CN107983599A - A kind of compound polyelectrolyte coating and preparation method thereof - Google Patents
A kind of compound polyelectrolyte coating and preparation method thereof Download PDFInfo
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- CN107983599A CN107983599A CN201711098931.XA CN201711098931A CN107983599A CN 107983599 A CN107983599 A CN 107983599A CN 201711098931 A CN201711098931 A CN 201711098931A CN 107983599 A CN107983599 A CN 107983599A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
- B05D3/0254—After-treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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Abstract
The invention discloses a kind of compound polyelectrolyte coating based on spraying technology, it is prepared based on compound polyelectrolyte, made annealing treatment after spraying, uniform, complete compound polyelectrolyte coating is finally prepared, this method drastically increases the preparation efficiency of coating and the utilization rate of polyelectrolyte material, while is greatly promoted the automatization level of preparation process.
Description
Technical field
The present invention relates to coat preparing technology field, in particular to a kind of compound polyelectrolyte coating and its system
Preparation Method.
Background technology
The macromolecule with ionizable ionic group is known as polyelectrolyte on strand
(Polyelectrolyte).When polyelectrolyte is dissolved in the very big solvent of dielectric constant, will dissociate, in the solution
Form macroion and many small molecular ions.Polyelectrolyte material includes the polyelectrolyte of synthesis, such as polyacrylic acid, polyphenyl
Sodium sulfonate, P4VP etc.；Natural polymer polyelectrolyte then mainly has chitosan, sodium alginate, hyaluronic acid
Sodium and the cellulose Jing Guo chemical modification, they are all derived from the polysaccharose substance of nature；In a larger sense, absolutely mostly
The number large biological molecule (such as DNA, protamine sulfate) related with vital movement is also all polyelectrolyte.
Due to the extensive source of polyelectrolyte material and its own unique physicochemical property, polyelectrolyte is widely used in
Surface and interface coatings art, photoelectric material, separation membrane material modification, battery diaphragm, biomaterial and equipment surfaces modification etc.
Aspect.The classical method for preparing polyelectrolyte coating be LBL self-assembly (Layer by layer self-assembly,
LBL) method, its basic principle is alternately submerged in the polyelectrolyte solution with opposite charges by base material, by poly-
Electrolyte electrostatic force in itself and other interaction (such as hydrogen bond, hydrophobic interaction, supermolecule Subjective and Objective phase interactions
With) etc., adsorb to form coating in the surface layer of material.Since assembling process requires material alternately to submerge in the solution, and
Many assembling process include cleaning step, and preparing polyelectrolyte coating by LBL self-assembly method will often take a substantial amount of time
With numerous and diverse step, therefore poor efficiency of this method in preparation process and the poor efficiency in raw material use aspects, limitation
Its application prospect in preparation of industrialization.In order to improve the efficiency of assembling, people continually develop research, wherein spraying auxiliary
The layer assembly helped has obtained extensive concern with spin coating auxiliary laminated assembling technology.The basic principle of spraying auxiliary layer assembly
It is by the way that polyelectrolyte solution is directly atomized, and alternating spray is to the surface of base material；Since it automates alternating spray
Speed quickly, therefore substantially increase the efficiency of assembling.The basic principle of spin coating auxiliary layer assembly is by by poly- electrolysis
Matter drop is added drop-wise to atwirl planar substrates material surface, since base material is in quick rotation status, accelerates not
The drop of absorption therefore equally accelerates the efficiency of assembling in the disengaging of material surface.But the improved group layer by layer of both the above
Dress process is still faced with serious waste of material, and spin coating auxiliary layer assembly is only applicable to the coating structure of planar materials
Build.Therefore, a kind of method for the structure polyelectrolyte coating for being provided simultaneously with simple, quick and high utilization rate of raw materials is still in
Blank.
In fact, layer assembly process of the polyelectrolyte material in substrate surface, is substantially that polyelectrolyte is controlled in material
Expect that surface forms the process of compound polyelectrolyte (Polyelectrolyte Complex).And at the same time, polyelectrolyte solution leads to
Crossing simple mixing just can form this compound.Based on this principle, it has been found that after compound polyelectrolyte is precipitated from
The heart just can collect out compound polyelectrolyte material.Compound polyelectrolyte shows efficient utilization rate of raw materials and simple system
Standby process, but so far, still not on the report using compound polyelectrolyte prepares coating.Therefore, if can base
In compound polyelectrolyte material, structure is a kind of rapidly and efficiently to prepare polyelectrolyte coating with easy method, this is for promoting
Polyelectrolyte material has great and profound significance in industrialized application.
The content of the invention
The present invention is explored a kind of complete using the efficient utilization rate of raw materials of compound polyelectrolyte and easy preparation characteristic
New prepares the method for polyelectrolyte coating, so that the preparation efficiency in the presence of improving conventional preparation method is low, automation journey
Spend the technical problems such as low and utilization rate of raw materials is low.
The technical solution adopted by the present invention is as follows：
A kind of preparation method of compound polyelectrolyte coating, including：
(1) prepared by compound polyelectrolyte stable suspension
Aqueous solution with positive charge polyelectrolyte and the aqueous solution with negative polyelectrolytes are mixed, obtain poly- electricity
Solve matter stable composite suspension；
(2) primary coating is prepared
The compound polyelectrolyte stable suspension that step (1) obtains is deposited into substrate material surface, obtains primary painting
Layer；
(3) make annealing treatment
The primary coating that step (2) obtains is positioned in take-in box, is handled using small molecule plasticizer steam annealing
Regular hour, up to the compound polyelectrolyte coating.
Based on compound polyelectrolyte, after primary coating deposition process carry out annealing is prepared the present invention
Uniformly, complete compound polyelectrolyte coating, this method drastically increase the preparation efficiency and polyelectrolyte material of coating
Utilization rate, while be greatly promoted the automatization level of preparation process.Wherein, according to the different qualities of final coating, just
The deposition process of level coating includes but are not limited to ultrasonic spraying, compressed air spraying, spin coating, dip-coating, volatilization deposition etc..More
Importantly, in order to further improve the efficiency of coating preparation and automation characteristic, the present invention preferably spraying technology is as poly- electricity
Solve the main preparation methods of matter composite coating.Spraying technology includes conventional compressed air atomizing spraying and ultrasonic atomizatio spray
Apply, the important method prepared as technological coating, spraying technology can significantly improve the uniformity and preparation efficiency of coating, at the same time
Uniform coating, therefore the main method prepared as coating of the present invention can be formed on complicated three-dimensional structure surface.
In order to make the compound polyelectrolyte stable suspension being prepared reach the demand that can be sprayed, specifically
Meet it is following some：(a) compound polyelectrolyte can stable suspersion in the solution, it is significantly heavy not occur in spraying process
Form sediment；(b) compound polyelectrolyte stable suspension can be uniformly dispersed in substrate, and drop self aggregation does not occur；(c) solvent volatilizees
Speed can meet spraying demand.
In order to adjust the stability of compound polyelectrolyte stable suspension, aqueous solution with positive charge polyelectrolyte and
The concentration of aqueous solution with negative polyelectrolytes is controlled between 0.1mg/ml to 10mg/ml.Carried preferably, working as
When the concentration of the aqueous solution of positive charge polyelectrolyte and aqueous solution with negative polyelectrolytes is 0.3~5mg/ml, prepare
Obtained compound polyelectrolyte particle diameter is more uniform, and suspension is more stablized.
The positive charge polyelectrolyte that carries can be poly-L-lysine (PLL), and linear polyethylene imines (LPEI), is propped up
Change polyethyleneimine (bPEI), nucleoprotamine, collagen, gelatin, chitosan etc..
Described with negative polyelectrolytes can be Sodium Hyaluronate (HA), heparin sodium (Heparin), polystyrene sulphur
Sour sodium (PSS), sodium alginate (Alginate), DNA (DNA), bovine serum albumin(BSA) (BSA), human serum albumins
(HSA) etc..
The mixed volume ratio of aqueous solution with positive charge polyelectrolyte and the aqueous solution with negative polyelectrolytes is
0.3~3：1.
In the compound polyelectrolyte stable suspension, the size of compound polyelectrolyte is 0.05~5 μm, as
It is preferred that the size of compound polyelectrolyte be 0.1~2 μm, at this time compound polyelectrolyte can in the solution the long period stablize
Suspend, so as to improve preparation stability.
In step (2), can by pouring, spin coating, dip-coating, air atomizing spraying, the technology such as Ultrasonic spraying will be poly-
Pentalyte stable suspension deposits to substrate material surface, it is contemplated that automated production requirement, preferably, selecting super
Sound atomizing spraying technology prepares primary coating, and the advantage of ultrasonic spraying technology is can be by ultrasonic atomizatio principle, by drop mist
Micron-sized fine drop is melted into, so as to accelerate the volatilization of solvent；Further, since atomized drop has preferable uniformity,
Therefore the coating uniformity finally obtained also greatly improves.
In addition, according to different application demands, in order to further improve the preparation efficiency of coating, it is ensured that polyelectrolyte is compound
Micron order drop of the thing stable suspension after ultrasonic atomizatio can spread into substrate surface well and self aggregation again does not occur,
Preferably, before carrying out coating deposition, being added in the compound polyelectrolyte stable suspension soluble easily in water has
For solvent to reduce the surface tension of solvent, addition is the 5~200% of compound polyelectrolyte stable suspension volume.Into
One step is preferred, and the addition of organic solvent is the 30~150% of compound polyelectrolyte stable suspension volume.Due to organic molten
The addition of agent destroys the hydrogen bond of hydrone to a certain extent, so as to reduce vaporization enthalpy, is conducive to the quick of atomized drop
It is dry to be deposited with coating.
The organic solvent soluble easily in water can be ethanol, acetone, ethyl acetate, tetrahydrofuran etc..
In step (2), base material can be metallic substrates (such as stainless steel, titanium alloy etc.), can also be polymer matrix
Bottom (such as polylactic acid, polyvinyl alcohol, polyether-ether-ketone, thermoplastic elastomer (TPE))；The time of spraying for 10 minutes to 2 it is small when.
But due to the stronger combination outlet capacity of polyelectrolyte material, there are certain journey for primary coating prepared by step (2)
The inhomogeneities of degree, therefore by making annealing treatment the uniformity of further raising coating.
The basic principle of annealing is that the sub-chain motion of compound polyelectrolyte is activated by the way of certain, passes through poly- electrolysis
The chain movement of matter itself come realize coating surface can minimumization, so as to achieve the purpose that to realize coating uniform.
Polyelectrolyte material passes through the modes such as electrostatic force, hydrogen bond and hydrophobic interaction in compound polyelectrolyte
Locking, the present invention activates the sub-chain motion of compound polyelectrolyte using small molecule plasticizer, preferably, described small point
Sub- plasticizer is organic molecule or water, wherein, organic molecule can be ethanol, ethyl acetate, toluene, tetrahydrofuran etc.,
The vapor partial pressure and temperature of organic molecule or water are controlled in take-in box, can Induced Annealing process progress.When small
When molecule plasticizer is organic molecule, the vapor partial pressure of organic molecule is 5~10KPa in take-in box；When small molecule increases
When modeling agent is water, humidity is 50~100% in take-in box.
Further preferably, the present invention activates the segment of compound polyelectrolyte using hydrone as small molecule plasticizer
Movement, the shielding electrostatic interaction that hydrone can be good with its dipole (dipole) property, in addition, hydrone is as small molecule
Plasticizer also can further destroy the interaction of hydrogen bond.
Humidity is 50~100% in the take-in box, and the control of humidity is the core of annealing process of the present invention, well
Humid control can promote the abundant aquation of compound polyelectrolyte (hydration), so that it is guaranteed that the activation of molecular chain movement and
The implementation of annealing process, preferably, humidity is 70~100% in the take-in box.
Temperature is 0~100 DEG C in the take-in box, preferred according to different polyelectrolyte material and demand, temperature
For 15~80 DEG C.
According to different polyelectrolyte material and demand, time of annealing for 5 minutes to 24 it is small when.
Present invention also offers a kind of compound polyelectrolyte coating being prepared by the above method, the polyelectrolyte
The thickness of composite coating is 0.1~100 micron.
Compared with prior art, the invention has the advantages that：
Traditional LBL self-assembly method on polyelectrolyte coating is prepared there is efficiency is low, waste of raw materials is serious and
The problems such as the degree of automation is low.Even if follow-up developments have gone out spraying and spin coating auxiliary layer assembly, a large amount of wastes of its raw material
Its prospect in preparation of industrialization is still limited with cumbersome preparation process.
Based on the present invention uses compound polyelectrolyte, primary coating is prepared using the methods of spraying technology, primary applies
Layer prepares compound polyelectrolyte coating by the method for annealing.Firstly, since the simplicity of recombination process, greatly
The cumbersome assembling process of layer assembly is improved, preparation efficiency has the lifting of the order of magnitude；Secondly, the present invention innovatively proposes to adopt
The mode handled with small molecule plasticizer steam annealing realizes the uniformity of coating；Further, since directly answered using polyelectrolyte
Compound prepares coating, raw material can realize nil waste, compared to waste of raw materials of traditional preparation process more than 90%, this hair
The bright utilization rate for drastically increasing raw material；Finally, supermatic prepared can be achieved based on spraying technology, the present invention
Journey, therefore drastically increase potentiality of the present invention in actual industrialization application.
Brief description of the drawings
Fig. 1 is the surface microscopic topographic figure of primary coating prepared by embodiment 1；
Fig. 2 is the microscopic appearance figure of PLL/HA compound polyelectrolyte coatings prepared by embodiment 1；
Fig. 3 is the surface roughness result figure of PLL/HA compound polyelectrolyte coatings prepared by embodiment 1.
Embodiment
For a further understanding of the present invention, below to the present invention's by taking general degradable high polymer material polylactic acid as an example
Preferred solution is described.These descriptions are merely illustrative the features and advantages of the present invention, the protection being not intended to limit the present invention
Scope.
Embodiment 1
It is prepared by poly-L-lysine/Sodium Hyaluronate (PLL/HA) composite coating
(1) prepared by compound polyelectrolyte stable suspersion solution
Prepare Sodium Hyaluronate (HA, the molecular weight 200000) aqueous solution of 2mg/ml and the poly-L-lysine of 1mg/ml
(PLL, molecular weight 70000) aqueous solution；Then, by PLL aqueous solutions fast drop into isometric HA aqueous solutions, and quickly stir
Mix 1 minute, mixing speed 1000rpm, obtains PLL/HA compound suspensions；
Then, addition and the isometric absolute ethyl alcohol of PLL/HA compound suspensions, and quickly stir one with 1000rpm
Minute.Stable PLL/HA compound suspensions are finally prepared, the particle diameter of PLL/HA complex nanometer granules is 180nm,
Surface Zeta potential is -18mV.
(2) ultrasonic spraying prepares primary coating
The PLL/HA compound suspensions being prepared in (1) are passed through into ultrasonic spraying technology spray deposition to polylactic acid base
Basal surface, the frequency of ultrasonic atomizatio is 100KHz, and the time of Ultrasonic spraying is 15 minutes, you can primary painting is prepared
Layer.
(3) annealing optimization coating
The primary coating being prepared in (2) is placed in closed take-in box, is annealed using vapor, humidity control
100% is made as, temperature control is 25 DEG C, when annealing time is 1 small.The molecular chain movement induced by vapor is finally prepared into
To smooth, uniform PLL/HA compound polyelectrolytes coating, coating layer thickness is 1 μm, and thickness can be controlled by spray time.
Fig. 1 is the surface microscopic topographic of primary coating prepared by the present embodiment step (2), it can be seen from the figure that primary
There are a degree of inhomogeneities for coating.
Fig. 2 is the microscopic appearance of PLL/HA compound polyelectrolytes coating manufactured in the present embodiment, wherein, Fig. 2 (a) is
The surface microscopic topographic of PLL/HA compound polyelectrolyte coatings, Fig. 2 (b) are the transversal of PLL/HA compound polyelectrolyte coatings
Face microscopic appearance, it can be seen from the figure that the surface of coating is smooth after final annealing.
The surface roughness of PLL/HA compound polyelectrolytes coating manufactured in the present embodiment is tested, such as Fig. 3 institutes
Show, the results show that the surface roughness of coating drops to below 10nm after final annealing.
Embodiment 2
It is prepared by poly-L-lysine/Sodium Hyaluronate (PLL/HA) composite coating
(1) prepared by compound polyelectrolyte stable suspersion solution
Prepare Sodium Hyaluronate (HA, the molecular weight 200000) aqueous solution of 2mg/ml and the poly-L-lysine of 1mg/ml
(PLL, molecular weight 70000) aqueous solution；Then, by PLL aqueous solutions fast drop into isometric HA aqueous solutions, and quickly stir
Mix 1 minute, mixing speed 1000rpm, obtains PLL/HA compound suspensions；The particle diameter of PLL/HA complex nanometer granules is
210nm, surface Zeta potential are -28mV.
(2) ultrasonic spraying prepares primary coating
The PLL/HA compound suspensions being prepared in (1) are passed through into ultrasonic spraying technology spray deposition to polylactic acid base
Basal surface, the frequency of ultrasonic atomizatio is 100KHz, and the time of Ultrasonic spraying is 30 minutes, you can primary painting is prepared
Layer.
(3) annealing optimization coating
The primary coating being prepared in (2) is placed in closed take-in box, is annealed using vapor, humidity control
100% is made as, temperature control is 25 DEG C, when annealing time is 1 small.The molecular chain movement induced by vapor is finally prepared
Smooth, uniform PLL/HA compound polyelectrolyte coatings are obtained, coating layer thickness is 1 μm, and thickness can pass through spray time control
System.
Embodiment 3
It is prepared by poly-L-lysine/Sodium Hyaluronate (PLL/HA) composite coating
(1) prepared by compound polyelectrolyte stable suspersion solution
Prepare Sodium Hyaluronate (HA, the molecular weight 200000) aqueous solution of 2mg/ml and the poly-L-lysine of 1mg/ml
(PLL, molecular weight 70000) aqueous solution；Then, by PLL aqueous solutions fast drop into isometric HA aqueous solutions, and quickly stir
Mix 1 minute, mixing speed 1000rpm, obtains PLL/HA compound suspensions；
Then, addition and the isometric absolute ethyl alcohol of PLL/HA compound suspensions, and quickly stir one with 1000rpm
Minute.Stable PLL/HA compound suspensions are finally prepared, the particle diameter of PLL/HA complex nanometer granules is 180nm,
Surface Zeta potential is -18mV.
(2) spin coating prepares primary coating
The PLL/HA compound suspensions being prepared in (1) are deposited into polylactic acid base surface by spin coating method,
The rotating speed of spin coating is 3000rpm, you can primary coating is prepared.
(3) annealing optimization coating
The primary coating being prepared in (2) is placed in closed take-in box, is annealed using vapor, humidity control
100% is made as, temperature control is 25 DEG C, when annealing time is 1 small.The molecular chain movement induced by vapor is finally prepared into
To smooth, uniform PLL/HA compound polyelectrolytes coating, coating layer thickness is 1 μm, and thickness can be controlled by spray time.
Embodiment 4
It is prepared by poly-L-lysine/Sodium Hyaluronate (PLL/HA) composite coating
(1) prepared by compound polyelectrolyte stable suspersion solution
Prepare Sodium Hyaluronate (HA, the molecular weight 200000) aqueous solution of 2mg/ml and the poly-L-lysine of 1mg/ml
(PLL, molecular weight 70000) aqueous solution；Then, by PLL aqueous solutions fast drop into isometric HA aqueous solutions, and quickly stir
Mix 1 minute, mixing speed 1000rpm, obtains PLL/HA compound suspensions；
Then, addition and the isometric absolute ethyl alcohol of PLL/HA compound suspensions, and quickly stir one with 1000rpm
Minute.Stable PLL/HA compound suspensions are finally prepared, the particle diameter of PLL/HA complex nanometer granules is 180nm,
Surface Zeta potential is -18mV.
(2) spraying prepares primary coating
The PLL/HA compound suspensions being prepared in (1) are deposited into polylactic acid base by air atomizing spraying technology
Basal surface, the time of air atomizing spraying is 30 minutes, you can primary coating is prepared.
(3) annealing optimization coating
The primary coating being prepared in (2) is placed in closed take-in box, is annealed using vapor, humidity control
60% is made as, temperature control is 15 DEG C, and annealing time is 30 minutes.The molecular chain movement induced by vapor is finally prepared into
To smooth, uniform PLL/HA compound polyelectrolytes coating, coating layer thickness is 2 μm, and thickness can be controlled by spray time.
Embodiment 5
It is prepared by poly-L-lysine/Sodium Hyaluronate (PLL/HA) composite coating
(1) prepared by compound polyelectrolyte stable suspersion solution
Prepare Sodium Hyaluronate (HA, the molecular weight 200000) aqueous solution of 2mg/ml and the poly-L-lysine of 1mg/ml
(PLL, molecular weight 70000) aqueous solution；Then, by PLL aqueous solutions fast drop into isometric HA aqueous solutions, and quickly stir
Mix 1 minute, mixing speed 1000rpm, obtains PLLHA compound suspensions；
Then, addition and the isometric tetrahydrofuran of PLLHA compound suspensions, and quickly stir one with 1000rpm
Minute.Finally it is prepared stable PLLHA compound suspensions, the particle diameter of PLL/HA complex nanometer granules is 180nm, table
Face Zeta potential is -18mV.
(2) ultrasonic spraying prepares primary coating
The PLL/HA compound suspensions being prepared in (1) are passed through into ultrasonic spraying technology spray deposition to stainless base steel
Basal surface, the frequency of ultrasonic atomizatio is 100KHz, and the time of Ultrasonic spraying is 30 minutes, you can primary painting is prepared
Layer.
(3) annealing optimization coating
The primary coating being prepared in (2) is placed in closed take-in box, is annealed using vapor, humidity
Control as 100%, temperature control is 25 DEG C, and annealing time is 40 minutes.The molecular chain movement induced by vapor is finally made
Standby to obtain smooth, uniform PLL/HA compound polyelectrolyte coatings, coating layer thickness is 2 μm, and thickness can pass through spray time
Control.
Embodiment 6
It is prepared by poly-L-lysine/Sodium Hyaluronate (PLL/HA) composite coating
(1) prepared by compound polyelectrolyte stable suspersion solution
Prepare Sodium Hyaluronate (HA, the molecular weight 200000) aqueous solution of 2mg/ml and the poly-L-lysine of 1mg/ml
(PLL, molecular weight 70000) aqueous solution；Then, by PLL aqueous solutions fast drop into isometric HA aqueous solutions, and quickly stir
Mix 1 minute, mixing speed 1000rpm, obtains PLLHA compound suspensions；
Then, addition and the isometric tetrahydrofuran of PLLHA compound suspensions, and quickly stir one with 1000rpm
Minute.Finally it is prepared stable PLLHA compound suspensions, the particle diameter of PLL/HA complex nanometer granules is 180nm, table
Face Zeta potential is -18mV.
(2) spraying prepares primary coating
The PLL/HA compound suspensions being prepared in (1) are deposited into stainless base steel by air atomizing spraying technology
Basal surface, the time of air atomizing spraying is 50 minutes, you can primary coating is prepared.
(3) annealing optimization coating
The primary coating being prepared in (2) is placed in closed take-in box, is annealed using vapor, humidity control
Be made as 100%, temperature control is 25 DEG C, annealing time for 30 minutes to 1 it is small when.By vapor induce molecular chain movement most
Smooth, uniform PLL/HA compound polyelectrolyte coatings are prepared eventually, coating layer thickness is 4 μm, and thickness can pass through spraying
Time control.
Embodiment 7
It is prepared by polyethyleneimine/polyacrylic acid (PEI/PAA) composite coating
(1) prepared by compound polyelectrolyte stable suspersion solution
Prepare branched polyethylene imine (bPEI, the molecular weight 50000) aqueous solution of 1mg/ml and the polypropylene of 1mg/ml
Sour (PAA, molecular weight 100000) aqueous solution；Then, by PEI aqueous solutions fast drop into isometric PAA aqueous solutions, and
Quick stirring 1 minute, mixing speed 1000rpm, obtains PEIPAA compound suspensions；
Then, addition and the isometric absolute ethyl alcohol of PEIPAA compound suspensions, and quickly stir one with 1000rpm
Minute.Stable PEIPAA compound suspensions are finally prepared, the particle diameter of PEI/PAA complex nanometer granules is 420nm,
Surface Zeta potential is -20mV.
(2) volatilization deposition prepares primary coating
The PEI/PAA compound suspensions being prepared in (1) are added in the container containing substrate, container is heated to
80 DEG C, so as to accelerate the volatilization of solvent, finally deposit to obtain primary coating in substrate surface.
(3) annealing optimization coating
The primary coating being prepared in (2) is placed in closed take-in box, is annealed using alcohol vapor, ethanol
Partial pressure is 7.8KPa, and temperature control is 25 DEG C, when annealing time is 1 small.The molecular chain movement induced by alcohol vapor is final
It is prepared smooth, uniform PEI/PAA compound polyelectrolyte coatings, coating layer thickness is 1 μm, and when thickness can pass through spraying
Between control.
Embodiment 8
It is prepared by polyethyleneimine/polyacrylic acid (PEI/PAA) composite coating
(1) prepared by compound polyelectrolyte stable suspersion solution
Prepare branched polyethylene imine (bPEI, the molecular weight 50000) aqueous solution of 1mg/ml and the polypropylene of 1mg/ml
Sour (PAA, molecular weight 100000) aqueous solution；Then, by PEI aqueous solutions fast drop into isometric PAA aqueous solutions, and soon
Speed stirring 1 minute, mixing speed 1000rpm, obtains PEIPAA compound suspensions；
Then, addition and the isometric absolute ethyl alcohol of PEIPAA compound suspensions, and quickly stir one with 1000rpm
Minute.Stable PEIPAA compound suspensions are finally prepared, the particle diameter of PEI/PAA complex nanometer granules is 420nm,
Surface Zeta potential is -20mV.
(2) ultrasonic spraying prepares primary coating
The PEI/PAA compound suspensions being prepared in (1) are closed by ultrasonic spraying technology spray deposition to NiTi
Gold surface, the frequency of ultrasonic atomizatio is 100KHz, and the time of Ultrasonic spraying is 50 minutes, you can primary is prepared
Coating.
(3) annealing optimization coating
The primary coating being prepared in (2) is placed in closed take-in box, is annealed using alcohol vapor, ethanol
Partial pressure is 7.8KPa, and temperature control is 25 DEG C, when annealing time is 1 small.The molecular chain movement induced by alcohol vapor is final
It is prepared smooth, uniform PEI/PAA compound polyelectrolyte coatings, coating layer thickness is 1 μm, and when thickness can pass through spraying
Between control.
Embodiment 9
It is prepared by polydimethyl diallyl ammonium chloride/kayexalate (PDDA/PSS) composite coating
(1) prepared by compound polyelectrolyte stable suspersion solution
Prepare polydimethyl diallyl ammonium chloride (PDDA, the molecular weight 200000) aqueous solution and 1mg/ml of 1mg/ml
Kayexalate (PSS, molecular weight 100000) aqueous solution；Then, by PDDA aqueous solutions fast drop to isometric PSS
In aqueous solution, and quickly stir 1 minute, mixing speed 1000rpm, obtains PDDA/PSS compound suspensions；
Then, addition and the isometric absolute ethyl alcohol of PDDA/PSS compound suspensions, and quickly stirred with 1000rpm
One minute.Stable PDDA/PSS compound suspensions are finally prepared, the particle diameter of PDDA/PSS complex nanometer granules is
220nm, surface Zeta potential are -25mV.
(2) ultrasonic spraying prepares primary coating
The PDDA/PSS compound suspensions being prepared in (1) are passed through into ultrasonic spraying technology spray deposition to polyethers ether
Ketone group basal surface, the frequency of ultrasonic atomizatio is 100KHz, and the time of Ultrasonic spraying is 50 minutes, you can primary is prepared
Coating.
(3) annealing optimization coating
The primary coating being prepared in (2) is placed in closed take-in box, is annealed using toluene vapor, toluene
Vapor partial pressure is 6KPa, and temperature control is 25 DEG C, when annealing time is 1 small.By toluene vapor induce molecular chain movement most
Smooth, uniform PDDA/PSS compound polyelectrolyte coatings are prepared eventually, coating layer thickness is 1 μm, and thickness can pass through spray
Apply time control.
Embodiment 10
It is prepared by collagen/heparin sodium Hep/Col composite coatings
(1) prepared by compound polyelectrolyte stable suspersion solution
Prepare collagen (Col, the molecular weight 300000) aqueous solution of 1mg/ml and heparin sodium (Hep, the molecular weight of 1mg/ml
18000) aqueous solution；Then, by Hep aqueous solutions fast drop into isometric Col aqueous solutions, and quickly stir 1 minute, stir
It is 1000rpm to mix speed, obtains Hep/Col compound suspensions；
Then, addition and the isometric absolute ethyl alcohol of Hep/Col compound suspensions, and quickly stirred with 1000rpm
One minute.Stable Hep/Col compound suspensions are finally prepared, the particle diameter of Hep/Col complex nanometer granules is
420nm, surface Zeta potential are 25mV.
(2) ultrasonic spraying prepares primary coating
The Hep/Col compound suspensions being prepared in (1) are passed through into ultrasonic spraying technology spray deposition to polylactic acid
Substrate surface, the frequency of ultrasonic atomizatio is 100KHz, and the time of Ultrasonic spraying is 50 minutes, you can primary painting is prepared
Layer.
(3) annealing optimization coating
The primary coating being prepared in (2) is placed in closed take-in box, is annealed using vapor, humidity control
100% is made as, temperature control is 25 DEG C, when annealing time is 1 small.The molecular chain movement induced by vapor is finally prepared into
To smooth, uniform Hep/Col compound polyelectrolytes coating, the thickness of coating is 1 μm, and thickness can pass through spray time control
System.
Embodiment 11
It is prepared by nucleoprotamine/DNA (Pra/DNA) composite coating
(1) prepared by compound polyelectrolyte stable suspersion solution
Prepare 2mg/ml nucleoprotamine (Pra, molecular weight 5000) aqueous solution and 2mg/ml DNA (DNA, point
Son measures 10000) aqueous solution；Then, by Pra aqueous solutions fast drop into isometric aqueous dna, and 1 point is quickly stirred
Clock, mixing speed 1000rpm, obtains Pra/DNA compound suspensions；
Then, addition and the isometric absolute ethyl alcohol of Pra/DNA compound suspensions, and quickly stirred with 1000rpm
One minute.Stable Pra/DNA compound suspensions are finally prepared, the particle diameter of Pra/DNA complex nanometer granules is
520nm, surface Zeta potential are -30mV.
(2) ultrasonic spraying prepares primary coating
The Pra/DNA compound suspensions being prepared in (1) are passed through into ultrasonic spraying technology spray deposition to substrate nickel
Titanium alloy surface, the frequency of ultrasonic atomizatio is 100KHz, and the time of Ultrasonic spraying is 20 minutes, you can primary is prepared
Coating.
(3) annealing optimization coating
The primary coating being prepared in (2) is placed in closed take-in box, is annealed using vapor, humidity control
100% is made as, temperature control is 25 DEG C, when annealing time is 1 small.The molecular chain movement induced by vapor is finally prepared into
To smooth, uniform Pra/DNA compound polyelectrolytes coating, coating layer thickness is 1 μm, and thickness can pass through spray time control
System.
Embodiment 12
It is prepared by poly-L-lysine/Sodium Hyaluronate (PLL/HA) composite coating
(1) prepared by compound polyelectrolyte stable suspersion solution
Prepare Sodium Hyaluronate (HA, the molecular weight 300000) aqueous solution of 2mg/ml and the poly-L-lysine of 1mg/ml
(PLL, molecular weight 70000) aqueous solution；Then, by PLL aqueous solutions fast drop into HA aqueous solutions (PLL aqueous solutions and HA water
The volume ratio of solution is 1:2), and quickly stir 1 minute, mixing speed 1000rpm, obtains PLLHA compound suspensions；
Then, add volume and be the ethanol solution of PLLHA compound suspensions 50%, and 1 is quickly stirred with 1000rpm
Minute.Finally it is prepared stable PLLHA compound suspensions, the particle diameter of PLL/HA complex nanometer granules is 210nm, table
Face Zeta potential is -35mV.
(2) ultrasonic spraying prepares primary coating
The PLL/HA compound suspensions being prepared in (1) are passed through into ultrasonic spraying technology spray deposition to thermoplastic elastomehc
Property body canal surface, the frequency of ultrasonic atomizatio is 150KHz, and time of Ultrasonic spraying is 30 minutes, you can is prepared just
Level coating.
(3) annealing optimization coating
The primary coating being prepared in (2) is placed in closed take-in box, is annealed using vapor, humidity control
75% is made as, temperature control is 40 DEG C, and annealing time is 60 minutes.The molecular chain movement induced by vapor is finally prepared into
To smooth, uniform PLL/HA compound polyelectrolytes coating, coating layer thickness is 2 μm, and thickness can be controlled by spray time.
Embodiment 13
It is prepared by collagen/heparin sodium Hep/Col composite coatings
(1) prepared by compound polyelectrolyte stable suspersion solution
Prepare collagen (Col, the molecular weight 300000) aqueous solution of 1mg/ml and heparin sodium (Hep, the molecular weight of 1mg/ml
18000) aqueous solution；Then, by Hep aqueous solutions fast drop into Col aqueous solutions, the volume of Hep aqueous solutions and Col aqueous solutions
Than for 1:2, and quickly stir 1 minute and obtain compound suspension, mixing speed 1000rpm, obtains Hep/Col compounds and hangs
Supernatant liquid；
Then, add volume and be the absolute ethyl alcohol of Hep/Col compound suspensions 80%, and quickly stirred with 1000rpm
Mix 1 minute.Stable Hep/Col compound suspensions are finally prepared, the particle diameter of Hep/Col complex nanometer granules is
350nm, surface Zeta potential are 38mV.
(2) ultrasonic spraying prepares primary coating
The Hep/Col compound suspensions being prepared in (1) are passed through into ultrasonic spraying technology spray deposition to polylactic acid
Rack surface, the frequency of ultrasonic atomizatio is 100KHz, and the time of Ultrasonic spraying is 50 minutes, you can primary painting is prepared
Layer.
(3) annealing optimization coating
The primary coating being prepared in (2) is placed in closed take-in box, is annealed using vapor, humidity control
80% is made as, temperature control is 40 DEG C, when annealing time is 1 small.The molecular chain movement induced by vapor is finally prepared into
To smooth, uniform Hep/Col compound polyelectrolytes coating, the thickness of coating is 0.5 μm.
Embodiment 14
It is prepared by nucleoprotamine/DNA (Pra/DNA) composite coating
(1) prepared by compound polyelectrolyte stable suspersion solution
Prepare 2mg/ml nucleoprotamine (Pra, molecular weight 5000) aqueous solution and 1mg/ml DNA (DNA, point
Son measures 30000) aqueous solution；Then, by Pra aqueous solutions fast drop into isometric aqueous dna, and 1 point is quickly stirred
Clock, mixing speed 1000rpm, obtains Pra/DNA compound suspensions；
Then, addition and the isometric absolute ethyl alcohol of Pra/DNA compound suspensions, and quickly stirred with 1000rpm
One minute.Stable Pra/DNA compound suspensions are finally prepared, the particle diameter of Pra/DNA complex nanometer granules is
480nm, surface Zeta potential are -18mV.
(2) ultrasonic spraying prepares primary coating
The Pra/DNA compound suspensions being prepared in (1) are passed through into ultrasonic spraying technology spray deposition to substrate nickel
Titanium alloy rack surface, the frequency of ultrasonic atomizatio is 100KHz, and the time of Ultrasonic spraying is 50 minutes, you can is prepared
Primary coating.
(3) annealing optimization coating
The primary coating being prepared in (2) is placed in closed take-in box, is annealed using vapor, humidity control
100% is made as, temperature control is 37 DEG C, when annealing time is 1 small.The molecular chain movement induced by vapor is finally prepared into
To smooth, uniform Pra/DNA compound polyelectrolytes coating, coating layer thickness is 2 μm.
Comparative example 1
It is prepared by poly-L-lysine/Sodium Hyaluronate (PLL/HA) composite coating
(1) prepared by compound polyelectrolyte stable suspersion solution
Prepare Sodium Hyaluronate (HA, the molecular weight 200000) aqueous solution of 2mg/ml and the poly-L-lysine of 1mg/ml
(PLL, molecular weight 70000) aqueous solution；Then, by PLL aqueous solutions fast drop into isometric HA aqueous solutions, and quickly stir
Mix 1 minute, mixing speed 1000rpm, obtains PLLHA compound suspensions；
Then, addition and the isometric tetrahydrofuran of PLLHA compound suspensions, and quickly stir one with 1000rpm
Minute.Finally it is prepared stable PLLHA compound suspensions, the particle diameter of PLL/HA complex nanometer granules is 180nm, table
Face Zeta potential is -18mV.
(2) ultrasonic spraying prepares primary coating
The PLL/HA compound suspensions being prepared in (1) are passed through into ultrasonic spraying technology spray deposition to stainless base steel
Basal surface, the frequency of ultrasonic atomizatio is 100KHz, and the time of Ultrasonic spraying is 30 minutes, you can primary painting is prepared
Layer.
(3) annealing optimization coating
The primary coating being prepared in (2) is placed in closed take-in box, is annealed using vapor, humidity control
It is made as 60%, temperature control is 37 DEG C, and annealing time needs week age to can be only achieved the purpose of coating levelling.
Claims (8)
- A kind of 1. preparation method of compound polyelectrolyte coating, it is characterised in that including：(1) prepared by compound polyelectrolyte stable suspensionAqueous solution with positive charge polyelectrolyte and the aqueous solution with negative polyelectrolytes are mixed, obtain polyelectrolyte Stable composite suspension；(2) primary coating is preparedThe compound polyelectrolyte stable suspension that step (1) obtains is deposited into substrate material surface, obtains primary coating；(3) make annealing treatmentThe primary coating that step (2) obtains is positioned in take-in box, is handled using small molecule plasticizer steam annealing certain Time, up to the compound polyelectrolyte coating.
- 2. the preparation method of compound polyelectrolyte coating according to claim 1, it is characterised in that in step (1), band There is the concentration of the aqueous solution of positive charge polyelectrolyte and the aqueous solution with negative polyelectrolytes to control to arrive in 0.1mg/ml Between 10mg/ml.
- 3. the preparation method of compound polyelectrolyte coating according to claim 1, it is characterised in that the poly- electrolysis In matter stable composite suspension, the size of compound polyelectrolyte is 0.05~5 μm.
- 4. the preparation method of compound polyelectrolyte coating according to claim 1, it is characterised in that carry out coating deposition Before, organic solvent soluble easily in water is added in the compound polyelectrolyte stable suspension to improve the preparation of coating Efficiency, addition are the 5~200% of compound polyelectrolyte stable suspension volume.
- 5. the preparation method of compound polyelectrolyte coating according to claim 1, it is characterised in that the small molecule Plasticizer is organic molecule or water, wherein, organic molecule is ethanol, ethyl acetate, toluene or tetrahydrofuran.
- 6. the preparation method of compound polyelectrolyte coating according to claim 1, it is characterised in that the annealing is held Humidity is 50~100% in device.
- 7. the preparation method of compound polyelectrolyte coating according to claim 1, it is characterised in that the annealing is held Temperature is 0~100 DEG C in device.
- 8. the compound polyelectrolyte that a kind of method according to any one of claim 1~7 claim is prepared applies Layer, it is characterised in that the thickness of the compound polyelectrolyte coating is 0.1~100 micron.
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| CN114246992A (en) * | 2021-12-28 | 2022-03-29 | 湖南华耀百奥医疗科技有限公司 | Degradable intravascular stent with slow-release drug coating and preparation method thereof |
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| CN102597078A (en) * | 2009-08-20 | 2012-07-18 | 巴斯夫欧洲公司 | Use of polyelectrolyte complexes as plasticizer barriers |
| WO2015119891A1 (en) * | 2014-02-04 | 2015-08-13 | Florida State University Research Foundation, Inc. | Rough polyelectrolyte complex coatings and methods of forming |
| CN105056767A (en) * | 2015-08-14 | 2015-11-18 | 浙江大学 | Preparation method for positively charged polyelectrolyte complex homogeneous pervaporation membrane |
| CN106770576A (en) * | 2017-01-20 | 2017-05-31 | 长沙理工大学 | A kind of method that one-step method prepares polyelectrolyte compound film electrode |
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| CN102597078A (en) * | 2009-08-20 | 2012-07-18 | 巴斯夫欧洲公司 | Use of polyelectrolyte complexes as plasticizer barriers |
| WO2015119891A1 (en) * | 2014-02-04 | 2015-08-13 | Florida State University Research Foundation, Inc. | Rough polyelectrolyte complex coatings and methods of forming |
| CN105056767A (en) * | 2015-08-14 | 2015-11-18 | 浙江大学 | Preparation method for positively charged polyelectrolyte complex homogeneous pervaporation membrane |
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