CN113368316A - Preparation method of self-assembled sulfosilane-PMMA medical composite film - Google Patents
Preparation method of self-assembled sulfosilane-PMMA medical composite film Download PDFInfo
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- CN113368316A CN113368316A CN202110481590.4A CN202110481590A CN113368316A CN 113368316 A CN113368316 A CN 113368316A CN 202110481590 A CN202110481590 A CN 202110481590A CN 113368316 A CN113368316 A CN 113368316A
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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
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/08—Materials for coatings
- A61L31/10—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
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified 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
- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/12—Nanosized materials, e.g. nanofibres, nanoparticles, nanowires, nanotubes; Nanostructured surfaces
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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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Abstract
The invention discloses a preparation method of a self-assembled sulfonic silane-PMMA medical composite membrane, which is characterized in that a self-assembling method is adopted to prepare a sulfonic silane-PMMA nano composite membrane on a human body implant material, and the method specifically comprises the following steps: the preparation method comprises the steps of pretreatment of an implant material, preparation of a sulfonic silane film, PMMA self-assembly and the like. Compared with the prior art, the invention has the advantages of uniform film distribution, compact film formation, simple process, low cost, no pollution to the environment and the like, the PMMA assembling solution is simple to prepare, not only has obvious antifriction effect, but also has good abrasion resistance, is expected to become an ideal boundary lubricating film of a micro machine, and is a preparation method with very good application prospect and practical value.
Description
Technical Field
The invention relates to the technical field of preparation of biomedical materials, in particular to a preparation method of a self-assembled sulfonic silane-PMMA medical composite film for a human body implant material.
Background
With the advance of high technology, the mechanical manufacturing industry is moving towards miniaturization, which involves tribological problems on the surfaces of the micromachines. Because of the advantages of high hardness, low cost, small surface roughness, etc., the application of the monocrystalline silicon material in the micro-electromechanical system is increasingly emphasized. However, the single crystal silicon material without surface treatment has high brittleness, and surface cracks are easy to peel off and wear and break under the action of low tensile stress, and are difficult to meet the use requirements, so that the surface micro-mechanical property of the silicon material needs to be improved by using a surface modification technology to improve the microscopic friction and wear property of the silicon material substrate.
At present, a self-assembly film is prepared on the surface of a single crystal substrate by a self-assembly method to improve and research the friction reduction and wear resistance of the surface of sulfonic silane. The self-assembled sulfonic silane-PMMA film is an organic two-dimensional molecular film formed by immersing a proper substrate into a solution containing organic matters and mainly through the chemical adsorption. And then, placing the substrate attached with the organic film into a prepared assembling solution containing PMMA, and assembling under certain conditions to obtain the sulfonic silane-PMMA composite film with high orderliness and orientation, compact structure and high stability. The research on the friction performance of the ordered molecular film has been one of the leading issues in the field of tribology, the film thickness of the self-assembled monolayer film has a limited adjustment range, and the requirements on the base material and the film-forming raw material are severe. The self-assembled sulfonic silane-PMMA composite film has the advantages of excellent mechanical property, simple preparation method, controllable chemical components, adjustable film thickness and the like, can be used as a film lubricating material, and has become a hotspot of extensive research.
According to the research of the literature, Chinese patent CN1358804A discloses a method for preparing a fatty acid self-assembly monomolecular ultrathin lubricating film on the surface of a solid film, which comprises the steps of self-assembling a layer of monomolecular fatty acid on the surface of the solid film, selecting fatty acid easy to adsorb on the surface of the solid to prepare a dilute solution, and quickly immersing the prepared ceramic film into the prepared dilute solution of fatty acid to react for 24-48 minutes at room temperature. The method needs 24-96 hours to prepare the precursor solution in the process of preparing the self-assembled film, the film forming period is long, a specific method is not involved in the process of treating the substrate, only an organic self-assembled film is prepared, and the improvement and research of the sulfonic silane on the film performance are not involved.
Disclosure of Invention
The invention aims to provide a preparation method of a self-assembled sulfonic silane-PMMA (polymethyl methacrylate) biomedical composite film aiming at the defects of the prior art, sulfonic silane is used as a substrate material of the biomedical composite film, and the sulfonic silane-PMMA nano composite film is prepared on the surface of the biological medical composite film by the self-assembly method, so that the friction reducing and wear resisting properties of the surface of the sulfonic silane are effectively improved, and the biological medical composite film which is good in mechanical property and friction property, smooth, compact and uniform is obtained.
The purpose of the invention is realized as follows: a preparation method of a self-assembly sulfosilane-PMMA medical composite membrane is characterized in that a self-assembly method is adopted to prepare a sulfosilane-PMMA nano composite membrane on a human body implant material, and the preparation method specifically comprises the following steps:
step a: pretreatment of implant materials
Soaking the human body implant material in aqua regia with the concentration of 20-30 wt%, heating and reacting for 5-6 hours, naturally cooling for 7-8 hours at room temperature, taking out the human body implant material, repeatedly washing with deionized water, cleaning, and drying, wherein the temperature of the heating reaction is 70-80 ℃.
Step b: preparation of sulfosilane film
Placing the pretreated human body implant material into a mercaptosilane self-assembly solution, standing for 8-12 hours, taking out, washing with acetone, chloroform and deionized water respectively, blow-drying with nitrogen, soaking in nitric acid with the concentration of 30-60 wt% for in-situ oxidation reaction for 2-3 hours at the reaction temperature of 70-80 ℃, oxidizing end mercapto groups into sulfonic groups in situ, and washing the human body implant material taken out after the in-situ oxidation reaction is finished with a large amount of deionized water, wherein the mercaptosilane self-assembly solution comprises the following components in molar concentration: 0.1-1 mmol/L of mercaptosilane, and benzene solution as solvent.
Step c: PMMA self-assembly
Placing the human body implant material with the surface attached with the sulfonic silane film in a PMMA solution for self-assembly to form a sulfonic silane-PMMA nano film on the surface of the human body implant material, wherein the PMMA solution comprises the following components in percentage by weight: titanate: 3.6-8%; ethanol content: 66-86%; ethylene diamine tetraacetic acid: 1-5%; ammonium chloride: 3-7%; urea: 12-27%, hydrochloric acid: 0.6 to 1.7 percent; the concentration of the hydrochloric acid is 25-30 wt%; the self-assembly time is 10-14 hours, and the self-assembly temperature is 70-90 ℃.
Compared with the prior art, the invention has the advantages of uniform film distribution, compact film formation, simple process, low cost, no pollution to the environment and the like, the PMMA assembly solution is simple to prepare, the PMMA self-assembly film prepared on the surface of the monocrystalline silicon substrate can reduce the friction coefficient from 0.8 when no film exists to about 0.1, the friction reducing effect is obvious, and the PMMA self-assembly film also has good abrasion resistance, is expected to become an ideal boundary lubricating film of a micro machine, and is a preparation method with very good application prospect and practical value.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples.
Example 1
1) Pretreating the human body implant material, soaking the human body implant material in 20 wt% of aqua regia, heating at 75 ℃ for 6 hours, naturally cooling at room temperature for 10 hours, taking out the human body implant material, repeatedly washing with deionized water, and then putting into a drying dish for drying.
2) The treated human body implant material is immersed into the components with the molar concentrations as follows: 0.4mmol/L of mercaptosilane and a benzene solution as a solvent, standing for 10 hours, taking out, washing with acetone, chloroform and deionized water respectively, blow-drying with nitrogen, placing in 35 wt% nitric acid, reacting at 80 ℃ for 2 hours, taking out, washing with a large amount of deionized water, and oxidizing the end mercapto groups into the required sulfonic groups in situ.
3) The human body implant material with the surface attached with the sulfosilane film is immersed into the components with the weight percentage: titanate: 4%, ethanol content: 68%, ethylenediaminetetraacetic acid: 3%, ammonium chloride: 5%, urea: 25%, hydrochloric acid: 1.2 percent (with the concentration of 30 percent by weight) of PMMA self-assembly solution, and assembling for 12 hours at the temperature of 80 ℃ to obtain the sulfosilane-PMMA self-assembly nano film.
The surface appearance, thickness and chemical components of the prepared sulfonic silane-PMMA self-assembled nano film are characterized by an SPM-9500 atomic force microscope, an L116E type elliptical polarized light measuring instrument and a PHI-5702 type X-photoelectron spectrometer (XPS). And measuring the friction coefficient of the film by adopting a point contact pure sliding micro-friction performance measuring instrument.
The results showed that the thickness of the silane self-assembled on the human implant material was 7nm and the thickness of the composite film was 25 nm. XPS spectrum shows that there are mercapto group in the silane film self-assembled on the surface of the human body implant material. After in-situ oxidation, high-valence sulfur elements exist, which indicates that the mercapto groups on the silane film on the surface are successfully oxidized into sulfonic groups in situ. The existence of titanium element is observed in an XPS spectrum of the surface of the substrate assembled in the PMMA solution, the binding energy of the titanium element generates chemical shift, the PMMA material and a functional group on the surface of the substrate generate complex reaction, and the index of sulfur element is very weak, so that the surface of the human body implant material is covered with a layer of PMMA nano film. And respectively measuring the friction coefficients of the clean human body implant material and the self-assembled titanium dioxide composite film on the surface of the human body implant material on a point contact pure sliding micro-friction performance measuring instrument. The PMMA self-assembly composite film prepared on the surface of the human body implant material can reduce the friction coefficient from 0.85 to 0.12 in the absence of the film, and has very obvious antifriction effect.
Example 2:
1) pretreating the human implant material, soaking the human implant material in 25 wt% of aqua regia, heating at 70 ℃ for 6 hours, naturally cooling at room temperature for 10 hours, taking out the human implant material, repeatedly washing with deionized water, and then putting into a drying dish for drying.
2) The treated human body implant material is immersed into the components with the molar concentrations as follows: 0.5mmol/L of mercaptosilane and benzene solution as solvent, standing for 10 hours, taking out, washing with acetone, chloroform and deionized water, blowing with nitrogen, placing in nitric acid with the concentration of 50 wt%, reacting for 2 hours at the temperature of 80 ℃, taking out, washing with a large amount of deionized water, and oxidizing the end mercapto group into the required sulfonic group in situ.
3) The human body implant material with the surface attached with the sulfosilane film is immersed into the components with the weight percentage: ethanol content: 80%, titanate: 3.7%, ethylenediaminetetraacetic acid: 1.5%, ammonium chloride: 4%, urea: 15%, concentrated hydrochloric acid: and (3) assembling the solution in a PMMA self-assembly solution with the concentration of 0.8 percent (30 weight percent) at the temperature of 80 ℃ for 12 hours to obtain the sulfosilane-PMMA self-assembly nano film.
The thin film was characterized using the experimental apparatus of example 1, and the results showed that the thickness of the silane self-assembled on the human implant material was 8nm and the thickness of the composite thin film was 40 nm. XPS (X-ray diffraction) spectra show that different film layers in a composite film self-assembled on the surface of a human implant material contain sulfonic groups, the index of silicon dioxide cannot be observed after a silane film is assembled, and after PMMA (polymethyl methacrylate) is assembled, a signal of the sulfonic groups is weak, so that a layer of sulfonic silane nano film is successfully assembled on the surface of the human implant material, and a layer of PMMA nano film is successfully assembled on the surface of the sulfonic silane film. And respectively measuring the friction coefficients of the clean human body implant material and the self-assembled PMMA on the surface of the human body implant material on a point contact pure sliding micro-friction performance measuring instrument. The PMMA self-assembled composite film prepared on the surface of the human body implant material can reduce the friction coefficient from 0.8 to 0.1 in the absence of the film, and has very obvious antifriction effect.
Example 3:
1) pretreating the human body implant material, soaking the human body implant material in 30 wt% of aqua regia, heating at 80 ℃ for 5 hours, naturally cooling at room temperature for 10 hours, taking out the human body implant material, repeatedly washing with deionized water, and then putting into a drying dish for drying.
2) The treated human body implant material is immersed into the components with the molar concentrations as follows: 1mmol/L of mercaptosilane and benzene solution as solvent, taking out, washing with acetone, chloroform and deionized water, blowing with nitrogen, reacting in 55 wt% concentration nitric acid at 75 deg.c for 2 hr, taking out, washing with great amount of deionized water to oxidize terminal mercapto into required sulfo group in situ.
3) The human body implant material with the surface attached with the sulfosilane film is immersed into the components with the weight percentage: ethanol content: 75%, titanate: 4%, ethylenediaminetetraacetic acid: 4.5%, ammonium chloride: 7%, urea: 25%, concentrated hydrochloric acid: assembling the mixture in 1.5 percent (with the concentration of 30 weight percent) PMMA self-assembly solution for 14 hours at the temperature of 75 ℃ to obtain the sulfosilane-PMMA self-assembly nano film.
The experimental apparatus in example 1 was used to characterize the thin film, and the results showed that the thickness of the self-assembled organic thin film was 6nm and the thickness of the composite thin film was between 40 nm. XPS spectrum shows that mercaptosilane film is successfully assembled on the surface of the substrate, and the mercapto group is oxidized into sulfonic group in situ; the PMMA material is assembled on the surface of the material, and the index of the sulfonic group is very weak, so that the surface of the human body implant material is successfully covered with a layer of sulfonic group-PMMA nano composite film. And respectively measuring the friction coefficients of the clean human body implant material and the self-assembled PMMA on the surface of the human body implant material on a point contact pure sliding micro-friction performance measuring instrument. The PMMA self-assembled composite film prepared on the surface of the human body implant material can reduce the friction coefficient from 0.8 to 0.1 in the absence of the film, and has very obvious antifriction effect.
The invention has simple process, low cost and no pollution to the environment. On the surface of the human body implant material, the molecule of the mercaptosilane contains hydrolyzable active groups, and a silane self-assembly film with mercapto groups on the surface is formed on the surface of a substrate by combining chemical construction of Si-O and the substrate material with the active groups of Si-OH. The human body implant material with the surface assembled with the mercaptosilane is placed into nitric acid solution and stands for a period of time, and the mercapto group on the surface of the film is oxidized into the sulfonic group in situ. And then placing the silane into a PMMA solution, and carrying out a complexing reaction between the-SO group and PMMA, thereby forming a layer of PMMA nano film on the surface of the silane. The invention has been described in further detail in order to avoid limiting the scope of the invention, and it is intended that all such equivalent embodiments be included within the scope of the following claims.
Claims (2)
1. A preparation method of a self-assembly sulfosilane-PMMA medical composite membrane is characterized in that a self-assembly method is adopted to prepare a sulfosilane-PMMA nano composite membrane on a human body implant material, and the preparation method specifically comprises the following steps:
step a: pretreatment of implant materials
Soaking the human body implant material in aqua regia with the concentration of 20-30 wt%, heating and reacting for 5-6 hours, naturally cooling for 7-8 hours at room temperature, cleaning the cooled human body implant material with deionized water, and drying, wherein the temperature of the heating reaction is 70-80 ℃;
step b: preparation of sulfosilane film
Placing the pretreated human body implant material into a mercaptosilane self-assembly solution, standing for 8-12 hours, forming a silane film on the surface of the human body implant material, taking out, washing with acetone, chloroform and deionized water respectively, blow-drying with nitrogen, soaking in nitric acid with the concentration of 30-60 wt% for in-situ oxidation reaction, forming a sulfosilane film on the surface of the human body implant material, taking out, and cleaning with deionized water, wherein the mercaptosilane assembly solution comprises the following components in molar concentration: 0.1-1 mmol/L of mercaptosilane, and a solvent is a benzene solution; the time of the in-situ oxidation reaction is 2-3 hours, and the reaction temperature is 70-80 ℃;
step c: PMMA self-assembly
Placing the human body implant material with the surface attached with the sulfonic silane film in a PMMA solution for self-assembly to form a sulfonic silane-PMMA nano film on the surface of the human body implant material, wherein the PMMA solution comprises the following components in percentage by weight: titanate: 3.6-8%; ethanol content: 66-86%; ethylene diamine tetraacetic acid: 1-5%; ammonium chloride: 3-7%; urea: 12-27%, hydrochloric acid: 0.6 to 1.7 percent; the concentration of the hydrochloric acid is 25-30 wt%; the self-assembly time is 10-14 hours, and the self-assembly temperature is 70-90 ℃.
2. The preparation method of the self-assembled sulfosilane-PMMA medical composite film according to claim 1, characterized in that the thickness of the sulfosilane film is 6-40 nm.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1670248A (en) * | 2005-01-20 | 2005-09-21 | 上海交通大学 | Method for preparing sulfonic silane-rare earth nanometer compound membrane on single crystal silicon sheet surface |
| CN101555629A (en) * | 2009-04-22 | 2009-10-14 | 上海第二工业大学 | Preparation method of self-assembled sulfonic acid group silane-titanium dioxide composite film on monocrystalline silicon substrate surface |
| CN102174239A (en) * | 2011-02-24 | 2011-09-07 | 南京师范大学 | Polymethyl methacrylate with micro-nano topological structure and preparation method and application thereof |
| CN110551180A (en) * | 2019-08-21 | 2019-12-10 | 华南理工大学 | Multifunctional implant with response effect and preparation method and application thereof |
| CN111671983A (en) * | 2020-06-12 | 2020-09-18 | 深圳清华大学研究院 | Biomedical material and preparation method thereof |
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- 2021-04-30 CN CN202110481590.4A patent/CN113368316A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1670248A (en) * | 2005-01-20 | 2005-09-21 | 上海交通大学 | Method for preparing sulfonic silane-rare earth nanometer compound membrane on single crystal silicon sheet surface |
| CN101555629A (en) * | 2009-04-22 | 2009-10-14 | 上海第二工业大学 | Preparation method of self-assembled sulfonic acid group silane-titanium dioxide composite film on monocrystalline silicon substrate surface |
| CN102174239A (en) * | 2011-02-24 | 2011-09-07 | 南京师范大学 | Polymethyl methacrylate with micro-nano topological structure and preparation method and application thereof |
| CN110551180A (en) * | 2019-08-21 | 2019-12-10 | 华南理工大学 | Multifunctional implant with response effect and preparation method and application thereof |
| CN111671983A (en) * | 2020-06-12 | 2020-09-18 | 深圳清华大学研究院 | Biomedical material and preparation method thereof |
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