CN114939226B - Pancreatin inactivation stent drainage tube applied to pancreaticojejunostomy and preparation method thereof - Google Patents

Abstract

The invention provides a pancreatin inactivation stent drainage tube applied to pancreaticojeostomy and a preparation method thereof, the stent drainage tube consists of a stent drainage tube framework and a pancreatin inactivation layer, the stent drainage tube framework is prepared by adopting a transparent medical PVC or Polyimide (PI) material through a 3D printing technology and is of a tubular structure with smooth outer surface and folded inner surface; the inactivation layer consists of one or two of nano Ag and Cu particle layers with a wrinkle structure; the inactivation layer is coated on the inner surface and the outer surface of the tubular structure framework; the outer surface is provided with barbs for fixation, side holes for observation and the like; this application is with solving current pancreas enteroanastomosis with support drainage tube and not having the active defect of deactivation pancreatin, improves pancreas enteroanastomosis's security, becomes "kiss of life" with "the kiss of death".

Description

Pancreatin inactivation stent drainage tube applied to pancreaticojejunostomy and preparation method thereof

Technical Field

The invention relates to the technical field of medical instruments for operations, in particular to a pancreatin inactivation stent drainage tube applied to pancreaticoenteroanastomosis and a preparation method thereof.

Background

The pancreas-intestine anastomosis operation is known as 'the first anastomosis in the world' and 'the anastomosis of death'. Because pancreatic fistula occurs when pancreatic anastomosis is not performed well, a large amount of pancreatic enzymes (including amylase, protease, lipase, etc.) in pancreatic juice erodes surrounding blood vessels and organs, thereby causing hemorrhagic infection, various complications of the abdomen and the whole body, which may lead to prolonged hospital stay and rapid death. At present, postoperative pancreas fistula complication can all take place inevitably to multiple pancreas intestines anastomosis technique of clinical application, in order to alleviate the adverse effect that pancreas fistula probably brought, often adopt the support drainage tube of building to carry out the drainage of stepping down, reduce the pancreatitus on the one hand because of the squeezing action of high pressure to the wound production, on the other hand can prevent the jam of pancreas ductus, lead to the pancreatitus to reveal from the wound, bring adverse effect.

At present, although the mode of taking a bracket drainage tube is adopted, the risk of the pancreaticotomy is reduced to a certain extent, the corrosion influence of pancreatin on the wound and surrounding tissues and organs is still inevitable. The main reason is that the existing stent drainage tube only plays a role in guiding flow and does not have the capability of changing the pancreatic enzyme corrosion performance flowing through the anastomotic site, so that the occurrence of 'death kiss' cannot be thoroughly avoided. Therefore, in order to completely solve this problem, it is necessary to develop a stent drainage tube that can change the pancreatic enzyme erosion performance flowing through the anastomotic site, i.e., to develop a stent drainage tube that can inactivate pancreatic enzymes to solve the above-mentioned problem.

Disclosure of Invention

The invention aims to provide a pancreatin inactivation stent drainage tube which is simple in structure, efficient, convenient, practical, economical and safe, solves the defect that the existing stent drainage tube for pancreaticoenteroanastomosis does not have the activity of inactivating pancreatin, improves the safety of pancreaticoenteroanastomosis, and changes 'kiss of death' into 'kiss of life'.

In order to achieve the above object, the present embodiment provides a pancreatin-inactivating stent drainage tube comprising a stent drainage tube skeleton and a pancreatin-inactivating layer; the framework of the stent drainage tube is of a tubular structure with a smooth outer surface and a large number of wrinkled layers on the inner surface; the outer surface of the stent drainage tube skeleton is also provided with a barb for fixation and a side hole for observation.

Furthermore, the framework of the stent drainage tube is made of transparent medical high polymer materials through 3D printing.

Further, the pancreatin inactivation layer is prepared by an inactivation layer plated with nano Ag or/and Cu particles.

Based on a general inventive concept, the invention also provides a preparation method of the pancreatin inactivation stent drainage tube, which comprises the following steps:

(1) Preparing a stent drainage tube skeleton made of a high-molecular polymer material by adopting a 3D printing method;

(2) The pancreatin inactivation layer is coated on the inner surface and the outer surface of the framework of the bracket drainage tube to obtain the pancreatin inactivation bracket drainage tube; the coating mode is any one or two of an ion exchange method and a chemical plating method:

further, the high molecular polymer material is polyvinyl chloride (PVC), and the specific steps in the step (1) are as follows:

step one, mixing a mixture of 1: (1~6) and a mixture of tetrahydrofuran and polybutylene adipate, wherein the ratio of the mixture to the tetrahydrofuran is 1: (1~4) magnetically stirring to form uniformly dispersed emulsion, standing for 1-3 h, eliminating bubbles, sealing, and storing to obtain skeleton printing ink;

and step two, carrying out forming printing by adopting a UV 3D printer, and preparing the PVC bracket drainage tube skeleton with a smooth outer surface and a large number of folds on the inner surface.

Further, the polymer material is Polyimide (PI), and the specific steps in the step (1) are as follows:

4, 4' -hexafluoroisopropylidene-phthalic anhydride (6 FDA), 2' -bistrifluoromethyl-biphenyldiamine (TFDB) and N, N ' -dimethylacetamide (DMAc) are used as raw materials

Weighing a certain amount of TFDB, 6FDA and DMAc in proportion, firstly putting the TFDB and the DMAc into a flask, stirring for 30-60min to fully dissolve, then adding the 6FDA into the flask for several times, only adding one half of the remaining 6FDA each time, stirring for 12-24 h under the protection of argon to obtain a polyamic acid solution, then adding a certain amount of phthalic anhydride, and stirring for 10-20 h to obtain a phthalic anhydride terminated polyamide solution which is used as 3D printing ink;

and step two, performing thermal imidization molding printing by adopting a selective laser sintering 3D printer to prepare the PI material support drainage tube framework with a smooth outer surface and a large number of folds on the inner surface.

Further, the preparation of the nanometer Ag particle inactivation layer of the PI pancreatin inactivation stent drainage tube comprises the following steps:

immersing a framework of a PI bracket drainage tube into hot alkali liquor (NaOH and KOH of 2.5 to 5M and 40 to 70 ℃) with a certain molar concentration for 10 to 30 min to open the polyimide of the inner surface layer and the outer surface layer of the polyimide tube, and complexing with alkali metal ions to generate polyamic acid salt; and after treatment, washing with deionized water, removing a surface alkali solution, immersing in a silver ammonia solution (0.04 to 0.5M) with a certain molar concentration, performing ion exchange for 5 to 30 min at room temperature, taking out, washing with deionized water, drying in the air at room temperature, performing thermal imidization reduction treatment for 1 to 2 h at 200 to 320 ℃, and obtaining the PI material stent drainage tube with the inner and outer surfaces plated with the nano Ag particle inactivation layer.

Further, the preparation of the nanometer Ag particle inactivation layer of the pancreatin inactivation stent drainage tube made of the PVC material comprises the following steps:

the method comprises the steps of performing stress relieving, oil removing, roughening and sensitizing pretreatment on a PVC stent drainage tube framework to obtain the PVC stent drainage tube framework with uniform and rough inner and outer surfaces, immersing the stent drainage tube framework in chemical silver plating solution (0.001-0.1M of silver nitrate, 10-50 mg/L of sodium thiosulfate, 0.001-0.01M of sodium hydroxide, 0.1-1.0% of ammonia water and 0.01-0.1M of glucose), performing chemical silver plating for 10-20 min at the temperature of 20-40 ℃, taking out, washing with deionized water, and airing at room temperature to obtain the PVC stent drainage tube with the inner and outer surfaces plated with nano Ag particle inactivation layers.

Further, the preparation of the nanometer Cu particle inactivation layer of the PI pancreatin inactivation stent drainage tube comprises the following steps:

after the framework of the PI bracket drainage tube is subjected to stress relief, oil removal, coarsening and sensitization pretreatment, the framework of the PI bracket drainage tube is immersed in electroless copper plating solution (0.001 to 0.1M of copper sulfate pentahydrate, 0.01 to 0.1M of disodium ethylene diamine tetraacetate, 0.1 to 1 mg/L of thiourea, 0.005 to 0.02M of potassium sodium tartrate, 0.01 to 0.05M of sodium hydroxide, 10 to 50 mg/L of sodium dodecyl sulfate, 8 to 20 mL/L of formaldehyde and 11 to 13.5 of pH), electroless copper plating is carried out at the temperature of 20-80 ℃ for 10-20 min, and the PI bracket drainage tube with the inner surface and the outer surface coated with the nanometer Cu particle inactivation layer is obtained after the PI bracket drainage tube is taken out, washed by deionized water and dried at room temperature.

Further, the preparation of the nanometer Cu particle inactivation layer of the pancreatin inactivation stent drainage tube made of the PVC material comprises the following steps:

after internal surface pretreatment such as stress relief, oil removal, coarsening and sensitization is carried out on the framework of the PVC bracket drainage tube, the framework of the bracket drainage tube is immersed in chemical copper plating solution (0.001-0.01M of copper sulfate pentahydrate, 0.005-0.02M of potassium sodium tartrate, 0.01-0.05M of sodium hydroxide, 0.01-0.05M of ethylene diamine tetraacetic acid, 8-20 mL/L of formaldehyde and 11-13.5 of pH value), chemical copper plating is carried out for 5-20 min at the temperature of 20-80 ℃, the bracket drainage tube is taken out, washed by deionized water and dried at room temperature, and the PVC bracket drainage tube with the nano Cu particle inactivation layer plated on the inner surface and the outer surface is obtained.

Further, the preparation of the nanometer Cu @ Ag composite inactivation layer of the PI or PVC material pancreatin inactivation support drainage tube comprises the following steps:

cleaning PI or PVC material pancreatin inactivated stent drainage tube coated with a Cu inactivated layer with deionized water, airing at room temperature, then immersing in chemical silver plating solution (0.001-0.1M of silver nitrate, 10-50 mg/L of sodium thiosulfate, 0.001-0.01M of sodium hydroxide, 0.1-1.0% of ammonia water and 0.01-0.1M of glucose), carrying out chemical silver plating at the temperature of 20-40 ℃ for 5-15 min, taking out, cleaning with deionized water, and airing at room temperature to obtain the PI or PVC material stent drainage tube framework with the inner and outer surfaces coated with the nano Cu @ Ag particle composite inactivated layer.

The pancreatin inactivation stent drainage tube of the invention brings the following beneficial effects in the aspects of structure, technology and the like:

(1) The nanometer Ag and Cu particle inactivation layer on the inner and outer surfaces of the drainage tube of the pancreatin inactivation stent changes the corrosion performance of pancreatin flowing through a pancreatin anastomotic stoma in situ, reduces the pancreatin fistula complication after the pancreatin anastomosis, lightens the adverse effect possibly brought by the pancreatin fistula, improves the safety of the pancreatin anastomosis, and changes 'kiss death' into 'kiss life';

(2) The 3D printing technology is adopted to realize that the scaffold drainage tube accurately prepares the inner surface of the fold structure, and the effective area of the inner surface inactivation layer can be greatly increased. On one hand, the effectiveness of an inactivation layer in a wound healing period (about 7 days) is ensured, the efficiency of pancreatic juice inactivation is improved, so that the corrosion effect on the wound when pancreatic juice in the intestinal tract flows backwards is reduced, on the other hand, the 3D printing technology can be used for quickly, accurately and controllably preparing the folded structure in an area manner, the large-scale industrial production of the folded structure is facilitated, and the preparation cost of the folded structure is reduced;

(3) The outer surface of the bracket drainage tube is also designed to be provided with an inactivation layer, so that the pancreatic juice flowing through the wound can be effectively inactivated for the second time, and the corrosion effect of the pancreatic juice on the wound is reduced again;

(4) The stent drainage tube framework is prepared from the conventional organic medical materials such as PI, PVC and the like which are nontoxic and have good biocompatibility, the manufacturing cost is low, and the stent drainage tube framework is suitable for large-scale production and popularization.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required in the embodiments will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.

FIG. 1 is a schematic side view of a pancreatin-inactivating stent drainage tube for pancreaticojejunostomy provided by an embodiment of the present invention;

fig. 2 is a schematic cross-sectional structure view of a pancreatin inactivation stent drainage tube for pancreatin enterostomy provided by an embodiment of the invention.

[ description of reference ]

1. A stent drainage tube; 2. An inner surface pleat structure deactivation layer; 3. An inactivation layer with a smooth outer surface; 4. a framework layer; 5 barbs.

Detailed Description

To make the technical problems, technical solutions and advantages of the present invention more apparent, the following detailed description is given with reference to the accompanying drawings and specific embodiments.

Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.

Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.

The postoperative pancreas fistula complication can all take place inevitably for clinical application's multiple pancreas intestines anastomosis technique, in order to alleviate the adverse effect that pancreas fistula probably brought, often adopt the bypass drainage pipe to reduce the pressure drainage, reduce the pancreatin on the one hand because of the squeezing action of high pressure to the wound production, on the other hand can prevent the jam of pancreas ductus, lead to the pancreatin to reveal from the wound, bring adverse effect. At present, although the risk of the pancreaticotomy is reduced to a certain extent by adopting a mode of a stented drainage tube, the corrosion influence of pancreatin on a wound and surrounding tissues and organs thereof still can be generated inevitably. The main reason is that the existing stent drainage tube only plays a role in guiding flow and does not have the capability of changing the pancreatic enzyme corrosion performance flowing through the anastomotic site, so that the occurrence of 'death kiss' cannot be thoroughly avoided.

Aiming at the technical problems, the invention provides a pancreatin inactivation stent drainage tube applied to pancreaticojejunostomy and a preparation method thereof.

Example 1

Weighing a certain amount of TFDB, 6FDA and DMAc, putting the TFDB and the DMAc into a flask, stirring for 30 min to fully dissolve, then adding the 6FDA into the flask by multiple times, adding only one half of the remaining part of the 6FDA each time, stirring for 24 h under the protection of argon to obtain a polyamic acid solution, adding a certain amount of phthalic anhydride, stirring for 20 h to obtain a phthalic anhydride terminated polyamide solution, and using the solution as 3D printing ink. And (3) performing forming printing by adopting a selective laser sintering 3D printer to prepare the PI-made bracket drainage tube framework with a smooth outer surface and a large number of folds on the inner surface.

The frame of the bracket drainage tube made of PI material is immersed in hot alkali liquor (NaOH solution at 40 ℃ and 2.5M) with a certain molar concentration for 30 min, so that polyimide on the inner surface layer of the polyimide tube is subjected to ring opening and is complexed with alkali metal ions to generate polyamic acid salt. And after treatment, washing with deionized water, removing a surface alkali solution, immersing into a silver ammonia solution (0.04M) with a certain molar concentration, performing ion exchange for 30 min at room temperature, taking out, washing with deionized water, drying at room temperature, performing thermal imidization reduction treatment at 300 ℃ for 1 h, and obtaining the PI stent drainage tube with the inner and outer surfaces plated with nano Ag particle inactivation layers.

Example 2

Weighing a certain amount of TFDB, 6FDA and DMAc, firstly putting the TFDB and the DMAc into a flask, stirring for 60min to fully dissolve, then adding the 6FDA into the flask in a plurality of times, only adding one half of the remaining part of the 6FDA each time, stirring for 12 h under the protection of argon to obtain a polyamic acid solution, adding a certain amount of phthalic anhydride, stirring for 10 h to obtain a phthalic anhydride terminated polyamide solution, and using the polyamic acid solution as 3D printing ink. And (3) performing forming printing by adopting a selective laser sintering 3D printer to prepare the PI-made bracket drainage tube framework with a smooth outer surface and a large number of folds on the inner surface.

The framework of the PI bracket drainage tube is immersed in hot alkali liquor (4.0M, 70 ℃ NaOH solution) with a certain molar concentration for 10 min, so that polyimide on the inner surface layer of the polyimide tube is subjected to ring opening and is complexed with alkali metal ions to generate polyamic acid salt. And after treatment, washing with deionized water to remove a surface alkali solution, immersing into a silver ammonia solution (0.3M) with a certain molar concentration, carrying out ion exchange for 5 min at room temperature, taking out, washing with deionized water, drying at room temperature, and carrying out thermal imidization reduction treatment on 2 h at 260 ℃ to obtain the PI material stent drainage tube with the inner and outer surfaces plated with nano Ag particle inactivation layers.

Example 3

Weighing a certain amount of TFDB, 6FDA and DMAc, putting the TFDB and the DMAc into a flask, stirring for 40min to fully dissolve, then adding the 6FDA into the flask in several times, only adding one half of the remaining part of the 6FDA each time, stirring for 18 h under the protection of argon to obtain a polyamic acid solution, adding a certain amount of phthalic anhydride, stirring for 15 h to obtain a phthalic anhydride terminated polyamide solution, and using the solution as 3D printing ink. And (3) performing forming printing by adopting a selective laser sintering 3D printer to prepare the PI material support drainage tube framework with a smooth outer surface and a large number of folds on the inner surface.

The framework of the PI bracket drainage tube is immersed in hot alkali liquor (2.5M, KOH solution of 40 ℃) with certain molar concentration for 30 min, so that polyimide on the inner surface layer of the polyimide tube is subjected to ring opening and is complexed with alkali metal ions to generate polyamic acid salt. And after treatment, washing with deionized water, removing a surface alkali solution, immersing into a silver ammonia solution (0.04M) with a certain molar concentration, performing ion exchange for 30 min at room temperature, taking out, washing with deionized water, drying at room temperature, performing thermal imidization reduction treatment at 300 ℃ for 1 h, and obtaining the PI material stent drainage tube with the inner and outer surfaces plated with nano Ag particle inactivation layers.

Example 4

Mixing the components in a mass ratio of 1:1, mixing polyvinyl chloride and butylene adipate, and dissolving in tetrahydrofuran, wherein the ratio of the mixture to the tetrahydrofuran is 1:1, magnetically stirring to form a uniformly dispersed milky solution, standing for 1-3 h, eliminating bubbles, sealing and storing, and using as skeleton printing ink. And (3) performing forming printing by adopting a UV 3D printer to prepare the support drainage tube skeleton which is made of PVC material and has a large number of folds on the smooth inner surface of the outer surface.

The framework of the PVC stent drainage tube is subjected to stress removal, oil removal, coarsening and sensitization pretreatment to obtain uniform and rough inner and outer surfaces, then the inner and outer surfaces are immersed into chemical silver plating solution (silver nitrate: 0.001M, sodium thiosulfate: 10 mg/L, sodium hydroxide: 0.001M, ammonia water content: 0.1%, glucose: 0.01M), chemical silver plating is carried out for 20 min at the temperature of 20 ℃, and the inner and outer surfaces are taken out, washed by deionized water and dried at room temperature to obtain the PVC stent drainage tube with the nano Ag particle inactivation layer plated on the inner and outer surfaces.

Example 5

Mixing the components in a mass ratio of 1:3, mixing the polyvinyl chloride and the succinic adipate, and dissolving in tetrahydrofuran, wherein the ratio of the mixture to the tetrahydrofuran is 1:2, magnetically stirring to form a uniformly dispersed emulsion solution, standing for 1-3 h, eliminating bubbles, sealing and storing, and using as skeleton printing ink. And (3) performing forming printing by adopting a UV 3D printer to prepare the support drainage tube skeleton which is made of PVC material and has a large number of folds on the smooth inner surface of the outer surface.

The framework of the PVC stent drainage tube is subjected to stress removal, oil removal, coarsening and sensitization pretreatment to obtain uniform and rough inner and outer surfaces, then the inner and outer surfaces are immersed into chemical silver plating solution (silver nitrate: 0.05M, sodium thiosulfate: 25 mg/L, sodium hydroxide: 0.005M, ammonia water content: 0.5%, glucose: 0.03M), chemical silver plating is carried out for 15 min at the temperature of 25 ℃, and the inner and outer surfaces are taken out, washed by ionized water and dried at room temperature to obtain the PVC stent drainage tube with the nano Ag particle inactivation layer plated on the inner and outer surfaces.

Example 6

Mixing the components in a mass ratio of 1:6, mixing polyvinyl chloride and butylene adipate, and dissolving in tetrahydrofuran, wherein the ratio of the mixture to the tetrahydrofuran is 1: and 4, magnetically stirring to form a uniformly dispersed emulsion solution, standing for 1-3 h, eliminating bubbles, sealing and storing, and using as skeleton printing ink. And (3) performing forming printing by adopting a UV 3D printer to prepare the PVC material bracket drainage tube skeleton with a large number of folds on the smooth inner surface of the outer surface.

The framework of the PVC stent drainage tube is subjected to stress removal, oil removal, coarsening and sensitization pretreatment to obtain uniform and rough inner and outer surfaces, then the inner and outer surfaces are immersed into chemical silver plating solution (silver nitrate: 0.1M, sodium thiosulfate: 50 mg/L, sodium hydroxide: 0.01M, ammonia water content: 1.0%, glucose: 0.1M), chemical silver plating is carried out for 10 min at the temperature of 40 ℃, and the inner and outer surfaces are taken out, washed by deionized water and dried at room temperature to obtain the PVC stent drainage tube with the nano Ag particle inactivation layer plated on the inner and outer surfaces.

Example 7

Weighing a certain amount of TFDB, 6FDA and DMAc, firstly putting the TFDB and the DMAc into a flask, stirring for 30 min to fully dissolve, then adding the 6FDA into the flask in a plurality of times, only adding one half of the remaining part of the 6FDA each time, stirring 24 h under the protection of argon to obtain a polyamic acid solution, adding a certain amount of phthalic anhydride, stirring 20 h to obtain a phthalic anhydride terminated polyamide solution, and using the polyamic acid solution as 3D printing ink. And (3) carrying out forming printing by adopting a selective laser sintering 3D printer to prepare the PI material stent drainage tube framework with a smooth outer surface and a large number of folds on the inner surface.

The PI stent drainage tube framework is subjected to stress removal, oil removal, coarsening and sensitization pretreatment to obtain the uniform and rough inner and outer surfaces, then is immersed in chemical copper plating solution (copper sulfate pentahydrate: 0.001M, disodium ethylene diamine tetraacetate: 0.01M, thiourea: 0.1 mg/L, potassium sodium tartrate: 0.005M, sodium hydroxide: 0.01M, sodium dodecyl sulfate: 10 mg/L, formaldehyde: 8 mL/L and pH value: 11), is subjected to chemical copper plating at the temperature of 20 ℃ for 20 min, and then is taken out, washed by deionized water and dried at room temperature to obtain the PI stent drainage tube with the inner and outer surfaces plated with the nano Cu particle inactivation layer.

Example 8

Weighing a certain amount of TFDB, 6FDA and DMAc, firstly putting the TFDB and the DMAc into a flask, stirring for 60min to fully dissolve, then adding the 6FDA into the flask in a plurality of times, only adding one half of the remaining part of the 6FDA each time, stirring for 12 h under the protection of argon to obtain a polyamic acid solution, adding a certain amount of phthalic anhydride, stirring for 10 h to obtain a phthalic anhydride terminated polyamide solution, and using the polyamic acid solution as 3D printing ink. And (3) performing forming printing by adopting a selective laser sintering 3D printer to prepare the PI-made bracket drainage tube framework with a smooth outer surface and a large number of folds on the inner surface.

The PI bracket drainage tube framework is subjected to stress removal, oil removal, coarsening and sensitization pretreatment to obtain the uniform and rough inner and outer surfaces, then is immersed in chemical copper plating solution (copper sulfate pentahydrate: 0.1M, disodium ethylene diamine tetraacetate: 0.1M, thiourea: 1 mg/L, potassium sodium tartrate: 0.02M, sodium hydroxide: 0.05M, sodium dodecyl sulfate: 50 mg/L, formaldehyde: 20 mL/L and pH value: 13.5), is subjected to chemical copper plating for 10 min at the temperature of 80 ℃, and then is taken out, washed by deionized water and dried at room temperature to obtain the PI bracket drainage tube with the inner and outer surfaces plated with the nano Cu particle inactivation layer.

Example 9

Weighing a certain amount of TFDB, 6FDA and DMAc, putting the TFDB and the DMAc into a flask, stirring for 40min to fully dissolve, then adding the 6FDA into the flask in several times, adding only one half of the remaining part of the 6FDA each time, stirring for 18 h under the protection of argon to obtain a polyamic acid solution, adding a certain amount of phthalic anhydride, stirring for 15 h to obtain a phthalic anhydride terminated polyamide solution, and using the solution as 3D printing ink. And (3) performing forming printing by adopting a selective laser sintering 3D printer to prepare the PI-made bracket drainage tube framework with a smooth outer surface and a large number of folds on the inner surface.

The PI bracket drainage tube framework is subjected to stress removal, oil removal, coarsening and sensitization pretreatment to obtain the uniform and rough inner and outer surfaces, then is immersed into chemical copper plating solution (copper sulfate pentahydrate: 0.005M, disodium ethylene diamine tetraacetate: 0.05M, thiourea: 0.5 mg/L, potassium sodium tartrate: 0.01M, sodium hydroxide: 0.03M, sodium dodecyl sulfate: 30 mg/L, formaldehyde: 15 mL/L and pH value: 12.5) and is injected into the bracket drainage tube, chemical copper plating is carried out at the temperature of 30 ℃ for 15 min, and the PI bracket drainage tube with the inner and outer surfaces plated with the nano Cu particle inactivation layer is obtained by taking out, washing with deionized water and airing at room temperature.

Example 10

Mixing the components in a mass ratio of 1:1, mixing polyvinyl chloride and butylene adipate, and dissolving in tetrahydrofuran, wherein the ratio of the mixture to the tetrahydrofuran is 1:1, magnetically stirring to form a uniformly dispersed milky solution, standing for 1-3 h, eliminating bubbles, sealing and storing, and using as skeleton printing ink. And (3) performing forming printing by adopting a UV 3D printer to prepare the support drainage tube skeleton which is made of PVC material and has a large number of folds on the smooth inner surface of the outer surface.

The framework of the PVC bracket drainage tube is subjected to stress removal, oil removal, coarsening and sensitization pretreatment to obtain the uniform and rough inner and outer surfaces, then is immersed into chemical copper plating solution (copper sulfate pentahydrate: 0.001M, potassium sodium tartrate: 0.005M, sodium hydroxide: 0.01M, ethylenediamine tetraacetic acid: 0.01M, formaldehyde: 8 mL/L, pH value: 11), is subjected to chemical copper plating at the temperature of 20 ℃ for 20 min, and is taken out, washed by deionized water and dried at room temperature to obtain the PVC bracket drainage tube with the inner and outer surfaces plated with the nano Cu particle inactivation layer.

Example 11

Mixing the components in a mass ratio of 1:3, mixing the polyvinyl chloride and the succinic adipate, and dissolving in tetrahydrofuran, wherein the ratio of the mixture to the tetrahydrofuran is 1:2, magnetically stirring to form a uniformly dispersed emulsion solution, standing for 1-3 h, eliminating bubbles, sealing and storing, and using as skeleton printing ink. And (3) performing forming printing by adopting a UV 3D printer to prepare the PVC material bracket drainage tube skeleton with a large number of folds on the smooth inner surface of the outer surface.

The framework of the PVC bracket drainage tube is subjected to stress removal, oil removal, coarsening and sensitization pretreatment to obtain the uniform and rough inner and outer surfaces, then is immersed into chemical copper plating solution (copper sulfate pentahydrate: 0.01M, potassium sodium tartrate: 0.02M, sodium hydroxide: 0.05M, ethylenediamine tetraacetic acid: 0.05M, formaldehyde: 20 mL/L, pH value: 13.5), chemical copper plating is carried out for 5 min at the temperature of 80 ℃, and the PVC bracket drainage tube with the inner and outer surfaces plated with the nano Cu particle inactivation layer is obtained after being taken out, washed by deionized water and dried at room temperature.

Example 12

Mixing the components in a mass ratio of 1:6, mixing polyvinyl chloride and butylene adipate, and dissolving in tetrahydrofuran, wherein the ratio of the mixture to the tetrahydrofuran is 1: and 4, magnetically stirring to form a uniformly dispersed emulsion solution, standing for 1-3 h, eliminating bubbles, sealing and storing, and using as skeleton printing ink. And (3) performing forming printing by adopting a UV 3D printer to prepare the support drainage tube skeleton which is made of PVC material and has a large number of folds on the smooth inner surface of the outer surface.

The method comprises the steps of carrying out stress removal, oil removal, coarsening and sensitization pretreatment on a framework of the PVC bracket drainage tube to obtain uniform and rough inner and outer surfaces, immersing the framework in chemical copper plating solution (copper sulfate pentahydrate: 0.005M, potassium sodium tartrate: 0.01M, sodium hydroxide: 0.03M, ethylenediamine tetraacetic acid: 0.03M, formaldehyde: 15 mL/L, pH value: 12.5), injecting the framework into the framework of the bracket drainage tube, carrying out chemical copper plating for 15 min at the temperature of 35 ℃, taking out, washing with deionized water, and airing at room temperature to obtain the PVC bracket drainage tube with the inner and outer surfaces plated with the nano Cu particle inactivation layer.

Example 13

Weighing a certain amount of TFDB, 6FDA and DMAc, firstly putting the TFDB and the DMAc into a flask, stirring for 60min to fully dissolve, then adding the 6FDA into the flask in a plurality of times, only adding one half of the remaining part of the 6FDA each time, stirring for 12 h under the protection of argon to obtain a polyamic acid solution, adding a certain amount of phthalic anhydride, stirring for 10 h to obtain a phthalic anhydride terminated polyamide solution, and using the polyamic acid solution as 3D printing ink. And (3) performing forming printing by adopting a selective laser sintering 3D printer to prepare the PI-made bracket drainage tube framework with a smooth outer surface and a large number of folds on the inner surface.

The PI stent drainage tube framework is subjected to stress removal, oil removal, coarsening and sensitization pretreatment to obtain uniform and rough inner and outer surfaces, then immersed in chemical copper plating solution (copper sulfate pentahydrate: 0.1M, disodium ethylene diamine tetraacetate: 0.1M, thiourea: 1 mg/L, potassium sodium tartrate: 0.02M, sodium hydroxide: 0.05M, sodium dodecyl sulfate: 50 mg/L, formaldehyde: 20 mL/L, pH value: 13.5), chemically plated with copper for 10 min at the temperature of 80 ℃, taken out, cleaned by deionized water, dried at room temperature to obtain the PI stent with an inner and outer surface plated with a nano-Cu particle inactivation layer, and immersed in the chemical silver plating solution (0.05 zxft 3265, sodium thiosulfate: 25 zxft 3579/L, sodium hydroxide: 0.79 m, dried at the temperature of 3500, silver nitrate and silver nitrate are taken out at the temperature of 0.5 ℃, and the PI drainage tube is cleaned by ammonia water to obtain a composite silver plating solution for silver nitrate and silver plating.

Example 14

Mixing the components in a mass ratio of 1:6, mixing polyvinyl chloride and butylene adipate, and dissolving in tetrahydrofuran, wherein the ratio of the mixture to the tetrahydrofuran is 1:4, magnetically stirring to form a uniformly dispersed milky solution, standing for 1-3 h, eliminating bubbles, sealing and storing, and using as skeleton printing ink. And (3) performing forming printing by adopting a UV 3D printer to prepare the PVC material bracket drainage tube skeleton with a large number of folds on the smooth inner surface of the outer surface.

The method comprises the steps of performing stress removal, oil removal, coarsening and sensitization pretreatment on a framework of the PVC stent drainage tube to obtain uniform and rough inner and outer surfaces, immersing the framework in a chemical copper plating solution (copper sulfate pentahydrate: 0.005M, potassium sodium tartrate: 0.01M, sodium hydroxide: 0.03M, ethylenediamine tetraacetic acid: 0.03M, formaldehyde: 15 mL/L and pH value: 12.5), injecting the framework into the framework, performing chemical copper plating for 15 min at the temperature of 35 ℃, taking out, cleaning with deionized water and drying at room temperature to obtain the PVC stent drainage tube with the inner and outer surface nano Cu particle inactivation layer, immersing the stent drainage tube with the chemical silver plating solution (silver nitrate: 0.1.1 zxft 3862, sodium thiosulfate: 50 4232/L, sodium hydroxide: 0.01 zxft 4234, the content: 1.0.0.1 zxft 5364, performing chemical silver plating on the surface of the stent drainage tube with the chemical silver plating, and taking out the composite silver plating solution at the temperature of the Cu particles, and taking out the Cu drainage tube, and drying at the temperature of Ag 5 ℃ to obtain the composite silver plating the Cu particles.

The scheme has the following advantages:

(1) The nano Ag and Cu particle inactivation layer on the inner surface and the outer surface of the drainage tube of the pancreatin inactivation stent changes the corrosion performance of pancreatin flowing through the pancreatin anastomotic stoma in situ, reduces the pancreatin fistula complication after the pancreatin anastomosis, lightens the adverse effect possibly brought by the pancreatin fistula, improves the safety of the pancreatin anastomosis, and changes 'death kiss' into 'life kiss';

(2) The 3D printing technology is adopted to realize that the stent drainage tube can accurately prepare the inner surface of the fold structure, and the effective area of the inactivation layer of the inner surface can be greatly increased. On one hand, the effectiveness of an inactivation layer in a wound healing period (about 7 days) is ensured, the efficiency of pancreatic juice inactivation is improved, so that the corrosion effect on the wound when pancreatic juice in the intestinal tract flows backwards is reduced, on the other hand, the 3D printing technology can be used for quickly, accurately and controllably preparing the folded structure in an area manner, the large-scale industrial production of the folded structure is facilitated, and the preparation cost of the folded structure is reduced;

(3) The outer surface of the bracket drainage tube is also designed to be provided with an inactivation layer, so that the pancreatic juice flowing through the wound can be effectively inactivated for the second time, and the corrosion effect of the pancreatic juice on the wound is reduced again;

(4) The stent drainage tube framework is prepared by adopting non-toxic and good-biocompatibility conventional organic medical materials such as PI, PVC and the like, has low manufacturing cost and is suitable for large-scale production and popularization.

While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (7)

1. A pancreatin inactivation stent drainage tube is applied to pancreaticojejunostomy and is characterized in that the pancreatin inactivation stent drainage tube comprises a stent drainage tube framework and a pancreatin inactivation layer; the pancreatin inactivation layer is prepared by being plated with a nano Ag or/and Cu particle inactivation layer;

the stent drainage tube framework is made of transparent medical high polymer materials through 3D printing; the framework of the stent drainage tube is of a tubular structure with a smooth outer surface and a large number of wrinkled layers on the inner surface; the outer surface of the stent drainage tube skeleton is also provided with barbs and side holes; the 3D printing technology is adopted to realize that the inner surface of the bracket drainage tube is accurately prepared into a fold structure, so that the effective area of an inner surface inactivation layer is greatly increased;

the preparation method of the pancreatin inactivation stent drainage tube comprises the following steps:

(1) Preparing 3D printing ink for later use, and preparing a stent drainage tube framework by adopting 3D molding printing of a medical high polymer material;

(2) The pancreatin inactivation layer is coated on the inner surface and the outer surface of the framework of the stent drainage tube to obtain the pancreatin inactivation stent drainage tube;

the high molecular polymer material is Polyimide (PI), and the specific steps in the step (1) are as follows:

weighing 2, 2' -bis (trifluoromethyl) -biphenyldiamine (TFDB), 4' -hexafluoroisopropylidene-phthalic anhydride (6 FDA) and N, N ' -dimethylacetamide (DMAc) according to a proportion for later use, putting the TFDB and the DMAc into a flask, stirring and fully dissolving, adding the 6FDA for several times, wherein the adding amount of each time is one half of the remaining 6FDA part, stirring under the protection of argon to obtain a polyamide acid solution, adding phthalic anhydride, stirring to obtain a polyamide solution with a phthalic anhydride end-capping for later use as 3D printing ink;

secondly, performing thermal imidization molding printing by adopting a selective laser sintering 3D printer to prepare a support drainage tube framework which is made of PI materials and has a smooth outer surface and a large number of folds on an inner surface;

the pancreatin inactivation layer is a nano Ag particle inactivation layer, and the specific preparation step in the step (2) is as follows: immersing the framework of the PI stent drainage tube in hot alkali liquor for soaking, washing with deionized water to remove surface alkali solution, immersing in silver ammonia solution, carrying out ion exchange reaction at room temperature, taking out, washing with deionized water, drying at room temperature, and carrying out thermal imidization reduction treatment to obtain the PI stent drainage tube with the inner and outer surfaces plated with nano Ag particle inactivation layers;

the hot alkali liquor: naOH and KOH with the temperature of 40 to 70 ℃ and the temperature of 2.5 to 5M; the concentration of the silver ammonia solution is 0.04 to 0.5M;

the ion exchange reaction time is 5 to 30 min;

the temperature of the thermal imidization reduction is 200 to 320 ℃, and the time is 1 to 2 hours.

2. The pancreatin-inactivating stent drainage tube according to claim 1, wherein the coating means in step (2) comprises one or both of ion exchange or electroless plating.

3. The pancreatin inactivation stent drainage tube according to claim 1, wherein the high polymer material is polyvinyl chloride (PVC), and the specific steps in step (1) are as follows:

step one, mixing PVC and succinic adipate according to a mass ratio, dissolving in tetrahydrofuran, magnetically stirring to form a uniformly dispersed emulsion solution, standing, eliminating bubbles, sealing, and preparing 3D printing ink for later use;

step two, performing forming printing by adopting a UV 3D printer, and preparing a PVC bracket drainage tube framework with a smooth outer surface and a large number of folds on the inner surface;

the mass ratio of the PVC to the butylene adipate is 1: (1~6); the mass ratio of the mixed PVC and butylene adipate to tetrahydrofuran is 1: (1~4).

4. The pancreatin-inactivating stent drainage tube according to claim 3, wherein the pancreatin-inactivating layer is a nano Ag particle-inactivating layer, and the specific preparation step of step (2) is as follows: performing stress removal, oil removal, coarsening and sensitization pretreatment on the PVC stent drainage tube skeleton, immersing the PVC stent drainage tube skeleton into chemical silver plating solution for chemical silver plating, taking out the PVC stent drainage tube skeleton, washing the PVC stent drainage tube skeleton with deionized water, and airing the PVC stent drainage tube skeleton at room temperature to obtain a PVC stent drainage tube with the inner surface and the outer surface plated with a nano Ag particle inactivation layer;

the chemical silver plating solution comprises: 0.001 to 0.1M of silver nitrate, 10 to 50 mg/L of sodium thiosulfate, and sodium hydroxide: 0.001 to 0.01M, ammonia water content: 0.1 to 1.0%, glucose: 0.01 to 0.1M;

the temperature of the chemical silver plating is 20-40 ℃, and the time of the chemical silver plating is 10-20 min.

5. The pancreatin-inactivating stent drainage tube according to claim 3, wherein the pancreatin-inactivating layer is a nano Cu particle-inactivating layer, and the specific preparation step of the step (2) is as follows: after internal surface pretreatment of stress removal, oil removal, coarsening and sensitization is carried out on the PVC material stent drainage tube skeleton in the step (1), the skeleton is immersed in chemical copper plating solution for chemical copper plating, taken out, washed by deionized water and dried at room temperature, and the PVC material stent drainage tube with the inside and outside surfaces plated with the nano Cu particle inactivation layer is obtained;

the chemical copper plating solution comprises the following steps: 0.001 to 0.1M of copper sulfate pentahydrate, 0.01 to 0.1M of disodium ethylene diamine tetraacetate, 0.1 to 1 mg/L of thiourea, and potassium sodium tartrate: 0.005 to 0.02M, sodium hydroxide: 0.01 to 0.05M, 10 to 50 mg/L of sodium dodecyl sulfate, formaldehyde: 8-20 mL/L, pH value: 11 to 13.5;

the temperature of the chemical copper plating is 20-80 ℃, and the time of the chemical copper plating is 5-20 min.

6. The pancreatin-inactivating stent drainage tube according to claim 1, wherein the pancreatin-inactivating layer is a nano-Cu particle-inactivating layer, and the specific preparation step of step (2) is as follows: after the framework of the PI bracket drainage tube in the step (1) is subjected to stress removal, oil removal, coarsening and sensitization pretreatment, the framework is immersed in chemical copper plating solution for chemical copper plating, and the framework is taken out, washed by deionized water and dried at room temperature to obtain the PI bracket drainage tube with the inner surface and the outer surface plated with the nano Cu particle inactivation layer;

the chemical copper plating solution comprises the following steps: 0.001 to 0.01M of copper sulfate pentahydrate, potassium sodium tartrate: 0.005 to 0.02M, sodium hydroxide: 0.01 to 0.05M, 0.01 to 0.05M of ethylene diamine tetraacetic acid, and formaldehyde: 8 to 20 mL/L, pH value: 11 to 13.5;

the temperature of the chemical copper plating is 20-80 ℃, and the time of the chemical copper plating is 10-20 min.

7. The pancreatin inactivation stent drainage tube according to claim 5 or 6, wherein the pancreatin inactivation layer is a nano Cu @ Ag particle composite inactivation layer, and the specific preparation step of the step (2) is as follows: immersing the PVC or PI stent drainage tube with the inner and outer surfaces plated with the nano Cu particle inactivation layer into chemical silver plating solution again for chemical copper plating, taking out, washing with deionized water, and drying at room temperature to obtain the PVC or PI stent drainage tube with the inner and outer surfaces plated with the nano Cu @ Ag particle composite inactivation layer;

the chemical silver plating solution comprises: 0.001 to 0.1M of silver nitrate, 10 to 50 mg/L of sodium thiosulfate, and sodium hydroxide: 0.001 to 0.01M, ammonia water content: 0.1 to 1.0%, glucose: 0.01 to 0.1M;

the temperature of the chemical silver plating is 20-40 ℃, and the time of the chemical silver plating is 5-15 min.

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