CN113041404A - Preparation method of medical catheter with ultrasonic imaging capability based on hydrophobic modified porous starch and product thereof - Google Patents
Preparation method of medical catheter with ultrasonic imaging capability based on hydrophobic modified porous starch and product thereof Download PDFInfo
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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
- A61L29/18—Materials at least partially X-ray or laser opaque
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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
- A61L29/04—Macromolecular materials
- A61L29/043—Polysaccharides
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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
- A61L29/04—Macromolecular materials
- A61L29/06—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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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
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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
- A61L29/146—Porous materials, e.g. foams or sponges
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/02—Esters
- C08B31/04—Esters of organic acids, e.g. alkenyl-succinated starch
Abstract
The invention discloses a preparation method of a medical catheter with ultrasonic imaging capability based on hydrophobic modified porous starch, which comprises the following steps: (1) dispersing starch in a buffer solution with the pH value of 4.7-4.9, adding a complex enzyme for enzymolysis, and preparing porous starch; (2) dispersing the porous starch obtained in the step (1) in deionized water, and reacting the porous starch with octenyl succinic anhydride in a system with the pH value of 8.0-8.5 to obtain hydrophobic porous starch; (3) Dispersing the hydrophobic porous starch obtained in the step (2) in deionized water, and reacting with Al in a system with the pH of 3.9-4.12(SO4)3Reacting to obtain composite modified porous starch; (4) and (3) blending the composite modified porous starch obtained in the step (3) with thermoplastic polyurethane granules, wherein the mass ratio of thermoplastic polyurethane to composite modified porous starch is 95/5-85/15, and extruding the mixture by a double-screw extruder to obtain the medical catheter.
Description
Technical Field
The invention belongs to the field of biomedical materials, and relates to a preparation method of a medical catheter with ultrasonic imaging capability based on hydrophobic modified porous starch and a product thereof.
Background
With the development of medical science, materials science, biology, chemistry and other disciplines, medical polymer materials are widely applied to the biomedical field. Firstly, the natural polymer material has good biocompatibility and no toxic or side effect, and is very suitable for medical use. And the cost is low, the source is wide, the biodegradation is easy, the disposable medical product is suitable to be made, and the problems that the traditional material product is expensive and causes environmental pollution and is difficult to degrade are solved. The porous starch as a novel modified starch has the advantages of wide raw material source, naturalness, safety, no toxicity, biodegradability, simple production process and the like, thereby having good application prospect. The starch becomes loose after forming a microporous structure, the mechanical strength is reduced, the length of a starch chain is reduced, the stability of viscosity is reduced, meanwhile, the starch particles are small and unstable in structure, and the starch particles are easy to disintegrate in the enzymolysis process, so that the stability of the rice starch particles is improved and the mechanical strength of the porous starch is enhanced by crosslinking modification, in addition, a large amount of hydroxyl groups exist in the porous starch molecules, only hydrophilic exists, and the porous starch particles are difficult to be uniformly blended with polyurethane particles, and because the polyurethane particles are hydrophobic, the blending capability of the porous starch particles can be improved by introducing hydrophobic groups into the porous starch molecules. Medical catheters have important applications mainly in infusion, drug delivery, blood collection, hemodialysis, and the like. The first uses polyvinyl chloride (PVC), Polyethylene (PE) and polypropylene (PP) as the catheter material, and later, polyamide, polyester, Polyurethane (PU) and other materials have been developed. Polyurethane is gradually becoming the preferred material for manufacturing medical catheters, especially medical catheters that need to be introduced into the human body, due to its advantages of good biocompatibility and stability, high strength, small friction factor and good flexibility. Commonly used catheters include peritoneal dialysis catheters, urinary catheters, central venous catheters, indwelling needle peripheral catheters, Percutaneous Transluminal Coronary Angioplasty (PTCA) balloon dilatation catheters, and the like. At present, the commonly used catheters are all made of synthetic polymer materials, most of the catheters have certain toxicity and are extremely unsafe to use, and the catheters after use are difficult to degrade and pollute the environment. Medical catheters have become an indispensable tool in medical treatment, and when a doctor inserts the catheter into a human body, an inexperienced doctor has difficulty in accurate positioning during intubation. Therefore, a medical catheter with ultrasonic imaging capability is developed, the inserted position of the catheter is monitored in real time by using an ultrasonic imaging technology, and accurate and correct introduction is particularly important.
Disclosure of Invention
In view of the above, the invention provides a preparation method of a medical catheter with ultrasonic imaging capability based on hydrophobic modified porous starch and a product thereof, and specifically provides the following technical scheme:
1. a preparation method of a medical catheter with ultrasonic imaging capability based on hydrophobic modified porous starch comprises the following preparation steps:
(1) dispersing starch in a buffer solution with the pH value of 4.7-4.9 to obtain a starch emulsion, and adding a complex enzyme for enzymolysis to prepare porous starch;
(2) dispersing the porous starch obtained in the step (1) in deionized water to obtain a porous starch emulsion, and reacting the porous starch emulsion with octenyl succinic anhydride in a system with the pH value of 8.0-8.5 to obtain hydrophobic porous starch;
(3) dispersing the hydrophobic porous starch obtained in the step (2) in deionized water to obtain a hydrophobic porous starch emulsion, and reacting the hydrophobic porous starch emulsion with Al2(SO4)3 in a system with the pH of 3.9-4.1 to obtain composite modified porous starch;
(4) and (3) blending the composite modified porous starch obtained in the step (3) with thermoplastic polyurethane granules, wherein the mass ratio of thermoplastic polyurethane to composite modified porous starch is 95/5-85/15, and extruding the mixture by a double-screw extruder to obtain the medical catheter based on the hydrophobic modified porous starch and having the ultrasonic imaging capability.
Further, the complex enzyme in the step (1) is prepared by mixing saccharifying enzyme and alpha-amylase in a mass ratio of 4: 1 and mixing.
Further, the mass fraction of the starch emulsion in the step (1) is 20-25%.
Further, the enzymolysis temperature in the step (1) is 40-45 ℃, and after the enzyme is finished, NaOH solution is added for reaction to inactivate the enzyme.
Further, the mass fraction of the porous starch emulsion in the step (2) is 25-30%.
Further, the reaction temperature in the step (2) is 40-45 ℃.
Further, after the reaction in the step (2) is finished, the pH is adjusted to be neutral.
Further, the mass fraction of the hydrophobic porous starch emulsion in the step (3) is 25-30%.
Further, the reaction temperature in the step (3) is 40-45 ℃.
2. The product prepared by the preparation method of the medical catheter with the ultrasonic imaging capability based on the hydrophobic modified porous starch has the ultrasonic imaging capability, the impact strength is 6.63-22.26 KJ/m2, the tensile strength is 9.0-18.4 MPa, the elongation at break is 71.9-495.9%, and the elastic modulus is 29.89-80.0 MPa.
The invention has the beneficial effects that: according to the invention, original starch is subjected to porous, hydrophobic and composite modification, and the composite modified hydrophobic porous starch (CLPSt) and Thermoplastic Polyurethane (TPU) granules are blended through a double-screw extrusion process, so that the obtained conduit material has a good ultrasonic imaging effect, and when 5% (mass fraction) of the composite crosslinked porous starch (CLPSt) is added, the ultrasonic imaging effect is particularly obvious. When the mass ratio of TPU to CLPSt is 95/5-85/15, the mechanical property of the TPU/CLPSt meets the use requirement of a medical catheter material, and the impact strength of the TPU/CLPSt is 6.63-22.26 KJ/m2The tensile strength is 9.0-18.4 MPa, the elongation at break is 71.9-495.9%, and the elastic modulus is 29.89-80.0 MPa, so that the material can meet the application requirements of the medical industry and has a better application prospect compared with the mechanical properties of the tracheal catheter produced in China, namely mechanical property experimental research on the tracheal catheter. The invention is provided withThe medical catheter with ultrasonic imaging capability has the advantages of low price of raw materials, nature, low toxicity and easy degradation.
In the process of preparing the porous starch, the pH value of the system is adjusted to the range claimed by the invention, so that the enzyme can perform enzymolysis under better conditions, and more and complete porous structures are obtained. The pH value is too low, the activity of the enzyme is not enough, and the enzymolysis cannot occur. The pH value is slightly high, the prepared porous starch is very broken, a complete porous structure cannot be obtained, and the enzyme is inactivated if the pH value is too high. The pH value of the system is adjusted to the range claimed by the invention in the process of preparing the hydrophobic porous starch, so that the esterification reaction is carried out in a forward direction, and the hydrophobic degree is higher. Because hydroxyl groups in the porous starch molecule are dissociated into oxygen anions under an alkaline environment, the oxygen anions undergo nucleophilic substitution reaction with partial positive charges on octenyl succinic anhydride to generate starch ester. The anhydride ring is opened, one end is bonded to the starch molecule via the ester group and the other end produces a carboxylic acid. The reason for adjusting the pH value of the system to the range claimed by the invention in the process of preparing the composite cross-linked starch is that Al3+The starch ester is easy to crosslink, the crosslinking degree is improved, and the hydrophobic porous starch with high crosslinking degree is finally obtained. Thereby improving the hydrophobicity of the starch and enhancing the mechanical strength, and being beneficial to blending with the thermoplastic polyurethane.
Drawings
In order to make the purpose, technical scheme and beneficial effect of the invention more clear, the invention provides the following drawings:
FIG. 1 is a scheme for preparing composite modified porous starch.
FIG. 2 is a graph showing the effect of ultrasonic testing on the catheter materials prepared in examples 1 to 5.
FIG. 3 is a graph comparing the mechanical properties of catheter materials prepared in examples 1-5.
Detailed Description
Preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings.
Example 1
1. FIG. 1 is a scheme diagram of a preparation scheme of composite modified porous starch, and the preparation method comprises the following specific steps:
(1) weighingDispersing a certain mass of common corn starch in CH with pH of 4.83COONa-CH3Preparing 22 mass percent of starch emulsion in COOH buffer solution, adding a certain amount of complex enzyme (saccharifying enzyme and alpha-amylase are mixed according to the mass ratio of 4: 1), performing enzymolysis at 40 ℃, after the reaction is finished, adding 0.1mol/L NaOH solution, reacting for about 15min to inactivate the enzyme, washing for 3 times by using deionized water and ethanol respectively, and drying in a forced air drying oven at 50 ℃ for 48h to obtain porous starch;
(2) weighing porous starch obtained in a certain mass (1), dispersing the porous starch in deionized water to prepare 25 mass percent of starch emulsion, placing the starch emulsion in an oil bath kettle at 40 ℃, continuously stirring, adjusting the pH of the starch emulsion to be within the range of 8.0-8.5, dropwise adding quantitative Octenyl Succinic Anhydride (OSA) within 1h, adding 0.1mol/L NaOH solution in the reaction process to maintain the pH of the system, adjusting the pH to be neutral by using 0.1mol/L HCl solution after the reaction is finished, washing with alcohol and water for multiple times, and drying a sample to obtain hydrophobic porous starch;
(3) weighing a certain mass of the hydrophobic porous starch obtained in the step (2), preparing starch emulsion with the concentration of 25% (mass fraction), adjusting the pH of a reaction system to be 4.0, placing the reaction system in an oil bath kettle at 40 ℃, continuously stirring, and adding a certain amount of Al2(SO4)3Adding 0.1mol/L NaOH solution in the reaction process to maintain the pH value of the system, after the reaction is finished, carrying out alcohol washing and water washing for many times, and drying for 48 hours at 55 ℃ in a blast drying oven to obtain the composite crosslinked porous starch.
2. The preparation method of the medical catheter with the ultrasonic imaging capability comprises the following specific steps:
blending the composite modified porous starch obtained in the step (3) with Thermoplastic Polyurethane (TPU) granules, wherein the ratio of TPU/CLPSt is 100/0, the rotating speed of a screw is 105r/min, the extrusion temperature is 190 ℃, mixing, adding the mixture into a double-screw extruder for extrusion, cooling to obtain a wire sample, and detecting the ultrasonic imaging effect of the wire sample; the obtained sample is granulated and injection-molded by an injection molding machine, the injection molding temperature is 195 ℃, and the mechanical property of the sample is characterized. The performance of the prepared medical catheter with ultrasonic imaging capability is tested as shown in fig. 2(a) and fig. 3. (FIG. 3(a) tensile Strength, (b) impact Strength, (c) elastic modulus, (d) elongation at Break)
As can be seen from (a) in fig. 2: the effect of ultrasound imaging of TPU/CLPSt 100/0 was not evident, and the location of the catheter material insertion was completely invisible.
As seen from FIG. 3, when the TPU/CLPSt is 100/0, the tensile strength, impact strength and elongation at break are the greatest, 26.02MPa and 22.26KJ/m respectively2561.91%; the elastic modulus is the smallest and is 29.89 MPa. Compared with the mechanical properties of the tracheal catheter produced in China, which is the research on the mechanical properties of the tracheal catheter, the tensile strength and the elongation at break of the tracheal catheter are higher than those of the tracheal catheter produced in the literature (the tensile strength is 6.12MPa, and the elongation at break is 41.74%), and the elastic modulus of the tracheal catheter is lower than that of the tracheal catheter produced in the literature (the elastic modulus is 627.56 MPa). As a medical catheter, the tensile strength and the elongation at break are better, while the elastic modulus is better, and the mechanical property of the embodiment can meet the use requirement of the medical catheter.
Example 2
1. FIG. 1 is a scheme diagram of a preparation scheme of composite modified porous starch, and the preparation method comprises the following specific steps:
(5) weighing a certain mass of common corn starch, and dispersing in CH with pH of 4.73COONa-CH3Preparing 20 percent (mass fraction) of starch emulsion in a COOH buffer solution, adding a certain amount of complex enzyme (saccharifying enzyme and alpha-amylase are mixed according to the mass ratio of 4: 1), performing enzymolysis at 40 ℃, after the reaction is finished, adding 0.1mol/L of NaOH solution, reacting for about 15min to inactivate the enzyme, washing for 3 times by using deionized water and ethanol respectively, and drying for 48h at 55 ℃ in a blast drying oven to obtain porous starch;
(6) weighing porous starch obtained in a certain mass (1), dispersing the porous starch in deionized water to prepare 28 mass percent of starch emulsion, placing the starch emulsion in an oil bath kettle at 40 ℃, continuously stirring, adjusting the pH of the starch emulsion to be within the range of 8.0-8.5, dropwise adding quantitative OSA within 1h, adding 0.1mol/L NaOH solution to maintain the pH of the system in the reaction process, adjusting the pH to be neutral by using 0.1mol/L HCl solution after the reaction is finished, and carrying out alcohol washing, water washing and sample drying for multiple times to obtain hydrophobic porous starch;
(7) weighing obtained in a certain mass (2)Preparing hydrophobic porous starch into 30% (mass fraction) starch emulsion, adjusting pH of reaction system to 4.0, placing in 40 deg.C oil bath, stirring, adding quantitative Al2(SO4)3Adding 0.1mol/L NaOH solution in the reaction process to maintain the pH value of the system, after the reaction is finished, carrying out alcohol washing and water washing for many times, and placing the obtained product in an air-blast drying oven for drying at 50 ℃ for 48 hours to obtain the composite modified porous starch (CLPSt).
2. The preparation method of the medical catheter with the ultrasonic imaging capability comprises the following specific steps:
and (3) blending the composite modified porous starch obtained in the step (3) with TPU granules, wherein the ratio of TPU/CLPSt is 95/5, the rotating speed of a screw is 110r/min, the extrusion temperature is 195 ℃, mixing, adding the mixture into a double-screw extruder for extrusion, cooling to obtain a wire sample, and detecting the ultrasonic imaging effect of the wire sample. And granulating the obtained sample, and performing injection molding by using an injection molding machine, wherein the injection molding temperature is 190 ℃ and the mechanical property of the sample is characterized. The obtained medical catheter having ultrasonic imaging ability was tested for properties such as tensile strength (b) and impact strength (c) elastic modulus (d) elongation at break (fig. 3 (a)) in fig. 2(b) and 3 (fig. 3 (a))
As can be seen from (b) in fig. 2: the effect of ultrasound imaging at TPU/CLPSt 95/5 is evident, and the location of catheter material insertion can be clearly seen, in sharp contrast to example 1.
As seen from FIG. 3, when the TPU/CLPSt is 95/5, the tensile strength is 25.28MPa and the impact strength is 11.11KJ/m2The elongation at break is 545.6 percent, the elastic modulus is 32.09MPa, and the material is compared with the mechanical property of the tracheal catheter produced in China in the experimental research on the mechanical property of the tracheal catheter in the literature. The tensile strength and elongation at break were higher than those in the literature (tensile strength of 6.12MPa and elongation at break of 41.74%), and the elastic modulus was lower than that in the literature (elastic modulus of 627.56 MPa). As a medical catheter, the tensile strength and the elongation at break are better, while the elastic modulus is better, and the mechanical property under the proportion can meet the use requirement of the medical catheter.
Example 3
1. FIG. 1 is a scheme diagram of a preparation scheme of composite modified porous starch, and the preparation method comprises the following specific steps:
(1) weighing a certain mass of common corn starch, and dispersing in CH with pH of 4.93COONa-CH3Preparing 25 percent (mass fraction) of starch emulsion in a COOH buffer solution, adding a certain amount of complex enzyme (saccharifying enzyme and alpha-amylase are mixed according to the mass ratio of 4: 1), performing enzymolysis at 40 ℃, after the reaction is finished, adding 0.1mol/L of NaOH solution, reacting for about 15min to inactivate the enzyme, washing for 3 times by using deionized water and ethanol respectively, and drying for 48h at 60 ℃ in a blast drying oven to obtain porous starch;
(2) weighing porous starch obtained in a certain mass (1), dispersing the porous starch in deionized water to prepare 30 mass percent of starch emulsion, placing the starch emulsion in an oil bath kettle at 40 ℃, continuously stirring, adjusting the pH of the starch emulsion to be within the range of 8.0-8.5, dropwise adding quantitative OSA within 1h, adding 0.1mol/L NaOH solution to maintain the pH of the system in the reaction process, adjusting the pH to be neutral by using 0.1mol/L HCl solution after the reaction is finished, and carrying out alcohol washing, water washing and sample drying for multiple times to obtain hydrophobic porous starch;
(3) weighing a certain mass of the hydrophobic porous starch obtained in the step (2), preparing starch emulsion with the concentration of 25% (mass fraction), adjusting the pH of a reaction system to be 4.0, placing the reaction system in an oil bath kettle at 40 ℃, continuously stirring, and adding a certain amount of Al2(SO4)3Adding 0.1mol/L NaOH solution in the reaction process to maintain the pH of the system, after the reaction is finished, carrying out alcohol washing and water washing for many times, and drying for 48 hours at 55 ℃ in a blast drying oven to obtain the composite modified porous starch (CLPSt).
2. The preparation method of the medical catheter with the ultrasonic imaging capability comprises the following specific steps:
and (3) blending the composite modified porous starch obtained in the step (3) with TPU granules, wherein the ratio of TPU/CLPSt is 90/10, the rotating speed of a screw is 108r/min, the extrusion temperature is 200 ℃, mixing, adding the mixture into a double-screw extruder for extrusion, cooling to obtain a wire sample, and detecting the ultrasonic imaging effect of the wire sample. The obtained sample was pelletized and injection molded by an injection molding machine at 185 ℃ and its mechanical properties were characterized. The performance of the medical catheter with ultrasonic imaging capability was tested as shown in fig. 2(c) and fig. 3(a) tensile strength, (b) impact strength, (c) elastic modulus, (d) elongation at break).
As can be seen from (c) in fig. 2: the TPU/CLPSt-90/10 results in an ultrasound imaging effect, clearly showing where the catheter material is inserted, in contrast to example 1.
As seen from FIG. 3, when the TPU/CLPSt is 90/10, the tensile strength is 21.34MPa and the impact strength is 10.48KJ/m2The elongation at break is 527.32 percent, the elastic modulus is 37.13MPa, and the material is compared with the mechanical property of the tracheal catheter produced in China in the literature, "experimental research on the mechanical property of the tracheal catheter". The tensile strength and elongation at break were higher than those in the literature (tensile strength of 6.12MPa and elongation at break of 41.74%), and the elastic modulus was lower than that in the literature (elastic modulus of 627.56 MPa). As a medical catheter, the tensile strength and the elongation at break are better, while the elastic modulus is better, and the mechanical property under the proportion can meet the use requirement of the medical catheter.
Example 4
1. FIG. 1 is a scheme diagram of a preparation scheme of composite modified porous starch, and the preparation method comprises the following specific steps:
(1) weighing a certain mass of common corn starch, and dispersing in CH with pH of 4.73COONa-CH3Preparing 24 percent (mass fraction) of starch emulsion in a COOH buffer solution, adding a certain amount of complex enzyme (saccharifying enzyme and alpha-amylase are mixed according to the mass ratio of 4: 1), performing enzymolysis at 40 ℃, after the reaction is finished, adding 0.1mol/L of NaOH solution, reacting for about 15min to inactivate the enzyme, washing for 3 times by using deionized water and ethanol respectively, and drying for 48h at 57 ℃ in a blast drying oven to obtain the porous starch, wherein the weight fraction of the porous starch is shown in figure 1.
(2) Weighing the porous starch obtained in a certain mass (1), dispersing the porous starch in deionized water to prepare 26 mass percent of starch emulsion, placing the starch emulsion in an oil bath kettle at 40 ℃, continuously stirring, adjusting the pH of the starch emulsion to be within the range of 8.0-8.5, dropwise adding quantitative OSA within 1h, adding 0.1mol/L NaOH solution in the reaction process to maintain the pH of the system, adjusting the pH to be neutral by using 0.1mol/L HCl solution after the reaction is finished, and carrying out alcohol washing, water washing and sample drying to obtain the hydrophobic porous starch, wherein the figure 1 shows that the pH is in the specification.
(3) Weighing a certain mass of the hydrophobic porous starch obtained in the step (2), preparing starch emulsion with the concentration of 28% (mass fraction), adjusting the pH of a reaction system to be 4.0, placing the reaction system in an oil bath kettle at 40 ℃, continuously stirring, and adding a certain amount of Al2(SO4)3Adding 0.1mol/L NaOH solution in the reaction process to maintain the pH of the system, after the reaction is finished, carrying out alcohol washing and water washing for multiple times, and drying for 48 hours at 60 ℃ in a blast drying oven to obtain the composite modified porous starch (CLPSt), as shown in figure 1.
2. The preparation method of the medical catheter with the ultrasonic imaging capability comprises the following specific steps:
and (3) blending the composite modified porous starch obtained in the step (3) with TPU granules, wherein the ratio of TPU/CLPSt is 85/15, the rotating speed of a screw is 106r/min, the extrusion temperature is 185 ℃, mixing, adding the mixture into a double-screw extruder for extrusion, cooling to obtain a wire sample, and detecting the ultrasonic imaging effect of the wire sample. And granulating the obtained sample, and performing injection molding by using an injection molding machine, wherein the injection molding temperature is 180 ℃, and the mechanical property of the sample is characterized. The performance of the resulting medical catheter with ultrasonic imaging capability was tested as shown in fig. 2(d) and fig. 3. (FIG. 3(a) tensile Strength, (b) impact Strength, (c) elastic modulus, (d) elongation at Break)
As can be seen from (d) in fig. 2: the TPU/CLPSt-85/15 results in an ultrasound imaging effect, clearly showing where the catheter material is inserted, in contrast to example 1.
As seen from FIG. 3, when TPU/CLPSt is 85/15, the tensile strength is 12.38MPa, the modulus of elasticity is 63.72MPa, and the impact strength and elongation at break are the smallest, respectively 6.63KJ/m2367.63 percent and the elastic modulus is 63.72MPa, compared with the mechanical property of the tracheal catheter produced in China in the experimental research on the mechanical property of the tracheal catheter in the literature. The tensile strength and elongation at break were higher than those in the literature (tensile strength of 6.12MPa and elongation at break of 41.74%), and the elastic modulus was lower than that in the literature (elastic modulus of 627.56 MPa). As a medical catheter, the tensile strength and the elongation at break are better, while the elastic modulus is better, and the mechanical property under the proportion can meet the use requirement of the medical catheter.
Example 5
1. FIG. 1 is a scheme diagram of a preparation scheme of composite modified porous starch, and the preparation method comprises the following specific steps:
(1) weighing a certain mass of common corn starch, and dispersing in CH with pH of 4.83COONa-CH3Preparing 23 percent (mass fraction) of starch emulsion in a COOH buffer solution, adding a certain amount of complex enzyme (saccharifying enzyme and alpha-amylase are mixed according to the mass ratio of 4: 1), performing enzymolysis at 40 ℃, after the reaction is finished, adding 0.1mol/L of NaOH solution, reacting for about 15min to inactivate the enzyme, washing for 3 times by using deionized water and ethanol respectively, and drying in a forced air drying oven at 50 ℃ for 48h to obtain porous starch;
(2) weighing porous starch obtained in a certain mass (1), dispersing the porous starch in deionized water to prepare 27% (mass fraction) of starch emulsion, placing the starch emulsion in an oil bath kettle at 40 ℃, continuously stirring, adjusting the pH of the starch emulsion to be within the range of 8.0-8.5, dropwise adding quantitative OSA within 1h, adding 0.1mol/L NaOH solution to maintain the pH of the system in the reaction process, adjusting the pH to be neutral by using 0.1mol/L HCl solution after the reaction is finished, and performing alcohol washing, water washing and sample drying to obtain hydrophobic porous starch;
(3) weighing a certain mass of the hydrophobic porous starch obtained in the step (2), preparing starch emulsion with the concentration of 29% (mass fraction), adjusting the pH of a reaction system to be 4.0, placing the reaction system in an oil bath kettle at 40 ℃, continuously stirring, and adding a certain amount of Al2(SO4)3Adding 0.1mol/L NaOH solution in the reaction process to maintain the pH of the system, after the reaction is finished, carrying out alcohol washing and water washing for many times, and drying for 48 hours at 55 ℃ in a blast drying oven to obtain the composite modified porous starch (CLPSt).
2. The preparation method of the medical catheter with the ultrasonic imaging capability comprises the following specific steps:
and (3) blending the composite modified porous starch obtained in the step (3) with TPU granules, wherein the ratio of TPU/CLPSt is 80/20, the rotating speed of a screw is 108r/min, the extrusion temperature is 180 ℃, mixing, adding the mixture into a double-screw extruder for extrusion, cooling to obtain a wire sample, and detecting the ultrasonic imaging effect of the wire sample. And granulating the obtained sample, and performing injection molding by using an injection molding machine, wherein the injection molding temperature is 190 ℃ and the mechanical property of the sample is characterized. The obtained medical catheter having ultrasonic imaging ability was tested for properties such as tensile strength, (b) impact strength, (c) elastic modulus, (d) elongation at break in FIGS. 2(e) and 3 (FIG. 3 (a))
As can be seen from (e) in fig. 2: the TPU/CLPSt-80/20 results in an ultrasound imaging effect, clearly showing where the catheter material is inserted, in contrast to example 1.
As seen from FIG. 3, when the TPU/CLPSt is 80/20, the tensile strength is at minimum 10.66MPa, the modulus of elasticity is at maximum 80.0MPa, and the impact strength is 8.79KJ/m2And the elongation at break is 372.06 percent, which is compared with the mechanical property of the tracheal catheter produced in China in the literature, "mechanical property experimental research of tracheal catheter". The tensile strength and elongation at break were higher than those in the literature (tensile strength of 6.12MPa and elongation at break of 41.74%), and the elastic modulus was lower than that in the literature (elastic modulus of 627.56 MPa). As a medical catheter, the tensile strength and the elongation at break are better, while the elastic modulus is better, and the mechanical property under the proportion can meet the use requirement of the medical catheter.
Finally, it is noted that the above-mentioned preferred embodiments illustrate rather than limit the invention, and that, although the invention has been described in detail with reference to the above-mentioned preferred embodiments, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the scope of the invention as defined by the appended claims.
Claims (10)
1. A preparation method of a medical catheter with ultrasonic imaging capability based on hydrophobic modified porous starch is characterized by comprising the following preparation steps:
(1) dispersing starch in a buffer solution with the pH value of 4.7-4.9 to obtain a starch emulsion, and adding a complex enzyme for enzymolysis to prepare porous starch;
(2) dispersing the porous starch obtained in the step (1) in deionized water to obtain a porous starch emulsion, and reacting the porous starch emulsion with octenyl succinic anhydride in a system with the pH value of 8.0-8.5 to obtain hydrophobic porous starch;
(3) hydrophobic porous starch obtained in step (2)Dispersing the powder in deionized water to obtain hydrophobic porous starch emulsion, and reacting with Al in a system with the pH of 3.9-4.12(SO4)3Reacting to obtain composite modified porous starch;
(4) and (3) blending the composite modified porous starch obtained in the step (3) with thermoplastic polyurethane granules, wherein the mass ratio of thermoplastic polyurethane to composite modified porous starch is 95/5-85/15, and extruding the mixture by a double-screw extruder to obtain the medical catheter based on the hydrophobic modified porous starch and having the ultrasonic imaging capability.
2. The method for preparing the medical catheter with ultrasonic imaging capability based on the hydrophobically modified porous starch as claimed in claim 1, wherein the complex enzyme in the step (1) is diastatic enzyme and alpha-amylase in a mass ratio of 4: 1 and mixing.
3. The method for preparing the medical catheter with ultrasonic imaging capability based on the hydrophobically modified porous starch as claimed in claim 1, wherein the starch emulsion in the step (1) is 20-25% by mass.
4. The preparation method of the medical catheter with the ultrasonic imaging capability based on the hydrophobically modified porous starch as claimed in claim 1, wherein the enzymolysis temperature in the step (1) is 40-45 ℃, and after the enzyme is completed, NaOH solution is added for reaction to inactivate the enzyme.
5. The method for preparing the medical catheter with ultrasonic imaging capability based on the hydrophobically modified porous starch as claimed in claim 1, wherein the mass fraction of the porous starch emulsion in the step (2) is 25-30%.
6. The method for preparing the medical catheter with ultrasonic imaging capability based on the hydrophobically modified porous starch as claimed in claim 1, wherein the reaction temperature in the step (2) is 40-45 ℃.
7. The method for preparing the medical catheter with ultrasonic imaging capability based on the hydrophobically modified porous starch as claimed in claim 1, wherein the pH is adjusted to be neutral after the reaction in the step (2) is finished.
8. The method for preparing the medical catheter with ultrasonic imaging capability based on the hydrophobically modified porous starch as claimed in claim 1, wherein the mass fraction of the hydrophobic porous starch emulsion in the step (3) is 25-30%.
9. The method for preparing the medical catheter with ultrasonic imaging capability based on the hydrophobically modified porous starch as claimed in claim 1, wherein the reaction temperature in the step (3) is 40-45 ℃.
10. The product prepared by the preparation method of the medical catheter with the ultrasonic imaging capability based on the hydrophobic modified porous starch according to any one of claims 1, wherein the product has the ultrasonic imaging capability and the impact strength of 6.63-22.26 KJ/m2The tensile strength is 9.0 to 18.4MPa, the elongation at break is 71.9 to 495.9%, and the elastic modulus is 29.89 to 80.0 MPa.
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