CN111138702A - Method for preparing anti-protein adhesion medical hose - Google Patents
Method for preparing anti-protein adhesion medical hose Download PDFInfo
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- CN111138702A CN111138702A CN201911348268.3A CN201911348268A CN111138702A CN 111138702 A CN111138702 A CN 111138702A CN 201911348268 A CN201911348268 A CN 201911348268A CN 111138702 A CN111138702 A CN 111138702A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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- Organic Chemistry (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention discloses a method for preparing a medical hose capable of resisting protein adhesion. The inner surface of the medical hose is treated by an ozone oxidation method, so that peroxide groups are obtained on the inner surface of the medical hose; pumping a reaction solution containing heparin sodium and polyethylene oxide into the inner wall of the medical hose, and performing grafting reaction by adopting ultrasonic assistance; and introducing nitrogen for purging after the reaction, and removing redundant reaction liquid to obtain the dry medical hose with the function of resisting protein adsorption. The prepared medical catheter material has high hydrophilicity and excellent stability, can improve the adhesion to bioactive substances such as protein in blood and the like, and reduces the occurrence of medical accidents such as blood coagulation, thrombus and the like. The preparation method is simple and easy to implement, has low requirements on equipment, and can realize industrial production. Has wide applicability in protein adsorption resistance on the surfaces of medical polymer materials and medical instruments, and can be widely used in clean and automatic workshops.
Description
Technical Field
The invention relates to a method for preparing a medical hose capable of resisting protein adhesion, and belongs to the technical field of medical materials.
Background
Point-of-care testing (POCT) refers to a clinical test that can be performed immediately at the patient's side, i.e., an analytical test method that can be performed immediately at the sampling site. The method not only saves various complicated processing procedures when the sample is detected in a laboratory, but also can obtain the detection result very quickly and accurately, but also can obtain some biological components such as: proteins, platelets, etc. can affect the accuracy of the instant assay.
At present, the research on the adsorption of protein on a solid-liquid interface has extremely important significance in the biomedical field. When blood is introduced into the catheter, after several seconds, protein can be adsorbed on the surface of the material catheter to form a protein adsorption layer, and then somatic cells and the adsorbed protein can be mutually identified through a surface receptor to initiate subsequent reactions, such as the action with platelets, osteoblasts, leukocytes or lymphocytes in the blood, and the initiation of blood coagulation, thrombus and the like. Therefore, a small error is generated in the POCT process, and in order to reduce the error in the detection process, the introduction of a material which is anti-adhesive to bioactive substances such as blood platelets, protein leukocytes and the like in blood is of great significance for improving the accuracy of the POCT.
Heparin sodium (Heparin sodium) can interfere with many links of the blood coagulation process and has an anticoagulant effect in vitro and in vivo. The mechanism of action is complex, and the inhibition of activated blood coagulation factors II, IX, X, XI and XII by the latter is enhanced mainly by binding to antithrombin III (AT-III), which later involves preventing platelet aggregation and destruction, preventing the formation of thromboplastin, preventing prothrombin from becoming thrombin, inhibiting thrombin, thereby preventing fibrinogen from becoming fibrin, and thus exerting anticoagulation.
Polyethylene oxide (PEO, or polyethylene glycol when the molecular weight is less than 10,000) is a typical hydrophilic substance. PEO has the following characteristics: low surface energy, unique water solution property, hydrophilicity, high chain fluidity, stability of spatial displacement and the like. PEO and its derivatives (containing functional groups such as p-toluenesulfonate, amino groups, carboxyl groups, aldehyde groups, etc. can also be introduced at both ends of the PEO or PEG chain) have demonstrated good biocompatibility. Furthermore, in the modification of new biomaterials, PEO as part of the material will impart new properties and functions to the material, such as hydrophilicity, flexibility, anticoagulation, and anti-macrophage phagocytosis, etc. Therefore, PEO has been widely used in many fields such as medicine, pharmacy, and biology.
At present, the medical appliance industry is increased by 9 percent on average in the whole world every year, becomes a new strut type industry in the 21 st century, medical hoses, particularly interventional catheters, have high technical content and added value, the domestic market has high hydrophilicity and high lubricity, polyurethane biomaterials depend on import, and related technologies are few.
Disclosure of Invention
In order to solve the problems, the invention provides a brand new preparation method of the medical hose made of the material resisting bioactive substances such as protein and the like, and the effect of the polyurethane medical catheter on the adsorption resistance of the bioactive substances such as protein and the like is greatly improved by using an ultrasonic-assisted method.
The first object of the present invention is to provide a method for preparing a medical hose resistant to protein adhesion, comprising the steps of:
(1) treating the inner surface of the medical hose by an ozone oxidation method to obtain peroxide groups on the inner surface of the medical hose so as to obtain an ozone activated medical hose;
(2) pumping a reaction solution containing heparin sodium and polyethylene oxide (PEO) into the inner wall of the medical hose, and performing grafting reaction by using ultrasonic assistance;
(3) and introducing nitrogen for purging after the reaction, and removing redundant reaction liquid to obtain the dry medical hose with the function of resisting protein adsorption.
Further, in the step (1), the medical hose is made of a polyurethane material, and the polyurethane material is one of polyester polyurethane, polyether polyurethane, aromatic isocyanate polyurethane and aliphatic isocyanate polyurethane.
Further, in the step (1), ozone oxidation is to treat the inner surface of the medical hose with ozone with the purity of 85-95% for 10-30 min.
Further, in the step (2), the content of heparin sodium in the reaction solution is 1% -5%, and the content of polyoxyethylene is 1% -5%. In the present invention, the reaction solution is mixed with heparin sodium and polyethylene oxide under the water bath condition at a temperature of 40 ℃ to 70 ℃.
Further, the molecular weight of the polyethylene oxide is 100000, 300000, 500000 or 1000000.
Further, in the step (2), the flow rate of the reaction liquid pumped into the inner wall of the medical hose is 1-3 mL/min.
Furthermore, the power of the ultrasound is 40-60W, the ultrasound time is 20-40 min, and the temperature is 40-60 ℃.
Further, in the step (3), the nitrogen purging time is 4-6 min.
The second purpose of the invention is to provide the medical hose with the protein adhesion resistance prepared by the method.
The third purpose of the invention is to provide the application of the medical hose for resisting protein adhesion in the medical field.
The invention has the beneficial effects that:
1. the prepared medical catheter material has high hydrophilicity and excellent stability, can improve the adhesion to bioactive substances such as protein in blood and the like, and reduces the occurrence of medical accidents such as blood coagulation, thrombus and the like.
2. The preparation method is simple and easy to implement, has low requirements on equipment, and can realize industrial production.
3. The method has wide applicability in protein adsorption resistance on the surfaces of medical polymer materials and medical instruments, and can be widely used in clean and automatic workshops.
4. The use of high-pollution materials is reduced, and the influence on the environment is small in the reaction process.
Detailed Description
The present invention is further described below in conjunction with specific examples to enable those skilled in the art to better understand the present invention and to practice it, but the examples are not intended to limit the present invention.
The technical scheme of the invention specifically comprises the following steps:
(A) treating the inner surface of the medical hose by ozone with the purity of about 90% through the inner wall of the catheter by an ozone oxidation method, and performing ozone oxidation for 20min to obtain peroxide groups on the surface of the polyurethane medical catheter, so as to obtain the polyurethane medical catheter activated by ozone;
(B) introducing a reaction solution containing 2% of heparin sodium and 3% of PEO with molecular weights of 100000, 300000 and 500000 into a polyurethane medical catheter through a peristaltic pump at a flow rate of 2ml/min, wherein the polyurethane medical catheter is positioned in an ultrasonic cleaner with the temperature of 50 ℃ and the power of 40-60W, and the grafting reaction is carried out by ultrasonic assistance for 30 min;
(C) and after the reaction is finished, introducing nitrogen for purging for 5min, and purging redundant reaction liquid to obtain the dry medical hose with the protein adsorption resistance function.
Example 1:
extracting ozone from an ozone bottle with the purity of 90%, and introducing the ozone into the inner wall of the medical hose to oxidize the inner surface, wherein the ozone oxidation reaction time is 20min, so as to obtain the medical hose activated by the ozone. Then, a reaction solution was prepared by mixing 2% heparin sodium, 3% high molecular weight (100000) polyethylene oxide and water in a water bath at 50 ℃. Adjusting the prepared reaction solution by a peristaltic pump, wherein the flow rate is about 2ml/min, introducing the reaction solution into the inner wall of the conduit, reacting for 30min, and simultaneously immersing the medical hose into which the reaction solution is introduced into an ultrasonic cleaner with the power of 40-60W for auxiliary ultrasonic treatment, wherein the ultrasonic temperature is 50 ℃. And after the reaction is completed, closing the peristaltic pump, introducing nitrogen, purging the medical hose for 5min, removing redundant reaction liquid, and drying to obtain the dry medical hose with the protein adsorption resistance function. The results of the fibrin adhesion test showed that the adhesion decreased by 85.6% with the unmodified tube wall as a control.
Example 2:
extracting ozone from an ozone bottle with the purity of 90%, and introducing the ozone into the inner wall of the medical hose to oxidize the inner surface, wherein the ozone oxidation reaction time is 20min, so as to obtain the medical hose activated by the ozone. Then, a reaction solution was prepared by mixing 2% heparin sodium, 3% high molecular weight (300000) polyethylene oxide and water in a water bath at 50 ℃. Adjusting the prepared reaction solution by a peristaltic pump, wherein the flow rate is about 2ml/min, introducing the reaction solution into the inner wall of the conduit, reacting for 30min, and simultaneously immersing the medical hose into which the reaction solution is introduced into an ultrasonic cleaner with the power of 40-60W for auxiliary ultrasonic treatment, wherein the ultrasonic temperature is 50 ℃. And after the reaction is completed, closing the peristaltic pump, introducing nitrogen, purging the medical hose for 5min, removing redundant reaction liquid, and drying to obtain the dry medical hose with the protein adsorption resistance function.
Example 3:
extracting ozone from an ozone bottle with the purity of 90%, and introducing the ozone into the inner wall of the medical hose to oxidize the inner surface, wherein the ozone oxidation reaction time is 20min, so as to obtain the medical hose activated by the ozone. Then, a reaction solution was prepared by mixing 2% heparin sodium, 3% high molecular weight (500000) polyethylene oxide and water in a water bath at 50 ℃. Adjusting the prepared reaction solution by a peristaltic pump, wherein the flow rate is about 2ml/min, introducing the reaction solution into the inner wall of the conduit, reacting for 30min, and simultaneously immersing the medical hose into which the reaction solution is introduced into an ultrasonic cleaner with the power of 40-60W for auxiliary ultrasonic treatment, wherein the ultrasonic temperature is 50 ℃. And after the reaction is completed, closing the peristaltic pump, introducing nitrogen, purging the medical hose for 5min, removing redundant reaction liquid, and drying to obtain the dry medical hose with the protein adsorption resistance function. The results of the fibrin adhesion test showed that the amount of adhesion was reduced by 87.3% with the unmodified tube wall as a control.
Example 4:
extracting ozone from an ozone bottle with the purity of 90%, and introducing the ozone into the inner wall of the medical hose to oxidize the inner surface, wherein the ozone oxidation reaction time is 20min, so as to obtain the medical hose activated by the ozone. Then, a reaction solution was prepared by mixing 2% heparin sodium, 3% high molecular weight (1000000) polyethylene oxide and water in a water bath at 50 ℃. Adjusting the prepared reaction solution by a peristaltic pump, wherein the flow rate is about 2ml/min, introducing the reaction solution into the inner wall of the conduit, reacting for 30min, and simultaneously immersing the medical hose into which the reaction solution is introduced into an ultrasonic cleaner with the power of 40-60W for auxiliary ultrasonic treatment, wherein the ultrasonic temperature is 50 ℃. And after the reaction is completed, closing the peristaltic pump, introducing nitrogen, purging the medical hose for 5min, removing redundant reaction liquid, and drying to obtain the dry medical hose with the protein adsorption resistance function.
The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention. The protection scope of the invention is subject to the claims.
Claims (10)
1. A method for preparing a medical hose resistant to protein adhesion, comprising the steps of:
(1) treating the inner surface of the medical hose by an ozone oxidation method to obtain peroxide groups on the inner surface of the medical hose so as to obtain an ozone activated medical hose;
(2) pumping a reaction solution containing heparin sodium and polyethylene oxide (PEO) into the inner wall of the medical hose, and performing grafting reaction by using ultrasonic assistance;
(3) and introducing nitrogen for purging after the reaction, and removing redundant reaction liquid to obtain the dry medical hose with the function of resisting protein adsorption.
2. The method according to claim 1, wherein in the step (1), the medical hose is made of a polyurethane material, and the polyurethane material is one of polyester polyurethane, polyether polyurethane, aromatic isocyanate polyurethane and aliphatic isocyanate polyurethane.
3. The method according to claim 1, wherein in the step (1), the ozone oxidation is performed by treating the inner surface of the medical hose with ozone having a purity of 85 to 95% for 10 to 30 min.
4. The method according to claim 1, wherein in the step (2), the reaction solution contains 1 to 5% of heparin sodium and 1 to 5% of polyoxyethylene.
5. The method according to claim 1, wherein the polyethylene oxide has a molecular weight of 100000, 300000, 500000 or 1000000.
6. The method according to claim 1, wherein in the step (2), the flow rate of the reaction solution pumped into the inner wall of the medical hose is 1-3 mL/min.
7. The method according to claim 1, wherein the power of the ultrasound is 40-60W, the ultrasound time is 20-40 min, and the temperature is 40-60 ℃.
8. The method according to claim 1, wherein in the step (3), the nitrogen purging time is 4-6 min.
9. A medical hose resistant to protein adhesion prepared by the method of any one of claims 1 to 8.
10. Use of the protein adhesion resistant medical hose according to claim 9 in the medical field.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911348268.3A CN111138702A (en) | 2019-12-24 | 2019-12-24 | Method for preparing anti-protein adhesion medical hose |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911348268.3A CN111138702A (en) | 2019-12-24 | 2019-12-24 | Method for preparing anti-protein adhesion medical hose |
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| CN111138702A true CN111138702A (en) | 2020-05-12 |
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| CN201911348268.3A Pending CN111138702A (en) | 2019-12-24 | 2019-12-24 | Method for preparing anti-protein adhesion medical hose |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5767108A (en) * | 1995-08-22 | 1998-06-16 | Medtronic, Inc. | Method for making improved heparinized biomaterials |
| CN101747523A (en) * | 2009-12-18 | 2010-06-23 | 东南大学 | Method for grafting polyoxyethylene or polyethylene glycol on surface of medical polyurethane in one step |
| CN102127204A (en) * | 2011-01-28 | 2011-07-20 | 苏州大学 | Preparation method of novel antibiotic anticoagulant polyurethane material |
| CN106730051A (en) * | 2016-12-27 | 2017-05-31 | 生纳科技(上海)有限公司 | Antithrombogenic Polymer biomaterial and its preparation method and application |
-
2019
- 2019-12-24 CN CN201911348268.3A patent/CN111138702A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5767108A (en) * | 1995-08-22 | 1998-06-16 | Medtronic, Inc. | Method for making improved heparinized biomaterials |
| CN101747523A (en) * | 2009-12-18 | 2010-06-23 | 东南大学 | Method for grafting polyoxyethylene or polyethylene glycol on surface of medical polyurethane in one step |
| CN102127204A (en) * | 2011-01-28 | 2011-07-20 | 苏州大学 | Preparation method of novel antibiotic anticoagulant polyurethane material |
| CN106730051A (en) * | 2016-12-27 | 2017-05-31 | 生纳科技(上海)有限公司 | Antithrombogenic Polymer biomaterial and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| 俞耀庭 等: "《生物医用材料》", 31 December 2000, 天津大学出版社 * |
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Application publication date: 20200512 |
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