CN108485512B - A kind of patterning porous polymer coating and preparation method thereof - Google Patents
A kind of patterning porous polymer coating and preparation method thereof Download PDFInfo
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- C09D105/00—Coating compositions based on polysaccharides or on their derivatives, not provided for in groups C09D101/00 or C09D103/00
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- C09D139/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Coating compositions based on derivatives of such polymers
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Abstract
The invention discloses a kind of patterning porous polymer coating, preparation method specifically includes that (1) by being chemically modified to obtain with the active modified polyanion of photo-crosslinking；(2) polycation is obtained into the loose coating material of rough surface, internal structure by layer assembly with having the active modified polyanion of photo-crosslinking；(3) coating by being placed in wet environment or with the smooth densification of water contact preparation；(4) ultraviolet light cross-linking of regioselectivity is carried out to coating by being carved with the photomask of certain pattern；(5) coating is placed in hydrochloric acid solution, realizes region pore to get the patterning porous polymer coating.The present invention has the characteristics that environmental-friendly, easy to operate, pore region controllable precise, can be used for preparing the selective pore coating of different shape, various sizes of region, and then realize the area load to functional moleculars such as dyestuff, drug molecule, quantum dots.
Description
Technical field
The present invention relates to functional coating fields, and in particular to a kind of patterning porous polymer coating and preparation method thereof.
Background technique
There is unique complexing and mutually separation row by the weak polyelectrolyte multilayer film that layer-by-layer is prepared
To carry out sour processing to it, it can be achieved that there is the preparation of the polymer coating of microcellular structure, this gives polyelectrolyte multilayer film
Application potential in fields such as ultrafiltration membrane, flocculant, encapsulation cell, drug deliveries.However, existing polyelectrolyte coating pore
Technology can only realize pore of the entire film layer without selection, be unable to satisfy such as photoelectric field area load semiconductor molecule, biology doctor
It is required with field cell patterning preparation etc..Therefore, the polyelectrolyte multilayer film with regioselectivity pore ability is badly in need of quilt
Preparation.
By the microphase-separated of control part, the preparation of regioselectivity pore coating material is realized, although its importance
It is self-evident but at present still without corresponding example.
Summary of the invention
The present invention provides a kind of patterning porous polymer coatings and preparation method thereof.By being introduced in coating material
Photo-crosslinking group, and the dynamic characteristic of coating itself is combined, realize local microphase-separated, to different shape, different sizes
Region realize selective pore to get patterning porous polymer coating.
The technical solution adopted by the present invention is as follows:
A kind of preparation method patterning porous polymer coating, comprising the following steps:
(1) polyanion and 4- nitrine anilinechloride are dissolved in the water by a certain percentage, in 1- (3- dimethylamino third
Base) catalysis of -3- ethyl carbodiimide lower reaction 12~72 hours, it obtains with the active modified polyanion of photo-crosslinking；
(2) it is dissolved in the water, is configured to certain by polycation and with the active modified polyanion of photo-crosslinking respectively
The solution of concentration and certain pH value；
(3) substrate impregnated to 1 in polycation aqueous solution~after sixty minutes, substrate is taken out；It places into and is handed over light
Join in active modified polyanion aqueous solution and impregnate 1~60 minute, substrate is taken out, to complete the painting of a deposition cycle
Layer preparation；It repeats the above steps, the preparation of the coating of multiple deposition cycles is completed in substrate, to obtain rough surface, interior
The coating material of portion's short texture；
(4) coating material that step (3) obtains is placed in wet environment or is contacted with water, obtain the coating of smooth densification
Material；
(5) photomask for being carved with certain pattern is covered on the coating material surface that step (4) obtains, after ultraviolet light
Cause partial cross-linking reaction；
(6) coating after partial cross-linking is placed in hydrochloric acid solution impregnate 1~60 minute it is more to get the patterning
Pore polymer coating.
In step (1), the molar ratio that adds of polyanion and 4- nitrine anilinechloride is 10:1~9, polyanion warp
4- nitrine anilinechloride is modified to have photolytic activity, and the covalent cross-linking with polycation can be achieved under ultraviolet lighting, reduce
Molecular chain movement ability.
In step (1), the concentration of polyanion in aqueous solution is 10~1000mg/mL, 1- (3- dimethylamino-propyl)-
The concentration of 3- ethyl carbodiimide is 10~200mg/mL, and reaction temperature is 0~30 DEG C.
In the present invention, the polyanion is polyacrylic acid, alginic acid, hyaluronic acid, kayexalate, heparin
At least one of sodium, milt DNA and polymethylacrylic acid.Preferably, the polyanion is polyacrylic acid, polyacrylic acid
Mole be 50,000~500,000；Further preferably, the mole of the polyacrylic acid be 100,000~
200,000。
In the present invention, the polycation is polyethyleneimine, polyallylamine hydrochloride, gelatin, polydiene propyl two
At least one of methylamine hydrochloride, nucleoprotamine, chitosan and polylysine.Preferably, the polycation is poly-
Aziridine, the mole of polyethyleneimine are 1,000~100,000, show good chain in an assembling process
Locomitivity；Further preferably, the mole of the polyethyleneimine is 20,000~50,000, this mole model
Polyethyleneimine strand in enclosing has better chain movement ability and assembly behavior.
In step (2), the concentration of polycation aqueous solution is 0.1~100mg/mL, and pH value is 8~11；With photo-crosslinking
The concentration of active modified polyanion aqueous solution is 0.1~100mg/mL, and pH value is 1~7.
The substrate is at least one of silicon wafer, glass, metal, quartz, ceramics, calcirm-fluoride and plastics.Preferably,
The substrate is silicon wafer, can provide deeper background colour, enhances the light and shade difference between region.
Preferably, it in step (3), after every time taking out substrate, is rinsed with water drying and carries out next step again.
In step (3), repeating said steps 5~500 times, i.e., the coating of 5~500 deposition cycles is completed in substrate
Preparation.
In step (4), the relative humidity of the wet environment is 70~100%, and the processing time in wet environment is 1
~72 hours；Preferably, the relative humidity of the wet environment is 90~100%, the processing time in wet environment is
10~24 hours.
In step (4), contacted with water refer to the coating material for obtaining step (3) be immersed in pH value be 1~12 water in or
The water that person is 1~12 to coating material surface spray pH value, processing time are 1~72 hour.
In the present invention, become the principle of smooth dense coating in coating preparation process by rough surface, short texture: in tide
Wet environment or with water contact process, hydrone increases polymer molecular chain flexibility, while moisture as a kind of plasticizer
The electrostatic screen effect that son has polyelectrolyte is so that polymer molecular chain locomitivity further increases.Therefore, polymer
Strand is easily reset, and so that the topology of coating surface and internal defect structure is disappeared, is obtained the film of smooth densification
Layer.
In step (5), the intensity of ultraviolet light is 1~10000 μ W/cm2, the irradiation time of ultraviolet light is 1~10000 second.
In step (6), the pH value of hydrochloric acid solution is 1~5.
In the present invention, the coating after partial cross-linking realizes the principle of regioselectivity pore in hydrochloric acid solution: uncrosslinked
The compound polyelectrolyte in region in an acidic solution, is easy to happen microphase-separated, and coat inside is caused hole occur.And it is crosslinked
Since the presence of photo-crosslinking group makes to form covalent cross-linking between molecule, molecular chain movement is limited and maintains original knot in region
Microphase-separated does not occur for structure, therefore, realizes the selective pore in uncrosslinked region to get patterning porous polymer coating is arrived.
It is a further object of the present invention to provide a kind of patterning porous polymer coatings prepared by the above method.
Compared with prior art, the present invention has the following advantages and effects:
The present invention controls the microphase-separated behavior of coating in acid condition using the method for selective light crosslinking, thus real
The regioselectivity pore of existing coating, the process have the characteristics that environmental-friendly, easy to operate, pore region controllable precise, can
For different shape, the preparation of the selective pore coating in various sizes of region, and then can be used for dyestuff, drug point
The area load of the functional moleculars such as son, quantum dot has a wide range of applications potentiality in chemistry, biology, Material Field.
Detailed description of the invention
Fig. 1 is polyethyleneimine/modified polypropene before the selectivity pore of generation area and after pore in embodiment 1
The scanning electron microscope (SEM) photograph on acid coated surface；
Fig. 2 is that various sizes of band array realizes the polyallylamine obtained after regioselectivity pore in embodiment 2
Hydrochloride/modified polyacrylic acid coating surface scanning electron microscope (SEM) photograph；
Fig. 3 is polyethyleneimine/modified hyaluronic acid coating surface that the pore of circular array region is realized in embodiment 3
Scanning electron microscope (SEM) photograph；
Fig. 4 is polyallylamine hydrochloride/modification alginic acid painting that the pore of square array column region is realized in embodiment 4
The scanning electron microscope (SEM) photograph of layer；
Fig. 5 is to realize that diallyl dimethyl amine hydrochlorate/modification of triangular array region pore is poly- in embodiment 5
The scanning electron microscope (SEM) photograph of sodium styrene sulfonate coating surface；
Fig. 6 is polydiene propyl before adsorpting dye molecule and after adsorpting dye molecule after banded zone pore in embodiment 7
Dimethylamine hydrochloride/modified heparin sodium coating surface shows fluorescent microscopy images；
Fig. 7 is the polyene before adsorbing quantum dot in embodiment 8 after banded zone pore and after absorption CdSe/ZnS quantum dot
Propylamine hydrochloride/modified hyaluronic acid coating surface shows fluorescent microscopy images.
Specific embodiment
The present invention is further illustrated below in conjunction with specific example.
Embodiment 1
(1) by polyacrylic acid and 4- nitrine anilinechloride, 8:1 is dissolved in ultrapure water in molar ratio, in 1- (3- diformazan
Aminopropyl) the lower reaction of -3- ethyl carbodiimide catalysis 24 hours, in system, the concentration of polyacrylic acid is 6mg/mL, 1- (3-
Dimethylamino-propyl) -3- ethyl carbodiimide concentration be 300mg/mL, obtain with the active modified polypropene of photo-crosslinking
Acid；
(2) the silicon wafer substrate cleaned up is impregnated 20 points in aq. polyethyleneimine (4mg/mL, pH value 9.0)
Zhong Hou cleans drying with ultrapure water；Place into that (4mg/mL, pH value are with the active modified polypropene aqueous acid of photo-crosslinking
4.0) it is impregnated in after twenty minutes, cleans drying with ultrapure water, rough surface is obtained after the above-mentioned two step 30 time of repetition, structure is dredged
The coating material of pine；
(3) step (2) obtained coating material is placed in the environment that relative humidity is 100% and is handled 24 hours, obtained
To the coating of smooth densification；
(4) photomask for being carved with multiple triangle patterns is placed in the coating surface that step (3) obtains, in 500 μ W/
cm2Initiation partial cross-linking reaction in 1800 seconds is irradiated under ultraviolet light；
(5) coating material after partial cross-linking is placed in the hydrochloric acid solution that pH is 2.0 and is impregnated 40 minutes, realize region
Selective pore is to get the patterning porous polymer coating (polyethyleneimine/modified polypropene is acid coated).
Fig. 1 is in the present embodiment before the selectivity pore of generation area and polyethyleneimine/modification poly- third after pore
The scanning electron microscope (SEM) photograph of olefin(e) acid coating surface.Observing Fig. 1 can find, polyethyleneimine/poly- third for the smooth densification that step (3) obtains
Olefin(e) acid coating is changed into the coating for realizing regioselectivity pore, and topology has significance difference between coating surface different zones
It is anisotropic.Uncrosslinked region obtains loose hole configurations, and cross-linked areas still maintains planarization and compactness.
Embodiment 2
(1) in aqueous solution by the 8:1 dissolution in molar ratio of polyacrylic acid and 4- nitrine anilinechloride, in 1- (3- diformazan
Aminopropyl) the lower reaction of -3- ethyl carbodiimide catalysis 48 hours, in system, the concentration of polyacrylic acid is 10mg/mL, 1- (3-
Dimethylamino-propyl) -3- ethyl carbodiimide concentration be 200mg/mL, obtain with the active modified polypropene of photo-crosslinking
Acid；
(2) leaching in polyallylamine hydrochloride aqueous solution (2mg/mL, pH value 9.5) by the silicon wafer substrate cleaned up
Bubble cleans drying after twenty minutes, with ultrapure water；Place into photo-crosslinking active modified polypropene aqueous acid (3mg/mL, pH value
It is impregnated 20 minutes to be 4.0) middle, cleans drying with ultrapure water.Rough surface, short texture are obtained after repeating the above steps 80 times
Coating material；
(3) step (2) obtained coating material is placed in the environment that relative humidity is 100% and is handled 24 hours, obtained
To the coating of smooth densification；
(4) it will be carved with various sizes of band photomask respectively and be placed in the coating surface that step (3) obtains, in 500 μ W/
cm2Initiation partial cross-linking reaction in 600 seconds is irradiated under ultraviolet light；
(5) coating material after partial cross-linking is placed in the hydrochloric acid solution that pH is 3.0 and is impregnated 30 minutes, realize region
Selective pore is to get the patterning porous polymer coating (polyallylamine hydrochloride/modified polypropene is acid coated).
Fig. 2 is that various sizes of band array realizes the polyallylamine obtained after regioselectivity pore in the present embodiment
Hydrochloride/modified polyacrylic acid coating surface scanning electron microscope (SEM) photograph.Observing Fig. 2 can find, the polyene of obtained smooth densification
Propylamine hydrochloride/polyacrylic acid coating can not only realize regional choice pore, while can be by using the light of different pattern
Exposure mask realizes pore area size and reconfigurable.
Embodiment 3
(1) in aqueous solution by the 8:1 dissolution in molar ratio of hyaluronic acid and 4- nitrine anilinechloride, in 1- (3- diformazan
Aminopropyl) the lower reaction of -3- ethyl carbodiimide catalysis 48 hours, in system, the concentration of hyaluronic acid is 8mg/mL, 1- (3-
Dimethylamino-propyl) -3- ethyl carbodiimide concentration be 500mg/mL, obtain with the active modified hyalomitome of photo-crosslinking
Acid；
(2) the silicon wafer substrate cleaned up is impregnated 30 in aq. polyethyleneimine (8mg/mL, pH value 10.0)
After minute, is cleaned up and dried up with ultrapure water；It places into the active modified hyaluronic acid aqueous solution (10mg/ of photo-crosslinking
ML, pH value 1.0) after middle immersion 30 minutes, is cleaned up and dried up with ultrapure water.Table is obtained after repeating the above steps 100 times
Face is coarse, short texture coating；
(3) step (2) obtained coating material is placed in water processing 72 hours, obtains the coating of smooth densification；
(4) photomask for being carved with circular array is placed in the coating surface that step (3) obtains, in 1000 μ W/cm2It is ultraviolet
Initiation partial cross-linking reaction in 600 seconds is irradiated under light；
(5) coating material after partial cross-linking is placed in the hydrochloric acid solution that pH is 2.0 and is impregnated 60 minutes, realize region
Selective pore is to get the patterning porous polymer coating (polyethyleneimine/modified hyaluronic acid coating).
Fig. 3 is polyethyleneimine/modified hyaluronic acid coating surface that the pore of circular array region is realized in the present embodiment
Scanning electron microscope (SEM) photograph.Observation Fig. 3 can have found that the circular array region not being crosslinked forms hole configurations, and carries out photo-crosslinking
Region maintain profile pattern and compactness.
Embodiment 4
(1) by alginic acid and 4- nitrine anilinechloride, 10:1 is dissolved in water in molar ratio, in 1- (3- dimethylamino third
Base) the lower reaction of -3- ethyl carbodiimide catalysis 50 hours, in system, the concentration of alginic acid is 4mg/mL, 1- (3- dimethylamino
Propyl) -3- ethyl carbodiimide concentration be 200mg/mL, obtain with the active modified alginic acid of photo-crosslinking；
(2) leaching in polyallylamine hydrochloride aqueous solution (5mg/mL, pH value 9.0) by the silicon wafer substrate cleaned up
Bubble cleans drying after ten minutes, with ultrapure water；It places into photo-crosslinking active modified seaweed aqueous acid (5mg/mL, pH
Value is impregnated after ten minutes to be 3.0) middle, cleans drying with ultrapure water.Rough surface is obtained after repeating the above steps 50 times, structure is dredged
The coating material of pine；
(3) the obtained painting of step (2) is placed in the environment that relative humidity is 100% and is handled 24 hours, put down
The coating of whole densification；
(4) photomask of quadrate array is placed in the coating surface that step (3) obtains, in 200 μ W/cm2Ultraviolet light
Lower irradiation initiation partial cross-linking reaction in 2400 seconds；
(5) coating material after partial cross-linking is placed in the hydrochloric acid solution that pH is 3.0 and is impregnated 30 minutes, realize region
Selective pore is to get the patterning porous polymer coating (polyallylamine hydrochloride/modification seaweed is acid coated).
Fig. 4 is to realize that polyallylamine hydrochloride/modification alginic acid of square array column region pore applies in the present embodiment
Layer.Observation Fig. 4 can have found that the square array column region not being crosslinked forms apparent hole configurations, and carries out photo-crosslinking
Region maintains smooth and compactness.
Embodiment 5
(1) by kayexalate and 4- nitrine anilinechloride, 7:1 is dissolved in water in molar ratio, in 1- (3- bis-
Methylaminopropyl) the lower reaction of -3- ethyl carbodiimide catalysis 48 hours, in system, the concentration of kayexalate is 10mg/
The concentration of mL, 1- (3- dimethylamino-propyl) -3- ethyl carbodiimide is 400mg/mL, is obtained with the active modification of photo-crosslinking
Kayexalate；
(2) by the silicon wafer substrate cleaned up, in diallyl dimethyl amine hydrochlorate aqueous solution, (8mg/mL, pH value are
10.0) it after being impregnated 30 minutes in, is cleaned up and is dried up with ultrapure water；It places into the active modified polystyrene of photo-crosslinking
After being impregnated 30 minutes in the aqueous solution (10mg/mL, pH value 1.0) of sodium sulfonate, is cleaned up and dried up with ultrapure water.In repetition
The coating of rough surface, short texture is obtained after stating step 100 time；
(3) the obtained painting of step (2) is placed in the environment that relative humidity is 100% and is handled 72 hours, put down
The coating of whole densification；
(4) photomask of triangular array is placed in the coating surface that step (3) obtains, in 1000 μ W/cm2Ultraviolet light
Lower irradiation initiation partial cross-linking reaction in 600 seconds；
(5) coating material after partial cross-linking is placed in the hydrochloric acid solution that pH is 4.0 and is impregnated 30 minutes, realize region
Selective pore is to get patterning porous polymer coating (the diallyl dimethyl amine hydrochlorate/modified polyphenyl second
Alkene sodium sulfonate coating).
Fig. 5 is diallyl dimethyl amine hydrochlorate/modification that the pore of triangular array region is realized in the present embodiment
The scanning electron microscope (SEM) photograph of kayexalate coating surface.Observing Fig. 5 can find, the triangular array region shape not being crosslinked
At hole configurations, and the region for carrying out photo-crosslinking maintains profile pattern and compactness.
Embodiment 6
(1) by milt DNA and 4- nitrine anilinechloride, 10:1 is dissolved in water in molar ratio, in 1- (3- dimethylamino
Propyl) the lower reaction of -3- ethyl carbodiimide catalysis 48 hours, in system, the concentration of milt DNA is 10mg/mL, 1- (3- diformazan
Aminopropyl) -3- ethyl carbodiimide concentration be 500mg/mL, obtain with the active modified milt DNA of photo-crosslinking；
(2) the silicon wafer substrate cleaned up is impregnated 40 minutes in nucleoprotamine aqueous solution (8mg/mL, pH value 8.0)
Afterwards, it is cleaned up and is dried up with ultrapure water；Place into the active modified milt DNA of photo-crosslinking aqueous solution (10mg/mL,
PH value is that 4.0) middle immersion after forty minutes, is cleaned up and dried up with ultrapure water.It is thick that surface is obtained after repeating the above steps 200 times
Rough, short texture coating；
(3) step (2) obtained coating is placed in water processing 48 hours, obtains the coating of smooth densification；
(4) photomask for being carved with band array is placed in the coating surface that step (3) obtains, in 300 μ W/cm2It is ultraviolet
Initiation partial cross-linking reaction in 1800 seconds is irradiated under light；
(5) coating material after partial cross-linking is placed in the hydrochloric acid solution that pH is 4.0 and is impregnated 30 minutes, realize region
Selective pore is to get the patterning porous polymer coating.
Embodiment 7
(1) by heparin sodium and 4- nitrine anilinechloride, 8:1 is dissolved in ultrapure water in molar ratio, in 1- (3- diformazan ammonia
Base propyl) the lower reaction of -3- ethyl carbodiimide catalysis 24 hours, in system, the concentration of heparin sodium is 12mg/mL, 1- (3- diformazan
Aminopropyl) -3- ethyl carbodiimide concentration be 300mg/mL, obtain with the active modified heparin sodium of photo-crosslinking；
(2) by the silicon wafer substrate cleaned up, in diallyl dimethyl amine hydrochlorate aqueous solution, (4mg/mL, pH value are
9.0) it is impregnated in after twenty minutes, cleans drying with ultrapure water；It places into the active modified heparin sodium water solution of photo-crosslinking
It is impregnated in (4mg/mL, pH value 4.0) after twenty minutes, cleans drying with ultrapure water, obtained after repeating above-mentioned two step 30 time
The coating material of rough surface, short texture；
(3) the obtained painting of step (2) is placed in the environment that relative humidity is 100% and is handled 24 hours, put down
The coating of whole densification；
(4) photomask for being carved with band array is placed in the coating surface that step (3) obtains, in 1000 μ W/cm2It is ultraviolet
Initiation partial cross-linking reaction in 1800 seconds is irradiated under light；
(5) coating material after partial cross-linking is placed in the hydrochloric acid solution that pH is 3.0 and is impregnated 40 minutes, realize region
Selective pore is to get patterning porous polymer coating (the diallyl dimethyl amine hydrochlorate/modified heparin sodium
Coating)；
(6) coating after realization regional choice pore that step (5) obtains is immersed in 100 μ g/mL rhodamine B solutions
It is taken out after 30 minutes, with the coating dried up after ultrapure water to get area load dye molecule.
Fig. 6 is polydiene propyl before adsorpting dye molecule and after adsorpting dye molecule after banded zone pore in the present embodiment
Dimethylamine hydrochloride/modified heparin sodium coating surface shows fluorescent microscopy images.Observing Fig. 6 can find, the item in uncrosslinked region
It is formed after hole with array region, it can be achieved that the absorption of dye molecule, color occurs under fluorescence microscope；And carry out photo-crosslinking
Afterwards in the film layer area of smooth densification can not adsorpting dye molecule realize area that is, on the basis of regioselectivity pore
The absorption of domain dye molecule.
Embodiment 8
(1) by hyaluronic acid and 4- nitrine anilinechloride, 3:1 is dissolved in ultrapure water in molar ratio, in 1- (3- diformazan
Aminopropyl) the lower reaction of -3- ethyl carbodiimide catalysis 72 hours, in system, the concentration of hyaluronic acid is 10mg/mL, 1- (3-
Dimethylamino-propyl) -3- ethyl carbodiimide concentration be 500mg/mL, obtain with the active modified hyalomitome of photo-crosslinking
Acid；
(2) leaching in polyallylamine hydrochloride aqueous solution (6mg/mL, pH value 9.0) by the silicon wafer substrate cleaned up
Bubble cleans drying after 30 minutes, with ultrapure water；Place into the active modified hyaluronic acid aqueous solution of photo-crosslinking (12mg/mL,
After pH value is 3.0) middle immersion 30 minutes, drying is cleaned with ultrapure water, it is thick to obtain surface after the above-mentioned two step 100 time of repetition
Rough, short texture coating material；
(3) step (2) obtained coating material is placed in water processing 24 hours, obtains the coating of smooth densification；
(4) photomask for being carved with band array is placed in the coating surface that step (3) obtains, in 1000 μ W/cm2It is ultraviolet
Initiation partial cross-linking reaction in 1800 seconds is irradiated under light；
(5) coating material after partial cross-linking is placed in the hydrochloric acid solution that pH is 3.0 and is impregnated 30 minutes, realize region
Selective pore is to get the patterning porous polymer coating (polyallylamine hydrochloride/modified hyaluronic acid coating)；
(6) painting after pore that step (5) obtains is placed on the CdSe/ZnS quantum dot solution that concentration is 200 μ g/mL
It is middle to impregnate 30 minutes, obtain the coating of area load quantum dot.
Fig. 7 is the polyallyl amine salt before adsorbing quantum dot in the present embodiment after banded zone pore and after absorption quantum dot
Hydrochlorate/modified hyaluronic acid coating surface shows fluorescent microscopy images.Observing Fig. 7 can find, the band array area in uncrosslinked region
Domain is formed after hole, it can be achieved that the load of quantum dot, excites fluorescence under fluorescence microscope；And carry out smooth densification after photo-crosslinking
Film layer area in can not load quantum dot, i.e., on the basis of regioselectivity pore, realize the negative of region quantum dot
It carries.
Claims (7)
1. a kind of preparation method for patterning porous polymer coating, which comprises the following steps:
(1) polyanion and 4- nitrine anilinechloride are dissolved in the water by a certain percentage, in 1- (3- dimethylamino-propyl)-
It the catalysis of 3- ethyl carbodiimide lower reaction 12~72 hours, obtains with the active modified polyanion of photo-crosslinking；
(2) it is dissolved in the water respectively by polycation and with the active modified polyanion of photo-crosslinking, is configured to a certain concentration
With the solution of certain pH value；
(3) substrate impregnated to 1 in polycation aqueous solution~after sixty minutes, substrate is taken out；It places into living with photo-crosslinking
Property modification polyanion aqueous solution in impregnate 1~60 minute, substrate is taken out, thus complete a deposition cycle coating system
It is standby；It repeats the above steps, the preparation of the coating of multiple deposition cycles is completed in substrate, to obtain rough surface, internal junction
The loose coating material of structure；
(4) coating material that step (3) obtains is placed in wet environment or is contacted with water, obtain the coating material of smooth densification
Material；
(5) photomask for being carved with certain pattern is covered on the coating material surface that step (4) obtains, caused after ultraviolet light
Partial cross-linking reaction；
(6) coating after partial cross-linking is placed in impregnate in hydrochloric acid solution 1~60 minute and is gathered to get the patterning is porous
Close object coating；
In step (1), the molar ratio that adds of polyanion and 4- nitrine anilinechloride is 10:1~9；
The polyanion is polyacrylic acid, alginic acid, hyaluronic acid, kayexalate, heparin sodium, milt DNA and gathers
At least one of methacrylic acid；
The polycation be polyethyleneimine, polyallylamine hydrochloride, gelatin, diallyl dimethyl amine hydrochlorate,
At least one of nucleoprotamine, chitosan and polylysine.
2. it is according to claim 1 patterning porous polymer coating preparation method, which is characterized in that it is described it is poly- yin from
Son is polyacrylic acid, and the mole of polyacrylic acid is 50,000~500,000.
3. it is according to claim 1 patterning porous polymer coating preparation method, which is characterized in that it is described it is poly- sun from
Son is polyethyleneimine, and the mole of polyethyleneimine is 1,000~100,000.
4. the preparation method of patterning porous polymer coating according to claim 1, which is characterized in that in step (4),
The relative humidity of the wet environment is 70~100%, and the processing time in wet environment is 1~72 hour；It is contacted with water
Refer to by the coating material that step (3) obtains be immersed in the water that pH value is 1~12 or to coating material surface spray pH value be 1~
12 water, processing time are 1~72 hour.
5. the preparation method of patterning porous polymer coating according to claim 1, which is characterized in that in step (5),
The intensity of ultraviolet light is 1~10000 μ W/cm2, and the irradiation time of ultraviolet light is 1~10000 second.
6. the preparation method of patterning porous polymer coating according to claim 1, which is characterized in that in step (6),
The pH value of hydrochloric acid solution is 1~5.
7. a kind of patterning porous polymer coating, which is characterized in that prepared by the described in any item methods of claim 1~6
It obtains.
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| CN112457518B (en) * | 2020-11-03 | 2022-11-25 | 浙江理工大学 | Laser foaming polyelectrolyte film and regional pore-forming process thereof |
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