CN112386747A - Ureteral stent tube with shape memory function and preparation method and application thereof - Google Patents
Ureteral stent tube with shape memory function and preparation method and application thereof Download PDFInfo
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- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
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- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/16—Materials with shape-memory or superelastic properties
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- A61L2400/00—Materials characterised by their function or physical properties
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- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
- C08J2475/06—Polyurethanes from polyesters
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- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
Abstract
The invention provides a ureteral stent tube with a shape memory function and a preparation method and application thereof, and relates to the fields of high polymer material processing and biomedicine. The invention utilizes the prepared PLGA and polycaprolactone-based polyurethane prepared by taking PCL-diol (polycaprolactone diol) as raw materials to be blended according to a certain proportion for melt extrusion molding, and then uses gelatin for modification, thereby preparing the gelatin modified ureteral stent tube with the deformation temperature close to body temperature, good elasticity, high flexibility, good shape memory performance, good biocompatibility and biodegradability. The product prepared by the invention effectively overcomes the problems of difficult intubation, uncomfortable long-term in vivo implantation, poor shape memory performance, difficult degradation of the material and the like. Therefore, the degradable shape memory ureteral stent tube has very important practical significance and application value.
Description
The original invention patent applied by the divisional patent is applied for 2017, 06 and 02 days, and the application numbers are as follows: 201710406473.5, entitled "a method for preparing ureteral stent tube with shape memory effect and application thereof".
Technical Field
The invention relates to the fields of polymer material processing and biomedicine, in particular to a ureteral stent tube with a shape memory function and a preparation method and application thereof.
Background
With the development and development of human civilization, the health level and the average life expectancy of Chinese people have been remarkably improved in recent years. However, various diseases related to the obstruction and damage of the urinary tract threaten the physical health of more and more people gradually, and seriously affect the quality of life of people. At present, in the process of treating various diseases related to urinary tract obstruction and injury, a ureteral stent plays an important role, and in the ureteral stent, a stent material which is the most critical part is mostly made of a high polymer material and is mainly classified into three main types: the first is an addition polymer comprising polyethylene and polytetrafluoroethylene stent tubing; the second type is a condensation polymer comprising polyurethane and a silica gel stent tube; the third is a block copolymer, mainly a polysiloxane stent tube. Among these materials, polyurethane and silica gel stent tubes are ideal in clinical various indexes, are heat-resistant high polymer, and have good elasticity and biocompatibility. The patient with long-term tube placement has no discomfort, is the preferred material for long-term tube placement, and is more suitable to be used as the ureteral stent material. However, clinical feedback information shows that the catheter has thick wall, poor uniformity, small inner diameter and poor rigidity, even if a guide wire is used for intubation, the guide wire is difficult to help, the material is not easy to degrade, shape memory is difficult to realize, and the clinical application difficulty is increased. Therefore, people hope to find a novel degradable ureteral stent material with a shape memory function through various approaches.
Polylactic acid (PLA) and polyglycolic acid (PGA) are the most typical synthetic degradable polymers, and are also the most structurally simple linear polyhydroxyalkanoates. They are the first degradable and absorbable materials approved by the FDA in the united states for clinical use and are the most widely studied and most used degradable biomaterials to date. Copolymers of PLA and PGA polylactic-co-glycolic acid (PLGA) has also been used for decades as absorbable sutures and is now widely used in tissue engineering. Polylactic acid polymers are very important thermotropic memory materials, and are the most widely studied materials in biodegradable shape memory polymers due to simple structure, easy realization of preparation conditions and excellent performance. The research of the novel degradable shape memory ureteral stent based on polylactic acid has more practical significance and application value.
The preparation of biodegradable ureteral stent tubes by using lactide, glycolide and epsilon-caprolactone monomers as raw materials has been reported in some documents and patents. CN1712426A adopts supercritical carbon dioxide fluid as reaction medium, metal oxide or metal salt as initiator, and lactide and glycolide mixture as raw material to prepare copolymer PLGA. In CN1672739, the material is epsilon-caprolactone-lactide copolymer or epsilon-caprolactone and lactide or/and glycolide copolymer, and the degradable and absorbable ureter stent is prepared. CN103374208A arranges two aliphatic polyesters with different degradation speeds from low to high or from high to low in sequence and connects the two aliphatic polyesters in a melting way to prepare wires, sheets, pipes, drug controlled release carriers, reinforced mesh fabrics, drug carriers, cartilage tissue culture scaffolds, scaffold tubes and the like which can be degraded in a gradient way. CN101422634 prepares biodegradable ureter stent tubes with different sizes, degradation rates and mechanical strength by a dip forming method. CN103041454A compounds L-lactide/epsilon-caprolactone copolymer and cross-linked polyvinylpyrrolidone, and the prepared ureteral stent has good biocompatibility, reduces the surface friction coefficient and increases the degradation rate. However, these studies focus on the study of their biodegradability, the shape memory effect and deformation temperature of ureteral stent are mentioned less, and no detailed report is made on their biocompatibility. The two ends of the ureteral stent tube are of coiled structures, one end of the ureteral stent tube is arranged in a renal pelvis, and the other end of the ureteral stent tube is arranged in a bladder, and the coiled structures at the two ends bring certain difficulties for the implantation of the ureteral stent tube in the operation process. The ureteral stent tube with shape memory can be pretreated before an operation, and the coiled structures at the two ends are straightened, so that the adverse effect caused by the coiled structures in the tube placing process is avoided, the pretreated stent tube is delivered to the corresponding part at a set implantation speed, and is restored to the original coiled structure at a normal human body temperature, and the supporting and drainage functions of the ureteral stent tube are further exerted.
Therefore, in order to meet the clinical performance requirements of the ureteral stent, on the basis of the research, according to the shape memory performance required by medical application, the polylactic-co-glycolic acid (PLGA) and the polycaprolactone-based polyurethane are utilized to prepare the ureteral stent which not only has good biodegradability and biocompatibility, but also has the shape memory effect.
Disclosure of Invention
The invention aims to provide a preparation and modification method of a medical shape memory ureter stent. In order to achieve the purpose, the invention utilizes the prepared PLGA and polycaprolactone-based polyurethane prepared by taking PCL-diol (polycaprolactone diol) as raw materials to be blended in a certain proportion for melt extrusion molding, and then gelatin is used for modification, so that the gelatin-modified ureteral stent tube which has the advantages of similar deformation temperature and body temperature, good elasticity, high flexibility, good shape memory performance, good biocompatibility and biodegradability is prepared. The problems of difficult intubation, uncomfortable implantation in vivo for a long time, poor shape memory performance, difficult degradation of the material and the like are solved. Therefore, the research on the degradable shape memory ureteral stent tube has very important practical significance and application value.
A ureteral stent tube with a shape memory function is prepared by the following steps:
(1) preparing PLGA by using L-lactide and glycolide monomers as raw materials by adopting a ring-opening polymerization method;
(2) PCL-diol monomer is used as raw material, and polycondensation method is adopted to prepare polycaprolactone-based polyurethane;
(3) mixing PLGA and polycaprolactone-based polyurethane, and preparing a hollow ureteral stent tube by a melt extrusion method;
(4) the prepared ureteral stent is subjected to plasma treatment, gelatin is fixed on the surface, and the performance of the surface of the ureteral stent is modified.
Further, the specific preparation method in the step (1) is as follows:
(1) the ring-opening polymerization method is adopted to prepare PLGA: mixing L-lactide and glycolide monomers according to the molar ratio of 5-9:1-5, adding a reactant, wherein the addition amount of the reactant is 1-2% of the total mass percent of the L-lactide and the glycolide, filling nitrogen into a reaction system, performing degassing treatment, and performing constant-temperature polymerization reaction at 140-160 ℃ for 6-10 hours after degassing; after the reaction is finished, adding an organic solvent A in proportion, wherein the total mass ratio of the organic solvent A to the system after the last step of constant-temperature polymerization is 5-15:1, and obtaining a polymer solution; dropwise adding the polymer solution into a precipitator A, stirring, and precipitating to obtain a purified product A, wherein the volume ratio of the polymer solution to the precipitator A is as follows: 1-2: 4-16; and drying the purified product A to constant weight to obtain PLGA.
Further, the reactant is a catalyst A and an initiator, and the addition proportion of the catalyst A to the initiator is 0.5-1% and 0.5-1% of the total mass percent of the L-lactide and the glycolide respectively;
further, the catalyst A is one of stannous octoate and stannous chloride, and the initiator is one of n-dodecanol and octadecanol;
further, the flow rate of the nitrogen is 0.4-0.7L/min, and degassing circulation is carried out for 2-4 times through the double-row pipe;
further, the organic solvent A is at least one of chloroform, dichloromethane and toluene, and the precipitant A is at least one of ethanol, methanol, diethyl ether and n-hexane;
further, the dropping speed of the polymer solution is 1-10 drops/second;
further, the drying temperature of the purified product A is 40-50 ℃;
further, the specific preparation method in the step (2) is as follows:
the polycaprolactone-based polyurethane is prepared by adopting a two-step polycondensation reaction: firstly, mixing PCL-diol with an organic solvent B according to a mass ratio of 1-3:3-7 to obtain a dissolved solution; adding isocyanate with the mass percent of 25-40% of PCL-diol, and stirring for 2-2.5h at the temperature of 60-80 ℃; adding chain extenders in sequence according to a proportion, mixing, adding a catalyst B according to a proportion, and raising the temperature to 85-95 ℃ for reaction for 10-12h to obtain a reaction solution; and cooling the reaction liquid to room temperature of 25-35 ℃, dropwise adding the reaction liquid into a precipitator B to obtain a purified product B, wherein the volume ratio of the reaction liquid to the precipitator B is 1:4-8, and drying the purified product B in a freeze dryer for 24 hours to finally obtain the polycaprolactone-based polyurethane.
Further, the addition proportion of the chain extender is 4-8% of the total mass of the reaction system after the isocyanate is added for reaction in the last step, and the addition proportion of the catalyst B is 0.3-0.8% of the total mass of the reaction system after the chain extender is added in the last step;
the dropping speed of the reaction liquid is 1-10 drops/second;
the organic solvent B is one of N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran and trichloromethane;
the isocyanate is one of diphenylmethane diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, 4,4' -dicyclohexylmethane diisocyanate, isophorone diisocyanate and L-lysine diisocyanate; the chain extender is one of 1, 4-butanediol, ethylene glycol, polyethylene glycol, propylene glycol and 1, 6-hexanediol;
the catalyst B is one of stannous octoate, stannous chloride and dibutyltin dilaurate;
the precipitant B is one of diethyl ether, methanol, ethanol and n-hexane;
further, the specific preparation method in the step (3) is as follows:
and blending PLGA and polycaprolactone-based polyurethane, and performing melt extrusion through an extruder to obtain the ureter hollow stent tube.
Further, blending PLGA and polycaprolactone-based polyurethane according to a mass ratio of 5-9:1-5, adding the mixture into an extruder, conveying the mixture forwards under the action of a screw rod to enable a high polymer material to be converted from a solid into a molten fluid state, enabling the high polymer melt to be in a tubular shape through a filter screen and a flow distribution plate, and then shaping, cooling and pulling the tubular shape to prepare the ureteral hollow stent tube.
The melt extrusion temperature is 160-180 ℃, the heat setting temperature is 90-110 ℃, and the cooling temperature is 25-30 ℃.
Further, the specific preparation method in the step (4) is as follows:
preparing a gelatin modified ureteral stent: treating the surface of the hollow ureteral stent by adopting oxygen plasma, wherein the gas pressure is 100-140mTorr, the power is 5-15W, the time duration is 0.5-3min, then soaking the hollow ureteral stent in a 1-5% by mass 3-aminopropyltriethoxysilane solution for 20-40min, then transferring the hollow ureteral stent to a 0.1-1% by mass 1, 5-glutaraldehyde solution for soaking for 5-15h, then soaking the hollow ureteral stent in a 0.05-0.15% by mass gelatin solution for 15-30h, and fixing the gelatin on the surface of the catheter stent.
Another object of the present invention is to provide a ureteral stent tube with a memory shape function, which is prepared by the above method, wherein the ureteral stent tube has a double J-shaped structure.
Another object of the present invention is to provide the use of the ureteral stent tube with a memory shape function as a material for preparing a ureteral stent tube.
Has the advantages that:
the ureteral stent is prepared by blending PLGA and polycaprolactone-based polyurethane and using a melt extrusion process, has shape memory effect and biodegradable property, effectively overcomes the defects of high brittleness, low mechanical strength and the like of single-component polylactic acid memory materials, has the phase transition temperature close to the normal body temperature of a human, has thin tube wall, good uniformity and high flexibility, expands the application of the single-component polylactic acid memory materials in the field of biomedicine, and has no toxic or side effect on a human body due to degradation products. The polycaprolactone-based polyurethane has low glass transition temperature, is suitable for the field of biomedicine, has good compatibility with PLGA, has shape memory effect, and expands the application range of clinical ureteral stent tubes. The gelatin is a natural polymer material extracted from animals, has a structure similar to that of organism tissues, and has good biocompatibility and biodegradability. After the gelatin is modified, the biocompatibility of the ureteral stent is improved, and the ureteral stent can be better suitable for the in-vivo environment without generating inflammatory reaction.
The copolymer prepared by the invention has good extrusion performance, simple process, low cost and easy industrial implementation. The obtained intelligent stent tube product has good temperature responsiveness, keeps good shape memory effect, is good in biocompatibility due to American FDA certification, and can be used for a human ureteral stent tube.
The obtained ureteral stent has tensile breaking strength of 20MPa, breaking elongation of 450%, compressive stress of 1380KPa, radial compression and elastic recovery rate of 86% or more, deformation temperature of 40 ℃ or more, shape fixing rate of 98% or more, shape recovery rate of 90% or more, initial water contact angle of 90% or less, and degradation time of 6-23 weeks.
The special double-J ureteral stent tube solves the difficulty brought by the curled structures at the two ends of the ureteral stent tube to the operation tube placement on the premise of realizing the function of the traditional ureteral stent tube, avoids the pain of taking the tube by the secondary operation of a patient, and reduces the occurrence of complications such as loss, infection and the like.
The ureteral stent provided by the invention can open the coiled structure into a straight tube through heating shaping and cooling shaping operations before an operation, so that the stent body can be implanted into a body more quickly and effectively in an aseptic environment, the operation is simple and convenient, and risks such as bacterial infection and the like caused by overlong operation time are avoided. Only preheating the ureteral stent tube to a temperature slightly higher than the body temperature (more than or equal to 40 ℃), straightening the coiled structures at the two ends of the stent tube, cooling to fix the shape, and gradually restoring the straightened coiled structures at the two ends of the stent tube to the original coiled state under the action of the body temperature after the ureteral stent tube is quickly implanted into a body.
The ureteral stent tube plays a role in supporting and draining in a ureter, and the retention time of the ureteral stent tube in a body is generally considered to be about 4 weeks at present. The biodegradation period of the ureteral stent provided by the invention is (6-23) weeks, and good appearance and mechanical properties can be kept within 4 weeks. The biocompatibility of the ureteral stent modified by the gelatin is obviously improved, and the body does not have any discomfort or rejection phenomenon.
It should be noted that the technical effect of the present invention is the result of mutual cooperation and interaction of each process step and parameter, and is not the superposition of simple processes, and the effect produced by the organic combination of each process is far superior to the superposition of each single process function and effect, and has better advancement and practicability.
Drawings
Fig. 1 is a process of a shape memory cycle of a ureteral stent.
Wherein (A) is the initial shape (shape1) of the ureteral stent tube; (B) the ureteral stent is in a shape (shape2) after being heated to a deformation temperature Ts (Ts is more than or equal to 40 ℃) and straightened under the action of external force; (C) in order to reduce the temperature of the ureteral stent to a shape fixing temperature Ta (Ta is 15-25 ℃), the shape under the condition of external force action is (shape 2'); (D) a shape (shape 2') that the ureteral stent tube maintains after external force is removed at Ta temperature; (E) the ureteral stent tube is in a shape (shape 1') which is recovered after continuously heating to Ts. Wherein, (a) the process of heating the ureteral stent tube to Ts and applying an external force; (b) cooling the ureteral stent to Ta; (c) removing the force exerted on the ureteral stent tube; (d) the ureteral stent tube is continuously heated to Ts.
Detailed description of the preferred embodiments
The invention is described below by means of specific embodiments. Unless otherwise specified, the technical means used in the present invention are well known to those skilled in the art. In addition, the embodiments should be considered illustrative, and not restrictive, of the scope of the invention, which is defined solely by the claims. It will be apparent to those skilled in the art that various changes or modifications in the components and amounts of the materials used in these embodiments can be made without departing from the spirit and scope of the invention.
Example 1 preparation method of ureteral stent tube with shape memory function
(1) The ring-opening polymerization method is adopted to prepare PLGA: adding L-lactide and glycolide monomers into a branch pipe reaction bottle according to the molar ratio of 7:3, adding a catalyst A accounting for 0.6 percent of the total mass percentage of the L-lactide and glycolide and an initiator accounting for 0.6 percent of the total mass percentage of the L-lactide and glycolide, filling nitrogen into the branch pipe reaction bottle, wherein the flow rate of the nitrogen is 0.5L/min, degassing and circulating for 3 times through a double-row pipe under the protection of the nitrogen, removing water and oxygen in a system, and closing a piston of the branch pipe reaction bottle; carrying out constant-temperature polymerization reaction for 8 hours at 150 ℃ under magnetic stirring; opening a piston of a branch pipe reaction bottle after the reaction is finished, adding an organic solvent A to dissolve the polymer, wherein the total mass ratio of the organic solvent A to the polymer generated by the reaction system is 10:1, and obtaining a polymer solution; and dropwise adding the polymer solution into the precipitant A, stirring at a constant speed until the polymer solution is completely dropwise added, continuously stirring for 4min until the precipitate is completely separated out to obtain a purified product A, airing the purified product A, and drying in a vacuum oven at 45 ℃ to constant weight to finally obtain PLGA.
The dropping speed of the polymer solution is 5 drops/second;
the volume ratio of the polymer solution to the precipitant A is as follows: 1: 6;
the catalyst A is stannous octoate; the initiator is n-dodecanol;
the organic solvent A is trichloromethane; the precipitant A is ethanol.
(2) The polycaprolactone-based polyurethane is prepared by adopting a two-step polycondensation reaction: firstly, sequentially adding PCL-diol and an organic solvent B into a three-necked bottle reaction device with a condensing tube and introduced with nitrogen according to the mass ratio of 1:3, and completely dissolving PCL-diol prepolymer by magnetic stirring to obtain a dissolved solution; adding isocyanate with the mass percent of 30% of PCL-diol, and stirring for 2 hours at 70 ℃; adding a chain extender accounting for 6 percent of the total mass of the raw materials of the reaction system, uniformly mixing, adding a catalyst B accounting for 0.5 percent of the total mass of the reactants in the step (2), and raising the temperature to 90 ℃ for reaction for 11 hours to obtain a reaction solution; and cooling the reaction liquid to room temperature, dropwise adding the reaction liquid into a precipitator B to obtain a purified product B, wherein the volume ratio of the reaction liquid to the precipitator B is 1:6, and drying the purified product B in a freeze dryer for 24 hours to finally obtain the polycaprolactone-based polyurethane.
The dropping speed of the polymer solution is 5 drops/second;
the organic solvent B is N, N-dimethylformamide;
the isocyanate is diphenylmethane diisocyanate; the chain extender is 1, 4-butanediol;
the catalyst B is stannous octoate;
the precipitator B is diethyl ether.
(3) Blending PLGA and polycaprolactone-based polyurethane according to a mass ratio of 7:3, adding the mixture into an extruder, conveying the mixture forwards under the action of a screw rod to enable a high polymer material to be converted from a solid into a molten fluid state, enabling the high polymer melt to enter a machine head for molding through a filter screen and a flow distribution plate to enable the high polymer melt to be tubular, and then shaping, cooling and pulling the mixture to prepare the ureteral hollow stent tube with the double J-shaped structure; the melt extrusion temperature is 160-180 ℃, the heat setting temperature is 90-110 ℃, and the cooling temperature is 25-30 ℃.
(4) Treating the surface of a hollow ureteral stent tube by oxygen plasma with the gas pressure of 120mTorr and the power of 10W for 1min, soaking the hollow ureteral stent tube in a 1% by mass 3-aminopropyltriethoxysilane solution for 30min, transferring the hollow ureteral stent tube to a 0.5% by mass 1, 5-glutaraldehyde solution, soaking the hollow ureteral stent tube for 12h, and then soaking the hollow ureteral stent tube in a 0.1% by mass gelatin solutionSoaking for 24h, and fixing gelatin on the surface of the catheter stent to obtain ureter stent tube with shape memory function and shape fixing rate Rf100% of the total amount of the polymer particles, and a shape recovery ratio RrThe content of the organic acid is 99%,
example 2 preparation method of ureteral stent tube with shape memory function
(1) The ring-opening polymerization method is adopted to prepare PLGA: adding L-lactide and glycolide monomers into a branch pipe reaction bottle according to the molar ratio of 5:1, adding a catalyst A accounting for 0.5 percent of the total mass percentage of the L-lactide and glycolide and an initiator accounting for 0.5 percent of the total mass percentage of the L-lactide and glycolide, filling nitrogen into the branch pipe reaction bottle, wherein the flow rate of the nitrogen is 0.4L/min, performing degassing circulation for 2-4 times through a double-row pipe under the protection of the nitrogen, removing water and oxygen in the system, and closing a piston of the branch pipe reaction bottle; carrying out polymerization reaction for 6 hours at the constant temperature of 140 ℃ under magnetic stirring; opening a piston of a branch pipe reaction bottle after the reaction is finished, adding an organic solvent A to dissolve the polymer, wherein the total mass ratio of the organic solvent A to the polymer generated by the reaction system is 5:1, and obtaining a polymer solution; dropwise adding the polymer solution into the precipitant A at a rate of 4-6 drops per second, stirring at a constant speed until the polymer solution is completely dropwise added, continuously stirring for 3min until the precipitate is completely separated out to obtain a purified product A, airing the purified product A, and drying in a vacuum oven at 40 ℃ to constant weight to finally obtain PLGA.
The volume ratio of the polymer solution to the precipitant A is as follows: 1:4.
The catalyst A is stannous chloride, and the initiator is octadecanol.
The organic solvent A is toluene, and the precipitator A is n-hexane.
(2) Sequentially adding the PCL-diol and the organic solvent B into a three-necked bottle reaction device with a condensation pipe and introduced with nitrogen according to the mass ratio of 3:7, and completely dissolving the PCL-diol prepolymer by magnetic stirring to obtain a dissolved solution; adding isocyanate with the mass percent of 25% of PCL-diol, and stirring for 2 hours at 60 ℃; adding a chain extender accounting for 4 percent of the total mass of the raw materials of the reaction system, uniformly mixing, adding a catalyst B accounting for 0.3 percent of the total mass of the reactants in the step (2), and raising the temperature to 85 ℃ for reaction for 10 hours to obtain a reaction solution; and cooling the reaction liquid to room temperature, dropwise adding the reaction liquid into a precipitator B at a speed of 4-6 per second to obtain a purified product B, wherein the volume ratio of the reaction liquid to the precipitator B is 1:4, and drying the purified product B in a freeze dryer for 24 hours to finally obtain the polycaprolactone-based polyurethane.
The organic solvent B is trichloromethane;
the isocyanate is L-lysine diisocyanate; the chain extender is 1, 6-hexanediol;
the catalyst B is dibutyltin dilaurate;
the precipitant B is n-hexane.
(3) The PLGA and the polycaprolactone-based polyurethane are blended according to the mass ratio of 5:1, added into an extruder and conveyed forwards under the action of a screw rod, so that a high polymer material is converted from a solid into a molten fluid state, enters a machine head through a filter screen and a flow distribution plate for molding, a high polymer melt is formed into a tubular shape, and then the hollow ureteral stent tube with the double J-shaped structure is prepared through shaping, cooling and traction.
The melt extrusion temperature is 160-180 ℃, the heat setting temperature is 90-110 ℃, and the cooling temperature is 25-30 ℃.
(4) Preparing a gelatin modified ureteral stent: treating the surface of a hollow ureteral stent tube by adopting oxygen plasma, wherein the gas pressure is 100mTorr, the power is 5W, the duration is 0.5min, soaking the hollow ureteral stent tube in a 5% by mass 3-aminopropyltriethoxysilane solution for 20min, transferring the hollow ureteral stent tube to a 0.1% by mass 1, 5-glutaraldehyde solution for soaking for 5h, soaking the hollow ureteral stent tube in a 0.05% by mass gelatin solution for 15h, and fixing the gelatin on the surface of a catheter stent to obtain the ureteral stent tube with the shape memory function, wherein the shape fixing rate R of the ureteral stent tube isf100% of the total amount of the polymer particles, and a shape recovery ratio RrThe content was 99%.
Example 3A method for preparing a ureteral stent with shape memory function
(1) The ring-opening polymerization method is adopted to prepare PLGA: adding L-lactide and glycolide monomers into a branch pipe reaction bottle according to the molar ratio of 9:5, adding a catalyst A and an initiator, wherein the catalyst A accounts for 1% of the total mass of the L-lactide and glycolide, the initiator accounts for 1%, filling nitrogen into the branch pipe reaction bottle, wherein the nitrogen flow is 0.7L/min, degassing for 2-4 times through double calandria under the protection of the nitrogen, removing water and oxygen in the system, and closing a piston of the branch pipe reaction bottle; carrying out constant-temperature polymerization reaction for 10 hours at 160 ℃ under magnetic stirring; opening a piston of a branch pipe reaction bottle after the reaction is finished, adding an organic solvent A to dissolve the polymer, wherein the total mass ratio of the organic solvent A to the polymer generated by the reaction system is 15:1, and obtaining a polymer solution; dropwise adding the polymer solution into the precipitant A at a rate of 10 drops per second, stirring at a constant speed until the polymer solution is completely dropwise added, continuously stirring for 5min until the precipitate is completely separated out to obtain a purified product A, drying the purified product A in a vacuum oven at 50 ℃ after airing, and drying to a constant weight to finally obtain PLGA.
The volume ratio of the polymer solution to the precipitant A is as follows: 1:8.
The catalyst A is stannous chloride, and the initiator is octadecanol.
The organic solvent A is dichloromethane and toluene, and the precipitant A is methanol and diethyl ether.
(2) Firstly, sequentially adding PCL-diol and an organic solvent B into a three-necked bottle reaction device with a condensing tube and introduced with nitrogen according to the mass ratio of 2:7, and completely dissolving PCL-diol prepolymer by magnetic stirring to obtain a dissolved solution; adding isocyanate with the mass percent of 40 percent of PCL-diol, and stirring for 2.5 hours at 80 ℃; adding a chain extender accounting for 8 percent of the total mass of the raw materials of the reaction system, uniformly mixing, adding a catalyst B accounting for 0.8 percent of the total mass of the reactants in the step (2), and raising the temperature to 95 ℃ for reaction for 12 hours to obtain a reaction solution; and cooling the reaction liquid to room temperature, dropwise adding the reaction liquid into the precipitant B at a speed of 10 drops per second to obtain a purified product B, wherein the volume ratio of the reaction liquid to the precipitant B is 1:8, and drying the purified product B in a freeze dryer for 24 hours to finally obtain the polycaprolactone-based polyurethane.
The organic solvent B is dimethyl sulfoxide;
the isocyanate is hexamethylene diisocyanate; the chain extender is propylene glycol;
the catalyst B is stannous chloride;
the precipitant B is ethanol.
(3) The PLGA and the polycaprolactone-based polyurethane are blended according to the mass ratio of 9:5, added into an extruder and conveyed forwards under the action of a screw rod, so that a high polymer material is converted from a solid into a molten fluid state, enters a machine head through a filter screen and a flow distribution plate for molding, a high polymer melt is formed into a tubular shape, and then the hollow ureteral stent tube with the double J-shaped structure is prepared through shaping, cooling and traction.
The melt extrusion temperature is 160-180 ℃, the heat setting temperature is 90-110 ℃, and the cooling temperature is 25-30 ℃.
(4) Treating the surface of a hollow ureteral stent tube by adopting oxygen plasma, wherein the gas pressure is 140mTorr, the power is 15W, the duration is 3min, soaking the hollow ureteral stent tube in a 3-aminopropyltriethoxysilane solution with the mass concentration of 5% for 40min, transferring the hollow ureteral stent tube to a 1, 5-glutaraldehyde solution with the mass concentration of 1% for soaking for 15h, soaking the hollow ureteral stent tube in a gelatin solution with the mass concentration of 0.15% for 30h, and fixing gelatin on the surface of a catheter stent to obtain the ureteral stent tube with the function of memorizing shape, wherein the shape fixing rate R of the ureteral stent tube is the shape fixing ratef100% of the total amount of the polymer particles, and a shape recovery ratio RrThe content of the organic acid is 99%,
example 4 in vitro experiments with application of ureteral stent tubes with shape memory Effect
The shape memory performance of the ureteral stent provided by the invention passes through the shape fixation rate RfAnd shape recovery RrTo characterize. Wherein R isfAnd RrThe calculation formula of (2) is as follows: rf＝(180°-θ)/180°，Rr＝θrAnd/180 degrees. The shape memory test adopts a folding-unfolding shape memory test method, and the results prepared by the embodiment show that the ureteral stent tube has the shape fixing rate R shown in figure 1fNot less than 98%, shape recovery rate Rr≥90％。
The degradation performance of the ureteral stent tube is measured by adopting an in-vitro degradation experiment, wherein the experimental group is the ureteral stent tube prepared in the embodiment, and the control group is a common medical ureteral stent tube.
Soaking ureter stent tube with mass of about 0.2g in urine of healthy volunteers for about 20 weeks at constant temperature of 36-39 deg.C, sampling every week, weighing, and determining degradation period to be (7-20) weeks.
The experimental data can obtain that the degradation process of the ureteral stent is firstly surface erosion, then the overall structure is destroyed, in the whole degradation process, macromolecules are decomposed into small molecules, and the small molecules are discharged out of a body along with metabolites, and the degradation period measured by the method refers to the time of the overall structure destruction.
The ureteral stent can be continuously used for 1-6 weeks, the shape fixing rate, the shape recovery rate, the structural performance and the like of the ureteral stent can keep good functionality, and compared with a control group, the ureteral stent can be automatically degraded and discharged along with urine without being taken out, so that the pain of a patient and the risk of infection are increased.
Example 5 clinical trials for the application of ureteral stent tubes with shape memory Effect
The ureteral stent tube prepared in the embodiment 1 of the invention is utilized to preheat the ureteral stent tube to 45 ℃, so that the coiled structures at the two ends of the stent tube are straightened, the shape is fixed by cooling, after the ureteral stent tube is rapidly implanted into a body, the coiled structures at the two ends of the stent tube can be automatically recovered and keep constant with the body temperature, and are stably fixed in the body, so that good supporting and drainage effects are achieved, the in-vivo biodegradation period of the ureteral stent tube is 7-18 weeks, and the ureteral stent tube can still keep good appearance and mechanical properties within 4-6 weeks of use; with the time being prolonged, the ureteral stent is gradually degraded in vivo and finally discharged out of the body along with urine.
The biocompatibility of the ureteral stent modified by the gelatin is obviously improved, the ureteral stent is continuously and naturally degraded, and no discomfort or rejection phenomenon occurs to an organism.
On the premise of realizing the function of the prior ureteral stent, the difficulty brought by the coiling structures at the two ends of the ureteral stent for the operation tube placement is solved, the pain of taking the tube by the secondary operation of a patient is avoided, and the occurrence of complications such as loss, infection and the like is reduced. The ureteral stent can be used for opening a coiled structure into a straight tube through heating shaping and cooling shaping operations before an operation, and then implanting the stent body into a body. The ureteral stent tube returns to the original curled state along with the rise of temperature under the induction of body temperature by the curled structure of which the two ends of the stent tube implanted into the body are straightened. The ureteral stent tube plays a role in supporting and draining in the ureter.
Claims (10)
1. A preparation method of a ureteral stent tube with a shape memory function is characterized by comprising the following steps: the method comprises the following steps:
(1) taking L-lactide and glycolide monomers as raw materials, and preparing a polylactic acid-glycolic acid copolymer by adopting a ring-opening polymerization method;
(2) PCL-diol monomer is used as raw material, and polycondensation method is adopted to prepare polycaprolactone-based polyurethane;
(3) mixing PLGA and polycaprolactone-based polyurethane, and preparing a hollow ureteral stent tube by a melt extrusion method;
(4) the prepared ureteral stent is subjected to plasma treatment, gelatin is fixed on the surface, and the performance of the surface of the ureteral stent is modified.
2. The method for preparing a ureteral stent tube with a shape memory function according to claim 1, wherein the method comprises the following steps: the step (1) is specifically as follows:
(1) the ring-opening polymerization method is adopted to prepare PLGA: mixing L-lactide and glycolide monomers according to the molar ratio of 5-9:1-5, adding a reactant, wherein the addition amount of the reactant is 1-2% of the total mass percent of the L-lactide and the glycolide, filling nitrogen into a reaction system, performing degassing treatment, and performing constant-temperature polymerization reaction at 140-160 ℃ for 6-10 hours after degassing; after the reaction is finished, adding an organic solvent A in proportion, wherein the total mass ratio of the organic solvent A to the system in the previous step of the reaction is 5-15:1, and obtaining a polymer solution; dropwise adding the polymer solution into a precipitator A, stirring, and precipitating to obtain a purified product A, wherein the volume ratio of the polymer solution to the precipitator A is as follows: 1-2: 4-16; and drying the purified product A to constant weight to obtain PLGA.
3. The method for preparing a ureteral stent tube with a shape memory function according to claim 1, wherein the method comprises the following steps: the step (2) is specifically as follows:
the polycaprolactone-based polyurethane is prepared by adopting a two-step polycondensation reaction: firstly, mixing PCL-diol with an organic solvent B according to a mass ratio of 1-3:3-7 to obtain a dissolved solution; adding isocyanate with the mass percent of 25-40% of PCL-diol, and stirring for 2-2.5h at the temperature of 60-80 ℃; adding chain extenders in sequence according to a proportion, mixing, adding a catalyst B according to a proportion, and raising the temperature to 85-95 ℃ for reaction for 10-12h to obtain a reaction solution; and cooling the reaction liquid to room temperature of 25-35 ℃, dropwise adding the reaction liquid into a precipitator B to obtain a purified product B, wherein the volume ratio of the reaction liquid to the precipitator B is 1:4-8, and drying the purified product B in a freeze dryer for 24 hours to finally obtain the polycaprolactone-based polyurethane.
4. The method for preparing a ureteral stent tube with a shape memory function according to claim 1, wherein the method comprises the following steps: the step (3) is specifically as follows:
and blending PLGA and polycaprolactone-based polyurethane according to the mass ratio of 5-9:1-5, and adding the blended mixture into an extruder to prepare the ureteral stent.
5. The method for preparing a ureteral stent tube with a shape memory function according to claim 1, wherein the method comprises the following steps: the step (4) is specifically as follows:
treating the surface of the hollow ureteral stent by adopting oxygen plasma, wherein the gas pressure is 100-140mTorr, the power is 5-15W, the time duration is 0.5-3min, then soaking the hollow ureteral stent in a 1-5% by mass 3-aminopropyltriethoxysilane solution for 20-40min, then transferring the hollow ureteral stent to a 0.1-1% by mass 1, 5-glutaraldehyde solution for soaking for 5-15h, then soaking the hollow ureteral stent in a 0.05-0.15% by mass gelatin solution for 15-30h, and fixing the gelatin on the surface of the catheter stent.
6. The method for preparing a ureteral stent tube with a shape memory function according to claim 2, wherein the method comprises the following steps: the reaction agent is a catalyst A and an initiator, the catalyst A is stannous octoate or stannous chloride, and the initiator is n-dodecanol or octadecanol.
7. The method for preparing a ureteral stent tube with a shape memory function according to claim 2, wherein the method comprises the following steps: the organic solvent A is at least one of chloroform, dichloromethane and toluene, and the precipitant A is at least one of ethanol, methanol, diethyl ether and n-hexane.
8. The method for preparing a ureteral stent tube with a shape memory function according to claim 3, wherein the method comprises the following steps: the organic solvent B is one of N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran and trichloromethane; the catalyst B is one of stannous octoate, stannous chloride and dibutyltin dilaurate; the precipitant B is one of diethyl ether, methanol, ethanol and n-hexane; the chain extender is one of 1, 4-butanediol, ethylene glycol, polyethylene glycol, propylene glycol and 1, 6-hexanediol.
9. A ureteral stent tube with a function of memorizing shape, which is prepared by the method of any one of the claims 1 to 8, wherein the ureteral stent tube has a double J-shaped structure.
10. Use of the ureteral stent tube with a memory shape function of claim 9 as a material for preparing a ureteral stent tube.
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| US11643550B2 (en) | 2018-04-05 | 2023-05-09 | Adolphe Merkle Institute, University Of Fribourg | Shape memory polymers |
| CN110065186B (en) * | 2019-04-25 | 2021-01-19 | 南京邦鼎生物科技有限公司 | Preparation method of degradable ureteral catheter |
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