CN107778446A

CN107778446A - Degradation time is controllable, the adjustable medical degradable polyurethane of elongation at break

Info

Publication number: CN107778446A
Application number: CN201710971002.9A
Authority: CN
Inventors: 不公告发明人
Original assignee: Circle Holds Biological Medicine Wuxi Co Ltd
Current assignee: Circle Holds Biological Medicine Wuxi Co Ltd
Priority date: 2017-10-18
Filing date: 2017-10-18
Publication date: 2018-03-09
Also published as: WO2019076178A1

Abstract

The present invention provides a kind of controllable degradation time, the adjustable medical degradable polyurethane of elongation at break, preparation method and applications, by adjusting the ratio of each component in polyurethane building-up process and selecting different chain extenders, PU performance can be controlled in very large range, such as PU degradation time, elongation at break, intensity, lubricity and hydrophilic and hydrophobic etc., according to regenerative medicine and the needs of the medicine equipment to implant, the medical degradable polyurethane of different performance can be selected.

Description

Degradation time is controllable, the adjustable medical degradable polyurethane of elongation at break

Technical field

The invention belongs to degradable biomaterial field, and in particular to a kind of degradation time is controllable, elongation at break is adjustable Medical degradable polyurethane, preparation method and applications, by adjust in polyurethane building-up process the ratio of each component and Different chain extenders is selected, PU elasticity and degradation time can be controlled in very large range, may be applicable to different soft and hard The intervention implantation various medical products of human body of the bio-compatible of degree.

Background technology

Polyurethane (PU) full name is polyurethanes, is big containing carbamate (- NHC00-) group on main chain The general designation of molecular compound, it be by organic diisocyanate or polyisocyanates and dihydroxy or polyol addition polymerization and Into.Shown in typical PU chemical constitutions, the main polymer chain be by soft segment (soft segment) of the glass transition temperature less than room temperature and Glass transition temperature forms higher than rigid chain segment (hard section) block of room temperature.In general, synthesized with polyethers or polyester diol, The soft segment of polymer is formed, the segment glass transition temperature is low, and polarity is weak, the continuous phase of its constituent material, assigns PU elasticity and controls Make PU lower temperature resistance, solvent resistance and weatherability etc.；And diisocyanate and the segment of chain extender reaction generation are hard section, The hard section chain glass transition temperature generally constituted is high, and polarity is strong, the functional groups of-CO-NH- present in hard section, forms molecule interchain Substantial amounts of hydrogen bond, interaction force is strong, exists with crystalline state, controls the performances such as PU intensity and heat resistance.PU hard section and The crystallization of difference and hard section of the soft segment in polarity in itself causes their thermodynamically incompatible, and has spontaneous separation Tendency, so hard section is easily clumped together to form microcell, be dispersed in the continuous phase of soft segment formation, form microphase-separated knot Structure.The advantage of this material be can by design different soft, hard section structure, length and distribution, relative scale and Change relative molecular mass etc., change PU performance, such as PU elasticity, modulus, intensity, extension at break in very large range Rate, wearability, lubricity, hydrophilic and hydrophobic, biocompatibility and biological stability etc..

The polyaminoester microball surface texture that can degrade is similar to biomembrane, and this chain structure causes polyurethane to have certain life Thing degradability, it is a kind of very promising regenerative medicine and the implantable medical material of human body.For obtain be adapted to different tissues or The needs of implantation instrument, prepare neither too hard, nor too soft, technical barrier of the controllable polyurethane of degradation time into this area.

Domestic and international more literature research, which report polyurethane material, has good mechanical performance, biocompatibility, blood The features such as compatibility and easy processing, it is very in fields such as slow releasing carrier of medication, medical surgical material, tissue engineering brackets Promising degradable medical material, it is a kind of composition of excellent compound rest.Lot of domestic and international document all discloses preparation It can drop the scheme of polyurethane, for example with 1,6- hexamethylene diisocyanates (HDI) be hard section, PCDL (PCDL) The polyurethane synthesized for soft segment, ethyl ester of lysine hydrochloride (Lys-OEt) as chain extender；Using 1B as raw material, by L- Converting carboxylate groups are ester group on lysine, and 1B diisocyanate (LDI) is synthesized under catalyst action and is divided respectively from different The polyethylene glycol (PEG) of son amount or the polyurethane for being copolymerized to obtain to hydroxyethyl piperazine (HEP)；By molecular weight be 2000 it is poly- (6-caprolactone) dihydric alcohol (PCL) and LDI reaction generation prepolymers, then it is poly- with chain extender BDO (BDO) reaction synthesis Urethane (PU) etc. than more typical patent document 200580014001.0 disclose it is a kind of with one-step method come the degradable poly for preparing Urethane, wherein one-step method be by the raw material mixed onces such as oligomer polyol, polyisocyanates, chain extender and other auxiliary agents, Cast, the method for reaction shaping, it is mainly used in generating the polyurethane elastomer of low modulus, and reaction product is difficult control, is obtained The molecular weight of product is very wide；General industry production high performance polyurethane uses two step method, first using polyester or PPG First and di-isocyanate reaction generates performed polymer, then generates polyurethane, obtained elastomer molecules with glycol or diamines chain extension Structural arrangement is regular, and mechanical property is more preferable, reproducible, and product property is easily controlled, therefore, the present invention stretches to prepare fracture The controllable high performance polyurethane of long rate, employs two step method to prepare.

Biodegradable stent includes high polymer material support and degradable metal support, wherein degradable high polymer material bag Include：PLLA, PLA, PGA, PDO and PCL, wherein PLLA have preferable rigidity, pliability, resistance to stability and heat resistance, Through being successfully applied to the coating material of metallic support and itself being prepared into support；Degradable metal timbering material have magnesium alloy and Ferroalloy materials, wherein magnesium alloy materials are increasingly becoming the main flow that biodegradable stent is studied with its excellent processing characteristics.Due to Alkaline environment and hydrogen caused by magnesium alloy materials degradation process, limit a large amount of uses；Due to blood vessel, tracheae and urethra etc. no It is different to the performance requirement of used in tissue engineering biomaterial with the histoorgan at position, therefore obtain and a series of there are different mechanics The biomaterial of performance, degradation property and processability etc. is most important, due to mechanical property existing for homogenous material with And acid or alkali environment the problems such as causing internal aseptic inflammation caused by degraded, therefore, finding suitable composite high-molecular material, adopt With more preferable support Design technique, compound rest has more preferable clinical value.

In degradable polyurethane preparation method in all open source literatures, all there is degradation speed in the hard section for obtaining polyurethane The problem of slow, causing polyurethane to be wholly absent in vivo needs long time, greatly limit it in regenerative medicine Use, to solve this technical barrier, prepare the controllable polyurethane of degradation time, our team are by grinding for many years Study carefully, devise the amino acid diamine chain stretching agent with degradation site, successfully synthesize required for different tissues organ it is various can Degradable polyurethane simultaneously realizes batch production, degradable polyurethane is developed into possibility for medical-related products.

The content of the invention

Medical drop the technical problem to be solved in the present invention is to provide a kind of degradation time is controllable, elongation at break is adjustable Polyurethane, preparation method and applications are solved, it is different by adjusting the ratio of each component and selection in polyurethane building-up process Chain extender, PU elasticity and degradation time can be controlled in very large range.

In order to solve the above technical problems, embodiments of the invention provide, a kind of degradation time is controllable, elongation at break is adjustable Medical degradable polyurethane, using dithiothreitol (DTT), dihydric alcohol, two amino of band amino acid, derivative and its salt and one One kind in the amino acids diamine that molecule dihydric alcohol is connected with two molecule amino acid with two ester bonds does chain extender, wherein ammonia It is as follows that base acids diamine makees chain extender typical structure formula：

Wherein, P is dihydric alcohol, and X is 2-20 numeral；M and n is the one kind for commonly using 20 kinds of amino acid.

Wherein, described degradation time is controllable, the adjustable medical degradable polyurethane of elongation at break, and soft segment can be GA、LA、PDO（Lanthanum Isopropoxide）, CL and PEG（200-2000）One or both of combination polymer, hard section choosing From diisocyanate, it is chosen in particular from：1,6- hexamethylene diisocyanate（HDI）, isoflurane chalcone diisocyanate（IPDI）、 Lysine methyl ester diisocyanate（LDI）, ethyl ester of lysine diisocyanate（LDI）, it is cis-cyclohexane diisocyanate, anti- Formula-cyclohexane diisocyanate, Isosorbide-5-Nitrae-butane diisocyanate, butane diisocyanate, 1,2- ethane diisocyanate, 1,3- propane diisocyanate, 4,4 '-methylene-bis- (cyclohexyl isocyanate), IPDI, 2,4, One or both of 4- trimethyls 1,6- hexane diisocyanates；Chain extender is using dithiothreitol (DTT), dihydric alcohol, two, band The amino acids that amino acid, derivative and its salt of amino and a molecule dihydric alcohol are connected with two molecule amino acid with two ester bonds One kind in diamine, it is as follows that the amino acids diamine makees chain extender typical structure formula：

Wherein P is dihydric alcohol, and X is 2-20 numeral, preferably 2-10；

Dihydric alcohol is chosen in particular from ethylene glycol, diethylene glycol (DEG), tetraethylene glycol, 1,3- propane diols, Isosorbide-5-Nitrae-butanediol, 1,5-PD, 1, One or both of 6- hexylene glycols, 1,7- heptandiols, 1,8- ethohexadiols, 1,9- nonanediols, 1,10- decanediols；

M and n is the one kind for commonly using 20 kinds of amino acid, and wherein m and n can be the same or different.

Such as：Two molecule phenylalanines and a molecule 1,3 propane diols after esterification by obtaining by two ester bonds The connected compound for possessing two ripple amino living, it is specific as follows：

Such as：Two molecule glycine and a molecule 1,3 propane diols pass through being connected by two ester bonds of being obtained after esterification Possess the compound of two ripple amino living, it is specific as follows：

Similar citing is such as：Two molecule alanine and a molecule 1,3 propane diols after esterification by obtaining by two esters The connected compound for possessing two ripple amino living of key, a molecule alanine and a molecule valine and a molecule 1,3 propane diols By the compound that possesses two ripple amino living for obtaining being connected by two ester bonds after esterification, two molecule leucines with One molecule 1,3 propane diols pass through the chemical combination that possesses two ripple amino living that obtains being connected by two ester bonds after esterification Thing, isoleucine are gathered around with leucine and a molecule 1,3 propane diols by what is obtained after esterification by what two ester bonds were connected There is the compound of two ripple amino living, two molecule phenylalanines and a molecule 1,3 propane diols are logical by what is obtained after esterification The connected compound for possessing two ripple amino living of two ester bonds is crossed, two molecule proline and a molecule 1,3 propane diols pass through ester Change the compound for possessing two ripple amino living being connected by two ester bonds obtained after reaction, two molecule tryptophans and a molecule 1st, 3 propane diols are by the compound that possesses two ripple amino living that obtains being connected by two ester bonds after esterification, two points Sub- serine and a molecule 1,3 propane diols possess two ripple ammonia living by what is obtained after esterification by what two ester bonds were connected The compound of base, two molecule cysteines and a molecule 1,3 propane diols after esterification by obtaining by two ester bond phases The compound for possessing two ripple amino living even, two molecule methionine and a molecule 1,3 propane diols after esterification by obtaining The compound for possessing two ripple amino living being connected by two ester bonds, two molecule asparagines and a molecule 1,3 propane diols Pass through the compound for possessing two ripple amino living being connected by two ester bonds obtained after esterification, two molecule glutamine Pass through the chemical combination for possessing two ripple amino living being connected by two ester bonds that is obtained after esterification with a molecule 1,3 propane diols Thing, two molecule threonines and a molecule 1,3 propane diols possess two by what is obtained after esterification by what two ester bonds were connected The compound of individual ripple amino living, a molecule aspartic acid and a molecule glutamic acid and a molecule 1,3 propane diols pass through esterification The compound for possessing two ripple amino living being connected by two ester bonds obtained afterwards, include the combination and and one of various amino acid Molecule 1,3 propane diols pass through the compound that possesses two ripple amino living that obtains being connected by two ester bonds after esterification.

The present invention also provides that a kind of degradation time is controllable, the preparation side of the adjustable medical degradable polyurethane of elongation at break Method, to control the elongation at break of polyurethane, prepared using two step method, specific preparation method is as follows：

（1）The synthesis of a variety of degradation times and the degradable polyurethane of physical property

Soft segment is selected from GA, LA, PDO（Lanthanum Isopropoxide）, CL and PEG（200-2000）One or both of polymerization Thing, one kind in the one kind of hard section in diisocyanate, preferably LDI, IPDI, HDI or 1,3- propane diisocyanate, Chain extender selection amino acid diamine, synthetic schemes are as follows：

Soft segment compound or composition and catalyst are placed in vacuum reaction bottle by inventory, are put into 70-140 DEG C of oil bath pan Middle reaction 4-24 h obtain the polymer of line style, then weigh the di-isocyanate reaction 0.5-12h of proper proportion, use appropriate solvent Dissolve or be directly added into amino acid diamine chain extension and connect, be evacuated and hermetically sealed bottleneck, be put into 0-120 DEG C of oil bath pan and react 2- 12h, obtain final product.

（2）Synthesis using amino acid as the degradable polyurethane of chain extender

Soft segment is selected from GA, LA, PDO（Lanthanum Isopropoxide）, CL and PEG（200-2000）One or both of polymer group Close, one kind in the one kind of hard section in diisocyanate, preferably LDI, IPDI, HDI or 1,3- propane diisocyanate, Chain extender is selected from amino acid, derivative and its salt of two amino of band, amino acid hydrochloride salt is specifically included, such as lysine methyl ester two Hydrochloride, ethyl ester of lysine dihydrochloride, cystine methyl esters dihydrochloride, cystine ethyl ester dihydrochloride, omithine methyl ester two One kind in hydrochloride, ornithine ethyl ester dihydrochloride, synthetic schemes are as follows：

Soft segment compound or compound are combined, PDO, PEG or monomer CL, LA, GA is referred specifically to and catalyst is placed in by inventory In vacuum reaction bottle, it is put into reaction 4-24 h in 70-140 DEG C of oil bath pan and obtains the polymer of line style, add diisocyanate 0.5-12h is reacted, the amino acids chain extender and triethylamine of proper proportion are dissolved or be directly added into appropriate solvent, is vacuumized simultaneously Bottleneck is sealed, is put into 50-150 DEG C of oil bath pan and continues to react 2-24h, obtain final product.

（3）Soft segment is selected from the degradable polyurethane of PPDO or PDO and CL copolymers：

Soft segment is selected from PPDO, PDO and GA or CL and PDO（Its percentage by weight is 1:10-10:1）One or both of it is poly- Compound combines, in the one kind of hard section in isocyanates, preferably LDI, IPDI, HDI or 1,3- propane diisocyanate One kind, chain extender selection 1, ammediol, synthetic schemes are as follows：

Anhydrous PPDO, PDO and GA or CL and PDO and catalyst by proportion are placed in vacuum reaction bottle, are put into 120-140 DEG C Oil bath pan in reaction 4-24 h obtain the polymer of line style, add the 1B di-isocyanate reaction 0.5- of proper proportion 12h, dissolved with appropriate solvent or be directly added into 1, ammediol, be put into vacuum reaction bottle, be evacuated and hermetically sealed bottleneck, be put into 2-24h is reacted in 50-150 DEG C of oil bath pan, obtains final product.

The one kind of the catalyst in tin class, zinc class or organic bismuth salt, dosage are the 0.001- of total amount of feeding 10wt%.

The tin catalyst is selected from organic tin catalyst dibutyltin dilaurylate, stannous octoate, dibutyl tin two Laurate, dioctyl tin, dibutyl tin, dialkyl tin, dimaleate, two mercaptan tin alkyls, mercaptan dioctyl tin etc., it is excellent Select stannous octoate.

The conventional bismuth class environmental protection catalyst assembly of the organic bismuth catalyst polyurethane industries among others, including bismuth neodecanoate, bay Sour bismuth, isooctyl acid bismuth, bismuth naphthenate etc., preferably bismuth neodecanoate.

Degradation time of the present invention is controllable, the adjustable medical degradable polyurethane of elongation at break, further can be with Chain extender or crosslinking agent are done from LTI or DTT, with the webbed cross-linked structure of shape, the polyurethane composition The elongation at break of thing is higher than 300MPa, and elongation at break is in the range of 30%~700%, and reaction is selected from one of following manner：

（1）By the degradable polyurethane of two step synthetic method described in claim 3, two sulphur are added during second step chain extension Threitol or LTI（Compare 1-30% with the weight of polyurethane）, squeezed in twin-screw of the moisture less than 10ppm Go out in machine and react 20 minutes, stirring polymerization extrusion, obtain the urethane composition with high elongation at tear；

（2）By the degradable polyurethane of two step synthetic method described in claim 3, contain during second step chain extension in moisture Amount is poured into kneading machine or kneader in the environment of being less than 10ppm, is directly added into dithiothreitol (DTT) or the isocyanic acid of lysine three Ester（Compare 1-30% with the weight of polyurethane）It is sufficiently stirred, normal-temperature reaction half an hour obtains having the described poly- of high elongation at tear Urethane composition；

（3）By the degradable polyurethane of the two step synthetic method described in claim 3, added during second step chain extension Anhydrous organic solvent（Tetrahydrofuran, dichloromethane or chloroform）Viscous solution is configured to, in moisture less than 10ppm's DTT is directly added under environment（Dithiothreitol (DTT)）Or LTI（Compare 1-30% with the weight of polyurethane）, reactant System's stirring or concussion mixing, vacuum drains organic solvent and obtains having the described poly- of high elongation at tear after normal-temperature reaction half an hour Urethane composition.

The application of polyurethane of the present invention or its composition in medical embedded material is prepared, polyurethane of the present invention are made To prepare the application in medical embedded material, the medical embedded material can be used alone, and can conform to other high polymer material systems Used into compound, can be used for implantation equipment, implantable artificial organs, contact artificial organs, support, interposing catheter, people Work skin, tissue engineering bracket and organ servicing unit, it is necessary to which further purifying removing has when as medical embedded material Malicious monomer or organic solvent.

The poly- ammonia of medical degradable that a kind of elongation at break of the present invention is adjustable, the adjustable security of degradation time is good Ester, can be compound with other degradation materials, and composite implantation material is made, specifically includes：Degradable high polymer material and it can drop Metal material is solved, wherein the weight ratio of the polyurethane and the degradable metal material is in 0.1-99%：1%-99.9% scopes Interior, the metal material includes iron of the purity more than 99.0%, purity is more than 99.0% magnesium, percentage by weight 1：0.01-10's Mg-Fe alloy, percentage by weight 1：0.01-1 Mg-Zn based alloy, percentage by weight 1：0.01-1 magnesium calcium alloy, again It is 1 to measure percentage：One or both of 0.01-0.1 Magnesium-aluminum alloys combine, preferably Mg-Fe alloy（Percentage by weight is preferred 1：0.01-0.1）, Mg-Zn based alloy（Percentage by weight preferably 1：0.01-0.1）, such as：Mg-Nd-Zn-Zr、Mg-Zn-Mn 、 Mg-Zn-Mn-Se-Cu alloys, Zn contents are 3.5wt%, and Mn contents are 0.5-1.0wt%, and Se contents are 0.4-1.0wt%, Cu contents are 0.2-0.5wt%, Mg surpluses；Magnesium calcium alloy（Percentage by weight preferably 1：0.01-0.1）, citing：Mg-Zn- Ca-Fe, Magnesium-aluminum alloys（Percentage by weight is preferably 1：0.01-0.1, citing：Aluminium（Al）：2.0-3.0wt.%, zinc（Zn）： 0.5-1.0wt.%, manganese（Mn）, Mg surpluses.

The weight ratio of the high polymer material is in 0.1-99% described in the polyurethane and high polymer material：1%-99.9% models In enclosing, wherein high polymer material, selected from PLA, polycaprolactone, poly- to dioxa cyclohexanone and its copolymer (PPDO, PGA- PPDO), gather to dioxa cyclohexanone（PPDO）, it is PTMC, PLA-trimethylene carbonate copolymer, poly- At least one of caprolactone-trimethylene carbonate copolymer, polyglycolic acid, Poly(D,L-lactide-co-glycolide, institute The viscosity average molecular weigh for stating biodegradable high polymer material is 500-1,000,000.

The method of degradable metal compound in degradable implantation material of the present invention, comprises the following steps：

（1）Degradable metal material is worked out, carved, etched or cut into the decorative pattern or lath-shaped of needs, preferably decorative pattern diameter For 0.01 to 3mm；

（2）Organic solvent is dissolved in by polyurethane of the present invention or with the composition of other high polymer materials（Selected from decane, tetrahydrochysene furan Mutter, one kind in isoamyl acetate, hexane, dichloromethane, chloroform, cyclohexanone, dimethylformamide and heptane or two Kind）In, coating material is made（The concentration of urethane composition described in coating is 5-50%）；

（3）Will（2）The coating material of middle preparation repeatedly dip-coating, spray or film be made and overlay on（1）The metallic support table of middle preparation Face, the compound rest with overlay film is made, the thickness of the overlay film is in the range of 0.001-1mm, preferably 0.01-0.5mm；

（4）Will（3）The overlay film frame of middle preparation is by dip-coating or spraying hydrophilic coating, and polishing grinding is into the biodegradable stent Compound.

The method of wherein described biodegradable stent compound, one of following method can also be included：

（1）By magnesium alloy powder（Diameier scope is：10nm-1mm）It is (molten with organic solvent with the solution of urethane composition Solve the urethane composition and be configured to the viscous solution of 20-90% concentration) it is well mixed, printed by 3D printer Go out to need the support of diameter and wall thickness, the dry organic solvent of heated-air drying volatilization, obtain the biodegradable stent compound；

（2）3D printer is set into two feeding devices, magnesium alloy powder is added in a feeding device（Diameier scope For：10nm-1mm）, the solution of urethane composition is added in another feeding device（Percentage concentration is configured to organic solvent For 20-90%）, two kinds of materials print the support being sized with shape, heated-air drying after mixing in proportion during the charging Volatilize dry organic solvent, obtains the biodegradable stent compound；

（3）3D printer sets two feeding devices, and magnesium alloy powder is added in a feeding device（Diameier scope is： 10nm-1mm）, in another feeding device in proportion（1：0.1-10）Urethane composition and PLA are added, is mixed molten Solution is in organic solvent, and it is 20-90% to be configured to percentage concentration with organic solvent, and two kinds of materials mix in proportion during charging The support being sized with shape is printed after conjunction, the dry organic solvent of heated-air drying volatilization, it is compound to obtain the biodegradable stent Thing；

（4）3D printer sets two feeding devices, and magnesium alloy powder is added in a feeding device（Diameier scope is： 10nm-1mm）, high-temperature fusion prints support on demand, and Passivation Treatment is standby；In another feeding device in proportion（1：0.1- 10）Urethane composition and PLA are added, is then mixed and is dissolved in organic solvent, hundred are configured to organic solvent It is 20-90% to divide concentration, and coating film is printed on support, the dry organic solvent of heated-air drying volatilization, obtains the biodegradable stent Compound.

Wherein described organic solvent, selected from toluene, paraxylene, decane, isoamyl acetate, hexane, benzene, dichloromethane Alkane, chloroform, cyclohexanone, ketone, dimethylformamide, heptane, dimethylamino formamide, tetrahydrofuran, petroleum ether, diformazan One or both of sulfoxide, ethylene glycol terephthalate, preferably tetrahydrofuran, chloroform, toluene, paraxylene, second One kind in isoamyl valerate or hexane.

Wherein described degradable polyurethane and metal material or the compound of high polymer material, its structure, composition and shape Shape is applied to blood vessel, vein, oesophagus, biliary tract, trachea-bronchial epithelial cell, small intestine, large intestine, urethra, ureter or other close to tubular body The fragment of passage, for example, as intravascular stent, trachea bracket, bronchial stent, urethra rack, Esophageal Stent, biliary tract rack, Ureter bracket（Double J pipe）, ureterostenosis section support, the support for small intestine, the support for large intestine, throat's implant, Bypass manifold or ileal stoma.

Concrete application includes：Implantation equipment, implantable artificial organs, contact artificial organs, support, interposing catheter, with And organ servicing unit, specifically include hone lamella, nail, spicule, bone rod, internal fixation of spine equipment, ligature, patella fracture fixator, bone wax, Bone renovating material, aneurysm clips, silver brain clip, blood vessel anastomosis clamp（Device）, shaping material, heart or tissue mending material, intraocular fill Filling chock material, intrauterine device, neural sticking patch；Implantable artificial organs specifically includes：It is artificial esophagus, artificial blood vessel, artificial vertebral body, artificial Joint, artificial urethra, artificial valve, artificial kidney, adopted breast, artificial skull, artificial jaw bone, artificial heart, artificial tendon, artitificial ear Snail, artificial anus sealer；Touch artificial organs specifically includes：Artificial larynx, artificial skin, artificial cornea；Stented vessel is specific Including：Support, prostate bracket, biliary tract rack, esophageal stents and ureter bracket；Organ servicing unit specifically includes：Plant Enter formula audiphone, artificial hepaticsupport system；Extracorporal circulatory system and blood processing apparatus：Pump, Blood storing and filtering device, Micro- Bolt Filter, filter Blood device, water filter（Ultrafiltration）, bubble removal device, pump line, bloody path；Haemodialysis equipment, filtering device for blood dialysis, blood filtering Device, blood purifying pipeline, dialysis bloody path, bloody path Plastic pump pipe, Arteriovenous puncture appliance, multi-layer planar type dialyzer, hollow fibre Tie up dialyzer, doughnut pass filter, absorber, plasma separator, blood detoxification（Perfusion irrigates）Device, blood purification follow in vitro Ring bloody path（Pipeline）, intraoperative autotransfusion machine；Intervene equipment：Catheter in blood vessel：Intravascular angiography catheter, balloon expandable are led Pipe, CVC, trocar peripheral catheters, miniature floating catheter, arteriovenous pressure catheter；Seal wire and pipe sheath, are specifically included： Stiff guide wire, soft head seal wire, arteria renalis seal wire, micro-wire, push seal wire, superslide seal wire, arterial sheath, vein blood vessel sheath, micropuncture Vagina vasorum；Embolism equipment, is specifically included：Filter, spring embolus, embolism microball, platinum microembolus, plugging device, intravenous injection (IV), central veins (CV), vascular access, lung heat buffering balloon, angiography, angioplasty balloons, Urology Surgery, spy Different conduit, pacemaker wires insulating barrier, artificial blood vessel, cardiac valves, heart-assist device, left ventricular assist device, sustainer Aortic balloon, TAH, hemodialyzer, haemodialysis, artificial lung, blood oxygen exchanger, blood perfusion, blood filtering, blood Flushing, artificial pancreas, breast implants, wound dressing, Facial reconstruction material, surgical adhesive, drug controlled release, artificial pipe Road, the flowing for strengthening body fluid and excretion, contraceptive, penile prosthesis etc..

Further：Biodegradable stent composition disclosed by the invention, it can need to increase it according to the soft or hard of support peritonaeum Its high polymer material, such as：PLA, polycaprolactone, gather to dioxa cyclohexanone and its copolymer (PPDO, PLA-PDO) Gather to dioxa cyclohexanone（PPDO）, PTMC, PLA-trimethylene carbonate copolymer, gather oneself in Ester-trimethylene carbonate copolymer, polyglycolic acid, PLA-co-glycolic acid, polyether-ether-ketone, polyethylene pyrrole Pyrrolidone and/or polyethylene glycol, poly- valerolactone, poly- ε-decalactone, polyactide, PGA, polyactide and PGA Copolymer, poly- ε-caprolactone, poly butyric, poly butyric ester, poly- hydroxyl valerate, poly butyric ester-copolymerization- Valerate, poly- (Isosorbide-5-Nitrae-dioxane -2,3- diketone), poly- (1,3- dioxane -2- ketone), poly- to dioxa Cyclohexanone, polyanhydride (such as poly-maleic anhydride), poly- hydroxyl-metacrylate, fibrin, polybutylcyanoacrylate, Polycaprolactone dimethylacrylate, poly- β-maleic acid, polycaprolactone butyl propyleneglycol acid esters, from oligomerization caprolactone two Multi-block polymer, polyethylene glycol and the polybutylene terephthalate of alcohol and oligomerization dioxanone glycol)), poly- new penta Lactone, polyglycolic acid carbonate, polycaprolactone-glycolide, poly- (γ-ethyl glutamate), poly- (DTH- imido Base carbonic ester), poly- (DTE- copolymerization-DT- carbonic esters), poly- (bisphenol-A-iminocarbonic ester), poe, polyglycolic acid It is carbonate, poly- trimethyl carbonate, poly- iminocarbonic ester, poly- (N- vinyl)-pyrrolidones, polyvinyl alcohol, poly- Esteramides, dealing with alcohol polyester, polyphosphate, polyphosphazene, poly- [to carboxyphenoxy) propane], poly- hydroxypentanoic acid, polyanhydride, poly- Polyurethane with amino acid residue, polyether ester (such as polyoxygenated in ethylene oxide-propylene oxide, flexibel polyurethane, main chain Ethene), polyalkylene oxalate, poe and its copolymer, carrageenan, fibrinogen, starch, collagen, containing egg One kind in white matter polymer, polyaminoacid, synthesis polyaminoacid, zein, the biodegradable high polymer material Viscosity average molecular weigh be 500~1000000, preferred polylactic acid material, according to scaffold degradation needs, more preferably PLGA (LA: G/A ratio is 1-3：1), such as：LA:GA ratio is 75：25；65：35 and 50：50 etc., polymer viscosity average molecular weigh is 5- 500000, preferred polymers viscosity average molecular weigh is 5-15 ten thousand, to improve the pliability of product, can also add nontoxic plasticizer, lemon Lemon acid tributyl (TBC), tributyl 2-acetylcitrate (ATBC), trioctyl trimellitate (TOTM), tri trimellitate (810) ester, inclined benzene Three sour glyceryl esters, tetraoctyl 1,2,4,5-benzenetetra-carboxylate, diethylene glycol dibenzoate, diethylene glycol dibenzoate, DPG hexichol first One kind in acid esters, DOTP, DOTP, dihexyl sebacate, epoxidized soybean oil or two More than kind.

Further：Degradable metal material disclosed by the invention is selected from, adding ingredient be iron, copper, zinc, cobalt, manganese, chromium, selenium, Iodine, nickel, fluorine, molybdenum, vanadium, tin, silicon, strontium, boron, rubidium, arsenic, silver, a kind of or more Zhang Yuansus combination, its composition weight of magnesium alloy materials Percentage is:Iron 0-2.0%, copper 0-2.0%, zinc 0-2.0%, cobalt 0-2.0%, manganese 0-2.0%, chromium 0-2.0%, selenium 0-2.0%, iodine 0- 2.0%th, nickel 0-2.0%, fluorine 0-2.0%, molybdenum 0-2.0%, vanadium 0-2.0%, tin 0-2.0%, silicon 0-2.0%, strontium 0-2.0%, boron 0-2.0%, Rubidium 0-2.0%, silver 0.1~4%；Including：High purity iron（Purity is more than 99.0%）, high purity magnesium（Purity is more than 99.0%）, Mg-Fe alloy （Percentage by weight is 1：0.01-10）, Mg-Zn based alloy（Percentage by weight is 1：0.01-1）, magnesium calcium alloy（Weight percent Than for 1：0.01-1）, Magnesium-aluminum alloys（Percentage by weight is 1：0.01-0.1）One or both of combination.Wherein magnesium iron closes Gold（Percentage by weight preferably 1：0.01-0.1）, Mg-Zn based alloy（Percentage by weight preferably 1：0.01-0.1）, such as：Mg-Nd- Zn-Zr, Mg-Zn-Mn, Mg-Zn-Mn-Se-Cu alloy, Zn contents are 3.5wt%, and Mn contents are 0.5-1.0wt%, and Se contains Measure as 0.4-1.0wt%, Cu contents are 0.2-0.5wt%, Mg surpluses；Magnesium calcium alloy（Percentage by weight preferably 1：0.01- 0.1）, such as：Mg-Zn-Ca-Fe, Magnesium-aluminum alloys（Percentage by weight is preferably 1：0.01-0.1, such as：Aluminium（Al）：2.0- 3.0wt.%, zinc（Zn）：0.5-1.0wt.%, manganese（Mn）, Mg surpluses：

Further：Coating bracket disclosed by the invention, its preparation process are as follows：

（1）Degradable metal material is worked out, carved, etched or cut into the decorative pattern of needs；

（2）By polymer A:Degradable medical polyurethane material is dissolved in organic solvent, and coating material is made（Material concentration 5- 50%, specifically polyurethane is dissolved in tetrahydrofuran solution, is made into 10-30% solution）；

（3）Will（1）The metallic support of middle preparation, passes through（2）Dip-coating, spraying either Electrospun are in rack surface repeatedly, at least Part coating forms the pillar of grid or grid, coating compound rest is made, the material thickness of coating is preferably 0.01-3mm, excellent Select between 0.01-0.5mm.

Peritonaeum support disclosed by the invention, its preparation process are as follows：

（1）Degradable metal material is worked out, carved, etched or cut into the decorative pattern or lath-shaped of needs；

（2）By polymer A:Degradable medical polyurethane material and polymer B:PLA（PLGA, LA:G/A ratio is 65：35, Viscosity average molecular weigh is 8-10 ten thousand）By 1：Film, preferably thickness 0.01-3mm, 0.1- is made in organic solvent in 2 mixed dissolutions 1mm；

（3）Will（1）The metallic support of middle preparation, passes through（2）Overlay film frame is made in metal material surface in the film roll of preparation；

（4）Will（3）The composite of middle preparation passes through dip-coating or spraying hydrophilic coating（Such as chitosan, hyaluronic acid, glue Aqueous solution etc. is made in former, cellulose）, dry, polish, be polished to overlay film frame.

Support disclosed by the invention, is prepared with 3D printing technique：

（1）One of preparation method：By magnesium alloy powder（Diameier scope is：10nm-1mm, preferably 1um-100um）With that can drop Solving medical polyurethane material solution, (organic dissolution dissolves, and is configured to the viscous solution of 20-90% percentage concentrations, and preferably 30-50% is dense The tetrahydrofuran or chloroform soln of degree) it is well mixed, the support for needing diameter and wall thickness is printed by 3D printer, heat The dry organic solvent that volatilizes is air-dried both to obtain；

（2）The two of preparation method：3D printer sets two feeding devices, and magnesium alloy powder is added in a feeding device（Powder Last diameter range is：10nm-1mm, preferably 1um-100um）, degradable medical polyurethane material is added in another feeding device Solution（It is 20-90% to be configured to percentage concentration with organic solvent, and preferably the tetrahydrofuran of 30-50% concentration or chloroform are molten Liquid）, two kinds of materials print the support being sized with shape after mixing in proportion during the charging, heated-air drying volatilizes Organic solvent both obtained；

（3）The three of preparation method：3D printer sets two feeding devices, and magnesium alloy powder is added in a feeding device（Powder Last diameter range is：10nm-1mm, preferably 1um-100um）, degradable medical polyurethane material is added in another feeding device With PLA in proportion（1：0.1-10）For mixed dissolution in organic solvent, it is 20- to be configured to percentage concentration with organic solvent 90%, the preferred tetrahydrofuran or chloroform soln of 30-50% concentration, after two kinds of materials mix in proportion during charging The support being sized with shape is printed, heated-air drying volatilizes organic solvent and both obtained；

（4）The four of preparation method：3D printer sets two feeding devices, and magnesium alloy powder is added in a feeding device（Powder Last diameter range is：10nm-1mm, preferably 1um-100um）, high-temperature fusion prints support on demand, and Passivation Treatment is standby；Separately Degradable medical polyurethane material and PLA are added in one feeding device in proportion（1：0.1-10）Mixed dissolution is in organic In solvent, it is 20-90% to be configured to percentage concentration with organic solvent, and coating film is printed on support, and heated-air drying volatilizes organic Solvent both obtained.

Wherein magnesium alloy powder（Diameier scope is：10nm-1mm, preferably 1um-100um）, can be dropped according to support The requirement for solving the time is passivated processing according to disclosed various methods, forms corrosion resistant nontoxic conversion film.

When preparing intravascular stent, on the bare bracket surface handled well, the crosslinking by anticoagulant composition by glutaraldehyde Anticoagulant composition is crosslinked and fixed by agent, and hemostatic composition can select hirudin, Heparan sulfate and its derivative such as complete Devulcanization and N- acetylated-heparin devulcanization and N- acetylated-heparin again again, the anti-freezing of blood clotting will not be activated by, which being prepared into, applies Layer；

When needing to prepare the support of degradation time length, corrosion resistant nontoxic conversion can be formed in degradable magnesium alloy surface passivation Film, conventional have phosphate conversion embrane method, phytic acid conversion film, rare-earth salts conversion embrane method and an organic matter conversion embrane method, or Bare bracket surface carries out fluorination treatment, and specific method is will to be polished for undressed biodegradable magnesium-alloy stent, in matter It is that 12~96h is soaked in 20~40% hydrofluoric acid to measure percentage.

Biodegradable stent composition of the present invention, it is characterised in that, can be in polyurethane material according to clinical needs Middle addition is commercially available or disclosed polypeptide, albumen and active component, including antiproliferative, anti-migration, anti-angiogenesis, Anti-inflammatory, anti-inflammatory, cell growth inhibition, cytotoxicity or the antithrombotic medicine with physiologically active, such as Xi Luomo Department, everolimus, Elidel, alkeran, ifosfamide, Trofosfamide, Chlorambucil, bendamustine, growth hormone release inhibiting hormone, Tacrolimus, ROX, daunomycin, ascosin, Ba Foluo mycins, Luo Mositing, endoxan, Estramustine, reach Carbazine, Abboticine, medecamycin, caspase, canavalin, Clarith, troleandomycin, catharanthine, length Spring new alkali, eldisine, vinorelbine, Etoposide, Teniposide, Nimustine, BCNU, busulfan, procarbazine, Treosulfan, Temozolomide, phosphinothioylidynetrisaziridine, Doxorubicin, Aclarubicin, epirubicin, mitoxantrone, idarubicin, it is rich come it is mould Element, mitomycin C, dactinomycin D, methopterin, fludarabine, fludarabine -5 '-dihydrogen orthophosphate, Cladribine, mercapto Purine, thioguanine, cytarabine, fluorouracil, gemcitabine, capecitabine, polyenoid taxol, carboplatin, cis-platinum, Ao Shali Him is cut down in platinum, rosuvastatin, Atorvastatin, Pravastatin, Pitavastatin, folimycin, cerivastatin, Simvastatin, Lip river Spit of fland, Fluvastatin, amsacrine, Irinotecan, Hycamtin, hydroxycarbamide, Miltefosine, Pentostatin, Aldesleukin, Wei Jia Acid, asparaginase, Pegaspargase, arimidex, Exemestane, Letrozole, formestane, aminoglutethimide, Bromerguride, bromine wheat Square ring peptide, elymoclavine, ergocristine, ergocritinine, Eg, ergonovine, ergosine, ergosinine, wheat The different new alkali in angle, ergotamine, ergotaminine, ergovaline, ergocorninine, ergocryptine, ergokryptinine, ergometrine, Lergotrile, lisuride, lysergol, ergotic acid, adriamycin, Azithromycin, spiramvcin, cepharanthine, 8- α-ergot Spirit, dimethyl ergoline, agroclavine, 1- pi-allyls lisuride, 1- pi-allyls Terguride, lysergic acid amides, ergot Diethylammonium salt, isolysergic acid, isolysergamide, isolysergic acid diethylamine, mesulergine, Distaval, (5- isoquinolin sulphonyl Base) homopiperazine, cyclosporin, the ω of inhibitors of smooth muscle cell proliferation 2, liserdol, methergine, two methergolines are new Alkali, pergolide, Proterguride and Terguride, celecoxib, ebomycin A and B, mitoxantrone, imuran, Mycophenolate, Antisense c-myc, antisense b-myc, betulic acid, camptothecine, wooden Pa Fosite, melanocyte promote hormone, work Property PROTEIN C, interleukin 1-β-inhibitor, β-lapachol, podophyllotoxin, betulin, the 2- ethyls hydrazine of podophyllic acid, not Plast booth, peg-interferon α-2b, Lenograstim, Filgrastim, Dacarbazine, basiliximab, daclizumab, choosing Select albumen, cetp inhibitors, cadherins, cell factor inhibitors, Transitional cell carcinomas inhibitor, thymosin extrasin α -1, fumaric acid and its ester, its salts, Tacalcitol, lapachol, nuclear factor kappaB, angiopeptin, Ciprofloxacin, fluorine Xi Ting, suppress the monoclonal antibody of muscle cell proliferation, be human/bovine basic fibroblast growth factor antagonist, probucol, preceding Row parathyrine, 1,11- escoparone -6- ketone, 1- hydroxyl -11- methoxy coumarin -6- ketone, scopolactone, Colchicin, nitric oxide donors, tamosifen, Fosfestrol, Medroxyprogesterone, cycloprovera, oestradiol benzoate, song Ni Site, Verapamil, staurosporine, β-estradiol, α-estradiol, estriol, oestrone, ethinyloestradiol, EGFR-TK suppression Preparation, Ciclosporin A, taxol and its derivative, synthesis and by natural origin obtain carbon suboxide macrocyclic oligomer and Its derivative, Chemiartrol, rantudil, Diclofenac, lonazolac, dapsone, adjacent carbamyl-phenoxy group-acetic acid, Lidocaine, Ketoprofen, mefenamic acid, tumor chalone, Avastin, HCQ, Anranofin, sodium aurothiomalate, Austria Sha Xiluo, celecoxib, β-sitosterol, Ademetionine, myrtecaine, laureth 9, vanillylnonanamide, a left side Menthol, benzocainum, Aescin, Ellipticine, demecolcine, CA-E, Yin Dannuoxin (indanocine), nocodazole, piroxicam, Meloxicam, chloroquine diphosphate, penicillamine, S100 albumen, Bacitracin, glass Glass binding protein precursor receptor antagonist, azelastine, guanidine radicals cyclase stimulators, the tissue depressant of metalloproteinases 1 and 2, Free nucleic acid, the nucleic acid for being incorporated to viral mediator, DNA and ribonucleic acid fragments, plasminogen activator inhibitor 1st, plasminogen activator inhibitor 2, ASON, vascular endothelial growth factor receptor inhibitors, insulin-like growth factor Acetylated-heparin, tissue are fine again by son 1, the activating agent from antibiotic group, penicillins, antithrombotic agent, desulfurization and N- Plasminogen-activating dose, GpIIb/IIIa platelet membranes acceptor, factor Xa inhibitor antibody, heparin, hirudin, r- hirudins, D- phenylalanine-proline-arginine-chloromethane ketone (D-phenylalanyl-L-prolyl-L-arginine Chloromethyl ketone), acetylcholinesteraseinhibitors inhibitors, sulfoprotein enzyme inhibitor, prostacyclin, Vapiprost, Interferon-' alpha ', β and γ, histamine antagonist, serotonin blockers, apoptosis inhibitor, apoptosis regulators, nucleoprotamine, Sodium salt, prourokinase, streptokinase, warfarin and the urokinase of 2- methyl thiazolium oxazolidine -2,4- dioctyl phthalate, vasodilator, Growth factor antagonist, Halofuginone, nifedipine, tocopherol, vitamin B1, B2, B6 and B12, the leaf in blood platelet source Acid, molsidomine, Tea Polyphenols, L-Epicatechin gallate, nutgall catechin gallic acid ester, leflunomide, A Nabai are stagnant Element, Etanercept, procainamide, retinoic acid, quinindium, Dimpyramidum Dimpyramidum, flecainide, Propafenone, Suo Taluo That, amiodarone, the steroids of natural or synthetic acquisition, Inonotus obliquus alcohol, Ma Kuier glucosides A, SASP, rely on primary glycosides, It is triamcinolone, mutamycin 6, suede trailing plants mushroom glucoside, Man Suoning, magpie kidney glucoside, hydrocortisone acetate, betamethasone, dexamethasone, non- Steroids anti-inflammatory material, antifungal, antiprotozoal, natural terpenoids, 4,7- epoxide rings anisomelic acid, drought Ground chrysanthemum terpene B1, B2, B3 and B7, glucosides tobeimosides, anti-dysentery Java brucea alcohol A, B and C, anti-dysentery yatanoside C, Java brucea are bitter Glycosides N and P, isodexyelephantopin, support careless lactone A and B, dihydroxypropyltheo-pylline A, B, C and D, Amethystoidin A white flower A and B, Nitidine Chloride, 12- β-hydroxyl gestation diene -3,20- diketone, longikaurin B, sculponeatin C, plan lack Rabdosia amethystoides terpene, Rabdosia racemosa terpene A and B, Chinese yew element A and B, thunder cough up Buddhist nun's alcohol), Triptolide, ursolic acid, jatamasic acid A, Isoiridogermanal, Variable-leaved Mayten alcohol, Guan Qiu grapheme A, cymarin, strophanthin, aristolochic acid, aminopterin-induced syndrome, hydroxyl Amine petrin, Anemonin, protoanemonin, jamaicin, chlorination Qie Libai elements, cicutexin, mufangchine, three-bristle cudrania tree isoflavones A, The salt of turmeric, Dihydronitidine, ginkgol, bilobol, gingko eo-acid etc. and above-mentioned activating agent, hydrate, solvate, Enantiomer, racemic compound, enantiomer mixture, diastereoisomer mixture and its mixture.

Wherein described implantation class medical product further comprises contrast agent, and the contrast agent selects selected from contrast agent：Often Use radiocontrast medium（Positive and negative contrast medium）Extremely analog, generally go back zirconium, barium, Dian, Manganese, iron, lanthanum, cerium, praseodymium, etc. With reference to or form complexed ionic species, preferably baric or iodine contrast agent, more preferably in zirconium dioxide, barium sulfate and Operand One kind.

The above-mentioned technical proposal of the present invention has the beneficial effect that：The present invention is by adjusting each group in polyurethane building-up process Point ratio and the different chain extender of selection, can control PU performance in very large range, such as PU degradation time, disconnected Elongation, intensity, lubricity and hydrophilic and hydrophobic etc. are split, can be according to regenerative medicine and the need of the medicine equipment to implant Want, select the polyurethane of different performance.

Embodiment

To make the technical problem to be solved in the present invention, technical scheme and advantage clearer, below in conjunction with specific implementation Example is described in detail.

Scheme one：The synthesis of the degradable polyurethane of a variety of degradation times and elongation at break

Note：The raw material advanced processing used in the present embodiment is less than 10ppm to water content, standby.

Embodiment 1

9.0g 6-caprolactones, 3.0g PEG-600, stannous octoate are weighed respectively（The 0.03wt% of total amount）As catalyst, add Enter in vacuum reaction bottle, add a magnetic stir bar, vacuumize/inflated with nitrogen circulates 3 times, and sealed under vacuumized conditions Vacuum reaction bottleneck, it is put into 140 DEG C of oil bath pan and reacts 24 h and obtain the polymer of line style.It is different that 2gL- lysines two are weighed again Cyanate and 0.6g glycine diamines, are evacuated and hermetically sealed bottleneck, are put into 50 DEG C of oil bath pan and react 4h, finally produced Thing.

Embodiment 2

9.0g 6-caprolactones, 0.5g PEG-600, stannous octoate are weighed respectively（The 0.03wt% of total amount）As catalyst, add Enter in vacuum reaction bottle, add a magnetic stir bar, vacuumize/inflated with nitrogen circulates 3 times, and sealed under vacuumized conditions Vacuum reaction bottleneck, it is put into reaction 18h in 140 DEG C of oil bath pan and obtains the polymer of line style.2.6gL- lysines two are weighed again Isocyanates and 0.68g phenylalanine diamines, are evacuated and hermetically sealed bottleneck, are put into 70 DEG C of oil bath pan and react 8h, obtain most End-product.

Embodiment 3

The lactide of 9.0g ε-, 1.0g PEG-200, new certain herbaceous plants with big flowers acid bismuth are weighed respectively（The 1.0wt% of total amount）As catalyst, add In vacuum reaction bottle, a magnetic stir bar is added, is vacuumized/inflated with nitrogen circulates 3 times, and is sealed under vacuumized conditions true Sky reaction bottleneck, is put into 130 DEG C of oil bath pan and reacts 24 h and obtain the polymer of line style.The isocyanide of 2gL- lysines two is weighed again Acid esters and 0.7g cysteine diamines, are evacuated and hermetically sealed bottleneck, are put into 70 DEG C of oil bath pan and react 4h, finally produced Thing.

Embodiment 4

3.0g ε-lactide, 6.0g 6-caprolactones, 1.5gPEG-400, stannous octoate are weighed respectively（The 0.03wt% of total amount）Make For catalyst, add in vacuum reaction bottle, add a magnetic stir bar, vacuumize/inflated with nitrogen circulates 3 times, and it is true in taking out Vacuum reaction bottleneck is sealed under empty condition, is put into 140 DEG C of oil bath pan and is reacted 6 h and obtain the polymer of line style.Weigh again 3gBDI and 1.5g leucine diamines, is evacuated and hermetically sealed bottleneck, is put into 50 DEG C of oil bath pan and reacts 4h, obtains final product.

Embodiment 5

2.0g 6-caprolactones, 6.0gPDO, 3.0g PEG-600, stannous octoate are weighed respectively（The 0.03wt% of total amount）As urging Agent, add in vacuum reaction bottle, add a magnetic stir bar, vacuumize/inflated with nitrogen circulates 3 times, and in vacuumizing bar Vacuum reaction bottleneck is sealed under part, is put into 140 DEG C of oil bath pan and is reacted 24 h and obtain the polymer of line style.9gL- is weighed again to rely Propylhomoserin diisocyanate and 3g proline diamines, are evacuated and hermetically sealed bottleneck, are put into 100 DEG C of oil bath pan and react 12h, obtain Final product.

Embodiment 6

9.0g 6-caprolactones, 3.0g PEG-600, You Ji bismuth salt are weighed respectively（The 3wt% of total amount）As catalyst, add true In empty reaction bulb, a magnetic stir bar is added, vacuumize/inflated with nitrogen circulates 3 times, and seal vacuum under vacuumized conditions Bottleneck is reacted, is put into 150 DEG C of oil bath pan and is reacted 14 h and obtain the polymer of line style.12gIPDI and 2.0g first sulphur is weighed again Propylhomoserin diamines, is evacuated and hermetically sealed bottleneck, is put into 60 DEG C of oil bath pan and reacts 24h, obtains final product.

Embodiment 7

9.0g 6-caprolactones, 1.0gPDO, stannous octoate are weighed respectively（The 0.03wt% of total amount）As catalyst, vacuum is added In reaction bulb, add a magnetic stir bar, vacuumize/inflated with nitrogen circulate 3 times, and under vacuumized conditions seal vacuum it is anti- Bottleneck is answered, is put into 140 DEG C of oil bath pan and reacts 18 h and obtain the polymer of line style, add 20ml DMSO or DMF dissolving reaction Product, then 5gL- lysine diisocyanates and 2g valine diamines are weighed, bottleneck is evacuated and hermetically sealed, is put into 50 DEG C of oil bath 4h is reacted in pot, obtains final product.

Embodiment 8

8.0g 6-caprolactones, 2.0g GA, stannous octoate are weighed respectively（The 0.03wt% of total amount）As catalyst, vacuum is added In reaction bulb, add a magnetic stir bar, vacuumize/inflated with nitrogen circulate 3 times, and under vacuumized conditions seal vacuum it is anti- Bottleneck is answered, is put into 120 DEG C of oil bath pan and is reacted 20 h and obtain the polymer of line style.6gL- lysine diisocyanates are weighed again With 2g hydroxyl proline diamines, bottleneck is evacuated and hermetically sealed, is put into 70 DEG C of oil bath pan and reacts 4h, obtain final product.

Embodiment 9

8.0g PDO, 0.5gGA, stannous octoate are weighed respectively（The 0.03wt% of total amount）As catalyst, vacuum reaction bottle is added In, add a magnetic stir bar, vacuumize/inflated with nitrogen circulate 3 times, and under vacuumized conditions seal vacuum reaction bottle Mouthful, it is put into reaction 12h in 90 DEG C of oil bath pan and obtains the polymer of line style, weighs 3gHDI and add in reaction bulb, react 2h, then 1g alanine diamines is added, bottleneck is evacuated and hermetically sealed, is put into 50 DEG C of oil bath pan and reacts 4h, obtain final product.

Embodiment 10

8.0g 6-caprolactones, 0.5g PEG-1000, organic bismuth salt are weighed respectively（The 0.3wt% of total amount）As catalyst, add In vacuum reaction bottle, a magnetic stir bar is added, is vacuumized/inflated with nitrogen circulates 3 times, and is sealed under vacuumized conditions true Sky reaction bottleneck, it is put into reaction 15h in 100 DEG C of oil bath pan and obtains the polymer of line style;Weigh the isocyanic acid of 3gL- lysines two Ester is added in reaction bulb, reacts 2h, and the phenylalanine diamines for adding 1.5g is put into vacuum reaction bottle, is evacuated and hermetically sealed bottle Mouthful, it is put into 40 DEG C of oil bath pan and reacts 4h, obtains final product.

Embodiment 11

9.00g 6-caprolactones, 3.00g PEG-600 are weighed respectively, and stannous octoate is added in test tube, added as catalyst One magnetic stir bar, vacuumize/inflated with nitrogen circulates 3 times, and test tube mouth sealed under vacuumized conditions, it is put into 140 DEG C of oil 24 h are reacted in bath and obtain the polymer of line style, then weigh 2gBDI and 0.8gBDO, are put into test tube, vacuumize simultaneously tube sealing Mouthful.It is put into 70 DEG C of oil bath pan and reacts 12h, obtains final product.

Embodiment 12

Weigh 1gLA, 9gGA, 1g1,3 propane diols, stannous octoate（The 0.03wt% of total amount）As catalyst, a magnetic is added Power stirrer, vacuumize/inflated with nitrogen circulate 3 times, and under vacuumized conditions seal test tube mouth, be put into 110 DEG C of oil bath pan React 12 h and obtain the polymer of line style, weigh 3gL- lysine diisocyanates and 0.6g1,3 propane diols, be put into vacuum reaction In bottle, vacuumize/inflated with nitrogen circulates and is evacuated and hermetically sealed bottleneck 3 times, it is put into 70 DEG C of oil bath pan and reacts 4h, is finally produced Thing.

Embodiment 13

Weigh poly- (hexa-methylene carbonic ester) glycol of 10g（Viscosity average molecular weigh 2000-3000）, organic bismuth salt（Total amount 0.03wt%）As catalyst, a magnetic stir bar is added, weighs 3gL- lysine diisocyanates and 0.6g alanine Diamines, it is put into vacuum reaction bottle, vacuumize/inflated with nitrogen circulates and is evacuated and hermetically sealed bottleneck 3 times, it is put into 70 DEG C of oil bath pan 4h is reacted, vacuum reaction bottle is taken out and is cooled to room temperature, obtains final product.

Embodiment 14

6.0gPDO, 3.0g PEG-600, stannous octoate are weighed respectively（The 0.03wt% of total amount）As catalyst, vacuum is added In reaction bulb, add a magnetic stir bar, vacuumize/inflated with nitrogen circulate 3 times, and under vacuumized conditions seal vacuum it is anti- Answer bottleneck, be put into 100 DEG C of oil bath pan react 16h obtain the polymer of line style, then weigh 2.4gIPDI, 0.6gHDI and 0.6g glycine diamines, is put into vacuum reaction bottle, is evacuated and hermetically sealed bottleneck, is put into 70 DEG C of oil bath pan and reacts.

Embodiment 15

Obtained polyurethane will be reacted above to be dissolved with chloroform, is paved into thick 0.5mm film, is cut into 1cm × 5cm film Block, test fracture productivity ratio are simultaneously placed in PBS solution simultaneously, 37 degree of incubations, observe degradation experiment, as a result as follows：

Scheme two：Synthesis using amino acid as the degradable polyurethane of chain extender

Embodiment 16

9.0g 6-caprolactones, 3.0g PEG-600, You Ji bismuth salt are weighed respectively（The 3wt% of total amount）As catalyst, add true In empty reaction bulb, a magnetic stir bar is added, vacuumize/inflated with nitrogen circulates 3 times, and seal vacuum under vacuumized conditions Bottleneck is reacted, reaction 14h in 130 DEG C of oil bath pan is put into and obtains the polymer of line style.2gIPDI and 2.0g lysines are weighed again Methyl esters dihydrochloride and triethylamine, are evacuated and hermetically sealed bottleneck, are put into 120 DEG C of oil bath pan and react 14h, are finally produced Thing.

Embodiment 17

9.0g 6-caprolactones, 0.5gPDO, stannous octoate are weighed respectively（The 0.03wt% of total amount）As catalyst, vacuum is added In reaction bulb, add a magnetic stir bar, vacuumize/inflated with nitrogen circulate 3 times, and under vacuumized conditions seal vacuum it is anti- Bottleneck is answered, is put into 130 DEG C of oil bath pan and is reacted 18 h and obtain the polymer of line style.20ml DMSO dissolving reaction products are added, 3gL- lysine diisocyanates and 2g ethyl ester of lysine dihydrochloride and triethylamine are weighed again, is evacuated and hermetically sealed bottleneck, are put Enter in 130 DEG C of oil bath pan and react 4h, obtain final product.

Embodiment 18

8.0g 6-caprolactones, 2.0gGA, stannous octoate are weighed respectively（The 0.03wt% of total amount）As catalyst, it is anti-to add vacuum Answer in bottle, add a magnetic stir bar, vacuumize/inflated with nitrogen circulates 3 times, and seal vacuum reaction under vacuumized conditions Bottleneck, it is put into 120 DEG C of oil bath pan and reacts 24 h and obtain the polymer of line style.Weigh again 6gL- lysine diisocyanates and 2g cystine methyl esters dihydrochlorides and triethylamine, are evacuated and hermetically sealed bottleneck, are put into 120 DEG C of oil bath pan and react 4h, obtain Final product.

Embodiment 19

12.0g PDO, 0.5gLA, stannous octoate are weighed respectively（The 0.03wt% of total amount）As catalyst, vacuum reaction is added Bottle in, add a magnetic stir bar, vacuumize/inflated with nitrogen circulate 3 times, and under vacuumized conditions seal vacuum reaction bottle Mouthful, it is put into reaction 24h in 100 DEG C of oil bath pan and obtains the polymer of line style, weighs 3gHDI and add in reaction bulb, react 2h, then 1g omithine methyl esters dihydrochloride and triethylamine are added, bottleneck is evacuated and hermetically sealed, is put into 100 DEG C of oil bath pan and reacts 4h, Obtain final product.

Embodiment 20

8.0gPDO, 0.5gGA, organic bismuth salt are weighed respectively（The 0.3wt% of total amount）As catalyst, vacuum reaction bottle is added In, add a magnetic stir bar, vacuumize/inflated with nitrogen circulate 3 times, and under vacuumized conditions seal vacuum reaction bottle Mouthful, it is put into 90 DEG C of oil bath pan and reacts 24 h and obtain the polymer of line style.The addition of 3gL- lysine diisocyanates is weighed again In reaction bulb, 2h is reacted, the phenylalanine diamines for adding 1.5g is put into vacuum reaction bottle, is evacuated and hermetically sealed bottleneck, puts Enter in 100 DEG C of oil bath pan and react 4h, obtain final product.

Scheme three：Soft segment is selected from the degradable polyurethane of PPDO, PDO and GA or PDO and CL copolymers：

Embodiment 21

9.00g PPDO glycol is weighed respectively（Molecular weight 2000）, 3gLDI and 0.6g1, ammediol, stannous octoate（Total amount 0.03wt%）As catalyst, add in vacuum reaction bottle, add a magnetic stir bar, vacuumize/inflated with nitrogen circulation 3 It is secondary, it is put into reaction 24h in 100 DEG C of oil bath pan and obtains final product.

Embodiment 22

Weigh 16gPDO and 1gGA to be placed in vacuum reaction bottle, be put into reaction 24h in 140 DEG C of oil bath pan and obtain the polymerization of line style Thing, 3g HDI reaction 0.5h are added, 1g 1, ammediol is added, is put into vacuum reaction bottle, is evacuated and hermetically sealed bottleneck, put Enter in 120 DEG C of oil bath pan and react 24h, obtain final product.

Embodiment 23

Weigh 6gPDO and 1gCL to be placed in vacuum reaction bottle, be put into reaction 12h in 130 DEG C of oil bath pan and obtain the polymerization of line style Thing, 2g BDI reaction 4h are added, 0.5g1, ammediol is added, is put into vacuum reaction bottle, is evacuated and hermetically sealed bottleneck, be put into 24h is reacted in 110 DEG C of oil bath pan, obtains final product.

Embodiment 24

Weigh 9gGA and 1gCL to be placed in vacuum reaction bottle, be put into 120 DEG C of oil bath pan, add dimethylbenzene, evaporation removes one Partial solvent, reaction 16h obtain the polymer of line style, add 2g LDI reaction 12h, add 1g1, ammediol, be put into 120 DEG C Oil bath pan in, react 12h under vacuum state, obtain final product.

Embodiment 25

9g Lanthanum Isopropoxides, 2g PEG-400, stannous octoate are weighed respectively（The 0.03wt% of total amount）As catalyst, add In vacuum reaction bottle, a magnetic stir bar is added, is vacuumized/inflated with nitrogen circulates 3 times, and is sealed under vacuumized conditions true Sky reaction bottleneck, it is put into reaction 18h in 100 DEG C of oil bath pan and obtains the polymer of line style.2gLDI and 0.6g1,3- third are weighed again Glycol, it is put into vacuum reaction bottle, is evacuated and hermetically sealed bottleneck, is put into 100 DEG C of oil bath pan and reacts 4h, finally produced Thing.

Method four：With DTT or LTI end-blockings or the polyurethane of crosslinking

In the second step of above example, when adding diisocyanate or chain extender progress chain extension, it is different to add 1B three Cyanate/DTT is blocked, and prepares the polyurethane of high elongation at tear, and wherein preparation method is exemplified below：

One of method：The polymer diol obtained by method provided in an embodiment of the present invention, it is less than 10ppm ring in moisture Reacted 20 minutes in double screw extruder extruder under border, stirring polymerization extrusion, the polyurethane for obtaining high elongation at tear is fine Dimension；

The two of method：The polymer diol obtained by method provided in an embodiment of the present invention, it is less than 10ppm ring in moisture Poured under border in kneading machine or kneader, be directly added into 1B triisocyanate/DTT and be sufficiently stirred, normal-temperature reaction half Hour both obtained；

The three of method：The polymer diol obtained by method provided in an embodiment of the present invention, add anhydrous organic solvent and be configured to Viscous solution, in the environment of moisture is less than 10ppm, it is directly added into 1B triisocyanate/DTT, reaction system Stirring or concussion mixing, vacuum is drained organic solvent and both obtained after normal-temperature reaction half an hour, and wherein organic solvent is selected from toluene, to two Toluene, decane, isoamyl acetate, hexane, benzene, dichloromethane, chloroform, 1,4 cyclohexanone, ketone, dimethylformamide, heptan One or both of alkane, dimethylamino formamide, tetrahydrofuran, petroleum ether, dimethyl sulfoxide, ethylene glycol terephthalate, It is preferred that one or both of tetrahydrofuran, dichloromethane, chloroform and 1,4 cyclohexanone are combined.

Embodiment is exemplified below：

Embodiment 26

6.00g 6-caprolactones and 3.00g Lanthanum Isopropoxides, 1.00gPEG300, organic bismuth salt are weighed respectively（Total amount 0.03wt%）As catalyst, add in vacuum reaction bottle, add a magnetic stir bar, vacuumize/inflated with nitrogen circulation 3 It is secondary, and vacuum reaction bottleneck is sealed under vacuumized conditions, it is put into 140 DEG C of oil bath pan and reacts 24 h and obtain the polymerization of line style Thing.5gL- lysine diisocyanates and 1.0g tetraethylene glycols are weighed again, are put into vacuum reaction bottle, are evacuated and hermetically sealed bottleneck, Be put into 70 DEG C of oil bath pan and react 4h, obtain final product, moisture be less than 10ppm in the environment of pour into kneading machine or In person's kneader, it is directly added into 2.0gL- LTIs and is sufficiently stirred, normal-temperature reaction half an hour both obtained.

Embodiment 27

6.00g 6-caprolactones, 2.00g PEG-400, stannous octoate are weighed respectively（The 0.03wt% of total amount）As catalyst, Add in vacuum reaction bottle, add a magnetic stir bar, vacuumize/inflated with nitrogen circulates 3 times, it is and close under vacuumized conditions Vacuum reaction bottleneck is sealed, is put into 140 DEG C of oil bath pan and is reacted 24 h and obtain the polymer of line style.Weigh again 6gIPDI and 0.6g1,5- pentanediol, it is put into vacuum reaction bottle, is evacuated and hermetically sealed bottleneck, is put into 100 DEG C of oil bath pan and reacts 4h, obtain To final product.

Embodiment 28

Weigh poly- (4- butyric esters) glycol of 10g（Molecular weight 4000）, stannous octoate（The 0.03wt% of total amount）As urging Agent, a magnetic stir bar is added, weighs 3gLDI and 0.6gBDO, is put into vacuum reaction bottle, vacuumize/inflated with nitrogen follows Ring is evacuated and hermetically sealed bottleneck 3 times, is put into 70 DEG C of oil bath pan and reacts 4h, and vacuum reaction bottle is taken out and is cooled to room temperature, Addition 0.6gL- LTIs are blocked in the environment of moisture is less than 10ppm, and 30min is stirred at room temperature and obtains Final product.

Embodiment 29

Weigh 10gPLGA glycol, stannous octoate（The 0.03wt% of total amount）As catalyst, a magnetic stir bar is added, 3gL- lysine diisocyanates and 0.6g1, ammediol are weighed, is put into vacuum reaction bottle, vacuumizes/inflated with nitrogen circulation 3 It is secondary to be evacuated and hermetically sealed bottleneck, 70 DEG C of oil bath pan reaction 4h is put into, in the environment of moisture is less than 10ppm, will be reacted Product is added in kneading machine, is added 0.6gDTT and is blocked, 30min is stirred at room temperature and obtains final product.

Embodiment 30

Glycolic (4g), L- lactic acid (12g) and BDO (1.1g) are weighed, 80 DEG C of high vacuum dry dehydrations in vacuum reaction bottle, Stop reaction after 150 DEG C of reaction 48h, add HDI (2g) and stannous octoate (0.02wt% of total amount) in 70 DEG C of oil baths 6h is reacted in pot, obtains final product, adding 0.6gL- LTIs under vacuum environment is blocked, room temperature concussion Or stirring 30min obtains final product.

Embodiment 31

Weigh glycolic (4g), DL- lactic acid (12g) and 1,6- hexylene glycol (1.8g), 80 DEG C of high vacuum in vacuum reaction bottle Drying and dehydrating, 150 DEG C are reacted stopping reaction after 24h, add IPDI (2g) and stannous octoate (0.02wt% of total amount) exists 6h is reacted in 70 DEG C of oil bath pan, obtains final product, vacuum reaction bottle is taken out and is cooled to room temperature, adds 1.0gL- lysines Triisocyanate is blocked, and is mediated stirring 30min repeatedly by kneader and is obtained final product.

Embodiment 32

Glycolic (8g), L- lactic acid (12g) and BDO (0.8g) are weighed, 80 DEG C of high vacuum dries take off in vacuum reaction bottle Water, 150 DEG C are reacted stopping reaction after 24h, add LDI (2.8g) and stannous octoate (0.02wt% of total amount) at 70 DEG C 6h is reacted in oil bath pan, vacuum reaction bottle is taken out and is cooled to room temperature, 20ml tetrahydrofurans is added and dissolves material, add 1.6g DTT are blocked, and stirring 30min obtains final product.Obtain final product.

Embodiment 33

Weigh poly- (hexa-methylene carbonic ester) glycol of 10g, stannous octoate（The 0.03wt% of total amount）As catalyst, add One magnetic stir bar, weighs 3gL- lysine diisocyanates and 0.6gBDO, is put into vacuum reaction bottle, vacuumizes/nitrogen charging Gas is circulated 3 times and is evacuated and hermetically sealed bottleneck, is put into 70 DEG C of oil bath pan and reacts 4h, and vacuum reaction bottle is taken out and is cooled to room Temperature, in the environment of moisture is less than 10ppm, adds 1.6gL- LTIs and blocked, is stirred at room temperature 30min obtains final product.

Biodegradable stent compound embodiment 1：Blood vessel covered stent

Its preparation process is as follows：

(1) degradable metal material is worked out, carved, etched or cut into the decorative pattern or lath-shaped of needs, stent diameter 1mm, Long 2cm；

(2) will（1）The support polishing of middle preparation, 24h is soaked in mass percent is 30% hydrofluoric acid, with 75% after taking-up Ethanol washing, dry；

(3) by polymer（The polyurethane that the present embodiment 2 obtains）It is dissolved in chloroform solvent, on tetrafluoroethene plate upper berth The film thick into 0.2-0.3mm；

(4) will（3）The film roll of preparation exists（1）The metallic support metal material surface of middle preparation, is made overlay film frame；

(5) will（4）The composite of middle preparation passes through dip-coating or spraying hydrophilic coating（Such as chitosan, hyaluronic acid, glue Aqueous solution etc. made of former, cellulose）, dry up, polish, be polished to overlay film frame.

Biodegradable stent compound embodiment 2：Urethra overlay film frame

Using double sacculus urethra rack made of silica gel material, support pressure or be attached on cylinder balloon, after being put into urethra, to Gas injection in sacculus, cylinder balloon strut support, are supported on urethra area.

Wherein peritonaeum urethra rack, its preparation process are as follows：

(1) degradable metal material is worked out, carved, etched or cut into the decorative pattern or lath-shaped of needs, stent diameter 3mm, Long 2cm；

(2) the degradable medical polyurethane material and polymer B obtained the present embodiment 8: PLGA（Wherein LA:G/A ratio is 70：30, viscosity average molecular weigh is 80,000）By 1：2 mixed dissolutions are paved into 0.2- in dichloromethane solvent on tetrafluoroethene plate Film thick 0.3mm；

(3) will（2）The film roll of preparation exists（1）The metallic support metal material surface of middle preparation, is made overlay film frame；

(4) will（3）The composite of middle preparation passes through dip-coating or spraying hydrophilic coating（Such as chitosan, hyaluronic acid, glue Aqueous solution etc. made of former, cellulose）, dry up, polish, be polished to overlay film frame.

Biodegradable stent compound embodiment 4：Ureter bracket

Its preparation process is as follows：

(1) by degradable metal material（The selection of alloying component ratio is by list 1 or content of magnesium 99%, Mn contents 1% Magnesium-manganese alloy）External diameter 1mm, wall thickness 0.2mm, long 40cm pipe are pulled into, is engraved as the decorative pattern needed；

(2) the degradable medical polyurethane material and polymer B obtained embodiment 29: PLGA（Wherein LA:G/A ratio is 60： 40, viscosity average molecular weigh is 30,000）By 1：1 mixed dissolution is paved into 0.2-0.3mm in dichloromethane solvent on tetrafluoroethene plate Thick film；

(4) will（3）The composite of middle preparation passes through dip-coating or spraying hydrophilic coating（Such as chitosan, hyaluronic acid, glue Aqueous solution etc. made of former, cellulose）, dry up, polish, being polished to overlay film ureter bracket.

Biodegradable stent compound embodiment 5：With 3D printing technique prepare can gradient degradation ureter bracket

From the 3D printer with two feeding devices, magnesium alloy powder is added in a feeding device（Powder diameter is 30- 80um）, high polymer material is added in another feeding device（Degradable medical polyurethane material and PLA are in proportion（1：1）, It is 30% solution to be configured to percentage concentration with chloroform）, ureter bracket length（15-40cm, uniformly it is divided into 8 sections）, magnesium alloy Powder：High polymer material weight ratio from（1：1-1：8）It is divided into 8 part gradient printings, prints the support being sized with shape, Heated-air drying volatilizes organic solvent and both obtained.

The support printed, the surface treatment such as dip-coating or spraying can be carried out according to product requirement.

Biodegradable stent compound embodiment 6：Intravascular stent is prepared with 3D printing technique

From the 3D printer with two feeding devices, magnesium alloy powder is added in a feeding device（Powder diameter is 30- 80um）, high-temperature fusion prints the support of setting decorative pattern on demand, and Passivation Treatment is standby, is added in another feeding device high Molecular material（Degradable medical polyurethane material and PLA are in proportion（1：3）, being configured to percentage concentration with chloroform is 50% solution）, coating film is printed, heated-air drying volatilizes organic solvent and both obtained.

Biodegradable stent compound embodiment 7：The implantation degradation experiment observation of urethra rack beasle dog

The double sacculus urethra racks that will be prepared in embodiment 1,2, use oxirane disinfection.6 body weight 12KG of selection or so ratio Lattice dog, the urethra for being implanted into dog respectively are observed, every group 3, the swelling degree of postoperative routine observation urethra area, serology, Histotomy is observed.Test result indicates that：Support in embodiment 1 starts to degrade after 2 weeks, and degraded in 6 weeks is complete；In embodiment 2 Support start to degrade within 4 weeks, 8 weeks are degradable, and urethra area tissue inflammation reaction is light, and histocompatbility is fine, have fine Supporting role.

Described above is the preferred embodiment of the present invention, it is noted that for those skilled in the art For, on the premise of principle of the present invention is not departed from, some improvements and modifications can also be made, these improvements and modifications It should be regarded as protection scope of the present invention.

Claims

1. a kind of degradation time is controllable, the adjustable medical degradable polyurethane of elongation at break, it is characterised in that is revived using two sulphur Sugar alcohol, dihydric alcohol, amino acid, derivative and its salt of two amino of band and a molecule dihydric alcohol and two molecule amino acid are with two One kind in the connected amino acids diamine of ester bond makees chain extender, wherein, amino acids diamine makees the structural formula of chain extender It is as follows：

,

Wherein, P is dihydric alcohol, and X is 2-20 numeral, and m and n are the one kind for commonly using 20 kinds of amino acid.

2. degradation time according to claim 1 is controllable, the adjustable medical degradable polyurethane of elongation at break, its feature It is, soft segment is the polymer of one or both of GA, LA, PDO, CL and PEG combination, and hard section is selected from diisocyanate, Hard section is chosen in particular from：1,6- hexamethylene diisocyanate, isoflurane chalcone diisocyanate, lysine methyl ester diisocyanate, Ethyl ester of lysine diisocyanate, cis-cyclohexane diisocyanate, trans-cyclohexane diisocyanate, Isosorbide-5-Nitrae-butane Diisocyanate, butane diisocyanate, 1,2- ethane diisocyanate, 1,3- propane diisocyanate, 4,4 '-methylene Base-bis- (cyclohexyl isocyanate), IPDI, 2,4,4- trimethyls 1, in 6- hexane diisocyanates It is one or two kinds of；

The dihydric alcohol is chosen in particular from ethylene glycol, diethylene glycol (DEG), tetraethylene glycol, 1,3- propane diols, Isosorbide-5-Nitrae-butanediol, 1,5- penta 2 Alcohol, 1,6- hexylene glycols, 1,7- heptandiols, 1,8- ethohexadiols, 1,9- nonanediols, one kind in 1,10- decanediols or two Kind.

3. a kind of degradation time is controllable, the preparation method of the adjustable medical degradable polyurethane of elongation at break, it is characterised in that To control the elongation at break of polyurethane, prepared using two step method, specific preparation method is as follows：

Soft segment is selected from one or both of GA, LA, PDO, CL and PEG polymer, and hard section is in diisocyanate One kind in one kind, preferably LDI, IPDI, HDI or 1,3- propane diisocyanate, chain extender selection amino acids diamines, is closed It is as follows into scheme：

Soft segment compound or composition and catalyst are placed in vacuum reaction bottle by inventory, are put into 70-140 DEG C of oil bath pan Middle reaction 4-24 h obtain the polymer of line style, then weigh the di-isocyanate reaction 0.5-12h of proper proportion, use appropriate solvent Dissolve or be directly added into amino acids diamines chain extension and connect, be evacuated and hermetically sealed bottleneck, be put into 0-120 DEG C of oil bath pan and react 2- 12h, final product is obtained,

Soft segment is selected from one or both of GA, LA, PDO, CL and PEG polymer, and hard section is in diisocyanate One kind in one kind, preferably LDI, IPDI, HDI or 1,3- propane diisocyanate, chain extender are selected from the ammonia of two amino of band Base acid, derivative and its salt, specifically include amino acid hydrochloride salt, such as lysine methyl ester dihydrochloride, the hydrochloric acid of ethyl ester of lysine two Salt, cystine methyl esters dihydrochloride, cystine ethyl ester dihydrochloride, omithine methyl ester dihydrochloride, the hydrochloric acid of ornithine ethyl ester two One kind in salt, synthetic schemes are as follows：

Soft segment compound or compound are combined, PDO, PEG or monomer CL, LA, GA is referred specifically to and catalyst is placed in by inventory In vacuum reaction bottle, it is put into reaction 4-24 h in 70-140 DEG C of oil bath pan and obtains the polymer of line style, add diisocyanate 0.5-12h is reacted, the amino acids chain extender and triethylamine of proper proportion are dissolved or be directly added into appropriate solvent, is vacuumized simultaneously Bottleneck is sealed, is put into 50-150 DEG C of oil bath pan and continues to react 2-24h, obtain final product；

（3）Soft segment is selected from the degradable polyurethane of PPDO, PDO and GA or PDO and CL copolymers：

Soft segment is selected from PPDO, PDO and GA or one or both of CL and PDO and combined, hard section in isocyanates one Kind, preferably one kind in LDI, IPDI, HDI or 1,3- propane diisocyanate, chain extender select 1, ammediol, synthesis side Case is as follows：

Anhydrous PPDO, PDO and GA or CL and PDO and catalyst by proportion are placed in vacuum reaction bottle, are put into 120-160 DEG C Oil bath pan in reaction 4-24 h obtain the polymer of line style, add the 1B di-isocyanate reaction 0.5- of proper proportion 12h, dissolved with appropriate solvent or be directly added into 1, ammediol, be put into vacuum reaction bottle, be evacuated and hermetically sealed bottleneck, be put into 2-24h is reacted in 50-150 DEG C of oil bath pan, obtains final product；

The one kind of the catalyst in stannous octoate, organic zinc or organic bismuth salt, dosage are the 0.001- of total amount of feeding 10wt%；The organic solvent is selected from high boiling solvent, specifically includes fatty alcohol, DMSO, DMF, 1,4- dioxane, positive fourth One kind in alcohol, isobutanol, dimethylbenzene and toluene；

Obtained degradable polyurethane elongation at break is different according to soft and hard segments component, adjustable in the range of 100%-700%.

4. degradation time according to claim 3 is controllable, the preparation of the adjustable medical degradable polyurethane of elongation at break Method, it is characterised in that the chain extender is selected from LTI or DTT, described with the webbed cross-linked structure of shape The elongation at break of urethane composition is higher than 300MPa, and elongation at break is in the range of 30%~700%, and reaction is selected from as follows One of mode：

（1）Degradable polyurethane prepared by two step method in claim 3, adds two sulphur threoses during second step chain extension Alcohol or LTI, reacted 20 minutes in double screw extruder of the moisture less than 10ppm, stirring polymerization is squeezed Go out, obtain the urethane composition with high elongation at tear；

（2）Degradable polyurethane prepared by two step method in claim 3 is small in moisture during second step chain extension Poured into the environment of 10ppm in kneading machine or kneader, be directly added into dithiothreitol (DTT) or LTI fills Divide stirring, normal-temperature reaction half an hour obtains the urethane composition with high elongation at tear；

（3）Degradable polyurethane prepared by two step method in claim 3, is added anhydrous organic during second step chain extension Solvent is configured to viscous solution, and DTT or LTI are directly added into the environment of moisture is less than 10ppm, Reaction system stirs or concussion mixing, and vacuum drains organic solvent and obtains having high elongation at tear after normal-temperature reaction half an hour Urethane composition.

5. a kind of degradation time any one of claim 1 ~ 4 is controllable, the adjustable medical degradable of elongation at break gathers The application of urethane, it is characterised in that for preparing medical embedded material, the medical embedded material can be used alone, can be compound Compound use is made in other high polymer material blendings, can be used for implantation equipment, implantable artificial organs, the artificial device of contact Official, support, interposing catheter, artificial skin, tissue engineering bracket and organ servicing unit, when as medical embedded material, Further purification is needed to remove toxic monomers or organic solvent.

6. degradation time according to claim 5 is controllable, the application of the adjustable medical degradable polyurethane of elongation at break, Characterized in that, the medical embedded material includes contrast agent, it is extremely similar that the contrast agent is selected from conventional radiocontrast medium Thing, in addition to zirconium, barium, Dian, Manganese, iron, lanthanum, cerium, praseodymium, etc. combination or form complexed ionic species.

7. a kind of degradation time any one of claim 1 ~ 4 is controllable, the adjustable medical degradable of elongation at break gathers The application of urethane, it is characterised in that the medical degradable polyurethane can be compound with degradation material, is made degradable compound Material is implanted into, the degradation material includes degradable high polymer material and degradable metal material, wherein, it is described medical to drop Polyurethane is solved with the weight ratio of degradable metal material in 0.1-99%：In the range of 1%-99.9%, the degradable metal material bag Include iron of the purity more than 99.0%, purity is more than 99.0% magnesium, percentage by weight 1：0.01-10 Mg-Fe alloy, weight percent Than for 1：0.01-1 Mg-Zn based alloy, percentage by weight 1：0.01-1 magnesium calcium alloy, percentage by weight 1：0.01- One or both of 0.1 Magnesium-aluminum alloys combine.

8. a kind of degradation time any one of claim 1 ~ 4 is controllable, the adjustable medical degradable of elongation at break gathers The application of urethane, it is characterised in that the medical degradable polyurethane is used to prepare biodegradable stent compound, including following step Suddenly：

（1）Degradable metal material is worked out, carved, etched or cut into the decorative pattern or lath-shaped metallic support of needs, preferably Decorative pattern a diameter of 0.01 to 3mm；

（2）Medical degradable polyurethane, polyurethane and the combination of other high polymer materials it will be dissolved in as described in claim 1-4 In solvent, coating material is made；

（3）By step（2）The coating material of preparation dip-coating, even application or is made film and is attached to step repeatedly（1）The gold of preparation Belong to rack surface, the compound rest with overlay film is made, the thickness of the overlay film is in the range of 0.001-1mm, preferably 0.01- 0.5mm；

（4）By step（3）The compound rest with overlay film of middle preparation is by dip-coating or spraying hydrophilic coating, and polishing grinding is into can Degraded scaffold complex.

9. a kind of degradation time any one of claim 1 ~ 4 is controllable, the adjustable medical degradable of elongation at break gathers The application of urethane, it is characterised in that the medical degradable polyurethane is used to prepare biodegradable stent compound, described degradable The preparation method of scaffold complex is one of following method：

（1）Magnesium alloy powder is well mixed with the solution of the urethane composition as any one of claim 1-4, led to Cross 3D printer and print the support for needing diameter and wall thickness, the dry organic solvent of heated-air drying volatilization, obtain biodegradable stent and answer Compound；

（2）3D printer is set into two feeding devices, adds magnesium alloy powder in a feeding device, another feeding device The solution of middle urethane composition of the addition as any one of claim 1-4, two kinds of materials during charging by than The support being sized with shape is printed after example mixing, the dry organic solvent of heated-air drying volatilization, it is compound to obtain biodegradable stent Thing；

（3）3D printer sets two feeding devices, magnesium alloy powder is added in a feeding device, in another feeding device Be proportionally added into urethane composition and PLA as any one of claim 1-4, be mixed be dissolved in it is organic In solvent, it is 20-90% to be configured to percentage concentration with organic solvent, and two kinds of materials print after being mixed in proportion during charging Go out the support being sized with shape, the dry organic solvent of heated-air drying volatilization, obtain biodegradable stent compound；

（4）3D printer sets two feeding devices, adds magnesium alloy powder in a feeding device, high-temperature fusion is beaten on demand Support is printed off, Passivation Treatment is standby；It is proportionally added into another feeding device poly- as any one of claim 1-4 Urethane composition and PLA, are then mixed and are dissolved in organic solvent, and being configured to percentage concentration with organic solvent is 20-90%, coating film is printed on support, the dry organic solvent of heated-air drying volatilization, obtains biodegradable stent compound.

10. the application of biodegradable stent compound prepared by a kind of any one of claim 8 or 9, it is characterised in that it is described Structure, composition and the shape of biodegradable stent compound be applied to blood vessel, vein, oesophagus, biliary tract, trachea-bronchial epithelial cell, small intestine, Large intestine, urethra, ureter or other fragments close to tubular body passage.