CN108485512A - 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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- CN108485512A CN108485512A CN201810213280.2A CN201810213280A CN108485512A CN 108485512 A CN108485512 A CN 108485512A CN 201810213280 A CN201810213280 A CN 201810213280A CN 108485512 A CN108485512 A CN 108485512A
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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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- 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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- C09D125/00—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 an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
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- C09D133/00—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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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 includes mainly：(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 with the active modified polyanion of photo-crosslinking by layer assembly；(3) coating by being positioned over 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 different shape, various sizes of region selective pore coating, and then realize to the area loads of the functional moleculars such as dyestuff, drug molecule, quantum dot.
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 technology
There is unique complexing and phase 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, cannot be satisfied such as photoelectric field area load semiconductor molecule, biology doctor
With requirements such as field cell patterning preparations.Therefore, the polyelectrolyte multilayer film with regioselectivity pore ability is badly in need of quilt
It prepares.
By controlling the microphase-separated of part, the preparation of regioselectivity pore coating material is realized, although its importance
It is self-evident but at present still without corresponding example.
Invention content
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, the local microphase-separated of regulation and control is realized, 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 of patterning porous polymer coating, includes the following steps：
(1) polyanion and 4- nitrine anilinechloride are dissolved in the water by a certain percentage, in 1- (3- dimethylaminos third
Base) the lower reaction of -3- ethyl carbodiimides catalysis 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
It is prepared by layer；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 positioned over wet environment or is contacted with water, obtain the coating of smooth densification
Material；
(5) photomask for being carved with certain pattern is covered in the coating material surface that step (4) obtains, after ultraviolet light
Cause partial cross-linking reaction；
(6) coating after partial cross-linking is positioned 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 anilinechlorides is 10:1~9, polyanion warp
4- nitrine anilinechlorides are 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), polyanion a concentration of 10~1000mg/mL in aqueous solution, 1- (3- dimethylamino-propyls)-
A concentration of 10~200mg/mL of 3- ethyl carbodiimides, reaction temperature are 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-
The mole of aziridine, polyethyleneimine is 1,000~100,000, shows 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), a concentration of 0.1~100mg/mL of polycation aqueous solution, pH value is 8~11；With photo-crosslinking
A concentration of 0.1~100mg/mL of active modified polyanion aqueous solution, pH value are 1~7.
The substrate is at least one of silicon chip, glass, metal, quartz, ceramics, calcirm-fluoride and plastics.Preferably,
The substrate is silicon chip, 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 complete the coating of 5~500 deposition cycles that is, in substrate
It prepares.
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 by the coating material that step (3) obtains 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 compliance, while moisture as a kind of plasticizer
Son makes polymer molecular chain locomitivity further increase the electrostatic screen effect that polyelectrolyte has.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：It is 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, realize the selective pore in uncrosslinked region to get to patterning porous polymer coating.
It is a further object of the present invention to provide a kind of patterning porous polymer coatings being prepared by the above method.
Compared with prior art, the present invention has the following advantages and effects：
Microphase-separated behavior of the present invention using the crosslinked method control coating of selective light in acid condition, to 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.
Description of the drawings
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
The scanning electron microscope (SEM) photograph of hydrochloride/modified polyacrylic acid coating surface；
Fig. 3 is polyethyleneimine/modified hyaluronic acid coating surface that circular array region pore is realized in embodiment 3
Scanning electron microscope (SEM) photograph；
Fig. 4 is the painting for polyallylamine hydrochloride/modification alginic acid that square array column region pore 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
The shows fluorescent microscopy images of dimethylamine hydrochloride/modified heparin sodium coating surface；
Fig. 7 is the polyene after banded zone pore before absorption quantum dot and after absorption CdSe/ZnS quantum dots in embodiment 8
The shows fluorescent microscopy images of propylamine hydrochloride/modified hyaluronic acid coating surface.
Specific implementation mode
It is further illustrated the present invention below in conjunction with specific example.
Embodiment 1
(1) by polyacrylic acid and 4- nitrine anilinechloride in molar ratio 8:1 is dissolved in ultra-pure water, in 1- (3- diformazans
Aminopropyl) the lower reaction of -3- ethyl carbodiimides catalysis 24 hours, in system, a concentration of 6mg/mL of polyacrylic acid, 1- (3-
Dimethylamino-propyl) -3- ethyl carbodiimides a concentration of 300mg/mL, obtain with the active modified polypropene of photo-crosslinking
Acid；
(2) the silicon chip substrate cleaned up is impregnated 20 points in aq. polyethyleneimine (4mg/mL, pH value 9.0)
Zhong Hou cleans drying with ultra-pure 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 ultra-pure water, rough surface is obtained after repetition above-mentioned two step 30 time, 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 positioned over the coating surface that step (3) obtains, in 500 μ W/
cm2It is irradiated under ultraviolet light and causes within 1800 seconds partial cross-linking reaction；
(5) coating material after partial cross-linking is positioned 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.Observation chart 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 pore space structure, and cross-linked areas still maintains planarization and compactness.
Embodiment 2
(1) by polyacrylic acid and 4- nitrine anilinechloride in molar ratio 8:1 dissolves in aqueous solution, in 1- (3- diformazans
Aminopropyl) the lower reaction of -3- ethyl carbodiimides catalysis 48 hours, in system, a concentration of 10mg/mL of polyacrylic acid, 1- (3-
Dimethylamino-propyl) -3- ethyl carbodiimides a concentration of 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 chip substrate cleaned up
Bubble cleans drying after twenty minutes, with ultra-pure water；Place into photo-crosslinking active modified polypropene aqueous acid (3mg/mL, pH value
It is impregnated 20 minutes to be 4.0) middle, drying is cleaned with ultra-pure 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 positioned over the coating surface that step (3) obtains, in 500 μ W/
cm2It is irradiated under ultraviolet light and causes within 600 seconds partial cross-linking reaction；
(5) coating material after partial cross-linking is positioned 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
The scanning electron microscope (SEM) photograph of hydrochloride/modified polyacrylic acid coating surface.Observation chart 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
Mask realizes pore area size and reconfigurable.
Embodiment 3
(1) by hyaluronic acid and 4- nitrine anilinechloride in molar ratio 8:1 dissolves in aqueous solution, in 1- (3- diformazans
Aminopropyl) the lower reaction of -3- ethyl carbodiimides catalysis 48 hours, in system, a concentration of 8mg/mL of hyaluronic acid, 1- (3-
Dimethylamino-propyl) -3- ethyl carbodiimides a concentration of 500mg/mL, obtain with the active modified hyalomitome of photo-crosslinking
Acid；
(2) the silicon chip substrate cleaned up is impregnated 30 in aq. polyethyleneimine (8mg/mL, pH value 10.0)
After minute, is cleaned up and dried up with ultra-pure water；It places into the active modified hyaluronic acid aqueous solution (10mg/ of photo-crosslinking
ML, pH value 1.0) in impregnate 30 minutes after, cleaned up and dried up with ultra-pure 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 positioned over the coating surface that step (3) obtains, in 1000 μ W/cm2It is ultraviolet
It is irradiated under light and causes within 600 seconds partial cross-linking reaction；
(5) coating material after partial cross-linking is positioned 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 circular array region pore is realized in the present embodiment
Scanning electron microscope (SEM) photograph.Observation chart 3 can be found, do not carried out crosslinked circular array region and formed pore space structure, and carry out photo-crosslinking
Region maintain profile pattern and compactness.
Embodiment 4
(1) by alginic acid and 4- nitrine anilinechloride in molar ratio 10:1 is dissolved in water, in 1- (3- dimethylaminos third
Base) the lower reaction of -3- ethyl carbodiimides catalysis 50 hours, in system, a concentration of 4mg/mL of alginic acid, 1- (3- dimethylaminos
Propyl) -3- ethyl carbodiimides a concentration of 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 chip substrate cleaned up
Bubble cleans drying after ten minutes, with ultra-pure 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, and drying is cleaned with ultra-pure 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 positioned over the coating surface that step (3) obtains, in 200 μ W/cm2Ultraviolet light
Lower irradiation causes partial cross-linking reaction for 2400 seconds；
(5) coating material after partial cross-linking is positioned 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 chart 4 can be found, do not carried out crosslinked square array column region and formed apparent pore space structure, and carry out photo-crosslinking
Region maintains smooth and compactness.
Embodiment 5
(1) by kayexalate and 4- nitrine anilinechloride in molar ratio 7:1 is dissolved in water, in 1- (3- bis-
Methylaminopropyl) the lower reaction of -3- ethyl carbodiimides catalysis 48 hours, in system, a concentration of 10mg/ of kayexalate
A concentration of 400mg/mL of mL, 1- (3- dimethylamino-propyls) -3- ethyl carbodiimides, obtains with the active modification of photo-crosslinking
Kayexalate；
(2) by the silicon chip 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 ultra-pure 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 ultra-pure 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 positioned over the coating surface that step (3) obtains, in 1000 μ W/cm2Ultraviolet light
Lower irradiation causes partial cross-linking reaction for 600 seconds；
(5) coating material after partial cross-linking is positioned 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 triangular array region pore is realized in the present embodiment
The scanning electron microscope (SEM) photograph of kayexalate coating surface.Observation chart 5 can be found, not carry out crosslinked triangular array region shape
At pore space structure, and the region for carrying out photo-crosslinking maintains profile pattern and compactness.
Embodiment 6
(1) by milt DNA and 4- nitrine anilinechloride in molar ratio 10:1 is dissolved in water, in 1- (3- dimethylaminos
Propyl) the lower reaction of -3- ethyl carbodiimides catalysis 48 hours, in system, a concentration of 10mg/mL of milt DNA, 1- (3- diformazans
Aminopropyl) -3- ethyl carbodiimides a concentration of 500mg/mL, obtain with the active modified milt DNA of photo-crosslinking；
(2) the silicon chip 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 ultra-pure 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 ultra-pure 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 positioned over the coating surface that step (3) obtains, in 300 μ W/cm2It is ultraviolet
It is irradiated under light and causes within 1800 seconds partial cross-linking reaction；
(5) coating material after partial cross-linking is positioned 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 in molar ratio 8:1 is dissolved in ultra-pure water, in 1- (3- diformazan ammonia
Base propyl) the lower reaction of -3- ethyl carbodiimides catalysis 24 hours, in system, a concentration of 12mg/mL of heparin sodium, 1- (3- diformazans
Aminopropyl) -3- ethyl carbodiimides a concentration of 300mg/mL, obtain with the active modified heparin sodium of photo-crosslinking；
(2) by the silicon chip substrate cleaned up, in diallyl dimethyl amine hydrochlorate aqueous solution, (4mg/mL, pH value are
9.0) it is impregnated in after twenty minutes, drying is cleaned with ultra-pure 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 ultra-pure 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 positioned over the coating surface that step (3) obtains, in 1000 μ W/cm2It is ultraviolet
It is irradiated under light and causes within 1800 seconds partial cross-linking reaction；
(5) coating material after partial cross-linking is positioned 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
The shows fluorescent microscopy images of dimethylamine hydrochloride/modified heparin sodium coating surface.Observation chart 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 in molar ratio 3:1 is dissolved in ultra-pure water, in 1- (3- diformazans
Aminopropyl) the lower reaction of -3- ethyl carbodiimides catalysis 72 hours, in system, a concentration of 10mg/mL of hyaluronic acid, 1- (3-
Dimethylamino-propyl) -3- ethyl carbodiimides a concentration of 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 chip substrate cleaned up
Bubble cleans drying after 30 minutes, with ultra-pure water；Place into the active modified hyaluronic acid aqueous solution of photo-crosslinking (12mg/mL,
PH value be 3.0) in impregnate 30 minutes after, clean drying with ultra-pure water, repeat after above-mentioned two step 100 time that obtain surface thick
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 positioned over the coating surface that step (3) obtains, in 1000 μ W/cm2It is ultraviolet
It is irradiated under light and causes within 1800 seconds partial cross-linking reaction；
(5) coating material after partial cross-linking is positioned 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 to the CdSe/ZnS quantum dot solutions of a concentration of 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 after banded zone pore before absorption quantum dot and after absorption quantum dot in the present embodiment
The shows fluorescent microscopy images of hydrochlorate/modified hyaluronic acid coating surface.Observation chart 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, fluorescence is excited 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 (10)
1. a kind of preparation method of patterning porous polymer coating, which is characterized in that include the following steps：
(1) polyanion and 4- nitrine anilinechloride are dissolved in the water by a certain percentage, in 1- (3- dimethylamino-propyls)-
The lower reaction of 3- ethyl carbodiimides catalysis 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 and lives with photo-crosslinking
Property modification polyanion aqueous solution in impregnate 1~60 minute, substrate is taken out, to 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 positioned over 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 in the coating material surface that step (4) obtains, caused after ultraviolet light
Partial cross-linking is reacted；
(6) coating after partial cross-linking is positioned over to impregnate in hydrochloric acid solution 1~60 minute and is gathered to get the patterning is porous
Close object coating.
2. the preparation method of patterning porous polymer coating according to claim 1, which is characterized in that in step (1),
The molar ratio that adds of polyanion and 4- nitrine anilinechlorides is 10:1~9.
3. the preparation method of patterning porous polymer coating according to claim 1, which is characterized in that it is described it is poly- it is cloudy from
Son is in polyacrylic acid, alginic acid, hyaluronic acid, kayexalate, heparin sodium, milt DNA and polymethylacrylic acid
It is at least one.
4. the preparation method of patterning porous polymer coating according to claim 3, which is characterized in that it is described it is poly- it is cloudy from
Son is polyacrylic acid, and the mole of polyacrylic acid is 50,000~500,000.
5. 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, polyallylamine hydrochloride, gelatin, diallyl dimethyl amine hydrochlorate, nucleoprotamine, chitosan
At least one of with polylysine.
6. it is according to claim 5 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.
7. 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.
8. 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, the irradiation time of ultraviolet light is 1~10000 second.
9. 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.
10. a kind of patterning porous polymer coating, which is characterized in that prepared by claim 1~9 any one of them method
It obtains.
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| CN110054984A (en) * | 2019-05-08 | 2019-07-26 | 常州大学 | A kind of preparation method of the covalent cross-linking self-healing antimicrobial coating of stable structure |
| CN110564232A (en) * | 2019-09-23 | 2019-12-13 | 浙江大学 | Patterned reversible porous coating and preparation method thereof |
| CN112457518A (en) * | 2020-11-03 | 2021-03-09 | 浙江理工大学 | Laser foaming polyelectrolyte film and area pore-forming process thereof |
| CN112795039A (en) * | 2021-01-15 | 2021-05-14 | 浙江理工大学 | Preparation method of foaming polyelectrolyte film |
| CN113262963A (en) * | 2021-04-08 | 2021-08-17 | 浙江大学 | Layered porous polyelectrolyte coating and preparation method thereof |
| CN113275222A (en) * | 2021-04-08 | 2021-08-20 | 浙江大学 | In-situ polymerization-based polymer coating with layered porous structure and preparation method thereof |
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| CN110564232B (en) * | 2019-09-23 | 2020-09-08 | 浙江大学 | Patterned reversible porous coating and preparation method thereof |
| CN112457518A (en) * | 2020-11-03 | 2021-03-09 | 浙江理工大学 | Laser foaming polyelectrolyte film and area pore-forming process thereof |
| CN112795039A (en) * | 2021-01-15 | 2021-05-14 | 浙江理工大学 | Preparation method of foaming polyelectrolyte film |
| CN113262963A (en) * | 2021-04-08 | 2021-08-17 | 浙江大学 | Layered porous polyelectrolyte coating and preparation method thereof |
| CN113275222A (en) * | 2021-04-08 | 2021-08-20 | 浙江大学 | In-situ polymerization-based polymer coating with layered porous structure and preparation method thereof |
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