CN107219194B - Preparation method and application of polyelectrolyte composite with stress-responsive patterned micro-nano structure - Google Patents

Abstract

The invention discloses a preparation method and application of a polyelectrolyte composite with a stress-responsive patterned micro-nano structure, and relates to a preparation method and application of the polyelectrolyte composite. The purpose of the present invention is to solve the problems that the existing humidity sensor is expensive, the composite sensor cannot realize industrial production, and the composite sensor does not have relative humidity, acidity and other detection indicators. Preparation methods: 1. Preparation of patterned PDMS stamps; 2. Preparation of polyelectrolyte composites; The polyelectrolyte composite with patterned micro-nano structure with stress response is used as a smart super see-through material, a scattering medium for stress response, and is used for quality detection of living food, humidity sensor, and humidity sensor. The present invention can obtain polyelectrolyte composites with stress-responsive patterned micro-nano structures.

Description

Preparation of stress-responsive patterned micro-nanostructured polyelectrolyte composites method and application

technical field

The invention relates to a preparation method and application of a polyelectrolyte composite.

Background technique

With the development of modernization, whether it is scientific research or industrial production, it is difficult to find a field that has nothing to do with humidity sensing. In real life, cell culture or food and battery production need to control the humidity below 70-80% to prevent bacterial growth and cause pollution. Appropriate air relative humidity can increase living comfort and improve physical health, while air Low relative humidity can cause dry, cracked and itchy skin. Although the measurement and control of degrees are particularly important to human beings, so far the hygrometers with fast response, small size, good linearity, and relatively stable hygrometers mainly come from Honeywell (Honeywell Company) in the United States and are expensive. However, the newly reported gold nanoparticle-organic cross-linked composite sensor based on electron tunneling effect and test resistance has never been able to achieve industrial production. In May 2015, France and Germany successively introduced laws to prohibit food waste. As the first French law in the world that prohibits supermarkets from discarding or destroying unsold food, it has clearly stipulated that if the food fails to be sold, the supermarket must put the food away. Donate to charities or food banks to get food into the hands of the poor. As long as the area of the supermarket exceeds 400 square meters, the boss must sign an agreement with these institutions, otherwise he will face a fine of 3,750 euros (27,900 yuan). Therefore, how to detect food will not pose a threat to human health and ensure that food is not wasted. Correspondingly, sensors for detecting indicators such as relative humidity, acidity or other indicators of food (potato chips, meat, vegetables, etc.) in supermarkets will have huge market prospects.

SUMMARY OF THE INVENTION

The purpose of the present invention is to solve the problems that the existing humidity sensor is expensive, the composite sensor cannot realize industrial production, and the composite sensor does not have relative humidity, acidity and other detection indicators, and provides a patterned micro-nano structure with stress response. Preparation method and application of polyelectrolyte composite.

The preparation method of a polyelectrolyte composite with a stress-responsive patterned micro-nano structure is specifically completed according to the following steps:

1. Preparation of patterned PDMS stamps:

Mix the polydimethylsiloxane prepolymer A and the curing agent B, firstly at a stirring speed of 200r/min～500r/min for 5min～8min, and then at a centrifugal speed of 3000r/min～4000r/min Centrifuge for 5 min to 8 min to obtain a mixed solution; pour the mixed solution into a petri dish with a patterned silicon substrate, and then vacuum the petri dish at a temperature of 60 ℃ to 80 ℃ for 1 h to 3 h to obtain on the silicon substrate The patterned PDMS stamp; the patterned PDMS stamp is peeled off from the silicon substrate to obtain the patterned PDMS stamp;

The mass ratio of the prepolymer A of the polydimethylsiloxane described in the step 1 and the curing agent B is 10:1;

Second, the preparation of polyelectrolyte composites:

The polyelectrolyte electron pair is added to the container, and then magnetically stirred at a temperature of 70°C to 80°C and a stirring speed of 300r/min to 800r/min for 15min to 25min to obtain a polyelectrolyte complex with a flocculent structure in the solution;

The polyelectrolyte electron pair described in step 2 is the mixed solution of PSS/PDDA or the mixed solution of PAA/PAH; the mixed solution of PSS/PDDA is the sodium chloride solution of sodium polystyrene sulfonate and polyacrylate The sodium chloride solution is mixed according to the volume ratio of 1:1; the mixed solution of PAA/PAH is the sodium chloride solution of polyacrylic acid and the sodium chloride solution of polycyclic aromatic hydrocarbons mixed according to the volume ratio of 1:1. ;

3. Take out the polyelectrolyte composite of flocculent structure from the solution, then cover the polyelectrolyte composite of flocculent structure on the patterned PDMS stamp obtained in step 1, and then transfer the polyelectrolyte covered with flocculent structure to the Apply 20kPa~130kPa to the patterned PDMS stamp of the composite, and then hold the pressure for 5min~15min at a temperature of 60℃~75℃ and a pressure of 20kPa~130kPa, and then transfer the transfer. The transfer time is 5min~15min, and then The polyelectrolyte complex was separated from the patterned PDMS stamp to obtain a polyelectrolyte complex with a stress-responsive patterned micro-nano structure;

The transfer described in step 3 is thermal transfer, and the transfer temperature is 60°C to 100°C;

The thickness of the polyelectrolyte composite with the stress-responsive patterned micro-nano structure described in step 3 is 0.1 μm˜30 μm.

Stress-responsive patterned micro-nanostructured polyelectrolyte complexes are used to judge stress-responsive responses to external environments based on light diffraction effects.

Stress-responsive patterned micro-nanostructured polyelectrolyte composites as smart super see-through materials.

Stress-responsive patterned micro-nanostructured polyelectrolyte composites for super-resolution technology.

Application of stress-responsive patterned micro-nanostructured polyelectrolyte complexes as stress-responsive scattering media.

Stress-responsive patterned micro-nanostructured polyelectrolyte complexes are used for quality detection of living food based on the change of reaction color and scattering under stress conditions.

Stress-responsive patterned micro-nanostructured polyelectrolyte complexes can be used in optical sensors based on the principle of structural change based on microbial degradation, and can be used in humidity sensors based on the principle of stress response to humidity. The principle of stress response can be used in pH sensors.

Advantages of the present invention:

1. The polyelectrolyte composite with a stress-responsive patterned micro-nano structure prepared by the present invention has a highly sensitive response to humidity, pH and other organic chemicals, and can effectively solve the problem that the existing humidity sensor is expensive and the composite sensor is expensive. The problem of industrialized production and composite sensors that do not have relative humidity, acidity and other detection indicators. The polyelectrolyte composite with a stress-responsive patterned micro-nano structure prepared by the invention can perform accurate, rapid and low-cost detection on foods containing polyelectrolyte food additives on the market; in addition, it is also very sensitive to low relative humidity, The relative humidity can be as low as 20%, and when the relative humidity is 20% to 100%, the color change of the polyelectrolyte composite with the stress-responsive patterned micro-nano structure prepared by the invention can be seen with the naked eye, and the result can be obtained. Knowing the change of relative humidity, which is impossible for many hygrometers on the market;

2. The polyelectrolyte composite with the stress-responsive patterned micro-nano structure prepared by the present invention is very sensitive to pH, temperature or hydrophobic chemical components, and is more beneficial to be widely used as a sensor. Even in aqueous solutions, the ionic strength in polyelectrolytes can be calculated. Since the polyelectrolyte composite with the stress-responsive patterned micro-nano structure prepared by the present invention has biodegradability, the growth of bacteria or the deterioration of the food itself can be detected;

3. In the present invention, in order to conveniently and effectively detect the preservation status of food and whether it can still be safely used by people, we prepared a polyelectrolyte composite with a stress-responsive patterned micro-nano structure through micro-contact printing technology. It has many phenomena such as metamaterials, and can respond sensitively to humidity, temperature, pH, and ionic strength to change its structure, and then irradiate it with laser or natural light, and read out the patterned micro-nano with stress-responsive structure through spectrum reading. The quality of food is judged by the reflection value or absorption value of the structural polyelectrolyte complex under the action of external stress conditions.

The present invention can obtain polyelectrolyte composites with stress-responsive patterned micro-nano structures.

Description of drawings

Figure 1 is a process flow diagram of a polyelectrolyte composite with a stress-responsive patterned micro-nano structure prepared in Example 1. In Figure 1, 1 is a polyelectrolyte composite with a flocculent structure, and 2 is a patterned PDMS seal. 3 is the square of the array on the patterned PDMS stamp, 4 is the transfer pressure and heat preservation, 5 is the height of the array on the patterned PDMS stamp is 10 μm, 6 is the square of the array on the patterned PDMS stamp The width is 10 μm, 7 is the polyelectrolyte composite after transfer, 8 is the separation of the polyelectrolyte composite from the patterned PDMS stamp, and 9 is the polyelectrolyte composite with stress-responsive patterned micro-nano structures;

FIG. 2 is a schematic diagram of a device that scatters after two laser pointers with different wavelengths in Example 1 pass through the polyelectrolyte composite with stress-responsive patterned micro-nano structures prepared in Example 1, and 1 in FIG. 2 is red Green laser pointer, 2 is the polyelectrolyte composite with stress-responsive patterned micro-nano structures prepared in Example 1, and 3 is a white screen;

Fig. 3 is the SEM image of the patterned PDMS seal obtained in the first step of Example 1;

4 is a SEM image of the polyelectrolyte composite with stress-responsive patterned micro-nano structures obtained in step 3 of Example 1;

Fig. 5 is the scattering picture produced by the green laser pointer through the patterned PDMS seal obtained in the first step of Example 1;

Fig. 6 is the surface structure of the real PDMS obtained by performing Fourier transform of Fig. 4;

7 is a picture of the polyelectrolyte composite with stress-responsive patterned micro-nano structures prepared in Example 1 placed under the condition of 35% humidity and irradiating the sample with a green laser pointer and scattering;

FIG. 8 is a picture of the polyelectrolyte composite with stress-responsive patterned micro-nano structures prepared in Example 1 placed under 100% humidity conditions irradiating the sample with a green laser pointer and scattering;

FIG. 9 is the characteristic size 1/Q curve of the polyelectrolyte composite with stress-responsive patterned micro/nano structures calculated by FIG. 7 , and 1 in FIG. 9 is the polyelectrolyte with stress-responsive patterned micro/nano structures The characteristic size 1/Q curve of the composite placed under the condition of 35% humidity, 2 is the characteristic size 1/Q curve of the polyelectrolyte composite with stress-responsive patterned micro-nano structure placed under the condition of 100% humidity ;

Fig. 10 is an enlarged view of A in Fig. 9, Fig. 10 is the characteristic size 1/Q curve of the polyelectrolyte composite with stress-responsive patterned micro-nano structure placed under the condition of 35% humidity, 2 is Characteristic size 1/Q curves of stress-responsive patterned micro-nanostructured polyelectrolyte composites placed under 100% humidity;

Fig. 11 is the Q-value curve of the polyelectrolyte composite with stress-responsive patterned micro-nano structure calculated by Fig. 7, and 1 in Fig. 11 is the placement of the polyelectrolyte composite with stress-responsive patterned micro-nano structure The Q value curve under the condition of 35% humidity, 2 is the Q value curve of the polyelectrolyte composite with stress-responsive patterned micro-nano structure placed under the condition of 100% humidity;

12 is a confocal scanning microscope image of the FITC channel of the polyelectrolyte composite with stress-responsive patterned micro-nanostructures prepared by cross-linking by heating;

Figure 13 is a confocal scanning laser microscope image of the RITC channel of the polyelectrolyte composite with stress-responsive patterned micro-nanostructures prepared by cross-linking under 100% humidity for 30 min;

14 is a confocal scanning microscope image of the RITC channel of the polyelectrolyte complex with stress-responsive patterned micro-nanostructures prepared by cross-linking by heating;

Fig. 15 is a bright field confocal scanning microscope image of the polyelectrolyte composite with stress-responsive patterned micro-nano structures prepared without cross-linking by heating under 100% humidity for 30 min;

Figure 16 is a picture of the polyelectrolyte composite with a stress-responsive patterned micro-nano structure prepared in Example 1 placed under the condition of 35% humidity and irradiating the sample with a green laser pointer and scattering;

FIG. 17 is a picture of the polyelectrolyte composite with the stress-responsive patterned micro-nano structure prepared in Example 1 placed under the condition of 100% humidity and irradiating the sample with a green laser pointer and scattering;

FIG. 18 is the characteristic size 1/Q curve of the polyelectrolyte composite with stress-responsive patterned micro-nano structures calculated from FIG. 16 , and 1 in FIG. 16 is the patterned micro-nano structure with stress response of Example 1. The characteristic size 1/Q curve of the structured polyelectrolyte composite placed under the condition of 35% humidity, 2 is the polyelectrolyte composite with stress-responsive patterned micro-nano structure prepared in Example 1 placed at 100% humidity The characteristic size 1/Q curve under the condition;

Fig. 19 is an enlarged view of part A in Fig. 18, and 1 in Fig. 19 is the feature size 1/Q of the polyelectrolyte composite with stress-responsive patterned micro-nano structures of Example 1 placed under the condition of 35% humidity Curve, 2 is the characteristic size 1/Q curve of the polyelectrolyte composite with stress-responsive patterned micro-nano structure prepared in Example 1 placed under the condition of 100% humidity;

FIG. 20 is the Q-value curve of the polyelectrolyte composite with stress-responsive patterned micro-nanostructures prepared in Example 1 calculated from FIG. 17 , and 1 in FIG. 20 is the pattern with stress-responsive prepared in Example 1 The Q value curve of the polyelectrolyte composite with the micro-nano structure of the micro-nano structure placed under the condition of 35% humidity, 2 is the polyelectrolyte composite with the stress-responsive patterned micro-nano structure prepared in Example 1 placed in the humidity of 100% The Q value curve under the condition;

Figure 21 is an ordinary optical microscope picture of the polyelectrolyte composite with stress-responsive patterned micro-nano structures prepared in Example 3;

Figure 22 is an ordinary optical microscope image of the polyelectrolyte composite with stress-responsive patterned micro-nano structures prepared in Example 3 placed under 100% humidity for 15 minutes;

Fig. 23 is a comparison diagram of the polyelectrolyte composite in the light dispersion measurement. In Fig. 23, 1 is the UV-Vis absorption spectrum of the patterned film of the polyelectrolyte composite obtained in step 3 of Example 1, and 2 is the flat polyelectrolyte composite. UV-Vis absorption spectra of thin films.

Detailed ways

Specific embodiment 1: This embodiment is a preparation method of a polyelectrolyte composite with a stress-responsive patterned micro-nano structure, which is specifically completed according to the following steps:

1. Preparation of patterned PDMS stamps:

Mix the polydimethylsiloxane prepolymer A and the curing agent B, firstly at a stirring speed of 200r/min～500r/min for 5min～8min, and then at a centrifugal speed of 3000r/min～4000r/min Centrifuge for 5 min to 8 min to obtain a mixed solution; pour the mixed solution into a petri dish with a patterned silicon substrate, and then vacuum the petri dish at a temperature of 60 ℃ to 80 ℃ for 1 h to 3 h to obtain on the silicon substrate The patterned PDMS stamp; the patterned PDMS stamp is peeled off from the silicon substrate to obtain the patterned PDMS stamp;

The mass ratio of the prepolymer A of the polydimethylsiloxane described in the step 1 and the curing agent B is 10:1;

Second, the preparation of polyelectrolyte composites:

The polyelectrolyte electron pair is added to the container, and then magnetically stirred at a temperature of 70°C to 80°C and a stirring speed of 300r/min to 800r/min for 15min to 25min to obtain a polyelectrolyte complex with a flocculent structure in the solution;

The polyelectrolyte electron pair described in step 2 is the mixed solution of PSS/PDDA or the mixed solution of PAA/PAH; the mixed solution of PSS/PDDA is the sodium chloride solution of sodium polystyrene sulfonate and polyacrylate The sodium chloride solution is mixed according to the volume ratio of 1:1; the mixed solution of PAA/PAH is the sodium chloride solution of polyacrylic acid and the sodium chloride solution of polycyclic aromatic hydrocarbons mixed according to the volume ratio of 1:1. ;

3. Take out the polyelectrolyte composite of flocculent structure from the solution, then cover the polyelectrolyte composite of flocculent structure on the patterned PDMS stamp obtained in step 1, and then transfer the polyelectrolyte covered with flocculent structure to the Apply 20kPa~130kPa to the patterned PDMS stamp of the composite, and then hold the pressure for 5min~15min at a temperature of 60℃~75℃ and a pressure of 20kPa~130kPa, and then transfer the transfer. The transfer time is 5min~15min, and then The polyelectrolyte complex was separated from the patterned PDMS stamp to obtain a polyelectrolyte complex with a stress-responsive patterned micro-nano structure;

The transfer described in step 3 is thermal transfer, and the transfer temperature is 60°C to 100°C;

The thickness of the polyelectrolyte composite with the stress-responsive patterned micro-nano structure described in step 3 is 0.1 μm˜30 μm.

The polydimethylsiloxane prepolymer A and curing agent B described in this embodiment are purchased from Dow Corning Corporation (USA), and the model is Poly(dimethylsiloxane) PDMS kit (Sylgard 184).

The advantages of this embodiment:

1. The polyelectrolyte composite with stress-responsive patterned micro-nano structure prepared in this embodiment has a highly sensitive response to humidity, pH and other organic chemicals, which can effectively solve the problem that the existing humidity sensor is expensive and composite The sensor cannot realize industrial production and the problem of composite sensor without relative humidity, acidity and other detection indicators. The polyelectrolyte composites with stress-responsive patterned micro-nano structures prepared in this embodiment can perform accurate, rapid and low-cost detection on foods containing polyelectrolyte food additives on the market; in addition, they are also very sensitive to low relative humidity , the relative humidity can be as low as 20%, when the relative humidity is 20% to 100%, the color change of the polyelectrolyte composite with the stress-responsive patterned micro-nano structure prepared by the present invention can be seen with the naked eye, and Knowing the change of relative humidity, which is impossible for many hygrometers on the market;

2. The polyelectrolyte composite with a stress-responsive patterned micro-nano structure prepared in this embodiment is very sensitive to pH, temperature or hydrophobic chemical components, and is more beneficial to be widely used as a sensor. Even in aqueous solutions, the ionic strength in polyelectrolytes can be calculated. Since the polyelectrolyte composite with the stress-responsive patterned micro-nano structure prepared in this embodiment has biodegradability, the growth of bacteria or the deterioration of the food itself can be detected;

3. In this embodiment, in order to conveniently and effectively detect the preservation status of food and whether it can still be used safely by people, we prepared a polyelectrolyte composite with a stress-responsive patterned micro-nano structure through micro-contact printing technology. It has many phenomena such as metamaterials, and can respond sensitively to humidity, temperature, pH, and ionic strength to change its structure, and then irradiate it with laser or natural light, and read out the patterned micro-nano with stress-responsive structure through spectrum reading. The quality of food is judged by the reflection value or absorption value of the structural polyelectrolyte complex under the action of external stress conditions.

In this embodiment, a polyelectrolyte composite with a stress-responsive patterned micro-nano structure can be obtained.

Embodiment 2: The difference between this embodiment and Embodiment 1 is that the patterned PDMS stamp described in step 1 is a cube whose side length of the array is 10 μm. Others are the same as the first embodiment.

Embodiment 3: The difference between this embodiment and Embodiment 1 or 2 is that the sodium chloride solution of sodium polystyrene sulfonate described in step 2 is sodium polystyrene sulfonate, sodium chloride and distilled water The mixed solution, the concentration of sodium polystyrene sulfonate in the sodium chloride solution of sodium polystyrene sulfonate is 2mg/mL, and the concentration of sodium chloride is 2mol/L; the sodium chloride solution of the polyacrylate It is a mixed solution of polyacrylate, sodium chloride and distilled water, the concentration of polyacrylate in the sodium chloride solution of polyacrylate is 2mg/mL, and the concentration of sodium chloride is 2mol/L. Others are the same as in the first or second embodiment.

Embodiment 4: The difference between this embodiment and Embodiments 1 to 3 is: the sodium chloride solution of polyacrylic acid described in step 2 is a mixed solution of polyacrylic acid, sodium chloride and distilled water, and the chlorinated solution of polyacrylic acid The concentration of polyacrylic acid in the sodium solution is 2mg/mL, and the concentration of sodium chloride is 2mol/L; the sodium chloride solution of the polycyclic aromatic hydrocarbons is the mixed solution of polycyclic aromatic hydrocarbons, sodium chloride and distilled water, and the polycyclic aromatic hydrocarbons The concentration of polycyclic aromatic hydrocarbons in the sodium chloride solution is 2mg/mL, and the concentration of sodium chloride is 2mol/L. Others are the same as those in Embodiments 1 to 3.

Embodiment 5: This embodiment is a polyelectrolyte composite with a stress-responsive patterned micro-nano structure, which is used to judge the stress response to the external environment based on the light diffraction effect.

Embodiment 6: This embodiment is the application of a polyelectrolyte composite with a stress-responsive patterned micro-nano structure as a smart super see-through material.

Embodiment 7: This embodiment is that the polyelectrolyte composite with stress-responsive patterned micro-nano structure is applied in super-resolution technology.

Embodiment 8: This embodiment is the application of a polyelectrolyte composite with a stress-responsive patterned micro-nano structure as a stress-responsive scattering medium.

Embodiment 9: This embodiment is a polyelectrolyte composite with a stress-responsive patterned micro-nano structure based on the change of reaction color and scattering under stress conditions for the quality detection of living food.

Embodiment 10: The present embodiment is that the polyelectrolyte composite with patterned micro-nano structure with stress response can be used in optical sensors based on the principle of microbial degradation, which can undergo structural changes, and can be used based on the principle of stress response to humidity. In the humidity sensor, the principle based on the stress response to pH can be used in the pH sensor.

Adopt the following examples to verify the beneficial effects of the present invention:

Embodiment 1: The preparation method of a polyelectrolyte composite with a stress-responsive patterned micro-nano structure is specifically completed according to the following steps:

1. Preparation of patterned PDMS stamps:

Mix the polydimethylsiloxane prepolymer A and the curing agent B, first stir at a stirring speed of 300 r/min for 5 min, and then centrifuge at a centrifugal speed of 3000 r/min for 5 min to obtain a mixed solution; Pour it into a petri dish with a patterned silicon substrate, and then vacuum the petri dish at 70 °C for 2 h to obtain a patterned PDMS stamp on the silicon substrate; peel the patterned PDMS stamp from the silicon substrate. , get the patterned PDMS stamp;

The mass ratio of the prepolymer A of the polydimethylsiloxane described in the step 1 and the curing agent B is 10:1;

The patterned PDMS stamp described in step 1 is a cube whose side length of the array is 10 μm;

Second, the preparation of polyelectrolyte composites:

The polyelectrolyte electron pair was added into the container, and then magnetically stirred for 20 min at a temperature of 75 °C and a stirring speed of 500 r/min to obtain a polyelectrolyte composite with a flocculent structure in the solution;

The polyelectrolyte electron pair described in step 2 is the mixed solution of PAA/PAH; the mixed solution of described PAA/PAH is the sodium chloride solution of polyacrylic acid and the sodium chloride solution of polycyclic aromatic hydrocarbons according to volume ratio 1:1 The sodium chloride solution of the polyacrylic acid is a mixed solution of polyacrylic acid, sodium chloride and distilled water, and the concentration of the polyacrylic acid in the sodium chloride solution of the polyacrylic acid is 2 mg/mL, and the concentration of the sodium chloride is 2mol/L; the sodium chloride solution of described polycyclic aromatic hydrocarbons is the mixed solution of polycyclic aromatic hydrocarbons, sodium chloride and distilled water, and the polycyclic aromatic hydrocarbon concentration in the sodium chloride solution of polycyclic aromatic hydrocarbons is 2mg/mL, and sodium chloride The concentration is 2mol/L;

3. Take out the polyelectrolyte composite of flocculent structure from the solution, then cover the polyelectrolyte composite of flocculent structure on the patterned PDMS stamp obtained in step 1, and then transfer the polyelectrolyte covered with flocculent structure to the Apply 75kPa to the patterned PDMS stamp of the composite, and then hold the pressure for 10min at a temperature of 60°C and a pressure of 75kPa, and then transfer for 10min, and then combine the polyelectrolyte composite with the patterned PDMS stamp. separation to obtain a polyelectrolyte composite with stress-responsive patterned micro-nano structures;

The transfer described in step 3 is thermal transfer, and the transfer temperature is 60°C;

The thickness of the polyelectrolyte composite with stress-responsive patterned micro-nano structures described in step 3 is 10 μm.

The polydimethylsiloxane prepolymer A and curing agent B described in step 1 of Example 1 were purchased from Dow Corning Corporation (USA), and the model is Poly(dimethylsiloxane) PDMS kit (Sylgard 184).

Embodiment 2: The difference between this embodiment and Embodiment 1 is that the transfer described in step 3 is thermal transfer, and the transfer temperature is 100°C. Other steps and parameters are the same as the first embodiment.

Embodiment 3: The difference between this embodiment and Embodiment 1 is that the polyelectrolyte electron pair described in step 2 is a mixture of PSS/PDDA; the mixture of PSS/PDDA is sodium polystyrene sulfonate The sodium chloride solution and the sodium chloride solution of polyacrylate are mixed according to the volume ratio of 1:1; the sodium chloride solution of the sodium polystyrene sulfonate is sodium polystyrene sulfonate, sodium chloride and The mixed solution of distilled water, the concentration of sodium polystyrene sulfonate in the sodium chloride solution of sodium polystyrene sulfonate is 2mg/mL, and the concentration of sodium chloride is 2mol/L; the sodium chloride of the polyacrylate The solution is a mixed solution of polyacrylate, sodium chloride and distilled water, the concentration of polyacrylate in the sodium chloride solution of polyacrylate is 2 mg/mL, and the concentration of sodium chloride is 2 mol/L. Other steps and parameters are the same as the first embodiment.

Figure 1 is a process flow diagram of a polyelectrolyte composite with a stress-responsive patterned micro-nano structure prepared in Example 1. In Figure 1, 1 is a polyelectrolyte composite with a flocculent structure, and 2 is a patterned PDMS seal. 3 is the square of the array on the patterned PDMS stamp, 4 is the transfer pressure and heat preservation, 5 is the height of the array on the patterned PDMS stamp is 10 μm, 6 is the square of the array on the patterned PDMS stamp The width is 10 μm, 7 is the polyelectrolyte composite after transfer, 8 is the polyelectrolyte composite separated from the patterned PDMS stamp, and 9 is the polyelectrolyte composite with stress-responsive patterned micro-nano structures.

The electron microscope pictures involved in the present invention are tested by an electron microscope (model: Quanta 3D ESEM, Hillsboro, USA); the optical photos are tested by a red-green laser pointer (wavelengths are 523,650nm, UK);

The polyelectrolyte composites with stress-responsive patterned micro-nanostructures (fixed sample distance from the laser pointer) were irradiated with red and green lasers (laser pointer with dual wavelengths, the wavelength of red light was 650 nm, and the wavelength of green light was 532 nm), respectively. and the distance of the sample from the white screen of the scattering picture), after obtaining the scattering picture, use the trigonometric function (Formula 1) to calculate the corresponding scattering angle value.

Q represents 1/nm, λ is the wavelength of the laser, and θ is the angle between the line connecting the laser irradiation point and the scattering center of the sample and the line connecting the laser irradiation point and the pattern scattering point. as shown in picture 2.

FIG. 2 is a schematic diagram of a device that scatters after two laser pointers with different wavelengths in Example 1 pass through the polyelectrolyte composite with stress-responsive patterned micro-nano structures prepared in Example 1, and 1 in FIG. 2 is red Green laser pointer, 2 is the polyelectrolyte composite with stress-responsive patterned micro-nano structures prepared in Example 1, and 3 is a white screen;

Fig. 3 is the SEM image of the patterned PDMS seal obtained in the first step of Example 1;

It can be seen from FIG. 3 that the pattern of the silicon substrate can be negatively replicated by the PDMS casting method, and the small convex pattern arrayed with the same size can be obtained from the micron-level small well pattern.

4 is a SEM image of the polyelectrolyte composite with stress-responsive patterned micro-nano structures obtained in step 3 of Example 1;

It can be seen from Figure 4 that the array patterned polyelectrolyte composite film can be prepared by the microcontact printing method, and the shape is regular.

Irradiate the patterned PDMS stamp obtained in step 1 of Example 1 with a green laser pointer, and the resulting scattering picture is shown in Figure 5;

Fig. 5 is the scattering picture produced by the green laser pointer through the patterned PDMS seal obtained in the first step of Example 1;

It can be seen from Figure 5 that the laser beam has a scattering effect through the patterned PDMS stamp.

The surface structure of the PDMS stamp obtained by Fourier transformation of Figure 5 is shown in Figure 6;

Fig. 6 is the surface structure of the real PDMS obtained by performing Fourier transform of Fig. 4;

It can be seen from FIG. 6 that the patterned PDMS stamp obtained in step 1 of Example 1 is an array of square protrusions at the micro-nano level.

We placed the polyelectrolyte composite with stress-responsive patterned micro-nano structures prepared in Example 1 in the test environment of different wavelengths of the laser pointer, and compared with different air humidity, as shown in Figure 7 and Figure 8;

7 is a picture of the polyelectrolyte composite with stress-responsive patterned micro-nano structures prepared in Example 1 placed under the condition of 35% humidity and irradiating the sample with a green laser pointer and scattering;

FIG. 8 is a picture of the polyelectrolyte composite with stress-responsive patterned micro-nano structures prepared in Example 1 placed under 100% humidity conditions irradiating the sample with a green laser pointer and scattering;

It can be seen from Fig. 7 and Fig. 8 that under different relative humidity environments, the patterned polyelectrolyte composite films have different scattering patterns for the passing green laser light.

FIG. 9 is the characteristic size 1/Q curve of the polyelectrolyte composite with stress-responsive patterned micro/nano structures calculated by FIG. 7 , and 1 in FIG. 9 is the polyelectrolyte with stress-responsive patterned micro/nano structures The characteristic size 1/Q curve of the composite placed under the condition of 35% humidity, 2 is the characteristic size 1/Q curve of the polyelectrolyte composite with stress-responsive patterned micro-nano structure placed under the condition of 100% humidity ;

From FIG. 9, the relationship between the laser scattering intensity and the feature map by size can be seen.

Fig. 10 is an enlarged view of A in Fig. 9, Fig. 10 is the characteristic size 1/Q curve of the polyelectrolyte composite with stress-responsive patterned micro-nano structure placed under the condition of 35% humidity, 2 is Characteristic size 1/Q curves of stress-responsive patterned micro-nanostructured polyelectrolyte composites placed under 100% humidity;

It can be seen from FIG. 10 that the feature map of the prepared patterned polyelectrolyte composite is about 10 microns in size.

Fig. 11 is the Q-value curve of the polyelectrolyte composite with stress-responsive patterned micro-nano structure calculated by Fig. 7, and 1 in Fig. 11 is the placement of the polyelectrolyte composite with stress-responsive patterned micro-nano structure The Q value curve under the condition of 35% humidity, 2 is the Q value curve of the polyelectrolyte composite with stress-responsive patterned micro-nano structure placed under the condition of 100% humidity;

It can be seen from Fig. 11 that the calculated Q values of the same patterned polyelectrolyte composite are significantly different under different humidity conditions.

In Example 2, the transfer temperature was 100°C, that is, cross-linking by heating, and the polyelectrolyte composite with stress-responsive patterned micro-nano structures prepared by cross-linking by heating in Example 2 was tested, as shown in Figure 12 ~15 shown;

12 is a confocal scanning microscope image of the FITC channel of the polyelectrolyte complex with stress-responsive patterned micro-nanostructures prepared by cross-linking by heating;

It can be seen from FIG. 12 that after the polyelectrolyte composite (PAA/PAH) is thermally cross-linked, the shape of the fluorescently labeled PEC is regular.

Figure 13 is a confocal scanning laser microscope image of the RITC channel of the polyelectrolyte composite with stress-responsive patterned micro-nanostructures prepared by cross-linking under 100% humidity for 30 min;

It can be seen from Figure 13 that the patterned polyelectrolyte composite film, after thermal crosslinking, can still maintain a relatively stable pattern structure even if the relative humidity of the environment is increased.

14 is a confocal scanning microscope image of the RITC channel of the polyelectrolyte complex with stress-responsive patterned micro-nanostructures prepared by cross-linking by heating;

It can be seen from Fig. 14 that the pattern of the prepared polyelectrolyte composite is regular.

Fig. 15 is a bright field confocal scanning microscope image of the polyelectrolyte composite with stress-responsive patterned micro-nano structures prepared without cross-linking by heating under 100% humidity for 30 min;

It can be seen from FIG. 15 that the patterned polyelectrolyte composite film without thermal crosslinking is difficult to maintain the integrity of the pattern under the condition of increasing the relative humidity of the environment.

Figure 16 is a picture of the polyelectrolyte composite with a stress-responsive patterned micro-nano structure prepared in Example 1 placed under the condition of 35% humidity and irradiating the sample with a green laser pointer and scattering;

It can be seen from Fig. 16 that under the condition of relative humidity of 35%, a relatively complete picture of laser scattering can be obtained.

FIG. 17 is a picture of the polyelectrolyte composite with the stress-responsive patterned micro-nano structure prepared in Example 1 placed under the condition of 100% humidity and irradiating the sample with a green laser pointer and scattering;

As can be seen from Figure 17, compared with the relative humidity of 35%, the relative humidity of 100% will destroy the pattern of the microstructure, so that the relative humidity of the environment at that time can be displayed through the laser scattering pattern, that is, the stress-responsive material can be used. effect.

FIG. 18 is the characteristic size 1/Q curve of the polyelectrolyte composite with stress-responsive patterned micro-nano structures calculated from FIG. 16 , and 1 in FIG. 16 is the patterned micro-nano structure with stress response of Example 1. The characteristic size 1/Q curve of the structured polyelectrolyte composite placed under the condition of 35% humidity, 2 is the polyelectrolyte composite with stress-responsive patterned micro-nano structure prepared in Example 1 placed at 100% humidity The characteristic size 1/Q curve under the condition;

Fig. 19 is an enlarged view of part A in Fig. 18, and 1 in Fig. 19 is the feature size 1/Q of the polyelectrolyte composite with stress-responsive patterned micro-nano structures of Example 1 placed under the condition of 35% humidity Curve, 2 is the characteristic size 1/Q curve of the polyelectrolyte composite with stress-responsive patterned micro-nano structure prepared in Example 1 placed under the condition of 100% humidity;

It can be seen from Figure 18 and Figure 19 that through the comparison of the feature sizes of the uncrosslinked polyelectrolyte composites at different relative humidity, it can be seen that when the relative humidity is high, the micron-level pattern changes significantly and loses the feature size. .

FIG. 20 is the Q-value curve of the polyelectrolyte composite with stress-responsive patterned micro-nanostructures prepared in Example 1 calculated from FIG. 17 , and 1 in FIG. 20 is the pattern with stress-responsive prepared in Example 1 The Q value curve of the polyelectrolyte composite with the micro-nano structure of the micro-nano structure placed under the condition of 35% humidity, 2 is the polyelectrolyte composite with the stress-responsive patterned micro-nano structure prepared in Example 1 placed in the humidity of 100% The Q value curve under the condition;

It can be seen from Fig. 20 that the Q values calculated at different relative humidity for the laser scattering pattern of the polyelectrolyte composite without thermal crosslinking. Compared with the cross-linked polyelectrolyte composite, the humidity change is more obvious.

Figure 21 is an ordinary optical microscope picture of the polyelectrolyte composite with stress-responsive patterned micro-nano structures prepared in Example 3;

It can be seen from Figure 21 that the uncrosslinked PSS/PDDA polyelectrolyte composite has a relatively complete pattern shape when the relative humidity is 35%.

Figure 22 is an ordinary optical microscope image of the polyelectrolyte composite with stress-responsive patterned micro-nano structures prepared in Example 3 placed under 100% humidity for 15 minutes;

It can be seen from Figure 22 that the uncrosslinked PSS/PDDA polyelectrolyte composite patterned film completely lost its original microstructure.

Fig. 23 is a comparison diagram of the polyelectrolyte composite in the light dispersion measurement. In Fig. 23, 1 is the UV-Vis absorption spectrum of the patterned film of the polyelectrolyte composite obtained in step 3 of Example 1, and 2 is the flat polyelectrolyte composite. UV-Vis absorption spectrum of the film;

It can be seen from FIG. 23 that the pattern structure for micro-nano is the basis for the formation of the laser scattering pattern.

Claims (10)

1. The preparation method of the polyelectrolyte composite of patterned micro-nano structure with stress response is characterized in that the method is specifically completed according to the following steps: 1. Preparation of patterned PDMS stamps: Mix the polydimethylsiloxane prepolymer A and the curing agent B, firstly at a stirring speed of 200r/min～500r/min for 5min～8min, and then at a centrifugal speed of 3000r/min～4000r/min Centrifuge for 5 min to 8 min to obtain a mixed solution; pour the mixed solution into a petri dish with a patterned silicon substrate, and then vacuum the petri dish at a temperature of 60 ℃ to 80 ℃ for 1 h to 3 h to obtain on the silicon substrate The patterned PDMS stamp; the patterned PDMS stamp is peeled off from the silicon substrate to obtain the patterned PDMS stamp; The mass ratio of the prepolymer A of the polydimethylsiloxane described in the step 1 and the curing agent B is 10:1; Second, the preparation of polyelectrolyte composites: The polyelectrolyte electron pair is added to the container, and then magnetically stirred at a temperature of 70°C to 80°C and a stirring speed of 300r/min to 800r/min for 15min to 25min to obtain a polyelectrolyte complex with a flocculent structure in the solution; The polyelectrolyte electron pair described in step 2 is the mixed solution of PSS/PDDA or the mixed solution of PAA/PAH; the mixed solution of PSS/PDDA is the sodium chloride solution of sodium polystyrene sulfonate and polyacrylate The sodium chloride solution is mixed according to the volume ratio of 1:1; the mixed solution of PAA/PAH is the sodium chloride solution of polyacrylic acid and the sodium chloride solution of polycyclic aromatic hydrocarbons mixed according to the volume ratio of 1:1. ; 3. Take out the polyelectrolyte composite of flocculent structure from the solution, then cover the polyelectrolyte composite of flocculent structure on the patterned PDMS stamp obtained in step 1, and then transfer the polyelectrolyte covered with flocculent structure to the Apply 20kPa~130kPa to the patterned PDMS stamp of the composite, and then hold the pressure for 5min~15min at a temperature of 60℃~75℃ and a pressure of 20kPa~130kPa, and then transfer the transfer. The transfer time is 5min~15min, and then The polyelectrolyte complex was separated from the patterned PDMS stamp to obtain a polyelectrolyte complex with a stress-responsive patterned micro-nano structure; The transfer described in step 3 is thermal transfer, and the transfer temperature is 60°C to 100°C; The thickness of the polyelectrolyte composite with the stress-responsive patterned micro-nano structure described in step 3 is 0.1 μm˜30 μm. 2 . The method for preparing a polyelectrolyte composite with stress-responsive patterned micro-nano structures according to claim 1 , wherein the patterned PDMS stamp in step 1 is an array with a side length of 10 μm. 3 . cube. 3. The preparation method of the polyelectrolyte composite with stress-responsive patterned micro-nano structures according to claim 1, wherein the sodium chloride solution of the sodium polystyrene sulfonate described in step 2 is a polyelectrolyte The mixed solution of sodium styrene sulfonate, sodium chloride and distilled water, the concentration of sodium polystyrene sulfonate in the sodium chloride solution of sodium polystyrene sulfonate is 2mg/mL, and the concentration of sodium chloride is 2mol/L; The sodium chloride solution of the polyacrylate is a mixed solution of polyacrylate, sodium chloride and distilled water, the concentration of the polyacrylate in the sodium chloride solution of the polyacrylate is 2 mg/mL, and the concentration of the sodium chloride is 2mol/L. 4. The preparation method of polyelectrolyte composite with stress-responsive patterned micro-nano structure according to claim 1, wherein the sodium chloride solution of polyacrylic acid described in step 2 is polyacrylic acid, chlorinated The mixed solution of sodium and distilled water, the concentration of polyacrylic acid in the sodium chloride solution of polyacrylic acid is 2mg/mL, and the concentration of sodium chloride is 2mol/L; the sodium chloride solution of described polycyclic aromatic hydrocarbons is polycyclic aromatic hydrocarbons, The mixed solution of sodium chloride and distilled water, the concentration of polycyclic aromatic hydrocarbons in the sodium chloride solution of polycyclic aromatic hydrocarbons is 2 mg/mL, and the concentration of sodium chloride is 2 mol/L. 5 . The application of the polyelectrolyte composite with stress-responsive patterned micro-nano structures as claimed in claim 1 , wherein the polyelectrolyte composite with stress-responsive patterned micro-nano structures is used based on the light diffraction effect. To judge the stress response to the external environment. 6. The application of the polyelectrolyte composite with stress-responsive patterned micro-nano structures as claimed in claim 1, wherein the polyelectrolyte composite with stress-responsive patterned micro-nano structures is used as a smart super see-through material application. 7. The application of the polyelectrolyte composite with stress-responsive patterned micro-nano structures as claimed in claim 1, wherein the polyelectrolyte composite with stress-responsive patterned micro-nano structures is applied to super resolution in technology. 8 . The application of the polyelectrolyte composite with stress-responsive patterned micro-nano structures as claimed in claim 1 , wherein the polyelectrolyte composite with stress-responsive patterned micro-nano structures is used as a stress-responsive polyelectrolyte composite. 9 . Scattering media applications. 9 . The application of the polyelectrolyte composite with stress-responsive patterned micro-nano structures according to claim 1 , wherein the polyelectrolyte composite with stress-responsive patterned micro-nano structures is based on stress conditions. 10 . Changes in reaction color and scattering are used for quality inspection of living food. 10. The application of the polyelectrolyte composite with stress-responsive patterned micro-nano structures as claimed in claim 1, wherein the polyelectrolyte composite with stress-responsive patterned micro-nano structures can occur based on microbial degradation The principle of structural change can be used in optical sensors, the principle based on stress response to humidity can be used in humidity sensor, and the principle based on stress response to pH can be used in pH sensor.