CN112457518A - Laser foaming polyelectrolyte film and area pore-forming process thereof - Google Patents

Laser foaming polyelectrolyte film and area pore-forming process thereof Download PDF

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CN112457518A
CN112457518A CN202011209588.3A CN202011209588A CN112457518A CN 112457518 A CN112457518 A CN 112457518A CN 202011209588 A CN202011209588 A CN 202011209588A CN 112457518 A CN112457518 A CN 112457518A
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film
polyelectrolyte film
polyanion
laser
polyelectrolyte
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CN112457518B (en
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陈夏超
张达
张昊
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Zhejiang University of Technology ZJUT
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Abstract

The invention discloses a laser foaming polyelectrolyte film and a regional pore-forming process thereof. The invention specifically comprises the steps of (1) obtaining modified polyanion with azide side groups through chemical modification; (2) preparing a polyelectrolyte film with uniform thickness by layer-by-layer self-assembly of polycations and modified polyanions with azide side groups; (3) placing the polyelectrolyte film in a humid environment or soaking the polyelectrolyte film in water for plasticizing treatment; (4) irradiating the film by using a laser beam with a certain wavelength and a certain intensity to initiate the decomposition of azide groups in the film, the generation and aggregation of nitrogen and the spontaneous formation of a bubble-shaped structure in the film; (5) and selectively pore-forming a local area of the film by setting a scanning path and an area of a laser beam to obtain the patterned porous polyelectrolyte film. The method has the characteristics of simple process, simple and convenient operation and controllable foaming area, and can be used for preparing the patterned porous polyelectrolyte film with different distribution characteristics.

Description

Laser foaming polyelectrolyte film and area pore-forming process thereof
Technical Field
The invention relates to the field of functional coatings, in particular to a laser foaming polyelectrolyte film and a regional pore-forming process thereof.
Background
Polyelectrolytes, also known as polyelectrolytes, are a class of linear or branched synthetic or natural polymers which contain ionizable groups in their structural units. The polyelectrolyte film prepared by the layer-by-layer self-assembly technology has unique supermolecule electrostatic effect, and the supermolecule effect of the polyelectrolyte film is regulated and treated by utilizing environmental stimuli such as acid, alkali, salt and the like, so that microporous structures of various types and sizes can be constructed, and the polyelectrolyte film is endowed with huge application potential in the fields of water treatment, drug delivery, tissue engineering and the like. However, the existing polyelectrolyte membrane pore-forming technology relates to complex multi-step operation, the process is not easy to control, and the regional regulation and control of the pore-forming process are difficult to realize, thus the requirements of local active substance embedding in the biomedical field, regional semiconductor loading in the photoelectric field and the like cannot be met. Therefore, a polyelectrolyte membrane with simple, rapid and regioselective pore-forming ability is urgently needed to be developed.
The formation and evolution of the bubble structure are realized by initiating the generation and aggregation of gas in the polymer material, and the method is one of important methods for preparing the microporous polymer material and has the advantages of simplicity and convenience in operation, rapidness, controllability and the like. Polyelectrolyte membranes with foaming capability would also have the above advantages, however there is currently no corresponding example.
Disclosure of Invention
The invention aims to provide a preparation method of a laser foaming polyelectrolyte film, aiming at the problems that the existing polyelectrolyte film pore-forming technology is complicated and the pore-forming process is difficult to realize regional regulation and control. By introducing photolysis groups on a polyelectrolyte main chain and applying a laser irradiation technology, gas generation and aggregation in the polyelectrolyte film are triggered, and a microporous structure is simply, conveniently and quickly prepared; selective pore-forming of local areas of the film is further realized by setting the scanning path and the scanning area of the laser beam.
The technical scheme adopted by the invention is as follows:
a preparation method of a laser foaming polyelectrolyte film comprises the following steps:
step (1): modified polyanion with azide side group is obtained by chemical modification.
And dissolving the polyanion and 4-azidoaniline hydrochloride into water according to a certain proportion, adding a catalyst, and carrying out catalytic reaction for 12-72 hours to obtain the modified polyanion with the photodecomposition group.
The polyanion has carboxyl or hydroxyl on the main chain and is at least one of polyacrylic acid, alginic acid, hyaluronic acid, polyvinyl alcohol, heparin and polymethacrylic acid. Preferably polyacrylic acid, the molar molecular weight is 50,000-500,000, more preferably 100,000-200,000.
The catalyst is 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide.
The molar ratio of the polyanion to the 4-azido aniline hydrochloride is 100: 1-10.
In the mixed reaction solution, the concentration of the polyanion is 1-1000 mg/mL, and the concentration of the catalyst 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide is 1-500 mg/mL.
The catalytic reaction temperature is 0-30 ℃.
Step (2): respectively dissolving polycation and the modified polyanion synthesized in the step (1) in water to prepare polycation aqueous solution and modified polyanion aqueous solution with certain concentration and certain pH value.
Preferably, the concentration of the polycation aqueous solution is 1-100 mg/mL, and the pH value is 7-11.
Preferably, the concentration of the modified polyanion aqueous solution is 1-100 mg/mL, and the pH is 1-6.
The polycation is at least one of polyethyleneimine, polyallylamine, gelatin, polydiallyldimethylamine, protamine, chitosan and polylysine. Preferably polyethyleneimine, and the molar molecular weight of the polyethyleneimine is 1,000-100,000, more preferably 20,000-50,000.
And (3): and (3) preparing the polyelectrolyte film with uniform thickness by layer-by-layer self-assembly of the polycation and the modified polyanion.
Soaking the substrate material in the polycation aqueous solution prepared in the step (2) for 1-120 minutes, and then soaking the substrate material in the modified polyanion aqueous solution prepared in the step (2) for 1-120 minutes, thereby completing a deposition cycle; and repeating the steps to finish a plurality of deposition cycles on the substrate, thereby obtaining the polyelectrolyte film with uniform thickness.
The substrate material is at least one of silicon chip, glass, quartz, metal, calcium fluoride, ceramic and plastic.
Preferably, the deposition cycle is repeated 5 to 500 times.
Preferably, after each immersion, the substrate is removed, rinsed with water and blown dry with nitrogen.
And (4): and (3) placing the polyelectrolyte film in a humid environment or soaking the polyelectrolyte film in water for plasticizing treatment.
Preferably, the relative humidity of the humid environment is 75-100%, and the treatment time is 1-72 hours.
Preferably, the soaking in water refers to soaking the polyelectrolyte film in pure water, and the treatment time is 1-72 hours.
And (5): and irradiating the porous polyelectrolyte film by using a laser beam with certain wavelength and certain intensity to initiate the decomposition of azide groups, the generation and aggregation of gas in the film and induce the spontaneous formation of a microporous structure in the polyelectrolyte film to obtain the porous polyelectrolyte film.
Preferably, the laser wavelength is 245-450 nm, and the laser irradiation intensity is 1-500W/cm2Laser, laserThe irradiation time is 1 to 1800 ms.
Preferably, selective pore-forming of a local area of the film is realized by setting a scanning path and an area of a laser beam, so as to obtain the patterned porous polyelectrolyte film.
An object of the present invention is to provide a laser foaming polyelectrolyte film prepared by the above method.
In the invention, the principle of placing the polyelectrolyte film in a humid environment or soaking the polyelectrolyte film in water for laser foaming is as follows: in a humid environment or in a contact process with water, water molecules diffuse into the film, the free volume between polyelectrolyte chain segments can be increased, and meanwhile, the electrostatic shielding effect of the water molecules on positive and negative charges weakens the supermolecule electrostatic effect between the chain segments, so that the movement capacity of polyelectrolyte molecular chains is greatly increased.
In the invention, polyanion modified 4-azidoaniline has photoactivity, can decompose azido side groups under laser irradiation to generate nitrogen, and gas generation and aggregation in a film promote migration and rearrangement of polymer chain segments, thereby realizing spontaneous formation and evolution of a bubble-shaped microporous structure in the film. The photolysis principle of the nitrine side group is as follows:
Figure BDA0002758231050000031
the invention has the beneficial effects that:
1) the invention reasonably initiates the generation and aggregation of gas in the polyelectrolyte film by introducing photolysis groups on the main chain of the polyelectrolyte and applying a laser irradiation technology under specific conditions, thereby simply, conveniently and quickly preparing the microporous structure.
2) The invention realizes pore-forming by the laser foaming principle and can realize the controllability of pore-forming areas.
3) The invention realizes the controllability of the pore structure by controlling the generation rate of nitrogen through laser irradiation with different intensities.
Drawings
FIG. 1 is a scanning electron microscope image of the cross-sectional morphology of the polyethyleneimine/polyacrylic acid thin film before and after laser irradiation in example 1: (a) before laser irradiation, and (b) after laser irradiation.
FIG. 2 is an optical photograph and a scanning electron micrograph of the cross-sectional morphology of the polylysine/polymethacrylic acid film after laser scanning in example 2, respectively: (a) is an optical photograph, and (b) is a scanning electron micrograph.
FIG. 3 is a scanning electron micrograph of an optical photograph and a cross-sectional morphology of the chitosan/hyaluronic acid film after laser scanning in example 3: (a) is an optical photograph, and (b) is a scanning electron micrograph.
FIG. 4 is a scanning electron micrograph of the pore morphology of the polyallylamine/polyvinyl alcohol film before laser irradiation and after laser irradiation of different intensities in example 4: (a) before laser irradiation, (b) is 100W/cm2After laser irradiation, (c) was 250W/cm2After laser irradiation, (d) is 500W/cm2After the laser irradiation.
Detailed Description
The invention is further illustrated by the following specific examples.
Example 1
(1) Dissolving polyacrylic acid with the molecular weight of 100,000 and 4-azidoaniline hydrochloride in pure water according to the molar ratio of 100:1, and reacting for 72 hours at 25 ℃ under the catalysis of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide, wherein the concentration of the polyacrylic acid is 100mg/mL, and the concentration of the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide is 200mg/mL, so as to obtain modified polyacrylic acid with a photodecomposition group;
(2) soaking a silicon wafer substrate in a polyethyleneimine aqueous solution (1mg/mL, pH value of 10.0) with the molecular weight of 20,000 for 30 minutes, then soaking the silicon wafer substrate in a modified polyacrylic acid aqueous solution (3mg/mL, pH value of 2.0) with a photolysis group for 30 minutes, and repeating the steps for 10 times to obtain a polyethyleneimine/polyacrylic acid film with a compact structure;
(3) putting the polyethyleneimine/polyacrylic acid film obtained in the step (2) in pure water for plasticizing treatment for 72 hours;
(4) the wavelength of the light is 365nm, and the intensity is 50W/cm2The film processed in the step (3) is irradiated by the laser beam for 1200ms, and the spontaneous formation of the bubble-shaped micropore structure in the polyethyleneimine/polyacrylic acid film is realized.
FIG. 1 is a scanning electron microscope image of the cross-sectional morphology of the polyethyleneimine/polyacrylic acid thin film before and after laser irradiation in the present example. As can be seen from the observation of FIG. 1, the polyethyleneimine/polyacrylic acid film subjected to the treatment of step (4) has a bubble-like microporous structure formed therein.
Example 2
(1) Dissolving polymethacrylic acid with the molecular weight of 50,000 and 4-azidoaniline hydrochloride in pure water according to the molar ratio of 100:2, and reacting for 24 hours at 30 ℃ under the catalysis of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide, wherein the concentration of the polymethacrylic acid is 1000mg/mL, and the concentration of the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide is 500mg/mL, so as to obtain modified polymethacrylic acid with a photolytic group;
(2) soaking a glass substrate in a polylysine aqueous solution (10mg/mL, pH value of 9.5) with the molecular weight of 50,000 for 60 minutes, then soaking the glass substrate in a modified polymethacrylic acid aqueous solution (20mg/mL, pH value of 5.0) with a photolysis group for 60 minutes, and repeating the steps for 500 times to obtain the polylysine/polymethacrylic acid film;
(3) placing the polylysine/polymethacrylic acid film obtained in the step (2) in an environment with the relative humidity of 100% for processing for 2 hours;
(4) the wavelength is 450nm, and the intensity is 500W/cm2Irradiating the film processed in the step (3) by the laser beam for 1800ms to realize the spontaneous formation of the internal microporous structure of the polylysine/polymethacrylic acid film;
(5) and selectively pore-forming a local area of the polylysine/polymethacrylic acid film by setting a scanning path of a laser beam to obtain the patterned porous film.
FIG. 2 is an optical photograph and a scanning electron microscope image of the cross-sectional morphology of the polylysine/polymethacrylic acid film after laser scanning in this example. Observing fig. 2, it can be found that after scanning by the laser beam, a line-shaped micropore area appears on the polylysine/polymethacrylic acid film, and one side of the edge of the laser irradiation area maintains a compact structure, and the other side of the edge presents a micropore structure.
Example 3
(1) Dissolving hyaluronic acid and 4-azidoaniline hydrochloride in pure water according to a molar ratio of 100:7, and reacting for 64 hours under the catalysis of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide at 30 ℃, wherein the concentration of the hyaluronic acid is 500mg/mL, and the concentration of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide is 300mg/mL, so as to obtain modified hyaluronic acid with a photodecomposition group;
(2) soaking the glass substrate in a chitosan aqueous solution (10mg/mL, pH value of 10.0) for 15 minutes, then soaking the glass substrate in a modified hyaluronic acid aqueous solution (50mg/mL, pH value of 1.0) with photolysis groups for 15 minutes, and repeating the steps for 100 times to obtain a chitosan/hyaluronic acid film;
(3) placing the chitosan/hyaluronic acid film obtained in the step (2) in an environment with the relative humidity of 75% for treating for 72 hours;
(4) the using wavelength is 245nm, and the intensity is 250W/cm2Irradiating the film processed in the step (3) by the laser beam for 6ms to realize the spontaneous formation of the bubble-shaped microporous structure in the chitosan/hyaluronic acid film;
(5) and selectively pore-forming a local area of the chitosan/hyaluronic acid film by setting a scanning path of a laser beam to obtain the patterned porous film.
FIG. 3 is an optical photograph and a scanning electron micrograph of the cross-sectional morphology of the chitosan/hyaluronic acid film after laser scanning in this example. Observing fig. 3, it can be found that after the chitosan/hyaluronic acid film is scanned by the laser beam, a line-shaped micropore area appears obviously, one side of the edge of the laser irradiation area maintains a compact structure, and the other side of the edge of the laser irradiation area presents a micropore structure.
Example 4
(1) Dissolving polyvinyl alcohol and 4-azidoaniline hydrochloride in pure water according to a molar ratio of 100:10, and reacting for 12 hours under the catalysis of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide at 0 ℃, wherein the concentration of hyaluronic acid is 2mg/mL, and the concentration of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide is 4mg/mL, so as to obtain modified polyvinyl alcohol with a photolytic group;
(2) soaking the glass substrate in polyallylamine aqueous solution (50mg/mL, pH value of 11.0) for 30 minutes, then soaking the glass substrate in modified polyvinyl alcohol aqueous solution (5mg/mL, pH value of 3.0) with photolysis groups for 30 minutes, and repeating the steps for 400 times to obtain a polyallylamine/polyvinyl alcohol film;
(3) placing the polyallylamine/polyvinyl alcohol film obtained in the step (2) in an environment with the relative humidity of 75% for treating for 48 hours;
(4) the wavelength is 245nm, the intensity is 100, 250 and 500W/cm2Irradiating the film processed in the step (3) by the laser beam for 50ms to realize the preparation of microporous structures with different sizes in the polyallylamine/polyvinyl alcohol film;
FIG. 4 is a scanning electron micrograph of the cross-sectional profile of the polyallylamine/polyvinyl alcohol film before laser irradiation and after laser irradiation of different intensities in this example. As can be seen from the observation of FIG. 4, microporous structures with different sizes appear in the polyallylamine/polyvinyl alcohol film after the laser beams with different intensities are irradiated.

Claims (10)

1. A preparation method of a laser foaming polyelectrolyte film is characterized by comprising the following steps:
step (1): modified polyanion with azide side group is obtained by chemical modification.
And dissolving the polyanion and 4-azidoaniline hydrochloride into water according to a certain proportion, adding a catalyst, and carrying out catalytic reaction for 12-72 hours to obtain the modified polyanion with the photodecomposition group.
The polyanion has carboxyl or hydroxyl on the main chain and is at least one of polyacrylic acid, alginic acid, hyaluronic acid, polyvinyl alcohol, heparin and polymethacrylic acid.
Step (2): respectively dissolving polycation and the modified polyanion synthesized in the step (1) in water to prepare polycation aqueous solution and modified polyanion aqueous solution with certain concentration and certain pH value.
The polycation is at least one of polyethyleneimine, polyallylamine, gelatin, polydiallyldimethylamine, protamine, chitosan and polylysine.
And (3): and (3) preparing the polyelectrolyte film with uniform thickness by layer-by-layer self-assembly of the polycation and the modified polyanion.
Soaking the substrate material in the polycation aqueous solution prepared in the step (2) for 1-120 minutes, and then soaking the substrate material in the modified polyanion aqueous solution prepared in the step (2) for 1-120 minutes, thereby completing a deposition cycle; and repeating the steps to finish a plurality of deposition cycles on the substrate, thereby obtaining the polyelectrolyte film with uniform thickness.
And (4): and (3) placing the polyelectrolyte film in a humid environment or soaking the polyelectrolyte film in water for plasticizing treatment.
And (5): irradiating the film by using a laser beam with certain wavelength and certain intensity to initiate the decomposition of azide groups, the generation and aggregation of gas in the film and induce the spontaneous formation of a microporous structure in the polyelectrolyte film to obtain a porous polyelectrolyte film; wherein the laser wavelength is 245-450 nm, and the laser irradiation intensity is 1-500W/cm2The laser irradiation time is 1-1800 ms.
2. The method of claim 1, wherein the polyanion is polyacrylic acid, and the molar molecular weight is 50,000 to 500,000; the polycation is polyethyleneimine, and the molar molecular weight of the polycation is 1,000-100,000.
3. The method of claim 1, wherein the catalyst is 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide.
4. The method for preparing the laser foaming polyelectrolyte film as claimed in claim 1, wherein the molar ratio of the polyanion to the 4-azidoaniline hydrochloride is 100: 1-10.
5. The method for preparing a laser foaming polyelectrolyte film as claimed in claim 1, wherein in the mixed reaction solution for synthesizing the modified polyanion, the concentration of the polyanion is 1-1000 mg/mL, and the concentration of the catalyst 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide is 1-500 mg/mL.
6. The method of claim 1, wherein the temperature of the catalytic reaction is 0-30 ℃.
7. The method for preparing a laser foaming polyelectrolyte film according to claim 1, wherein the concentration of the polycation aqueous solution is 1-100 mg/mL, the pH value is 7-11; the concentration of the modified polyanion aqueous solution is 1-100 mg/mL, and the pH value is 1-6.
8. The method according to claim 1, wherein the relative humidity of the humid environment in the step (4) is 75-100%, and the treatment time is 1-72 hours; the soaking in water means that the polyelectrolyte film is soaked in pure water, and the treatment time is 1-72 hours.
9. The method according to claim 1, wherein the step (5) comprises selectively forming pores in a local region of the film by setting a scanning path and a scanning region of a laser beam, thereby obtaining the patterned porous polyelectrolyte film.
10. A laser foamed polyelectrolyte film prepared by the method of any one of claims 1-9.
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