy silicane, vinyl silane triisopropoxide or its two or more composition.
Wherein, the polymeric transition layer of described chemical coupling laminar surface, preferred polybutylcyanoacrylate family macromolecule.Described polybutylcyanoacrylate, comprise monomeric homopolymer of a series of cyanoacrylates and copolymer, described homopolymer and copolymer are preferably from paracyanogen base acrylic acid methyl ester., paracyanogen base ethyl acrylate, paracyanogen base butyl acrylate, paracyanogen base 1-Octyl acrylate, paracyanogen base butyl acrylate-monooctyl ester copolymer or its two or more composition.Described polybutylcyanoacrylate family macromolecule, its preferred chemical constitution expression formula is as follows:
Wherein, n=1～18, C
nH
2n+1Be C
1～C
18Various isomer alkyl, particularly C
1～C
8Various isomer alkyl; M=1～18, G
mH
2m+1Be C
1～C
18Various isomer alkyl, particularly C
1～C
8Various isomer alkyl.
Wherein, x=2～1000, y=2～1000.
Need to prove that following formula only is two kinds of monomeric copolymerization structures of cyanoacrylate of expression, for the professional of polymeric material field, can also be generalized to monomeric copolymerization situation more than three kinds and three kinds fully.
Wherein, described degraded macromolecular functional layer, the known degraded macromolecular material of technical staff that comprises field of polymer technology, described degraded macromolecular material is preferably from: polylactic acid (poly-hydracrylic acid, PLA), polyglycolic acid (PGA), polylactic acid-glycolic guanidine-acetic acid copolymer (PLG), polycaprolactone (PCL), paracyanogen base acrylic acid methyl ester., paracyanogen base ethyl acrylate, paracyanogen base butyl acrylate, paracyanogen base 1-Octyl acrylate, the Polyalkylcyanoacrylanano copolymer, poly hydroxy ethyl acrylate, polyvinyl pyrrolidone, poe, the composition of one or more in the synthesized degradable macromolecular materials such as polyamino acid, the molecular weight of described synthesized degradable macromolecular material is preferably 1,000-1, between 000,000.
Wherein, described degradable high polymer material also can be preferably from the composition of one or more in the natural degradable macromolecular materials such as collagen protein, gelatin, agar, glucosan, chitosan, hyaluronic acid, the molecular weight of described natural degradable macromolecular material is preferably 1,000-1, between 000,000.
Technical scheme of the present invention provides a kind of preparation method of biodegradable stent composite simultaneously, and described method preferably contains following steps simultaneously:
(1) surface clean of metal alloy;
(2) surface preparation of metal alloy;
(3) growth of alloy surface chemical coupling layer;
(4) polymerization of coupling layer surface polymeric transition layer;
(5) graft reaction of transition zone superficial degradation functional polymer.
Wherein, the surface clean of described step (1) metal alloy, preferable methods is: carried out each 5-30 of ultrasonic cleaning minute with acetone, dehydrated alcohol, deionized water successively, preferred 10-20 minute, remove surface and oil contaminant; Polish step by step with 280～1000# abrasive paper for metallograph, use deionized water and dehydrated alcohol ultrasonic cleaning 5-30 minute respectively, preferred 10-20 minute, dry then; In nitric acid-methanol solution of 10%, soak, carry out chemical polishing, take out the back and rinse well with deionized water.
Wherein, the surface preparation of described step (2) metal alloy, adopt the known certain methods of professional person of Metal Material Science or mechanical field to carry out, preferably certainly: chromate conversion embrane method, phosphoric acid-potassium permanganate conversion embrane method, stannate conversion embrane method, rare-earth conversion coatings method, cobaltatess conversion embrane method, fluoride transform embrane method, biomimetic method deposited hydroxyl apatite, processes of carbonate treatment, alkali heat treatment, anodic oxidation, plasma micro-arc oxidation, shot peening strengthening, finish rolling hardening, Zn is ion implantation or Ti is ion implantation.
The further preferred fluorinated thing of the present invention transforms embrane method, preferable methods is: the HF acid solution of preparation 2-40%, the preferred 20-30% of concentration is with metal alloy immersion treatment 24 hours in solution, then with deionized water and dehydrated alcohol ultrasonic cleaning 10 minutes and dry respectively.
Wherein, the growth of described step (3) alloy surface chemical coupling layer, preferable methods is: with one or more the combination in silane coupling agent vinyl triethoxysilane, vinyl silane tri-butyl peroxy, aminoethyl aminopropyl trimethoxysilane, 3-methacryloxypropyl trimethoxy silane, aminopropyl triethoxysilane, 3-glycidyl ether oxygen propyl trimethoxy silicane, the vinyl silane triisopropoxide, be mixed with the solution that concentration is 0.1-10%, the preferred 0.5-1% of described concentration; The mixture of solvent for use preferred water, alcohol or water/alcohol, described solvent is ethanol, isopropyl alcohol more preferably; Preferred acetic acid is made catalyst, and pH value is transferred to 3.5-5.5; Be dipped in 20-60 second in the solution at the metal alloy surface brushing solution of silane of cleaning or with sample, treat its surface drying after, put into the baking oven heat ageing, temperature 80-120 ℃, time 10-60 minute, cool to room temperature then with the furnace.
Wherein, the polymerization of described step (4) coupling layer surface polymeric transition layer preferably adopts anionic polymerisation technology to carry out.From molecular structure, be connected with strong electron-withdrawing group group on the double-linked carbon of cyanoacrylate monomer, two bonding electron cloud density are reduced, monomer thereby show strong electrophilicity, very high reactivity is arranged, in reagent such as water, alcohol, weak base, polyreaction fast can take place.Polyreaction formula following (is example with the Tisuacryl):
Preferable methods is: deionized water, ionic emulsifying agent, nonionic emulsifier are mixed with aqueous emulsion, described aqueous emulsion concentration is preferably 1-3%, the preferred DBSA of described ionic emulsifying agent, the preferred polysorbate of described nonionic emulsifier, wherein the ratio of ionic emulsifying agent and nonionic emulsifier is preferably 6: 1-2: 1; Add water soluble starter, preferred potassium peroxydisulfate of described initiator or Ammonium persulfate., the preferred 0.1-2% of concentration, the acid-base value of adjusting system is preferably pH1-2; Under stirring, 500-800rpm drips the cyanoacrylate monomer then, monomer is preferably from the blending constituent of one or more in methyl 2-cyanoacrylate, cyanacrylate, Tisuacryl, the octyl 2-cyanoacrylate, total monomer is preferably 2-40%, at room temperature react preferred 10-120 of response time minute.
Wherein, the graft reaction of described step (5) transition zone superficial degradation functional polymer, preferable methods is: the degradability polymer, described polymer is preferably from polylactic acid, polyglycolic acid, polylactic acid-glycolic guanidine-acetic acid copolymer, polycaprolactone, paracyanogen base acrylic acid methyl ester., paracyanogen base ethyl acrylate, paracyanogen base butyl acrylate, paracyanogen base 1-Octyl acrylate, the Polyalkylcyanoacrylanano copolymer, poly hydroxy ethyl acrylate, polyvinyl pyrrolidone, poe, polyamino acid, collagen protein, gelatin, agar, glucosan, chitosan, hyaluronic acid or two or more blending constituents, the molecular weight of described polymer is preferably 1,000-1,000, between 000, described polymer dissolution is in coordinative solvent, described solvent is preferably from deionized water, ethanol, acetone, butanone, Ketohexamethylene, isopropyl alcohol, butanols, ethyl acetate, butyl acetate, chloroform or acetonitrile, the concentration of polymer solution is preferably 0.1-40%, the preferred 50-95 of reaction temperature ℃, preferred 10-200 of response time minute, use ethanol at last successively, deionized water is clean with the sample rinsing, vacuum drying, sealing is preserved.
Disclosed a kind of biodegradation prop composite of technique scheme and preparation method thereof one of has the following advantages at least, preferably has the following advantages simultaneously:
(1) many gradient scaffoldings composite of the present invention has excellent mechanical property, degradation property and bio-compatible performance, simultaneously can also absorb the curative drug required with appendix, be particularly suitable for non-vessel lumen such as esophagus, bile duct, intestinal, urethra, trachea narrow, block or tumor treatment;
(2) degradation rate of prop composite of the present invention has adjustable, controllability, and a plurality of levels such as the kind of the composition of the composition of the thickness of corrosion-resistant coating that can be by metal base surface and density, silane coupled layer and structure, polymeric transition layer and molecular weight, degradable macromolecule functional layer and molecular weight are regulated and control;
(3) surface of prop composite of the present invention has the degradable macromolecule functional layer, its inherent abundant organo-functional group can greatly improve the kind and the quantity of the entrained medicine of support, and can improve the fixed stability of medicine, can realize fixing different medicine and doses by adjusting factors such as surperficial high molecular kind, molecular weight, thickness.
(4) preparation method of biodegradable stent composite of the present invention is simple and practical, raw material is easy to get, cost is lower, is easy to realize suitability for industrialized production, can be non-vessel lumen such as esophagus, bile duct, intestinal, urethra, trachea narrow, block or tumor is opened up new therapeutic scheme.
Described degrading composite of technique scheme and preparation method thereof is except that can be used for making the intraluminal stents such as esophagus, bile duct, intestinal, urethra, trachea, blood vessel, also can be used for making other medical devices or goods, described device or goods preferably from: artificial bone, nail, bone connector, bone suture, stitching with anchor, vertebra basin, hemostatic clamp, mosquito forceps, hemostasis plate, hemostasis screw, tissue adhesive or sealant.
Description of drawings
Accompanying drawing 1 is the support sketch map of biological degradable composite material of the present invention
Accompanying drawing 2 is that A portion in the accompanying drawing 1 is at the multilamellar level composite construction sketch map perpendicular to the I direction
Reference numeral is as follows:
1. degradable medical metallic matrix, 2. silane chemistry coupling layer, 3. polymeric transition layer, 4. degradable macromolecule functional layer.
The specific embodiment
Below in conjunction with drawings and Examples, technical scheme of the present invention is described in further details, following examples are used to illustrate the present invention, limit the scope of the invention but be not used in.
A kind of biodegradation prop composite of the present invention, its support sketch map as shown in Figure 1, its multilamellar level composite construction as shown in Figure 2, described composite construction comprises: the matrix 1 that medical metal or its alloy constitute, invest the chemical coupling layer 2 on described matrix 1 surface, invest the polymeric transition layer 3 on described chemical coupling layer 2 surface, and the degradable macromolecule functional layer 4 that is fixed in described polymeric transition layer 3 surface.
Described medical metal or its alloy substrate 1, preferably magnesium, ferrous metal or its alloy, described magnesium metal or its alloy, the preferably magnesium alloy that becomes greater than one or more system combinations of 50% magnalium series alloy, magnesium manganese series alloy, magnesium zinc series alloy, magnesium zirconium series alloy, magnesium rare earth metal alloy, magnesium lithium series alloy, magnesium calcium series alloy or magnesium silver series alloy from: pure magnesium (99.9%), content of magnesium; Described ferrous metal or its alloy, preferably certainly: pure iron or iron content the alloy 50% or more of iron-holder more than 99.9%.
The described chemical coupling layer 2 that invests matrix 1 surface, the silane that preferably has organo-functional group, preferably certainly: the composition of one or more in VTES, vinyl silane tri-butyl peroxy, aminoethyl aminopropyl trimethoxysilane, 3-methacryloxypropyl trimethoxy silane, aminopropyl triethoxysilane, 3-glycidyl ether oxygen propyl trimethoxy silicane, the vinyl silane triisopropoxide.Metallic matrix 1 is after silane treatment, form one deck Silan-based Thin Films on its surface, this rete not only has certain antiseptic property, and the chemical coupling effect of silylation layer can improve the bond strength of polymeric transition layer 3 and degradable macromolecule functional layer 4 and metallic matrix 1 effectively.
The described polymeric transition layer 3 that invests chemical coupling layer 2 surface, have excellent biocompatibility and vivo degradation, preferably certainly: the compositions of one or more in paracyanogen base acrylic acid methyl ester., paracyanogen base ethyl acrylate, paracyanogen base butyl acrylate, paracyanogen base 1-Octyl acrylate, the paracyanogen base butyl acrylate-monooctyl ester copolymer.The cyano functional group that polymeric transition layer 3 contains has high reaction activity, can greatly improve degraded macromolecular functional layer 4 and the firm degree of combining of chemical coupling layer 2, and the mode of general surface introducing degraded macromolecular layer 4 is cladding process or dip coating, mainly be a kind of physical absorption combination, come off easily.
The described degradable macromolecule functional layer 4 that is fixed in polymeric transition layer 3 surface, preferably certainly: polylactic acid (poly-hydracrylic acid, PLA), polyglycolic acid (PGA), polylactic acid-glycolic guanidine-acetic acid copolymer (PLG), polycaprolactone (PCL), paracyanogen base acrylic acid methyl ester., paracyanogen base ethyl acrylate, paracyanogen base butyl acrylate, paracyanogen base 1-Octyl acrylate, the Polyalkylcyanoacrylanano copolymer, poly hydroxy ethyl acrylate, polyvinyl pyrrolidone, poe, polyamino acid, collagen protein, gelatin, agar, glucosan, chitosan, the composition of one or more in the hyaluronic acid.Because the chemism reaction of chemical coupling layer 2 and polymeric transition layer 3 is arranged, and degradable macromolecule functional layer 4 is tight and firm in the combination on metallic matrix 1 surface, is not easy to come off.
Described degrading composite of the above specific embodiment and preparation method thereof is except that can be used for making the intraluminal stents such as esophagus, bile duct, intestinal, urethra, trachea, blood vessel, also can be used for making other medical devices or goods, described device or goods preferably from: artificial bone, nail, bone connector, bone suture, stitching with anchor, vertebra basin, hemostatic clamp, mosquito forceps, hemostasis plate, hemostasis screw, tissue adhesive or sealant.
Provide the several preferred embodiments of preparation method of biodegradation prop composite of the present invention below, two Comparative Examples are provided simultaneously.
(1) selects for use purity greater than high-purity magnesium metal of 99.9%, carried out ultrasonic cleaning each 20 minutes with acetone, dehydrated alcohol, deionized water successively, remove surface and oil contaminant; Polish step by step with 280～1000# abrasive paper for metallograph, use deionized water and dehydrated alcohol ultrasonic cleaning 20 minutes then respectively, dry then; In nitric acid-methanol solution of 10%, soak, carry out chemical polishing, take out the back and rinse well with deionized water.
(2) preparation 30% HF acid solution with magnesium metal immersion treatment 24 hours in solution, with deionized water and dehydrated alcohol ultrasonic cleaning 10 minutes and dry respectively, forms medical metal matrix 1 then.
(3) compound concentration is VTES/alcoholic solution of 1%, adds acetic acid and makes catalyst, and pH value is transferred to 3.5-5.5; Sample was dipped in the solution 60 seconds, treat its surface drying after, put into the baking oven heat ageing, 80 ℃ of temperature, 60 minutes time, cool to room temperature then with the furnace, form silane chemistry coupling layer 2.
(4) deionized water, DBSA, polysorbate are mixed with 1% aqueous emulsion, wherein the ratio of DBSA and polysorbate is 2: 1; The potassium peroxydisulfate that adds 0.5% concentration, the pH value of adjusting system is between 1-2; Drip Tisuacryl then under 800rpm stirs, total monomer 40% was at room temperature reacted 60 minutes, formed polymeric transition layer 3.
(5) polylactic acid (molecular weight 300,000), polycaprolactone (molecular weight 60,000) are dissolved in the chloroform in 2: 1 ratios, prepare the polymer solution of 30% concentration, under 80 ℃ temperature, react then, 4 hours time, form degraded macromolecular functional layer 4, use ethanol, deionized water that the sample rinsing is clean at last successively, vacuum drying, sealing is preserved.
Prepared degrading composite mechanical strength height, good toughness, cell-cytotoxic reaction are 1 grade, good biocompatibility, in simulated body fluid weightless slowly and evenly, the high molecular functional layer does not have and comes off.
Embodiment 2
(1) selecting content of magnesium for use is 85% magnesium zircaloy, carries out ultrasonic cleaning each 20 minutes with acetone, dehydrated alcohol, deionized water successively, removes surface and oil contaminant; Polish step by step with 280～1000# abrasive paper for metallograph, use deionized water and dehydrated alcohol ultrasonic cleaning 20 minutes then respectively, dry then; In nitric acid-methanol solution of 10%, soak, carry out chemical polishing, take out the back and rinse well with deionized water.
(2) preparation 40% HF acid solution is with magnesium alloy immersion treatment 24 hours in solution, then with deionized water and dehydrated alcohol ultrasonic cleaning 10 minutes and dry respectively.
(3) compound concentration is aminopropyl triethoxysilane/aqueous isopropanol of 1%, adds acetic acid and makes catalyst, and pH value is transferred to 3.5-5.5; Sample was dipped in the solution 60 seconds, treat its surface drying after, put into the baking oven heat ageing, 85 ℃ of temperature, cool to room temperature with the furnace then at 60 minutes time.
(4) deionized water, DBSA, polysorbate are mixed with 1% aqueous emulsion, wherein the ratio of DBSA and polysorbate is 2: 1; The potassium peroxydisulfate that adds 0.5% concentration, the pH value of adjusting system is between 1-2; Drip Tisuacryl then under 800rpm stirs, total monomer 40% was at room temperature reacted 60 minutes.
(5) polylactic acid (molecular weight 300,000), polycaprolactone (molecular weight 60,000) are dissolved in the chloroform in 2: 1 ratios, prepare the polymer solution of 30% concentration, under 80 ℃ temperature, react then, 4 hours time, use ethanol, deionized water that the sample rinsing is clean at last successively, vacuum drying, sealing is preserved.
Prepared degrading composite mechanical strength height, good toughness, cell-cytotoxic reaction are 1 grade, good biocompatibility, in simulated body fluid weightless slowly and evenly, the high molecular functional layer does not have and comes off.
(1) selecting content of magnesium for use is 95% magnesium-manganese alloy, carries out ultrasonic cleaning each 20 minutes with acetone, dehydrated alcohol, deionized water successively, removes surface and oil contaminant; Polish step by step with 280～1000# abrasive paper for metallograph, use deionized water and dehydrated alcohol ultrasonic cleaning 20 minutes then respectively, dry then; In nitric acid-methanol solution of 10%, soak, carry out chemical polishing, take out the back and rinse well with deionized water.
(2) preparation 35% HF acid solution is with magnesium alloy immersion treatment 24 hours in solution, then with deionized water and dehydrated alcohol ultrasonic cleaning 10 minutes and dry respectively.
(3) compound concentration is VTES/alcoholic solution of 2%, adds acetic acid and makes catalyst, and pH value is transferred to 3.5-5.5; Sample was dipped in the solution 60 seconds, treat its surface drying after, put into the baking oven heat ageing, 90 ℃ of temperature, cool to room temperature with the furnace then at 60 minutes time.
(4) deionized water, DBSA, polysorbate are mixed with 1.5% aqueous emulsion, wherein the ratio of DBSA and polysorbate is 3: 1; The potassium peroxydisulfate that adds 1% concentration, the pH value of adjusting system is between 1-2; Drip Tisuacryl then under 800rpm stirs, total monomer 35% was at room temperature reacted 60 minutes.
(5) polylactic acid-glycolic guanidine-acetic acid copolymer (molecular weight 200,000) is dissolved in the butanone, prepares the polymer solution of 20% concentration, under 85 ℃ temperature, react then, 6 hours time, use ethanol, deionized water that the sample rinsing is clean at last successively, vacuum drying, sealing is preserved.
Prepared degrading composite mechanical strength height, good toughness, cell-cytotoxic reaction are 1 grade, good biocompatibility, in simulated body fluid weightless slowly and evenly, the high molecular functional layer does not have and comes off.
Embodiment 4
(1) selecting iron content for use is 99.99% pure iron metal, carries out ultrasonic cleaning each 30 minutes with acetone, dehydrated alcohol, deionized water successively, removes surface and oil contaminant; Polish step by step with 280～1000# abrasive paper for metallograph, use deionized water and dehydrated alcohol ultrasonic cleaning 30 minutes then respectively, dry then; In nitric acid-methanol solution of 10%, soak, carry out chemical polishing, take out the back and rinse well with deionized water.
(2) preparation 30% HF acid solution is with ferrous metal immersion treatment 24 hours in solution, then with deionized water and dehydrated alcohol ultrasonic cleaning 10 minutes and dry respectively.
(3) compound concentration is VTES/alcoholic solution of 2%, adds acetic acid and makes catalyst, and pH value is transferred to 3.5-5.5; Sample was dipped in the solution 60 seconds, treat its surface drying after, put into the baking oven heat ageing, 90 ℃ of temperature, cool to room temperature with the furnace then at 60 minutes time.
(4) deionized water, DBSA, polysorbate are mixed with 1.5% aqueous emulsion, wherein the ratio of DBSA and polysorbate is 3: 1; The potassium peroxydisulfate that adds 1% concentration, the pH value of adjusting system is between 1-2; Drip Tisuacryl then under 800rpm stirs, total monomer 35% was at room temperature reacted 60 minutes.
(5) polylactic acid-glycolic guanidine-acetic acid copolymer (molecular weight 200,000) is dissolved in the butanone, prepares the polymer solution of 20% concentration, under 85 ℃ temperature, react then, 6 hours time, use ethanol, deionized water that the sample rinsing is clean at last successively, vacuum drying, sealing is preserved.
Prepared degrading composite mechanical strength height, good toughness, cell-cytotoxic reaction are 1 grade, good biocompatibility, in simulated body fluid weightless slowly and evenly, the high molecular functional layer does not have and comes off.
Comparative Examples 1
(1) selecting content of magnesium for use is 95% magnesium-manganese alloy, carries out ultrasonic cleaning each 20 minutes with acetone, dehydrated alcohol, deionized water successively, removes surface and oil contaminant; Polish step by step with 280～1000# abrasive paper for metallograph, use deionized water and dehydrated alcohol ultrasonic cleaning 20 minutes then respectively, dry then; In nitric acid-methanol solution of 10%, soak, carry out chemical polishing, take out the back and rinse well with deionized water.
(2) preparation 35% HF acid solution is with magnesium alloy immersion treatment 24 hours in solution, then with deionized water and dehydrated alcohol ultrasonic cleaning 10 minutes and dry respectively.
(3) deionized water, DBSA, polysorbate are mixed with 1.5% aqueous emulsion, wherein the ratio of DBSA and polysorbate is 3: 1; The potassium peroxydisulfate that adds 1% concentration, the pH value of adjusting system is between 1-2; Drip Tisuacryl then under 800rpm stirs, total monomer 35% was at room temperature reacted 60 minutes.
(4) polylactic acid-glycolic guanidine-acetic acid copolymer is dissolved in the butanone, prepares the polymer solution of 20% concentration, under 85 ℃ temperature, react then, 6 hours time, use ethanol, deionized water that the sample rinsing is clean at last successively, vacuum drying, sealing is preserved.
Prepared degrading composite mechanical strength height, good toughness, cell-cytotoxic reaction is 1 grade, good biocompatibility, but weight loss rate is very fast in simulated body fluid, and non-uniform corrosion takes place, the high molecular functional layer has obscission, shows that the introducing of chemical coupling layer 2 and chemism thereof can obviously promote polymeric transition layer 3 and high molecular functional layer 4 fixing on metallic matrix 1 surface.
Comparative Examples 2
(1) selecting iron content for use is 99.99% pure iron metal, carries out ultrasonic cleaning each 30 minutes with acetone, dehydrated alcohol, deionized water successively, removes surface and oil contaminant; Polish step by step with 280～1000# abrasive paper for metallograph, use deionized water and dehydrated alcohol ultrasonic cleaning 30 minutes then respectively, dry then; In nitric acid-methanol solution of 10%, soak, carry out chemical polishing, take out the back and rinse well with deionized water.
(2) preparation 30% HF acid solution is with ferrous metal immersion treatment 24 hours in solution, then with deionized water and dehydrated alcohol ultrasonic cleaning 10 minutes and dry respectively.
(3) compound concentration is VTES/alcoholic solution of 2%, adds acetic acid and makes catalyst, and pH value is transferred to 3.5-5.5; Sample was dipped in the solution 60 seconds, treat its surface drying after, put into the baking oven heat ageing, 90 ℃ of temperature, cool to room temperature with the furnace then at 60 minutes time.
(4) polylactic acid-glycolic guanidine-acetic acid copolymer is dissolved in the butanone, prepares the polymer solution of 20% concentration, under 85 ℃ temperature, react then, 6 hours time, use ethanol, deionized water that the sample rinsing is clean at last successively, vacuum drying, sealing is preserved.
Prepared degrading composite mechanical strength height, good toughness, cell-cytotoxic reaction is 1 grade, good biocompatibility, but weight loss rate is very fast in simulated body fluid, and non-uniform corrosion takes place, the high molecular functional layer has obscission, shows that the introducing of polymeric transition layer 3 and chemism thereof can obviously promote high molecular functional layer 4 fixing on metallic matrix 1 surface.
Should be pointed out that the above specific embodiment can make those skilled in the art more fully understand the innovation invention, but limit the innovation invention never in any form.Therefore; invention has been described in detail to the innovation although this description is with reference to accompanying drawing; but; those skilled in the art are to be understood that; all do not break away from the spirit of the innovation invention and the technical scheme and the improvement thereof of scope, and it all should be encompassed in the middle of the protection domain of the innovation patent of invention.
Claims (13)
1. a biodegradation prop composite is characterized in that, described composite comprises:
The matrix that constitutes by medical metal or its alloy;
Invest the chemical coupling layer of described matrix surface;
Invest the polymeric transition layer of described chemical coupling laminar surface;
Be fixed in the degradable macromolecule functional layer of described polymeric transition laminar surface.
2. a kind of biodegradation prop composite as claimed in claim 1, it is characterized in that, described medical metal or its alloy, preferably magnesium, ferrous metal or its alloy, described magnesium metal or its alloy, preferably certainly: pure magnesium (99.9%), content of magnesium are greater than the silver-colored series alloy of 50% magnalium series alloy, magnesium manganese series alloy, magnesium zinc series alloy, magnesium zirconium series alloy, magnesium rare earth metal alloy, magnesium lithium series alloy, magnesium calcium series alloy or magnesium, described ferrous metal or its alloy, preferably certainly: pure iron or iron content the alloy 50% or more of iron-holder more than 99.9%.
3. a kind of biodegradation prop composite as claimed in claim 1, it is characterized in that, the described chemical coupling layer that invests matrix surface, the silane that preferably has organo-functional group, in its molecular structure, have simultaneously: (1) can with inorganic material chemically combined reactive group, described group is preferably from chloro, methoxyl group, ethyoxyl, methoxy ethoxy or acetoxyl group; And (2) can with the chemically combined reactive group of organic material, described group is preferably from vinyl, amino, epoxy radicals, methacryloxy, sulfydryl or urea groups, described chemical coupling layer, preferably certainly: VTES, vinyl silane tri-butyl peroxy, aminoethyl aminopropyl trimethoxysilane, 3-methacryloxypropyl trimethoxy silane, aminopropyl triethoxysilane, 3-glycidyl ether oxygen propyl trimethoxy silicane or vinyl silane triisopropoxide.
4. a kind of biodegradation prop composite as claimed in claim 1 is characterized in that, described polymeric transition layer, and preferred polybutylcyanoacrylate family macromolecule, described polybutylcyanoacrylate family macromolecule, its preferred chemical constitution expression formula is as follows:
Wherein, n=1～18, C
nH
2n+1Be C
1～C
18Various isomer alkyl, particularly C
1～C
8Various isomer alkyl; M=1～18, C
mH
2m+1Be C
1～C
18Various isomer alkyl, particularly C
1～C
8Various isomer alkyl;
Wherein, x=2～1000, y=2～1000;
Described polybutylcyanoacrylate family macromolecule, preferably certainly: paracyanogen base acrylic acid methyl ester., paracyanogen base ethyl acrylate, paracyanogen base butyl acrylate, paracyanogen base 1-Octyl acrylate or paracyanogen base butyl acrylate-monooctyl ester copolymer.
5. a kind of biodegradation prop composite as claimed in claim 1, it is characterized in that, described degraded macromolecular functional layer, preferably certainly: polylactic acid, polyglycolic acid, polylactic acid-glycolic guanidine-acetic acid copolymer, polycaprolactone, paracyanogen base acrylic acid methyl ester., paracyanogen base ethyl acrylate, paracyanogen base butyl acrylate, paracyanogen base 1-Octyl acrylate, Polyalkylcyanoacrylanano copolymer, poly hydroxy ethyl acrylate, polyvinyl pyrrolidone, poe, polyamino acid, collagen protein, gelatin, agar, glucosan, chitosan or hyaluronic acid.
6. the preparation method of a biodegradation prop composite is characterized in that, described preparation method preferably comprises following steps simultaneously:
(1) surface clean of metal alloy;
(2) surface preparation of metal alloy;
(3) growth of alloy surface chemical coupling layer;
(4) polymerization of coupling layer surface polymeric transition layer;
(5) graft reaction of transition zone superficial degradation functional polymer.
7. the preparation method of a kind of biodegradation prop composite as claimed in claim 6, it is characterized in that, the surface clean of described metal alloy, method for optimizing is: carried out each 5-30 of ultrasonic cleaning minute with acetone, dehydrated alcohol, deionized water successively, preferred 10-20 minute, remove surface and oil contaminant; Polish step by step with 280～1000# abrasive paper for metallograph, use deionized water and dehydrated alcohol ultrasonic cleaning 5-30 minute respectively, preferred 10-20 minute, dry then; In nitric acid-methanol solution of 10%, soak, carry out chemical polishing, take out the back and rinse well with deionized water.
8. the preparation method of a kind of biodegradation prop composite as claimed in claim 6, it is characterized in that, the surface preparation of described metal alloy, method for optimizing is: the chromate conversion embrane method, phosphoric acid-potassium permanganate transforms embrane method, stannate transforms embrane method, the rare-earth conversion coatings method, cobaltatess transform embrane method, fluoride transforms embrane method, the biomimetic method deposited hydroxyl apatite, processes of carbonate treatment, the alkali heat treatment, anodic oxidation, plasma micro-arc oxidation, shot peening strengthening, finish rolling hardening, Zn is ion implantation or Ti is ion implantation, more preferably fluoride transforms embrane method, method for optimizing is: the HF acid solution of preparation 2-40%, the preferred 20-30% of concentration, with metal alloy immersion treatment 24 hours in solution, then with deionized water and dehydrated alcohol ultrasonic cleaning 10 minutes and dry respectively.
9. the preparation method of a kind of biodegradation prop composite as claimed in claim 6, it is characterized in that, the growth of described alloy surface chemical coupling layer, method for optimizing is: with one or more the combination in the described silane coupler of claim 3, be mixed with the solution that concentration is 0.1-10%, the preferred 0.5-1% of described concentration; The mixture of solvent for use preferred water, alcohol or water/alcohol, more preferably ethanol, isopropyl alcohol; Preferred acetic acid is made catalyst, and pH value is transferred to 3.5-5.5; Be dipped in 20-60 second in the solution at the metal alloy surface brushing solution of silane of cleaning or with sample, treat its surface drying after, put into the baking oven heat ageing, temperature 80-120 ℃, time 10-60 minute, cool to room temperature then with the furnace.
10. the preparation method of a kind of biodegradation prop composite as claimed in claim 6, it is characterized in that, the polymerization of described coupling layer surface polymeric transition layer, the preferred anionic polymerisation technology that adopts is carried out, preferred method is: with deionized water, ionic emulsifying agent, nonionic emulsifier is mixed with aqueous emulsion, described aqueous emulsion concentration is preferably 1-3%, the preferred DBSA of described ionic emulsifying agent, the preferred polysorbate of described nonionic emulsifier, wherein the ratio of ionic emulsifying agent and nonionic emulsifier is preferably 6: 1-2: 1; Add water soluble starter, preferred potassium peroxydisulfate of described initiator or Ammonium persulfate., the preferred 0.1-2% of concentration, the acid-base value of adjusting system is preferably pH 1-2; Drip the described cyanoacrylate monomer of claim 4 then under 500-800rpm stirs, total monomer is preferably 2-40%, at room temperature reacts preferred 10-120 of response time minute.
11. the preparation method of a kind of biodegradation prop composite as claimed in claim 6, it is characterized in that, the graft reaction of described transition zone superficial degradation functional polymer, preferable methods is: with the described degradability polymer dissolution of claim 5 in coordinative solvent, described solvent is preferably from deionized water, ethanol, acetone, butanone, Ketohexamethylene, isopropyl alcohol, butanols, ethyl acetate, butyl acetate, chloroform or acetonitrile, the concentration of polymer solution is preferably 0.1-40%, the preferred 50-95 of reaction temperature ℃, preferred 10-200 of response time minute, use ethanol at last successively, deionized water is clean with the sample rinsing, vacuum drying, sealing is preserved.
12. intraluminal stents such as esophagus, bile duct, intestinal, urethra, trachea or blood vessel that obtained by each described biological degradable composite material of claim 1-11 and preparation method thereof, and artificial bone, nail, bone connector, bone suture, stitching are with anchor, vertebra basin, hemostatic clamp, mosquito forceps, hemostasis plate, medical device or goods such as hemostasis screw, tissue adhesive or sealant.
13. each described degrading composite of claim 1-5 is as the purposes of intraluminal stents such as esophagus, bile duct, intestinal, urethra, trachea or blood vessel, and artificial bone, nail, bone connector, bone suture, stitching are with the purposes of medical device such as anchor, vertebra basin, hemostatic clamp, mosquito forceps, hemostasis plate, hemostasis screw, tissue adhesive or sealant or goods.
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