CN113698717A - Medical polymer material and preparation method and application thereof - Google Patents
Medical polymer material and preparation method and application thereof Download PDFInfo
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- CN113698717A CN113698717A CN202111058942.1A CN202111058942A CN113698717A CN 113698717 A CN113698717 A CN 113698717A CN 202111058942 A CN202111058942 A CN 202111058942A CN 113698717 A CN113698717 A CN 113698717A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/02—Applications for biomedical use
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Abstract
The invention discloses a medical polymer material and a preparation method and application thereof, which comprises the steps of preparing amino modified polytetrafluoroethylene, preparing oxidized graphene grafted polytetrafluoroethylene and loading titanium dioxide on the polytetrafluoroethylene material2，PAMAM‑NH2Is a high molecular dendritic polymer, and simultaneously the graphene oxide contains a large amount of carboxyl and epoxy groups, PAMAM-NH2NH of the surface2Can react with functional groups in the graphene oxide, and then titanium dioxide is loaded on the surface of the material by a sol-gel method, so that the biocompatibility of the material is improved.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a medical high polymer material and a preparation method and application thereof.
Background
Polytetrafluoroethylene (PTFE, abbreviated as PTFE) is a high molecular polymer prepared by polymerizing tetrafluoroethylene as a monomer, and has the following characteristics: high temperature resistance, and the working temperature reaches 250 ℃; the low temperature resistance is realized, the mechanical toughness is good at low temperature, and the elongation of 5 percent can be kept even if the temperature is reduced to-196 ℃; corrosion resistance, inertia to most chemicals and solvents, strong acid and alkali resistance, water resistance and various organic solvents resistance; the weather resistance is good, and the best aging life in plastics is achieved; high lubrication, which is the lowest coefficient of friction in solid materials; the adhesion is avoided, the surface tension in the solid material is the minimum, and no substance is adhered; it is non-toxic, has physiological inertia, and has no adverse reaction when being implanted into human body for a long time.
At present, polytetrafluoroethylene is often used as a material of a medical drainage tube, a gastrointestinal tube and a catheter, some medical tubes can stay in a human body for several days as required, certain rejection reaction can be generated in the indwelling process, fiber deposition is formed on the tube wall, the catheter can be blocked in the indwelling period, the drainage effect is influenced, the probability of infection is increased, postoperative regular nursing and flushing are needed, the long-term result is local fiber deposition, scar reaction is caused, postoperative organ dysfunction is seriously caused, such as intestinal obstruction, urethral stricture, infertility caused by oviduct blockage, and the like, and therefore, certain requirements are placed on biocompatibility of the material.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a medical polymer material, a preparation method and application thereof, and solves the technical problem that the existing polytetrafluoroethylene material is poor in biocompatibility.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a medical polymer material comprises the following steps:
(1) under the ultrasonic condition, polytetrafluoroethylene material and PAMAM-NH are mixed2Reacting the solution, and cleaning and drying the material after the reaction is finished to obtain the amino modified polytetrafluoroethylene;
(2) soaking the amino modified polytetrafluoroethylene in a graphene oxide solution, and washing to obtain a graphene oxide grafted polytetrafluoroethylene material;
(3) uniformly mixing tetrabutyl titanate, acetic acid and ethanol, then dropwise adding a hydrochloric acid solution into the mixture, controlling the temperature to be 40-45 ℃ in the dropwise adding process, continuously stirring the mixture for 2-3 hours after the dropwise adding is finished, and adjusting the pH value of the solution to obtain uniform and stable titanium dioxide sol;
(4) adding titanium dioxide sol into deionized water, controlling the concentration to be 4-8 wt%, then soaking the graphene oxide grafted polytetrafluoroethylene material into the sol, taking out, washing with deionized water, then soaking into the sol again, taking out, washing with deionized water, and then drying to obtain the medical high polymer material.
Preferably, in the step (1), the ultrasonic treatment conditions are as follows: the ultrasonic frequency is 20kHz-12 MHz; the power density of the ultrasound is 0.1-400W/cm2。
Preferably, in step (1), PAMAM-NH2The concentration of the solution is 2-8g/L, the reaction temperature is 20-40 ℃, and the reaction time is 60-120 min.
Preferably, in the step (2), the graphene oxide solution accounts for 2-5% by mass, and the soaking time is 60-120 min.
Preferably, in the step (3), the volume ratio of tetrabutyl titanate to acetic acid to ethanol is 1:2-5: 2-5.
Preferably, in the step (3), the concentration of the hydrochloric acid solution is 0.5-1.0 mol/L.
Preferably, in step (3), the pH of the solution is 6.8 to 7.2.
Preferably, in the step (4), the drying conditions are as follows: drying at 50-60 deg.C for 3-5min, and drying at 100-120 deg.C for 3-5 min.
The invention also provides a medical polymer material obtained by the preparation method.
The invention also discloses application of the medical polymer material, wherein the application comprises a medical drainage tube, a gastrointestinal tube and a catheter.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention provides a medical polymer material, a preparation method and application thereof, wherein polytetrafluoroethylene can generate h under the action of ultrasonic waves+、·OH、·O2-Reactive species with strong oxidizing power and active species with strong reducing power such as e-And H, the surface grafting of PAMAM-NH on the polytetrafluoroethylene can be realized by activating the polytetrafluoroethylene2。
(2) The invention provides a medical polymer material, a preparation method and application thereof, PAMAM-NH2Is a high molecular dendritic polymer, and simultaneously the graphene oxide contains a large amount of carboxyl and epoxy groups, PAMAM-NH2NH of the surface2Can react with functional groups in graphene oxide, and then titanium dioxide is loaded on the surface of the material by a sol-gel method.
(3) The invention provides a medical polymer material and a preparation method and application thereof, and the biocompatibility of the material is improved by loading graphene oxide and titanium dioxide on the surface of a polytetrafluoroethylene material.
Detailed Description
The present invention will be described in more detail with reference to specific preferred embodiments, but the present invention is not limited to the following embodiments.
It should be noted that, unless otherwise specified, the chemical reagents involved in the present invention are commercially available.
Example 1
A preparation method of a medical polymer material comprises the following steps:
(1) at the ultrasonic frequency of 80kHz and the ultrasonic power density of 20W/cm2Under the condition, polytetrafluoroethylene is soaked in 100mL of 2g/L PAMAM-NH2Reacting in the solution at 20 ℃ for 60min, and after the reaction is finished, cleaning and drying the material to obtain amino modified polytetrafluoroethylene;
(2) soaking the amino modified polytetrafluoroethylene in 100mL of 4 wt% graphene oxide solution for 60min, and washing to obtain a graphene oxide coated polytetrafluoroethylene material;
(3) stirring and mixing 10mL of tetrabutyl titanate, 20mL of acetic acid and 20mL of ethanol uniformly, then dropwise adding 2mL of 0.5mol/L hydrochloric acid solution, controlling the temperature at 40 ℃ in the dropwise adding process, continuously stirring for 2 hours after the dropwise adding is finished, and adjusting the pH value of the solution to 7.0 to obtain uniform and stable titanium dioxide sol;
(4) adding 8g of titanium dioxide sol into 200mL of deionized water, then soaking the graphene oxide grafted polytetrafluoroethylene material into the sol, then taking out, washing with the deionized water, then soaking into the sol again, taking out, washing with the deionized water, drying at 50 ℃ for 3min, and then drying at 100 ℃ for 3min to obtain the medical high polymer material.
Example 2
A preparation method of a medical polymer material comprises the following steps:
(1) the ultrasonic frequency is 60kHz, and the power density of the ultrasonic is 60W/cm2Under the condition, polytetrafluoroethylene is soaked in 100mL of PAMAM-NH with the concentration of 4g/L2Reacting in the solution at 20 ℃ for 80min, and after the reaction is finished, cleaning and drying the material to obtain amino modified polytetrafluoroethylene;
(2) soaking the amino modified polytetrafluoroethylene in 100mL of 2 wt% graphene oxide solution for 60min, and washing to obtain a graphene oxide coated polytetrafluoroethylene material;
(3) stirring and mixing 10mL of tetrabutyl titanate, 30mL of acetic acid and 30mL of ethanol uniformly, then dropwise adding 2mL of 0.5mol/L hydrochloric acid solution, controlling the temperature at 40 ℃ in the dropwise adding process, continuously stirring for 2 hours after the dropwise adding is finished, and adjusting the pH value of the solution to 7.0 to obtain uniform and stable titanium dioxide sol;
(4) adding 10g of titanium dioxide sol into 200mL of deionized water, then soaking the graphene oxide grafted polytetrafluoroethylene material into the sol, then taking out, washing with the deionized water, then soaking into the sol again, taking out, washing with the deionized water, drying at 50 ℃ for 3min, and then drying at 100 ℃ for 3min to obtain the medical high polymer material.
Example 3
A preparation method of a medical polymer material comprises the following steps:
(1) at the ultrasonic frequency of 100kHz and the power density of the ultrasonic wave of 60W/cm2Under the condition, polytetrafluoroethylene is soaked in 100mL of PAMAM-NH with the concentration of 4g/L2Reacting in the solution at 20 ℃ for 60min, and after the reaction is finished, cleaning and drying the material to obtain amino modified polytetrafluoroethylene;
(2) soaking the amino modified polytetrafluoroethylene in 100mL of 3 wt% graphene oxide solution for 60min, and washing to obtain a graphene oxide coated polytetrafluoroethylene material;
(3) stirring and mixing 10mL of tetrabutyl titanate, 30mL of acetic acid and 20mL of ethanol uniformly, then dropwise adding 2mL of 0.6mol/L hydrochloric acid solution, controlling the temperature at 40 ℃ in the dropwise adding process, continuously stirring for 2 hours after the dropwise adding is finished, and adjusting the pH value of the solution to 7.0 to obtain uniform and stable titanium dioxide sol;
(4) adding 12g of titanium dioxide sol into 200mL of deionized water, then soaking the graphene oxide grafted polytetrafluoroethylene material into the sol, then taking out, washing with the deionized water, then soaking into the sol again, taking out, washing with the deionized water, drying at 50 ℃ for 3min, and then drying at 100 ℃ for 3min to obtain the medical high polymer material.
Example 4
A preparation method of a medical polymer material comprises the following steps:
(1) the ultrasonic frequency is 60kHz, and the power density of the ultrasonic is 20W/cm2Under the condition, the polytetrafluoroethylene is soaked in 100mL of PAMAM-NH with the concentration of 6g/L2Reacting in the solution at 20 ℃ for 80min, and after the reaction is finished, cleaning and drying the material to obtain amino modified polytetrafluoroethylene;
(2) soaking the amino modified polytetrafluoroethylene in 100mL of 5 wt% graphene oxide solution for 60min, and washing to obtain a graphene oxide coated polytetrafluoroethylene material;
(3) stirring and mixing 10mL of tetrabutyl titanate, 40mL of acetic acid and 50mL of ethanol uniformly, then dropwise adding 2mL of 0.6mol/L hydrochloric acid solution, controlling the temperature at 40 ℃ in the dropwise adding process, continuously stirring for 2 hours after the dropwise adding is finished, and adjusting the pH value of the solution to 7.0 to obtain uniform and stable titanium dioxide sol;
(4) adding 15g of titanium dioxide sol into 200mL of deionized water, then soaking the graphene oxide grafted polytetrafluoroethylene material into the sol, then taking out, washing with the deionized water, then soaking into the sol again, taking out, washing with the deionized water, drying at 50 ℃ for 3min, and then drying at 100 ℃ for 3min to obtain the medical high polymer material.
The biocompatibility of the biomedical polymer materials prepared in examples 1 to 4 is examined, and the specific method is as follows: by using Cell Countingkit 8(CCK8) to test the growth viability of the cells, human bone marrow mesenchymal stem cells (HBMSC) were cultured to the third generation, the cells were plated in 96-well plates at 37.0 ℃ with 5% CO2After the cells are cultured in a partial pressure cell incubator for 24 hours, a CCK8 test is carried out, the relative proliferation rate of the cells is calculated through cell counting, a control group is used for cell culture by adopting a polytetrafluoroethylene material, and the experimental results are shown in the following table:
| relative cell proliferation Rate (%) | |
| Example 1 | 127.8 |
| Example 2 | 131.5 |
| Example 3 | 129.1 |
| Example 4 | 130.6 |
| Control group | 102.3 |
Finally, it is to be noted that: the above examples do not limit the invention in any way. It will be apparent to those skilled in the art that various modifications and improvements can be made to the present invention. Accordingly, any modification or improvement made without departing from the spirit of the present invention is within the scope of the claimed invention.
Claims (10)
1. The preparation method of the medical polymer material is characterized by comprising the following steps:
(1) under the ultrasonic condition, polytetrafluoroethylene material and PAMAM-NH are mixed2Reacting the solution, and cleaning and drying the material after the reaction is finished to obtain the amino modified polytetrafluoroethylene;
(2) soaking the amino modified polytetrafluoroethylene in a graphene oxide solution, and washing to obtain a graphene oxide grafted polytetrafluoroethylene material;
(3) uniformly mixing tetrabutyl titanate, acetic acid and ethanol, then dropwise adding a hydrochloric acid solution into the mixture, controlling the temperature to be 40-45 ℃ in the dropwise adding process, continuously stirring the mixture for 2-3 hours after the dropwise adding is finished, and adjusting the pH value of the solution to obtain uniform and stable titanium dioxide sol;
(4) adding titanium dioxide sol into deionized water, controlling the concentration to be 4-8 wt%, then soaking the graphene oxide grafted polytetrafluoroethylene material into the sol, taking out, washing with deionized water, then soaking into the sol again, taking out, washing with deionized water, and then drying to obtain the medical high polymer material.
2. The method for preparing a medical polymer material according to claim 1, wherein in the step (1), the ultrasonic treatment conditions are as follows: the ultrasonic frequency is 20kHz-12 MHz; the power density of the ultrasound is 0.1-400W/cm2。
3. The method for preparing a polymer material for medical use according to claim 1, wherein in the step (1), PAMAM-NH2The concentration of the solution is 2-8g/L, the reaction temperature is 20-40 ℃, and the reaction time is 60-120 min.
4. The method for preparing a medical polymer material according to claim 1, wherein in the step (2), the mass fraction of the graphene oxide solution is 2-5%, and the soaking time is 60-120 min.
5. The method for preparing a medical polymer material according to claim 1, wherein in the step (3), the volume ratio of tetrabutyl titanate, acetic acid and ethanol is 1:2-5: 2-5.
6. The method for preparing a medical polymer material according to claim 5, wherein in the step (3), the concentration of the hydrochloric acid solution is 0.5 to 1.0 mol/L.
7. The method for preparing a polymer material for medical use according to claim 5, wherein in the step (3), the pH of the solution is 6.8 to 7.2.
8. The method for preparing a polymer material for medical use according to claim 1, wherein in the step (4), the drying conditions are as follows: drying at 50-60 deg.C for 3-5min, and drying at 100-120 deg.C for 3-5 min.
9. A polymer material for medical use obtained by the production method according to any one of claims 1 to 8.
10. The use of the medical polymer material according to claim 9, wherein the use comprises medical drainage tubes, gastrointestinal tubes and urinary catheters.
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| CN202111058942.1A CN113698717A (en) | 2021-09-08 | 2021-09-08 | Medical polymer material and preparation method and application thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130316004A1 (en) * | 2011-02-07 | 2013-11-28 | Life Technologies Corporation | Compositions and methods for stabilizing susceptible compounds |
| US20160257927A1 (en) * | 2015-03-03 | 2016-09-08 | Ucl Business Plc | Three-dimensional cell culture using nanofiber slurries and nano-structured substrates |
| CN108786491A (en) * | 2018-06-01 | 2018-11-13 | 浙江大学 | A kind of poly-dopamine/triclosan/titania coextruded film and preparation method thereof |
| CN110354315A (en) * | 2019-06-21 | 2019-10-22 | 淮阴工学院 | A kind of fibroin albumen/graphene/titanium dioxide bone tissue engineering scaffold preparation method of three-dimensional porous antibacterial |
-
2021
- 2021-09-08 CN CN202111058942.1A patent/CN113698717A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130316004A1 (en) * | 2011-02-07 | 2013-11-28 | Life Technologies Corporation | Compositions and methods for stabilizing susceptible compounds |
| US20160257927A1 (en) * | 2015-03-03 | 2016-09-08 | Ucl Business Plc | Three-dimensional cell culture using nanofiber slurries and nano-structured substrates |
| CN108786491A (en) * | 2018-06-01 | 2018-11-13 | 浙江大学 | A kind of poly-dopamine/triclosan/titania coextruded film and preparation method thereof |
| CN110354315A (en) * | 2019-06-21 | 2019-10-22 | 淮阴工学院 | A kind of fibroin albumen/graphene/titanium dioxide bone tissue engineering scaffold preparation method of three-dimensional porous antibacterial |
Non-Patent Citations (1)
| Title |
|---|
| 李国平等: "Ag/PAMAM树形分子纳米复合材料对PTFE膜性能的影响", 《当代化工》 * |
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