CN112142914A - Antibacterial fluorosilicone material copolymer and application thereof - Google Patents
Antibacterial fluorosilicone material copolymer and application thereof Download PDFInfo
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- CN112142914A CN112142914A CN202011037754.6A CN202011037754A CN112142914A CN 112142914 A CN112142914 A CN 112142914A CN 202011037754 A CN202011037754 A CN 202011037754A CN 112142914 A CN112142914 A CN 112142914A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
- A61L29/08—Materials for coatings
- A61L29/085—Macromolecular materials
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
- A61L29/14—Materials characterised by their function or physical properties, e.g. lubricating compositions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
- C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2420/00—Materials or methods for coatings medical devices
- A61L2420/02—Methods for coating medical devices
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2420/00—Materials or methods for coatings medical devices
- A61L2420/06—Coatings containing a mixture of two or more compounds
Abstract
The invention discloses an antibacterial fluorosilicone material copolymer which is characterized by comprising 1- (4, 5-dimethyl-1-vinyl-1H-pyrrole-2-yl) -2,2, 2-trifluoroethane ketone, 2-trimethylsiloxy-1, 1,1,5,5, 5-hexafluoro-2-pentene-4-ketone, (6,6,7,7,8,8, 8-heptafluoro-2, 2-dimethyl-3, 5-octanedionate) silver and (5R) -5- [ (1E,3R) -4, 4-difluoro-3-hydroxy-4-phenyl-1-butenyl ] -1- [6- (1H-tetrazole-5-yl) hexyl ] -2-pyri-ne Copolymers formed by copolymerization of pyrrolidone. The antibacterial fluorosilicone material copolymer prepared by the invention can be applied to preparation of medical catheters, and has good mechanical properties, weather resistance and continuous antibacterial effect.
Description
Technical Field
The invention relates to the technical field of medical instruments, in particular to a medical catheter and a preparation method thereof.
Background
In recent years, the number of patients with systemic or hemiplegia due to brain diseases such as cerebral apoplexy or spinal injuries, non-neurogenic bladder diseases such as obstruction due to prostatic hypertrophy, urethral stricture or postoperative urinary retention, and neurogenic bladder diseases such as spina bifida or multiple sclerosis has been increasing year by year due to the increase in the elderly population, traffic accidents, industrial disasters, and the like. When treating these patients, continuous catheterization is needed to empty their bladder, and when catheterization, a medical catheter is needed, which is a safe, effective and well-compatible diagnostic and therapeutic tool, and its application is becoming more and more extensive.
At present, the catheters used in medicine are pipelines made of natural rubber, silicon rubber or polyvinyl chloride, the catheters have urinary tract infection and allergy caused by the histocompatibility of materials and urethra more or less, the surface particles are thick and have poor lubricity, the growth of bacterial biomembranes is easily induced, the patients are easy to generate burning pain in the process of entering the bladder through the urethra, and even inflammation is caused by injuring mucous membranes, so that inconvenience is brought to medical treatment and nursing, unnecessary pain is caused to the patients, meanwhile, the hidden danger of medical disputes is increased, and the life health safety of the patients is threatened.
In order to improve the bacteriostatic property and lubricity of the catheter, researchers make many efforts, and the method for improving the bacteriostatic property is mainly to spray a layer of hydrosol or lubricating gel containing bacteriostatic agents or antibiotics on the outer layer of the rubber catheter, so that the method is easy to cause the falling of coating materials in the subsequent operation process, and has no practical clinical application; in addition, a method for adding a bacteriostatic agent into the surface treatment liquid of the catheter to realize that the catheter carries the bacteriostatic agent cannot effectively improve the tissue compatibility of the catheter and increase the stability of the bacteriostatic agent. The technical measure for improving the lubricity is to coat lubricants such as paraffin oil or complex iodine on the surface of the catheter, but the paraffin oil is not absorbed by mucous membranes and is easy to cause other diseases, the complex iodine often wipes the local part of the catheter when in use and cannot play a comprehensive lubricating effect, and the methods do not improve the hydrophilicity of the catheter, improve the difficulty of intubation and increase the pain of patients.
Therefore, the development of a catheter with continuous antibacterial effect, excellent surface hydrophilic lubricity, flexibility and comfort and easy intubation becomes a problem to be solved urgently in the industry, and is an urgent need for clinical and practical application.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides the medical catheter and the preparation method thereof, and the preparation method is simple and feasible, has easily obtained raw materials and low price, and is suitable for large-scale production; the prepared medical catheter has excellent comprehensive performance, continuous antibacterial effect, excellent surface hydrophilic lubricity, flexibility and comfort, and easy intubation, can effectively prevent urinary tract infection, simultaneously reduce urethral mucosa damage, improve treatment effect and reduce pain of patients.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows: a medical catheter comprises a catheter body and a coating coated on the surface of the catheter body, wherein the catheter body is made of a fluorine-silicon material copolymer, polyurethane and 1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-diketone modified fullerene; the coating on the surface of the catheter body is prepared by chemical reaction of raw materials of 1, 1-methylenebis [3- (2-hydroxyethyl) -2-pyrrolidone ], 1,3, 3-tetramethyl-1, 3-bis- [2- [ 7-oxidbicyclo [4.1.0] hept-3-yl ] ethyl ] disiloxane and polylactic acid.
Furthermore, the fluorine-silicon material copolymer is prepared by 1- (4, 5-dimethyl-1-vinyl-1H-pyrrole-2-yl) -2,2, 2-trifluoroethane ketone, 2-trimethylsiloxy-1, 1,1,5,5, 5-hexafluoro-2-pentene-4-ketone, (6,6,7,7,8,8, 8-heptafluoro-2, 2-dimethyl-3, 5-octanedionate) silver, (5R) -5- [ (1E,3R) -4, 4-difluoro-3-hydroxy-4-phenyl-1-butenyl ] -1- [6- (1H-tetrazol-5-yl) hexyl ] -2-pyrrolidone.
Preferably, the preparation method of the catheter body comprises the following steps:
i1- (4, 5-dimethyl-1-vinyl-1H-pyrrol-2-yl) -2,2, 2-trifluoroethane ketone, 2-trimethylsiloxy-1, 1,1,5,5, 5-hexafluoro-2-penten-4-one, (6,6,7,7,8,8, 8-heptafluoro-2, 2-dimethyl-3, 5-octanedionate) silver, (5R) -5- [ (1E,3R) -4, 4-difluoro-3-hydroxy-4-phenyl-1-butenyl ] -1- [6- (1H-tetrazol-5-yl) hexyl ] -2-pyrrolidone, a salt thereof, a hydrate thereof, and a hydrate thereof, Adding an initiator, an emulsifier and water into a high-boiling-point solvent, stirring and reacting for 6-8 hours at 70-80 ℃ in the atmosphere of nitrogen or inert gas, then separating out in water, washing the separated polymer for 3-5 times by using ethanol, and then drying for 15-20 hours at 75-85 ℃ in a vacuum drying oven to obtain a fluorosilicone material copolymer;
II, dispersing the fullerene in an organic solvent, adding 1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-dione into the organic solvent, stirring the mixture at the temperature of between 50 and 60 ℃ for reaction for 6 to 8 hours, and then removing the organic solvent by rotary evaporation to obtain 1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-dione modified fullerene;
III, adding the copolymer prepared in the step I, the 1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-dione modified fullerene prepared in the step II and polyurethane into a double-screw extruder for extrusion molding to obtain the catheter body.
Preferably, the 1- (4, 5-dimethyl-1-vinyl-1H-pyrrol-2-yl) -2,2, 2-trifluoroethan-one, 2-trimethylsiloxy-1, 1,1,5,5, 5-hexafluoro-2-penten-4-one, (6,6,7,7,8,8, 8-heptafluoro-2, 2-dimethyl-3, 5-octanedionate) silver, (5R) -5- [ (1E,3R) -4, 4-difluoro-3-hydroxy-4-phenyl-1-butenyl ] -1- [6- (1H-tetrazol-5-yl) hexyl ] -2-pyrrolidone, the compound of step I, The mass ratio of the initiator, the emulsifier, the water and the high-boiling point solvent is 1:1:1:1 (0.03-0.05):0.04 (20-25): 20-25).
Preferably, the initiator is selected from one or more of sodium persulfate, potassium persulfate, ammonium persulfate and azobisisobutyronitrile.
Preferably, the emulsifier is one or more selected from sodium dodecyl sulfate salt, sodium dodecyl sulfonate salt, fatty alcohol-polyoxyethylene ether, sorbitan fatty acid ester polyoxyethylene ether and sorbitan fatty acid ester.
Preferably, the high boiling point solvent is selected from one or more of dimethyl sulfoxide, N-dimethylformamide and N-methylpyrrolidone.
Preferably, the inert gas is selected from one of helium, neon and argon.
Preferably, the mass ratio of the fullerene, the organic solvent and the 1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-diketone in the step II is (3-5): 10-15): 1.
Preferably, the organic solvent is selected from one or more of ethanol, acetonitrile, acetone and tetrahydrofuran.
Preferably, the mass ratio of the copolymer, the 1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-dione modified fullerene and the polyurethane in the step III is 1:0.1 (3-5).
Preferably, the extrusion temperature of the double-screw extruder is 230-250 ℃, and the screw rotating speed is 1000-1200 r/min.
Preferably, the preparation method of the coating on the surface of the catheter body comprises the following steps: dissolving 1, 1-methylenebis [3- (2-hydroxyethyl) -2-pyrrolidone ], 1,3, 3-tetramethyl-1, 3-bis- [2- [ 7-oxidocyclo [4.1.0] hept-3-yl ] ethyl ] disiloxane in N-methylpyrrolidone to form a solution, adding an alkaline catalyst into the solution, stirring and reacting at 80-90 ℃ for 10-12 hours, adding polylactic acid into the solution, continuing to keep the temperature and stir for reacting for 3-5 hours, then adjusting the pH to 7 by adding hydrochloric acid, filtering, and removing the solvent by rotary evaporation to obtain the coating on the surface of the catheter body.
Preferably, the mass ratio of the 1, 1-methylenebis [3- (2-hydroxyethyl) -2-pyrrolidone ], the 1,1,3, 3-tetramethyl-1, 3-bis- [2- [ 7-oxidocyclo [4.1.0] hept-3-yl ] ethyl ] disiloxane, the N-methylpyrrolidone, the basic catalyst and the polylactic acid is 1:1.5 (10-15): 0.5-0.7): 0.1.
Preferably, the alkaline catalyst is selected from one or more of sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide.
Preferably, the preparation method of the medical catheter comprises the following steps: adding the coating on the surface of the catheter body into isopropanol, stirring for 1-2 hours at 40-60 ℃ to obtain a coating solution, soaking the catheter body subjected to cleaning and disinfection treatment in the coating solution for 3-5 hours, taking out and naturally drying, and then performing sterilization treatment to obtain the medical catheter.
Preferably, the mass ratio of the coating on the surface of the catheter body to the isopropanol is 1 (0.5-1).
Adopt the produced beneficial effect of above-mentioned technical scheme to lie in:
1) the medical catheter provided by the invention has the advantages of simple and feasible preparation method, easily available raw materials, low price and suitability for large-scale production.
2) The medical catheter provided by the invention overcomes the defects that the performance stability of the catheter in the prior art is poor, urinary tract infection and allergy are caused by the histocompatibility of materials and the urethra, the surface particles are thick and lose lubricity, the growth of bacterial biofilms is easily induced, a patient is easily burnt and painful in the process of entering the bladder through the urethra, and even inflammation is caused by mucosa injury.
3) The medical catheter provided by the invention has small smell and toxicity, is safer and more environment-friendly to use, the surface coating is prepared by condensation polymerization of 1, 1-methylenebis [3- (2-hydroxyethyl) -2-pyrrolidone ], 1,3, 3-tetramethyl-1, 3-bis- [2- [ 7-oxidbicyclo [4.1.0] hept-3-yl ] ethyl ] disiloxane, the hydrophilic property and the lubricity are good, the hydrophilic property and the lubricity are better than that of introducing a pyrrolidone structure in a branched chain form, and the introduction of a substance with good biocompatibility by a polylactic acid end capping is beneficial to improving the biocompatibility of the catheter and reducing urinary tract infection and allergy; and the coating has good compatibility with the catheter body and strong adhesive force.
4) According to the medical catheter provided by the invention, the catheter body is prepared by blending polyurethane and a copolymer and adding modified fullerene, firstly, the copolymer introduces a fluorine-silicon material and an azole structure, so that the mechanical property and weather resistance of the material can be obviously improved, and the performance stability of the material is ensured; secondly, silver ions and an azole structure are introduced to have a synergistic effect to play an antibacterial role; thirdly, a pyrrolidone structure is introduced, the structure is similar to that of pyrrolidone in the coating, and the shape compatibility of the coating and the catheter body is improved; modified fullerene is introduced to improve lubricity and strength, and compatibility and dispersibility of the material are improved through modification; the polyurethane structure can ensure the excellent mechanical properties of the material, such as elasticity, toughness and the like, and has good compatibility with the copolymer and the coating.
5) The medical catheter provided by the invention has the advantages that the components and the structures are mutually matched and cooperate to form an integral system, so that the medical catheter provided by the invention has excellent comprehensive performance, good antibacterial hydrophilic lubricity and prolonged service life.
Detailed Description
In order to make the technical solutions of the present invention better understood and make the above features, objects, and advantages of the present invention more comprehensible, the present invention is further described with reference to the following examples. The examples are intended to illustrate the invention only and are not intended to limit the scope of the invention.
The raw materials described in the following examples of the present invention are from Shanghai spring Xin import & export trade company, Inc.
Example 1
A medical catheter comprises a catheter body and a coating coated on the surface of the catheter body, wherein the catheter body is made of 1- (4, 5-dimethyl-1-vinyl-1H-pyrrole-2-yl) -2,2, 2-trifluoroethane ketone, 2-trimethylsiloxy-1, 1,1,5,5, 5-hexafluoro-2-pentene-4-one, (6,6,7,7,8,8, 8-heptafluoro-2, 2-dimethyl-3, 5-octanedionic acid) silver, and (5R) -5- [ (1E,3R) -4, 4-difluoro-3-hydroxy-4-phenyl-1-butenyl ] -1- [6- (1H-tetrazole-5-yl) hexyl ] -2- (5H-tetrazole-ethyl-methyl-2-methyl-ethyl-1-methyl-2-ethyl-methyl-ethyl-2-methyl-ethyl-4 -copolymers formed by copolymerisation of pyrrolidones, polyurethanes and 1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-dione modified fullerenes; the coating on the surface of the catheter body is prepared by chemical reaction of raw materials of 1, 1-methylenebis [3- (2-hydroxyethyl) -2-pyrrolidone ], 1,3, 3-tetramethyl-1, 3-bis- [2- [ 7-oxidbicyclo [4.1.0] hept-3-yl ] ethyl ] disiloxane and polylactic acid.
The preparation method of the catheter body comprises the following steps:
i100 g of 1- (4, 5-dimethyl-1-vinyl-1H-pyrrol-2-yl) -2,2, 2-trifluoroethane-none, 100g of 2-trimethylsiloxy-1, 1,1,5,5, 5-hexafluoro-2-penten-4-one, 100g of (6,6,7,7,8,8, 8-heptafluoro-2, 2-dimethyl-3, 5-octanedionato) silver, (5R) -5- [ (1E,3R) -4, 4-difluoro-3-hydroxy-4-phenyl-1-butenyl ] -1- [6- (1H-tetrazol-5-yl) hexyl ] -2-pyrrolidone, 100g of, Adding 3g of sodium persulfate, 4g of sodium dodecyl sulfate and 2000g of water into 2000g of dimethyl sulfoxide, stirring and reacting for 6 hours at 70 ℃ in a nitrogen atmosphere, then precipitating in water, washing the precipitated polymer for 3 times by using ethanol, and then drying for 15 hours at 75 ℃ in a vacuum drying oven to obtain a fluorosilicone material copolymer;
II, dispersing 30g of fullerene in 100g of ethanol, adding 10g of 1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-dione into the mixture, stirring the mixture at 50 ℃ for reacting for 6 hours, and then performing rotary evaporation to remove the ethanol to obtain 1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-dione modified fullerene;
III, adding 100g of the copolymer prepared in the step I, 10g of 1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-dione modified fullerene prepared in the step II and 300g of polyurethane into a double-screw extruder for extrusion molding to obtain the catheter body.
The extrusion temperature of the double-screw extruder is 230 ℃, and the screw rotating speed is 1000 r/min.
The preparation method of the coating on the surface of the catheter body comprises the following steps: 100g of 1, 1-methylenebis [3- (2-hydroxyethyl) -2-pyrrolidone ] and 150g of 1,1,3, 3-tetramethyl-1, 3-bis- [2- [ 7-oxidocyclo [4.1.0] hept-3-yl ] ethyl ] disiloxane are dissolved in 1000g of N-methylpyrrolidone to form a solution, 50g of sodium carbonate is added into the solution, the solution is stirred and reacted for 10 hours at the temperature of 80 ℃, 10g of polylactic acid is added into the solution, the solution is kept warm and stirred and reacted for 3 hours, then the pH is adjusted to 7 by adding hydrochloric acid, and the solution is filtered and rotary-evaporated to remove the solvent, so that the coating on the surface of the catheter body is obtained.
The preparation method of the medical catheter comprises the following steps: adding 100g of the coating on the surface of the catheter body into 50g of isopropanol, stirring for 1 hour at 40 ℃ to obtain a coating solution, soaking the catheter body subjected to cleaning and disinfection treatment in the coating solution for 3 hours, taking out the catheter body, naturally drying, and then performing sterilization treatment to obtain the medical catheter.
Example 2
A medical catheter comprises a catheter body and a coating coated on the surface of the catheter body, wherein the catheter body is made of 1- (4, 5-dimethyl-1-vinyl-1H-pyrrole-2-yl) -2,2, 2-trifluoroethane ketone, 2-trimethylsiloxy-1, 1,1,5,5, 5-hexafluoro-2-pentene-4-one, (6,6,7,7,8,8, 8-heptafluoro-2, 2-dimethyl-3, 5-octanedionic acid) silver, and (5R) -5- [ (1E,3R) -4, 4-difluoro-3-hydroxy-4-phenyl-1-butenyl ] -1- [6- (1H-tetrazole-5-yl) hexyl ] -2- (5H-tetrazole-ethyl-methyl-2-methyl-ethyl-1-methyl-2-ethyl-methyl-ethyl-2-methyl-ethyl-4 -copolymers formed by copolymerisation of pyrrolidones, polyurethanes and 1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-dione modified fullerenes; the coating on the surface of the catheter body is prepared by chemical reaction of raw materials of 1, 1-methylenebis [3- (2-hydroxyethyl) -2-pyrrolidone ], 1,3, 3-tetramethyl-1, 3-bis- [2- [ 7-oxidbicyclo [4.1.0] hept-3-yl ] ethyl ] disiloxane and polylactic acid.
The preparation method of the catheter body comprises the following steps:
i100 g of 1- (4, 5-dimethyl-1-vinyl-1H-pyrrol-2-yl) -2,2, 2-trifluoroethane-none, 100g of 2-trimethylsiloxy-1, 1,1,5,5, 5-hexafluoro-2-penten-4-one, 100g of (6,6,7,7,8,8, 8-heptafluoro-2, 2-dimethyl-3, 5-octanedionato) silver, (5R) -5- [ (1E,3R) -4, 4-difluoro-3-hydroxy-4-phenyl-1-butenyl ] -1- [6- (1H-tetrazol-5-yl) hexyl ] -2-pyrrolidone, 100g of, Adding 3.5g of potassium persulfate, 4g of sodium dodecyl sulfonate and 2100g of water into 2100g of N, N-dimethylformamide, stirring and reacting for 6.5 hours at 73 ℃ in a helium atmosphere, then precipitating in water, washing the precipitated polymer for 4 times by using ethanol, and then placing in a vacuum drying oven for drying for 16 hours at 77 ℃ to obtain a fluorosilicone material copolymer;
II, dispersing 350g of fullerene in 1150g of acetonitrile, adding 100g of 1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-dione, stirring and reacting at 53 ℃ for 6.5 hours, and then removing the acetonitrile by rotary evaporation to obtain 1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-dione modified fullerene;
III, adding 100g of the copolymer prepared in the step I, 10g of 1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-dione modified fullerene prepared in the step II and 350g of polyurethane into a double-screw extruder for extrusion molding to obtain the catheter body.
The extrusion temperature of the double-screw extruder is 235 ℃, and the screw rotating speed is 1050 r/min.
The preparation method of the coating on the surface of the catheter body comprises the following steps: 100g of 1, 1-methylenebis [3- (2-hydroxyethyl) -2-pyrrolidone ] and 150g of 1,1,3, 3-tetramethyl-1, 3-bis- [2- [ 7-oxidocyclo [4.1.0] hept-3-yl ] ethyl ] disiloxane are dissolved in 1200g of N-methylpyrrolidone to form a solution, 55g of potassium carbonate is added into the solution, the solution is stirred and reacted for 10.5 hours at 83 ℃, 10g of polylactic acid is added into the solution, the solution is kept warm and stirred and reacted for 3.5 hours, hydrochloric acid is added into the solution to adjust the pH value to 7, and then the solution is filtered and evaporated to remove the solvent, so that the coating on the surface of the catheter body is obtained.
The preparation method of the medical catheter comprises the following steps: adding 100g of the coating on the surface of the catheter body into 65g of isopropanol, stirring for 1.2 hours at 45 ℃ to obtain a coating solution, soaking the catheter body subjected to cleaning and disinfection treatment in the coating solution for 3.5 hours, taking out and naturally drying, and then performing sterilization treatment to obtain the medical catheter.
Example 3
A medical catheter comprises a catheter body and a coating coated on the surface of the catheter body, wherein the catheter body is made of 1- (4, 5-dimethyl-1-vinyl-1H-pyrrole-2-yl) -2,2, 2-trifluoroethane ketone, 2-trimethylsiloxy-1, 1,1,5,5, 5-hexafluoro-2-pentene-4-one, (6,6,7,7,8,8, 8-heptafluoro-2, 2-dimethyl-3, 5-octanedionic acid) silver, and (5R) -5- [ (1E,3R) -4, 4-difluoro-3-hydroxy-4-phenyl-1-butenyl ] -1- [6- (1H-tetrazole-5-yl) hexyl ] -2- (5H-tetrazole-ethyl-methyl-2-methyl-ethyl-1-methyl-2-ethyl-methyl-ethyl-2-methyl-ethyl-4 -copolymers formed by copolymerisation of pyrrolidones, polyurethanes and 1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-dione modified fullerenes; the coating on the surface of the catheter body is prepared by chemical reaction of raw materials of 1, 1-methylenebis [3- (2-hydroxyethyl) -2-pyrrolidone ], 1,3, 3-tetramethyl-1, 3-bis- [2- [ 7-oxidbicyclo [4.1.0] hept-3-yl ] ethyl ] disiloxane and polylactic acid.
The preparation method of the catheter body comprises the following steps:
i100 g of 1- (4, 5-dimethyl-1-vinyl-1H-pyrrol-2-yl) -2,2, 2-trifluoroethane-none, 100g of 2-trimethylsiloxy-1, 1,1,5,5, 5-hexafluoro-2-penten-4-one, 100g of (6,6,7,7,8,8, 8-heptafluoro-2, 2-dimethyl-3, 5-octanedionato) silver, (5R) -5- [ (1E,3R) -4, 4-difluoro-3-hydroxy-4-phenyl-1-butenyl ] -1- [6- (1H-tetrazol-5-yl) hexyl ] -2-pyrrolidone, 100g of, Adding 4g of ammonium persulfate, 4g of fatty alcohol-polyoxyethylene ether and 2300g of water into 2300g of N-methylpyrrolidone, stirring and reacting for 7 hours at 75 ℃ in a neon atmosphere, then separating out in water, washing the separated polymer for 4 times by using ethanol, and then placing in a vacuum drying oven for drying for 17.5 hours at 80 ℃ to obtain a fluorosilicone material copolymer;
II, dispersing 400g of fullerene in 1300g of acetone, adding 100g of 1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-dione into the mixture, stirring the mixture at the temperature of 55 ℃ for reaction for 7 hours, and then removing the acetone by rotary evaporation to obtain 1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-dione modified fullerene;
III, adding 100g of the copolymer prepared in the step I, 10g of 1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-dione modified fullerene prepared in the step II and 400g of polyurethane into a double-screw extruder for extrusion molding to obtain the catheter body.
The extrusion temperature of the double-screw extruder is 240 ℃, and the screw rotating speed is 1100 r/min.
The preparation method of the coating on the surface of the catheter body comprises the following steps: 100g of 1, 1-methylenebis [3- (2-hydroxyethyl) -2-pyrrolidone ] and 150g of 1,1,3, 3-tetramethyl-1, 3-bis- [2- [ 7-oxidocyclo [4.1.0] hept-3-yl ] ethyl ] disiloxane are dissolved in 1300g of N-methylpyrrolidone to form a solution, 60g of sodium hydroxide is added into the solution, the solution is stirred and reacted for 11 hours at 86 ℃, 10g of polylactic acid is added into the solution, the solution is kept warm and stirred and reacted for 4 hours, then the pH is adjusted to 7 by adding hydrochloric acid, and the solution is filtered and rotary-evaporated to remove the solvent, so that the coating on the surface of the catheter body is obtained.
The preparation method of the medical catheter comprises the following steps: adding 100g of the coating on the surface of the catheter body into 75g of isopropanol, stirring for 1.6 hours at 50 ℃ to obtain a coating solution, soaking the catheter body subjected to cleaning and disinfection treatment in the coating solution for 5 hours, taking out the catheter body, naturally drying, and then performing sterilization treatment to obtain the medical catheter.
Example 4
A medical catheter comprises a catheter body and a coating coated on the surface of the catheter body, wherein the catheter body is made of 1- (4, 5-dimethyl-1-vinyl-1H-pyrrole-2-yl) -2,2, 2-trifluoroethane ketone, 2-trimethylsiloxy-1, 1,1,5,5, 5-hexafluoro-2-pentene-4-one, (6,6,7,7,8,8, 8-heptafluoro-2, 2-dimethyl-3, 5-octanedionic acid) silver, and (5R) -5- [ (1E,3R) -4, 4-difluoro-3-hydroxy-4-phenyl-1-butenyl ] -1- [6- (1H-tetrazole-5-yl) hexyl ] -2- (5H-tetrazole-ethyl-methyl-2-methyl-ethyl-1-methyl-2-ethyl-methyl-ethyl-2-methyl-ethyl-4 -copolymers formed by copolymerisation of pyrrolidones, polyurethanes and 1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-dione modified fullerenes; the coating on the surface of the catheter body is prepared by chemical reaction of raw materials of 1, 1-methylenebis [3- (2-hydroxyethyl) -2-pyrrolidone ], 1,3, 3-tetramethyl-1, 3-bis- [2- [ 7-oxidbicyclo [4.1.0] hept-3-yl ] ethyl ] disiloxane and polylactic acid.
The preparation method of the catheter body comprises the following steps:
i100 g of 1- (4, 5-dimethyl-1-vinyl-1H-pyrrol-2-yl) -2,2, 2-trifluoroethane-none, 100g of 2-trimethylsiloxy-1, 1,1,5,5, 5-hexafluoro-2-penten-4-one, 100g of (6,6,7,7,8,8, 8-heptafluoro-2, 2-dimethyl-3, 5-octanedionato) silver, (5R) -5- [ (1E,3R) -4, 4-difluoro-3-hydroxy-4-phenyl-1-butenyl ] -1- [6- (1H-tetrazol-5-yl) hexyl ] -2-pyrrolidone, 100g of, Adding 4.5g of initiator, 4g of emulsifier and 2400g of water into 2450g of high-boiling-point solvent, stirring and reacting for 7.5 hours at 78 ℃ in an argon atmosphere, then precipitating in water, washing the precipitated polymer for 4 times by using ethanol, and then placing in a vacuum drying oven for drying for 18 hours at 83 ℃ to obtain a fluorosilicone material copolymer; the initiator is a mixture formed by mixing sodium persulfate, potassium persulfate, ammonium persulfate and azobisisobutyronitrile according to a mass ratio of 1:2:3: 1; the emulsifier is a mixture formed by mixing sodium dodecyl sulfate, sodium dodecyl sulfonate, fatty alcohol-polyoxyethylene ether, sorbitan fatty acid ester polyoxyethylene ether and sorbitan fatty acid ester according to the mass ratio of 2:3:5:4: 3; the high-boiling-point solvent is a mixture formed by mixing dimethyl sulfoxide, N-dimethylformamide and N-methylpyrrolidone according to the mass ratio of 3:2: 3;
II, dispersing 450g of fullerene in 1450g of organic solvent, adding 100g of 1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-dione into the mixture, stirring the mixture at 58 ℃ for reaction for 7.7 hours, and then removing the organic solvent by rotary evaporation to obtain 1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-dione modified fullerene; the organic solvent is a mixture formed by mixing ethanol, acetonitrile, acetone and tetrahydrofuran according to a mass ratio of 1:1:2: 2;
III, adding 100g of the copolymer prepared in the step I, 10g of 1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-dione modified fullerene prepared in the step II and 450g of polyurethane into a double-screw extruder for extrusion molding to obtain the catheter body.
The extrusion temperature of the double-screw extruder is 245 ℃, and the rotating speed of the screw is 1150 r/min.
The preparation method of the coating on the surface of the catheter body comprises the following steps: dissolving 100g of 1, 1-methylenebis [3- (2-hydroxyethyl) -2-pyrrolidone ] and 150g of 1,1,3, 3-tetramethyl-1, 3-bis- [2- [ 7-oxidocyclo [4.1.0] hept-3-yl ] ethyl ] disiloxane in 1450g of N-methylpyrrolidone to form a solution, adding 65g of an alkaline catalyst into the solution, stirring and reacting at 88 ℃ for 11.5 hours, then adding 10g of polylactic acid, continuing to keep the temperature and stirring and reacting for 4.5 hours, then adding hydrochloric acid to adjust the pH value to 7, filtering, and removing the solvent by rotary evaporation to obtain a coating on the surface of the catheter body; the alkaline catalyst is a mixture formed by mixing sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide according to the mass ratio of 1:2:1: 1.
The preparation method of the medical catheter comprises the following steps: adding 100g of the coating on the surface of the catheter body into 95g of isopropanol, stirring for 1.8 hours at 58 ℃ to obtain a coating solution, soaking the catheter body subjected to cleaning and disinfection treatment in the coating solution for 4.5 hours, taking out and naturally drying, and then performing sterilization treatment to obtain the medical catheter.
Example 5
A medical catheter comprises a catheter body and a coating coated on the surface of the catheter body, wherein the catheter body is made of 1- (4, 5-dimethyl-1-vinyl-1H-pyrrole-2-yl) -2,2, 2-trifluoroethane ketone, 2-trimethylsiloxy-1, 1,1,5,5, 5-hexafluoro-2-pentene-4-one, (6,6,7,7,8,8, 8-heptafluoro-2, 2-dimethyl-3, 5-octanedionic acid) silver, and (5R) -5- [ (1E,3R) -4, 4-difluoro-3-hydroxy-4-phenyl-1-butenyl ] -1- [6- (1H-tetrazole-5-yl) hexyl ] -2- (5H-tetrazole-ethyl-methyl-2-methyl-ethyl-1-methyl-2-ethyl-methyl-ethyl-2-methyl-ethyl-4 -copolymers formed by copolymerisation of pyrrolidones, polyurethanes and 1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-dione modified fullerenes; the coating on the surface of the catheter body is prepared by chemical reaction of raw materials of 1, 1-methylenebis [3- (2-hydroxyethyl) -2-pyrrolidone ], 1,3, 3-tetramethyl-1, 3-bis- [2- [ 7-oxidbicyclo [4.1.0] hept-3-yl ] ethyl ] disiloxane and polylactic acid.
The preparation method of the catheter body comprises the following steps:
i100 g of 1- (4, 5-dimethyl-1-vinyl-1H-pyrrol-2-yl) -2,2, 2-trifluoroethane-none, 100g of 2-trimethylsiloxy-1, 1,1,5,5, 5-hexafluoro-2-penten-4-one, 100g of (6,6,7,7,8,8, 8-heptafluoro-2, 2-dimethyl-3, 5-octanedionato) silver, (5R) -5- [ (1E,3R) -4, 4-difluoro-3-hydroxy-4-phenyl-1-butenyl ] -1- [6- (1H-tetrazol-5-yl) hexyl ] -2-pyrrolidone, 100g of, Adding 5g of azodiisobutyronitrile, 4g of sorbitan fatty acid ester polyoxyethylene ether and 2500g of water into 2500g of dimethyl sulfoxide, stirring and reacting for 8 hours at 80 ℃ in a nitrogen atmosphere, then separating out in water, washing the separated polymer for 5 times by using ethanol, and then drying for 20 hours at 85 ℃ in a vacuum drying oven to obtain a fluorosilicone material copolymer;
II, dispersing 50g of fullerene in 150g of tetrahydrofuran, adding 10g of 1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-dione into the mixture, stirring the mixture at the temperature of 60 ℃ for reacting for 8 hours, and then performing rotary evaporation to remove the organic solvent to obtain 1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-dione modified fullerene;
III, adding 100g of the copolymer prepared in the step I, 10g of 1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-dione modified fullerene prepared in the step II and 500g of polyurethane into a double-screw extruder for extrusion molding to obtain the catheter body.
The extrusion temperature of the double-screw extruder is 250 ℃, and the screw rotating speed is 1200 r/min.
The preparation method of the coating on the surface of the catheter body comprises the following steps: dissolving 100g of 1, 1-methylenebis [3- (2-hydroxyethyl) -2-pyrrolidone ] and 150g of 1,1,3, 3-tetramethyl-1, 3-bis- [2- [ 7-oxidocyclo [4.1.0] hept-3-yl ] ethyl ] disiloxane in 1500g of N-methylpyrrolidone to form a solution, adding 70g of potassium hydroxide into the solution, stirring and reacting at 90 ℃ for 12 hours, then adding 10g of polylactic acid into the solution, continuing to keep the temperature and stirring and reacting for 5 hours, then adding hydrochloric acid to adjust the pH to 7, filtering, and removing the solvent by rotary evaporation to obtain the coating on the surface of the catheter body.
The preparation method of the medical catheter comprises the following steps: adding 100g of the coating on the surface of the catheter body into 100g of isopropanol, stirring for 2 hours at 60 ℃ to obtain a coating solution, soaking the catheter body subjected to cleaning and disinfection treatment in the coating solution for 5 hours, taking out the catheter body, naturally drying, and then performing sterilization treatment to obtain the medical catheter.
Comparative example
The commercially available medical catheter is prepared from a silicon rubber material.
The medical catheters obtained in the above examples 1 to 5 and comparative example were subjected to performance tests, and the test methods and test results are shown in table 1.
TABLE 1
As can be seen from table 1, the medical urinary catheter disclosed in the embodiment of the present invention has better antibacterial property and biocompatibility and better mechanical property compared with commercially available medical urinary catheters.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. An antibacterial fluorosilicone material copolymer is characterized in that the fluorosilicone material copolymer is prepared from 1- (4, 5-dimethyl-1-vinyl-1H-pyrrole-2-yl) -2,2, 2-trifluoroethane ketone, 2-trimethylsiloxy-1, 1,1,5,5, 5-hexafluoro-2-pentene-4-ketone, (6,6,7,7,8,8, 8-heptafluoro-2, 2-dimethyl-3, 5-octanedionate) silver, and (5R) -5- [ (1E,3R) -4, 4-difluoro-3-hydroxy-4-phenyl-1-butenyl ] -1- [6- (1H-tetrazole-5-yl) hexyl ] -2-pyrrolidone Polymerized to form a copolymer.
2. The antibacterial fluorosilicone material copolymer of claim 1, wherein the preparation method of the fluorosilicone material copolymer comprises the following steps: 1- (4, 5-dimethyl-1-vinyl-1H-pyrrol-2-yl) -2,2, 2-trifluoroethane, 2-trimethylsiloxy-1, 1,1,5,5, 5-hexafluoro-2-penten-4-one, (6,6,7,7,8,8, 8-heptafluoro-2, 2-dimethyl-3, 5-octanedionate) silver, (5R) -5- [ (1E,3R) -4, 4-difluoro-3-hydroxy-4-phenyl-1-butenyl ] -1- [6- (1H-tetrazol-5-yl) hexyl ] -2-pyrrolidone, and, Adding an initiator, an emulsifier and water into a high boiling point solvent, stirring and reacting for 6-8 hours at 70-80 ℃ in the atmosphere of nitrogen or inert gas, then separating out in water, washing the separated polymer for 3-5 times by using ethanol, and then drying for 15-20 hours at 75-85 ℃ in a vacuum drying oven to obtain the fluorosilicone material copolymer.
3. The antibacterial fluorosilicone material copolymer of claim 2, wherein the initiator is one or more selected from the group consisting of sodium persulfate, potassium persulfate, ammonium persulfate, and azobisisobutyronitrile.
4. The antibacterial fluorosilicone material copolymer of claim 2, wherein the emulsifier is one or more selected from sodium dodecyl sulfate, sodium dodecyl sulfonate, fatty alcohol-polyoxyethylene ether, sorbitan fatty acid ester polyoxyethylene ether, and sorbitan fatty acid ester.
5. The antibacterial fluorosilicone material copolymer of claim 2, wherein the high boiling point solvent is one or more selected from dimethyl sulfoxide, N-dimethylformamide and N-methylpyrrolidone.
6. The application method of the antibacterial fluorosilicone material copolymer as claimed in any one of claims 1 to 5, wherein the antibacterial fluorosilicone material copolymer is applied to preparation of a medical catheter.
7. The method for applying the antibacterial fluorosilicone material copolymer as claimed in claim 6, wherein the antibacterial fluorosilicone material copolymer, the 1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-dione modified fullerene and polyurethane are added into a twin-screw extruder to be extruded and molded to obtain the catheter body.
8. The method for applying the antibacterial fluorosilicone material copolymer according to claim 7, wherein the preparation method of the 1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-dione modified fullerene comprises the following steps: dispersing fullerene in an organic solvent, adding 1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-dione into the organic solvent, stirring the mixture at 50-60 ℃ for reacting for 6-8 hours, and removing the organic solvent by rotary evaporation to obtain the 1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-dione modified fullerene.
9. The method for applying the antibacterial fluorosilicone material copolymer according to claim 8, wherein the organic solvent is one or more selected from ethanol, acetonitrile, acetone and tetrahydrofuran.
10. The method for applying the antibacterial fluorosilicone material copolymer as claimed in claim 7, wherein the surface of the catheter body is coated with a coating, and the coating is prepared by chemical reaction of raw materials 1, 1-methylenebis [3- (2-hydroxyethyl) -2-pyrrolidone ], 1,3, 3-tetramethyl-1, 3-bis- [2- [ 7-oxidocyclo [4.1.0] hept-3-yl ] ethyl ] disiloxane and polylactic acid.
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| CN202011037750.8A Withdrawn CN112043940A (en) | 2018-09-23 | 2018-09-23 | Bacteriostatic hydrophilic catheter |
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| CN101812265A (en) * | 2009-02-24 | 2010-08-25 | 赛诺医疗科学技术有限公司 | Hydrophilic coat solution applied to surface of medicinal instrument and preparation method thereof |
| CN102921049A (en) * | 2012-09-28 | 2013-02-13 | 深圳清华大学研究院 | Antibacterial medical catheter and preparation method thereof |
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