CN109908407A - Film material with function and preparation method thereof with nitric oxide storage performance - Google Patents
Film material with function and preparation method thereof with nitric oxide storage performance Download PDFInfo
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Abstract
The invention discloses the film material with function and preparation method thereof with nitric oxide storage performance, are related to bio-medical material field of engineering technology.The preparation method of film material with function with nitric oxide storage performance includes: to deposit amine based polymer film layer in substrate material surface, then reacts to obtain two alfin of azo with nitric oxide using the secondary amine in the amine based polymer of material surface.The film material with function includes base material, and amine based polymer film layer is deposited on base material, and contains glycol azo alkene in amine based polymer film layer.Contain glycol azo alkene in amine based polymer film layer, there is nitric oxide storage performance.By that can cover responseless primary amine groups in the new performance of imparting material, avoid material that the adverse reactions such as adherency and the blood coagulation of albumen and bacterium occur in use in amine based polymer surface deposit functional layers.
Description
Technical field
The present invention relates to bio-medical material field of engineering technology, and in particular to the function of nitric oxide storage performance
Energy thin-film material and preparation method thereof.
Background technique
In recent years, biomaterial is widely used in clinic due to its excellent property.Biomaterial is being applied to machine
When body, tissue, blood of organism etc. are touched first, simultaneously as its surface can adsorb the egg from extracellular matrix
It is white, it is grown from cell or tissue adherency is influenced.Using material surface modifying technology, i.e., in the case where not influencing the block property of material,
The characteristic for only changing material surface, remains good mechanical performance, can effectively improve its biocompatibility.
In existing report, it is thin that plasma polymerization or Chemical enhancement vapor deposition polymerization thin film technique prepare amine based polymer
Film focuses primarily upon film outer surface and introduces bioactive molecule, improves its biocompatibility.Not only to retain in coating
A large amount of secondary amines cannot be effectively utilized, and with the primary amine for being lost film surface exposure of the biomolecule of outer surface
Base will lead to the increase of blood coagulation risk.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation method of film material with function with nitric oxide storage performance,
It is intended to carry out nitric oxide production fixation using the secondary amine in amine based polymer, realizes nitric oxide production storage.
Another object of the present invention is to provide a kind of film material with function with nitric oxide storage performance, films
Layer stores nitric oxide using glycol azo alkene, and surface avoids the hair of adherency and the blood coagulation of albumen and bacterium using functional layer
It is raw, while assigning material new function.
The present invention solves its technical problem and adopts the following technical solutions to realize.
The invention proposes a kind of preparation method of film material with function with nitric oxide storage performance, including it is as follows
Step:
Amine based polymer film layer is deposited in substrate material surface, then utilizes the amine based polymer and an oxygen of material surface
Change nitrogen to react to obtain two alfin of azo.
The present invention also proposes a kind of film material with function with nitric oxide storage performance, including base material, substrate
Deposited on materials has amine based polymer film layer, and contains glycol azo alkene in amine based polymer film layer；
Preferably, glycol azo alkene is to react to be formed with nitric oxide using the secondary amine in amine based polymer；
Preferably, amine based polymer film layer is also deposited with functional layer, wherein the deposit of functional layer is selected from polyoxy second
Any one in alkene, polyethylene glycol, tetraethylene glycol dimethyl ether, polyvinyl alcohol and dimethyl silicone polymer；It is more preferably poly-
Ethylene oxide；
Preferably, base material is selected from one of metal and ceramics or a variety of；More preferably stainless steel, ceramics, iron and
Any one or more in its alloy and cobalt-base alloys；
It is highly preferred that the film material with function with nitric oxide storage performance has nitric oxide storage using above-mentioned
The preparation method of the film material with function of energy is prepared.
The embodiment of the present invention provides a kind of having for the preparation method of film material with function with nitric oxide storage performance
Beneficial effect is: then it utilizes the secondary amine in amine based polymer by depositing amine based polymer film layer on base material
It reacts to obtain two alfin of azo with nitric oxide.On the one hand take full advantage of secondary amine in amine based polymer, avoid using
The adverse reactions such as adherency and blood coagulation of albumen and bacterium in the process；On the other hand obtained two alfin of azo exist in water or
Nitric oxide production release may be implemented under physiological condition, there is nitric oxide storage performance.
The present invention also provides a kind of film material with function with nitric oxide storage performance, including base material and
The amine based polymer film layer deposited on base material, and contain glycol azo alkene in amine based polymer film layer,
Nitric oxide can be discharged under later period physiological condition, and there is nitric oxide storage performance.By being deposited on amine based polymer surface
Functional layer can cover responseless primary amine groups in the new performance of imparting material, material is avoided to occur in use
The adverse reactions such as the adherency and blood coagulation of albumen and bacterium.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be to needed in the embodiment attached
Figure is briefly described, it should be understood that the following drawings illustrates only certain embodiments of the present invention, therefore is not construed as pair
The restriction of range for those of ordinary skill in the art without creative efforts, can also be according to this
A little attached drawings obtain other relevant attached drawings.
Fig. 1 is the testing result figure of NO release in multifunction film layer obtained in the embodiment of the present invention；
Fig. 2 is to obtain the inhibitory effect figure that thin-film material adheres to albumen in the embodiment of the present invention and comparative example；
Fig. 3 is to obtain the blood compatibility test result of thin-film material in the embodiment of the present invention and comparative example.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
Below to the film material with function provided in an embodiment of the present invention with nitric oxide storage performance and its preparation side
Method is specifically described.
A kind of preparation method of film material with function with nitric oxide storage performance provided in an embodiment of the present invention,
Include the following steps:
S1, surface preparation
Before the deposition for carrying out amine based polymer film layer, sputter clean is carried out to base material, so that amido polymerize
Object reaches better deposition effect.
Base material is selected from one of metal and ceramics or a variety of；Preferably stainless steel, ceramics, iron and its alloy and cobalt
Any one or more in based alloy.The scope of application of base material is very wide, be not limited to it is above several, but use these types
Material can make the application field of material more wide as base material.
It include: that base material is placed in reaction chamber during sputter clean, control reacts indoor pressure and is
0.01-30Pa, the flow for being passed through argon gas is 0.01-30sccm, radio-frequency power 0-1500W, pulsed bias 0-800V, sputtering
Time is 0.5-10h；Preferably, during sputter clean, reacting indoor pressure is 0.1-15Pa, is passed through the flow of argon gas
For 0.5-8sccm, radio-frequency power 60-150W, pulsed bias 300-500V, sputtering time 0.1-1h.In sputter clean
When control operating parameter be advisable for above range, material can be made more effectively to be cleaned, reinforcing material surface and amido are poly-
Close the bond strength of object.
The deposition of S2, amine based polymer
Amine based polymer film layer is deposited in substrate material surface, which can be polymerize or be changed using pulsed plasma
The method for learning enhancing vapor deposition.Preferably, the raw material for preparing amine based polymer is selected from ammonia, allylamine, triethylamine, triethylene
Diamines, N, any one in N- diisopropylethylamine, benzhydrylamine and 4- ethylene aniline.Inventors have found that above several amine
Based polyalcohol is adapted to form film layer on the surface of the material.
Specifically, the deposition process of amine based polymer film layer is using amine based polymer as presoma in base material table
Face deposit 0.01-10h, preferably 1-3h, general control amine based polymer film layer with a thickness of 0.01nm-5 μm.
Specifically, the deposition of amine based polymer film layer is 0.01- with flow using the method for pulsed plasma polymerization
30sccm argon gas is discharge gas, and reaction chamber vacuum degree is 0.01-30Pa, and control radio-frequency power is 0-1500W, back bias voltage 0-
800V, pulse duty factor 0-100%；Preferably, the flow of argon gas is 0.1-8sccm, and reaction chamber vacuum degree is 0.01-
15Pa, radio-frequency power 10-150W, back bias voltage 0-200V, pulse duty factor 0-100%.It was deposited in amine based polymer
Cheng Zhong, the method being polymerize using pulsed plasma is easy to operate, and parameters control is advisable within the above range, partial parameters
It can be with value to " 0 ", such as back bias voltage, radio-frequency power and pulse duty factor.
S3, secondary amine are reacted with nitric oxide
It reacts to obtain two alfin of azo with nitric oxide using the amine based polymer of material surface, reaction principle is as follows:
In the anion of azo diene
Form (NONOate) is unstable in physiological conditions (pH=7.4,37 DEG C), easily release NO, and half-life period is a few minutes to several small
When differ.
Specifically, the preparation process of two alfin of azo includes: to be immersed in the material with amine based polymer film layer
In reaction system liquid, it is passed through nitric oxide in the reaction vessel and reacts 1-10 days；Preferably 1-5 days.Secondary amine and nitric oxide
It reacts to obtain two alfin of azo under the conditions of can be existing for no catalyst, this may be the solvent by being added
It for basic solvent, also known as " protophilic solvent ", is easy to protonate secondary amine in film, NO is made to be easy to that parent occurs with secondary amine
Core addition reaction.In addition, be added sodium methoxide be also mainly used for medical industry, be used as in organic synthesis condensing agent, chemical reagent,
The catalyst etc. of edible oil and fat processing.
Further, reaction system liquid in methanol/sodium methoxide, ether, acetonitrile, tetrahydrofuran and acetone it is any one
The reaction system that kind, preferably methanol and sodium methoxide are formed；The concentration of sodium methoxide is every ml methanol pair in reaction system liquid
Answer 20-35mg sodium methoxide.The reaction system formed selected from methanol and sodium methoxide is conducive to secondary amine using the strong basicity of sodium methoxide
Nucleophilic addition occurs with nitric oxide after Hydrogen Proton on base.
Further, in amine based polymer and nitric oxide reaction process, the pressure in reaction vessel is 0.01-1MPa,
The purity of nitric oxide gas is 1-100%；Preferably, the pressure in reaction vessel is 0.2-1MPa, nitric oxide gas
Purity is 80-99.999%；When secondary amine and nitric oxide are reacted, the parameters such as operating pressure, nitric oxide concentration are for reaction
Rate and conversion ratio have a significant impact, and operating pressure and nitric oxide concentration control are advisable within the above range.
Preferably, after amine based polymer and nitric oxide have reacted, material is washed and dried, is drawn so as to subsequent
Enter functional layer, and prevents from introducing excessive unreacted raw material in the product.
The introducing of S4, functional layer
In two alfin surface deposit functional layers of azo；Wherein, the deposit of functional layer is selected from polyoxyethylene, poly- second two
Any one in alcohol, tetraethylene glycol dimethyl ether, polyvinylpyrrolidone and polyvinyl alcohol；Preferably polyoxyethylene.It adopts
With the raw material of above several functional layers should the method for pulsed plasma polymerization or Chemical enhancement vapor deposition deposited,
Surface primary amine groups can be covered when assigning the new performance of material, avoid the material adherency of albumen and bacterium and solidifying in use
The adverse reactions such as blood occur.Above several deposits materials are mainly the anti-microbial property of reinforcing material afterwards on the surface of the material, wherein drawing
Enter polyoxyethylene and be able to suppress protein adherence, reaches the building on decontamination surface, while function of surface is a variety of by single steering
Synergistic function.
Polyoxyethylene is deposited on to the method using plasma polymerization on two alfin surface of azo, is in deposition process
Polyoxyethylene gas as reaction gas, in reaction chamber vacuum degree be 0.01-30Pa, back bias voltage 0-800V, pulse duty factor
Under conditions of 0-100%, time 0.01-10h；It is highly preferred that vacuum degree is 0.1-15Pa in reaction chamber, radio-frequency power is
Under conditions of 10-150W, radio-frequency power 0-200W, back bias voltage 0-200V, pulse duty factor are 0-100%, the time is
0.01-5h.The operating parameter control of using plasma polymerization can be such that functional layer is preferably deposited within the above range
Two alfin surface of azo has good bond strength with material surface, and the thickness of film forming is also more suitable, substantially
0.01nm-5μm。
The embodiment of the invention also provides a kind of film material with function with nitric oxide storage performance, including substrate material
Expect, be deposited with amine based polymer film layer on base material, and contains glycol azo alkene in amine based polymer film layer.Glycol
Azo alkene can discharge nitric oxide in physiological conditions, and material itself is made to have nitric oxide production storge quality.
Specifically, glycol azo alkene is to react to be formed with nitric oxide using the secondary amine in amine based polymer, specifically
It please refers to about the introduction in preparation method.
Preferably, functional layer is also deposited in amine based polymer film layer, wherein the deposit of functional layer is selected from polyoxy second
Any one in alkene, polyethylene glycol, tetraethylene glycol dimethyl ether, polyvinyl alcohol and dimethyl silicone polymer；It is more preferably poly-
Ethylene oxide.Material is set to have other effects, such as antibiotic property while having nitric oxide storage performance by loading functional layer
Energy.
Further, base material is selected from one of metal and ceramics or a variety of；More preferably stainless steel, ceramics, iron
And its any one or more in alloy and cobalt-base alloys.Film material with function with nitric oxide storage performance is using upper
Preparation method is stated to be prepared.
Feature and performance of the invention are described in further detail with reference to embodiments.
Embodiment 1
The present embodiment provides a kind of preparation methods of film material with function with nitric oxide storage performance comprising with
Lower step:
(1) surface preparation.Stainless steel bio-medical material and equipment surfaces are placed in reaction chamber sample stage, using true
Reaction chamber air pressure is down to 0.01Pa by sky pump, is passed through the argon gas that flow is 0.01sccm, radio-frequency power 0W, and pulsed bias is
0V, time are the sputter clean of 0h.
(2) deposition of amine based polymer.Reaction chamber vacuum degree is set to come back to 0.01Pa after having cleaned, being passed through flow is
0.01sccm argon gas is passed through ammonia as reaction gas as discharge gas, radio-frequency power be 0W, back bias voltage 0V, arteries and veins
Rush duty ratio be 0% under conditions of, the time be 0.01h plasma polymerization deposition, obtain amine based polymer film layer.
(3) secondary amine and nitric oxide reaction.Acetonitrile is submerged to above-mentioned thin-film surface, is placed in closed container side by side
Except air, being passed through purity is 1% nitric oxide gas, and keeps pressure after 0.01MPa, reaction 1 day, methanol be cleaned and dried to
With.
(4) deposition of functional layer.Above-mentioned sample is put into plasma polymerization chamber, is down to vacuum degree
0.01Pa, is passed through polyethylene glycol gas as reaction gas, operating pressure 0.01Pa, radio-frequency power 0W, back bias voltage 0V,
Under conditions of pulse duty factor is 0%, the time is 0.01h plasma polymerization deposition, is obtained with nitric oxide storage and table
Face decontaminates multifunction film.
Embodiment 2
The present embodiment provides a kind of preparation methods of film material with function with nitric oxide storage performance comprising with
Lower step:
(1) surface preparation.Titanium alloy medical material and equipment surfaces are placed in reaction chamber sample stage, utilize vacuum pump
30Pa is down in reaction chamber air pressure, be passed through flow be 30sccm argon gas, radio-frequency power 1500W, pulsed bias 800V, when
Between be 10h sputter clean.
(2) deposition of amine based polymer.Reaction chamber vacuum degree is set to come back to 30Pa after having cleaned, being passed through flow is
30sccm argon gas is passed through allylamine as reaction gas as discharge gas, radio-frequency power is 1500W, back bias voltage is
Under conditions of 800V, pulse duty factor are 100%, the time is 10h plasma polymerization deposition, obtains amine based polymer film
Layer.
(3) secondary amine and nitric oxide reaction.Ether is submerged to above-mentioned thin-film surface, is placed in closed container side by side
Except air, being passed through purity is 100% nitric oxide gas, and keeps pressure after 1MPa, reaction 10 days, methanol be cleaned and dried to
With.
(4) deposition of functional layer.Above-mentioned sample is put into plasma polymerization chamber, is down to 30Pa to vacuum degree,
Tetraethylene glycol dimethyl ether gas is passed through as reaction gas, operating pressure 30Pa, radio-frequency power 1500W, back bias voltage are
Under conditions of 800V, pulse duty factor are 100%, the time is 10h plasma polymerization deposition, is obtained with nitric oxide storage
And surface decontaminates multifunction film.
Embodiment 3
The present embodiment provides a kind of preparation methods of film material with function with nitric oxide storage performance comprising with
Lower step:
(1) surface preparation.Iron bio-medical material and equipment surfaces are placed in reaction chamber sample stage, utilize vacuum pump
0.1Pa is down in reaction chamber air pressure, be passed through flow be 0.5sccm argon gas, radio-frequency power 60W, pulsed bias 300V, when
Between be 0.1h sputter clean.
(2) deposition of amine based polymer.Reaction chamber vacuum degree is set to come back to 0.01Pa after having cleaned, being passed through flow is
0.1sccm argon gas is passed through triethylamine as reaction gas as discharge gas, radio-frequency power be 10W, back bias voltage 0V,
Under conditions of pulse duty factor is 0%, the time is 1h plasma polymerization deposition, obtains amine based polymer film layer.
(3) secondary amine and nitric oxide reaction.Methanol/sodium methoxide solution (every ml methanol corresponds to 20mg sodium methoxide) is soaked
It not to above-mentioned thin-film surface, places in closed container and excludes air, being passed through purity is 80% nitric oxide gas, and is kept
After 0.2MPa, reaction 5 days, methanol is cleaned and dried stand-by pressure.
(4) deposition of functional layer.Above-mentioned sample is put into plasma polymerization chamber, is down to 0.1Pa to vacuum degree,
Polyvinyl alcohol gas is passed through as reaction gas, operating pressure 0.1Pa, radio-frequency power 10W, back bias voltage 0V, pulse account for
Under conditions of sky ratio is 0%, the time is 0.01h plasma polymerization deposition, obtains decontaminating with nitric oxide storage and surface
Multifunction film.
Embodiment 4
The present embodiment provides a kind of preparation methods of film material with function with nitric oxide storage performance comprising with
Lower step:
(1) surface preparation.Titanium alloy bio-medical material and equipment surfaces are placed in reaction chamber sample stage, using true
Reaction chamber air pressure is down to 15Pa by sky pump, is passed through the argon gas that flow is 8sccm, radio-frequency power 150W, pulsed bias 500V,
Time is the sputter clean of 1h.
(2) deposition of amine based polymer.Reaction chamber vacuum degree is set to come back to 15Pa after having cleaned, being passed through flow is
8sccm argon gas is passed through allylamine as reaction gas as discharge gas, radio-frequency power be 150W, back bias voltage 200V,
Under conditions of pulse duty factor is 100%, the time is 3h plasma polymerization deposition, obtains amine based polymer film layer.
(3) secondary amine and nitric oxide reaction.Methanol/sodium methoxide solution (every ml methanol corresponds to 35mg sodium methoxide) is soaked
Not to above-mentioned thin-film surface, places in closed container and exclude air, being passed through purity is 99.99% nitric oxide gas, and
Keep pressure after 1MPa, reaction 1 day, methanol is cleaned and dried stand-by.
(4) deposition of functional layer.Above-mentioned sample is put into plasma polymerization chamber, is down to 15Pa to vacuum degree,
Polyoxyethylene gas is passed through as reaction gas, operating pressure 15Pa, radio-frequency power 150W, back bias voltage 200V, pulse
Under conditions of duty ratio is 100%, the time is 5h plasma polymerization deposition, obtains decontaminating with nitric oxide storage and surface
Multifunction film.
Test example 1
The detection of NO release is carried out with the product being prepared in embodiment 4, test result is shown in Fig. 1, test method: using
Chemiluminescence NO analyzer (NOA) (Seivers 280i, Boulder, CO) is in PBS (pH=7.4), in 37 DEG C of measurement glycol
The NO of azo alkene Modified Membrane discharges.PPAm indicates that plasma polyallylamine film, PEO indicate polyoxyethylene in Fig. 1.
As shown in Figure 1, the thin-film material being prepared in the embodiment of the present invention has excellent storage energy to nitric oxide
Power, it is after the time of 60min or so that nitric oxide releasing is complete.
Test example 2
The thin-film material that embodiment 4 and comparative example 1 obtain adheres to fibrin, test method: passing through outfit
Quartz crystal microbalance (QCM-D, Q-senseAB, the Sweden) real-time monitoring monitored that dissipates is fixed in PPAam film surface
Fibrinogen amount.PPAam is deposited in quartz wafer (diameter 10mm, frequency 5MHz, Au coating) and is placed in QCM-D
Flow chamber in.Chamber is flowed into the rate of 50 μ L/min of PBS buffer solution, after fundamental curve is stablized, contains fibrin
The PBS solution of former (0.5mg/mL) is passed through with identical flow velocity.Finally, by the thorough washing chamber of PBS solution to remove sample
The residual fibers proteinogen of physical absorption on surface.Test result is shown in Fig. 2.
As can be seen from Figure 2, the functionalization film being prepared in the embodiment of the present invention can effectively inhibit relative to comparative example 1
Adherency to albumen, the function film in embodiment 4 are 5.6 times of the PPAm of nonfunctionalization modification to the rejection ability of albumen,
Show that the multifunction film of this patent preparation has the function of excellent albumen adhesion inhibition.
Test example 3
The blood compatibility of thin-film material obtained in testing example 4, and with only containing amine based polymer film layer
Material compares, test method: the anticoagulant property of different surfaces is detected by the half animal blood experiment in vivo that the time is 2h.
Blood circulation experiment takes off the sample marked at sample after terminating, and benefit weighs with scale thrombus quality.Test result is shown in
Fig. 3 reaches as seen from the figure compared to the PPAm of nonfunctionalization modification by the film modified sample Penetration ration of multifunction
100%.Show that the multifunction film of this patent preparation significantly improves material surface blood compatibility.
In conclusion a kind of preparation side of film material with function with nitric oxide storage performance provided by the invention
Then method utilizes the secondary amine and an oxygen in amine based polymer by depositing amine based polymer film layer on base material
Change nitrogen to react to obtain two alfin of azo.On the one hand the secondary amine in amine based polymer is taken full advantage of, is avoided in use process
The adverse reactions such as the adherency and blood coagulation of albumen and bacterium occur；On the other hand two alfin of azo obtained is in water presence or life
Nitric oxide production release may be implemented under the conditions of reason, there is nitric oxide storage performance.
The present invention also provides a kind of film material with function with nitric oxide storage performance, including base material and
The amine based polymer film layer deposited on base material, and contain glycol azo alkene in amine based polymer film layer,
Nitric oxide can be discharged under later period physiological condition, and there is nitric oxide storage performance.
Embodiments described above is a part of the embodiment of the present invention, instead of all the embodiments.Reality of the invention
The detailed description for applying example is not intended to limit the range of claimed invention, but is merely representative of selected implementation of the invention
Example.Based on the embodiments of the present invention, obtained by those of ordinary skill in the art without making creative efforts
Every other embodiment, shall fall within the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of the film material with function with nitric oxide storage performance, which is characterized in that including walking as follows
It is rapid:
Amine based polymer film layer is deposited in substrate material surface, then utilizes the secondary amine in the amine based polymer of material surface
It is reacted with nitric oxide and generates two alfin of azo.
2. the preparation method of the film material with function according to claim 1 with nitric oxide storage performance, feature
It is, the preparation process of two alfin of azo includes: to be immersed in the material with the amine based polymer film layer instead
It answers in system liquid, is passed through nitric oxide in the reaction vessel and reacts 1-10 days；Preferably 1-5 days；
Preferably, the reaction system liquid is any one in methanol/sodium methoxide, ether, acetonitrile, tetrahydrofuran and acetone
The reaction system that kind, preferably methanol and sodium methoxide are formed；
It is highly preferred that the concentration of the sodium methoxide described in the reaction system liquid is that every ml methanol corresponds to 20-35mg sodium methoxide.
3. the preparation method of the film material with function according to claim 2 with nitric oxide storage performance, feature
It is, in the amine based polymer and the nitric oxide reaction process, the pressure in reaction vessel is 0.01-1MPa, described
The purity of nitric oxide gas is 1-100%；
Preferably, the pressure in the reaction vessel is 0.2-1MPa, and the purity of the nitric oxide gas is 80-
99.999%；
Preferably, after the amine based polymer and the nitric oxide have reacted, material is washed and dried.
4. the preparation method of the film material with function according to claim 1 with nitric oxide storage performance, feature
It is, is polymerize in the process of substrate material surface deposition amine based polymer film layer using pulsed plasma or chemistry increases
The method being vapor-deposited by force；
Preferably, the deposition process of the amine based polymer film layer is using amine based polymer as presoma in the substrate material
Expect that surface deposits 0.01-10h, preferably 1-3h；
Preferably, the raw material for preparing the amine based polymer is selected from ammonia, allylamine, triethylamine, triethylene diamine, N, and N- bis- is different
Any one in propylethylamine, benzhydrylamine and 4- ethylene aniline.
5. the preparation method of the film material with function according to claim 4 with nitric oxide storage performance, feature
It is, the deposition of the amine based polymer film layer is 0.01-30sccm with flow using the method for pulsed plasma polymerization
Argon gas is discharge gas, and reaction chamber vacuum degree is 0.01-30Pa, and control radio-frequency power is 0-1500W, back bias voltage 0-800V,
Pulse duty factor is 0-100%；
Preferably, the flow of argon gas is 0.1-8sccm, and reaction chamber vacuum degree is 0.01-15Pa, radio-frequency power 10-150W, is born
Bias is 0-200V, pulse duty factor 0-100%.
6. the preparation method of the film material with function according to claim 4 or 5 with nitric oxide storage performance,
It is characterized in that, before the deposition for carrying out the amine based polymer film layer, sputter clean is carried out to the base material；
Preferably, include: that the base material is placed in reaction chamber during the sputter clean, control the reaction
Indoor pressure is 0.01-30Pa, and the flow for being passed through argon gas is 0.01-30sccm, radio-frequency power 0-1500W, pulsed bias
For 0-800V, sputtering time 0.5-10h；
It is highly preferred that reacting indoor pressure is 0.1-15Pa during sputter clean, the flow for being passed through argon gas is 0.5-
8sccm, radio-frequency power 60-150W, pulsed bias 300-500V, sputtering time 0.1-1h.
7. the preparation method of the film material with function according to claim 1 with nitric oxide storage performance, feature
It is, the preparation method further includes in the two alfin surface deposit functional layers of azo；
Wherein, the deposit of the functional layer is selected from polyoxyethylene, polyethylene glycol, tetraethylene glycol dimethyl ether, polyvinyl pyrrole
Any one in pyrrolidone and polyvinyl alcohol；Preferably polyoxyethylene.
8. the preparation method of the film material with function according to claim 7 with nitric oxide storage performance, feature
It is, polyoxyethylene is deposited on to the method using plasma polymerization on the two alfin surface of azo；
It preferably, is polyoxyethylene gas in the polyoxyethylene deposition process as reaction gas, vacuum degree is in reaction chamber
Under conditions of 0.01-30Pa, back bias voltage 0-800V, pulse duty factor are 0-100%, time 0.01-10h；
It is highly preferred that vacuum degree is 0.1-15Pa, radio-frequency power 10-150W, radio-frequency power 0-200W, negative bias in reaction chamber
Under conditions of pressure is 0-200V, pulse duty factor is 0-100%, time 0.01-5h.
9. the preparation method of the film material with function according to claim 1 with nitric oxide storage performance, feature
It is, the base material is selected from one of metal and ceramics or a variety of；Preferably stainless steel, ceramics, iron and its alloy and
Any one or more in cobalt-base alloys.
10. a kind of film material with function with nitric oxide storage performance, which is characterized in that including base material, the base
It is deposited with amine based polymer film layer on bottom material, and contains glycol azo alkene in the amine based polymer film layer；
Preferably, the glycol azo alkene is to react to be formed with nitric oxide using the secondary amine in the amine based polymer；
Preferably, antibacterial decontamination function layer is also deposited in the amine based polymer film layer, wherein the antibacterial decontamination function
The deposit of layer is in polyoxyethylene, polyethylene glycol, tetraethylene glycol dimethyl ether, polyvinyl alcohol and dimethyl silicone polymer
Any one；More preferably polyoxyethylene；
Preferably, the base material is selected from one of metal and ceramics or a variety of；More preferably stainless steel, ceramics, iron and
Any one or more in its alloy and cobalt-base alloys；
It is highly preferred that any one of described film material with function application claim 1-9 with nitric oxide storage performance institute
The preparation method for the film material with function with nitric oxide storage performance stated is prepared.
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| CN201910194088.8A Pending CN109908407A (en) | 2019-03-14 | 2019-03-14 | Film material with function and preparation method thereof with nitric oxide storage performance |
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Cited By (1)
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| CN111910441A (en) * | 2020-08-06 | 2020-11-10 | 南京诺全生物医疗科技有限公司 | Antibacterial chip and preparation method and application thereof |
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