CN113248731A - PNIPAm/PPy composite hydrogel and preparation method and application thereof - Google Patents
PNIPAm/PPy composite hydrogel and preparation method and application thereof Download PDFInfo
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
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Abstract
The invention belongs to the field of high polymer materials, and particularly relates to PNIPAm/PPy composite hydrogel and a preparation method and application thereof. The PNIPAm/PPy composite hydrogel is prepared by taking the PNIPAm hydrogel as a matrix and quickly carrying out phase transition through the absorption of heat by PPy. The polypyrrole has a larger p-pi conjugated framework and a high electron delocalized structure, shows excellent light amplification and light capture characteristics in a near infrared region, has good stability and high photothermal conversion efficiency, and is used for adapting to climate change and adjusting the transmittance of sunlight. The energy-saving effect is remarkable, and the PNIPAm rapidly changes the phase to reduce the transmission of near infrared light in summer, thereby playing a role in cooling; the effect of indoor temperature rise is achieved by absorbing the near infrared light to radiate heat indoors in winter. Meanwhile, the visible light transmittance of the curtain is approximately zero after phase change, and the curtain can play a role of an intelligent curtain. The PNIPAm/PPy composite hydrogel provided by the invention has the advantages of simple preparation method and low cost, and is beneficial to industrial production and application.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to PNIPAm/PPy composite hydrogel and a preparation method and application thereof.
Background
At present, the energy consumption of buildings accounts for about 40% of the total energy consumption of national economy, the window has poor heat insulation performance, and is the most serious part of energy loss in building components, and the energy loss caused by the window exceeds 50% of the energy consumption of the buildings. Therefore, reasonable control of heat exchange between the window and the outside is important for building energy conservation. The solar radiation energy is mainly concentrated in the wavelength range of 0.25-2.5 microns and comprises ultraviolet light (UV), visible light (Vis) and near infrared light (NIR), wherein the NIR radiation energy exceeds 50% of the total solar radiation energy, so that the near NIR transmission is reduced in summer, the NIR transmission is increased in winter, and the solar radiation energy has profound significance for building energy conservation.
Currently common intelligent windows include thermochromic, gasochromic, electrochromic and other intelligent windows. The thermochromic intelligent window can respond to the change of the environmental temperature and spontaneously change the state, so that the transmission of near infrared light is adjusted, and the thermochromic intelligent window is an optimal building energy-saving material. Common thermochromic materials include: VO (vacuum vapor volume)2Ionic liquids, perovskites, thermochromic hydrogels, and the like. Since the thermochromic hydrogel is closest to the building energy-saving temperature requirement (28 ℃), the thermochromic hydrogel attracts much attention in recent years. The poly-N-isopropylacrylamide (PNIPAm) is common thermochromic hydrogel, has hydrophilic amide groups and hydrophobic isopropyl groups, and when the temperature is lower than the lowest eutectic temperature (LCST), polymer chains stretch due to the action of hydrogen bonds, the solution is transparent, and near infrared light is allowed to penetrate as far as possible; when the temperature is higher than LCST, hydrogen bonds are broken, polymer chains are aggregated, the solution is opaque,effectively block near infrared light from passing through. But the method has the defect of slow response speed, and the application of the method in the intelligent window is seriously influenced.
Disclosure of Invention
In view of the above, the present invention aims to overcome the defects in the prior art and provide a PNIPAm/PPy composite thermochromic hydrogel. The hydrogel combines thermochromic hydrogel (PNIPAm) with photothermal conversion material polypyrrole (PPy), and overcomes the defect of low response speed of the PNIPAm hydrogel. When the infrared light-transmitting window is applied to an intelligent window, the transmission of near infrared light can be reduced in summer, the indoor heat radiation is reduced, and the indoor heat loss is reduced in winter, so that the effects of being warm in winter and cool in summer are achieved.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides PNIPAm/PPy composite hydrogel, wherein the PPy in the composite hydrogel is microspherical, the average particle size is 400-800 nm, and the PNIPAm is network; the PPy grows on the surface of the network-shaped PNIPAm in a microsphere form.
The invention also provides a preparation method of the PNIPAm/PPy composite hydrogel, which comprises the following steps:
(1) stirring PVP in pure water to form PVP micelles, adding PNIPAm and BIS in an inert atmosphere, uniformly mixing, adding KPS, and carrying out polymerization reaction for a period of time to obtain PNIPAm hydrogel;
(2) PVP is stirred in pure water to form PVP micelles, pyrrole and KPS are added and mixed evenly, and a soluble PPy solution is obtained through low-temperature reaction;
(3) and (3) adding the PPy solution prepared in the step (2) into the PNIPAm hydrogel obtained in the step (1), ultrasonically stirring uniformly at a low temperature, dialyzing to obtain a PNIPAm/PPy composite hydrogel system, and carrying out vacuum freeze drying to obtain the PNIPAm/PPy composite hydrogel.
Further, the dosage relationship of PVP, pure water, PNIPAm, BIS and KPS in the step (1) is as follows: 0.02-0.1 g: 50mL of: 0.5-1 g: 0.005-0.16 g: 0.02-0.032 g.
Dissolving at the stirring temperature of 35-50 ℃ in the step (1), wherein the stirring time is 30-60 min; the temperature of the polymerization reaction is 60-70 ℃, and the time is 4-6 h.
The usage relationship of PVP, pure water, pyrrole and KPS in the step (2) is as follows: 0.2-0.8 g: 50mL of: 0.35-0.69 mL: 1.85-2.7 g.
The low-temperature reaction in the step (2) is carried out for 1-3 hours in an environment with the temperature lower than 5 ℃.
The volume ratio of the PPy solution to the PNIPAm hydrogel in the step (3) is 1: 1-10; the low temperature is less than 5 ℃, and the ultrasonic time is 0.5-1 h; and the dialysis is carried out for 48-72 h by using a 1000 Da dialysis bag.
Further, the PVP is PVP-K30, and the molecular weight is 44000-54000.
The invention also provides application of the PNIPAm/PPy composite hydrogel in the field of thermochromic materials. Specifically, PNIPAm/PPy composite hydrogel is used as filling and packaged between device interlayers, and is applied to the fields of intelligent response, intelligent glass, flexible devices and aerospace.
Compared with the prior art, the invention has the beneficial effects that:
the PNIPAm/PPy composite hydrogel is prepared by taking poly-N-isopropyl acrylamide hydrogel as a matrix and rapidly carrying out phase transition through the absorption of heat by a conjugated polymer polypyrrole. The polypyrrole has a larger p-pi conjugated framework and a high electron delocalized structure, shows excellent light amplification and light capture characteristics in a near infrared region, has good stability and high photothermal conversion efficiency, and is used for adapting to climate change and adjusting the transmittance of sunlight. The energy-saving effect is remarkable, and the PNIPAm rapidly changes the phase to reduce the transmission of near infrared light in summer, thereby playing a role in cooling; the effect of indoor temperature rise is achieved by absorbing the near infrared light to radiate heat indoors in winter. Meanwhile, the visible light transmittance of the curtain is approximately zero after phase change, and the curtain can play a role of an intelligent curtain. The PNIPAm/PPy composite hydrogel provided by the invention has the advantages of simple preparation method and low cost, and is beneficial to industrial production and application.
Drawings
FIG. 1 is a FT-IR plot of the PPy, PNIPAm and PNIPAm/PPy composite hydrogels prepared in example 1;
FIG. 2 is an SEM image of the PPy, PNIPAm, PNIPAm/PPy composite hydrogel prepared in example 1; wherein a is PPy, b is PNIPAm, and c-d are PNIPAm/PPy;
FIG. 3 is a schematic view of a laminated glass assembly;
FIG. 4 is a schematic view of a thermal insulation performance test;
FIG. 5 is a graph of temperature change;
fig. 6 is a graph of infrared imaging after different times.
Detailed Description
The invention discloses PNIPAm/PPy composite hydrogel and a preparation method and application thereof. Those skilled in the art can modify the process parameters appropriately to achieve the desired results with reference to the disclosure herein. It is expressly intended that all such similar substitutes and modifications which would be obvious to one skilled in the art are deemed to be included in the invention. The embodiments described below are only a part of the embodiments of the present invention, and not all of them. While the methods and products of the present invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications of the methods described herein, as well as other suitable variations and combinations, may be made to implement and use the techniques of the present invention without departing from the spirit and scope of the invention.
Unless otherwise specified, the reagents involved in the examples of the present invention are all commercially available products, and all of them are commercially available.
Example 1
(1) Preparation of PNIPAm hydrogel:
dissolving 0.02g of polyvinylpyrrolidone (PVP) with the molecular weight of 58000 into 50mL of pure water, transferring the pure water into a 250 mL three-neck flask, stirring the pure water at 35 ℃ for 60 min to form stable micelles, adding 1g of PNIPAm and 0.01 g of cross-linking agent N, N' -methylenebis (acrylamide) (BIS) under the stirring inert atmosphere at 60 ℃, uniformly stirring the mixture, heating the mixture to 60 ℃, adding 0.02g of initiator potassium persulfate (KPS) after the temperature is stable, stirring the mixture at 60 ℃ for 4 h, naturally cooling the mixture to room temperature to obtain PNIPAm hydrogel, and performing vacuum freeze drying to obtain the PNIPAm hydrogel solid.
(2) Preparation of soluble PPy solution:
dissolving 0.2 g of PVP with the molecular weight of 58000 into 50mL of pure water, stirring uniformly to form a gel, transferring the gel into a 250 mL single-neck flask, adding 0.69 mL of pyrrole and 2.7 g of KPS into the PVP solution, reacting for 2 hours in an ice-water bath (<5 ℃) to obtain a soluble PPy solution, and carrying out vacuum freeze drying to obtain PPy powder.
(3) Preparation of PNIPAm/PPy composite hydrogel:
and (3) adding 10mL of the PPy solution prepared in the step (2) into 10mL of the PNIPAm hydrogel obtained in the step (1), ultrasonically stirring for 1h at low temperature (<5 ℃), copolymerizing incompletely polymerized PPy and PNIPAm to enable the PPy to grow on the surface of the PNIPAm, dialyzing for 48 h by using a 1000 Da dialysis bag, removing residual initiator crosslinking agent in the solution, obtaining a PNIPAm/PPy composite hydrogel system, and performing vacuum freeze drying to obtain the PNIPAm/PPy composite hydrogel.
FIG. 1 is a FT-IR plot of the PPy, PNIPAm and PNIPAm/PPy composite hydrogels prepared in this example; as can be seen from FIG. 1, PNIPAm is 3266 cm-1from-N-H-stretching vibration, 2971 cm-1Stretching vibration from-C-H-, 1653 cm-1Stretching vibration from-C-N-, 1541 cm-1A telescopic absorption peak from C = O; PPy is at 3266 cm-1from-N-H-stretching vibration, 1700 cm-1Stretching vibration from pyrrole-C-N-, 1050 cm-1Characteristic peak at pyrrole = C-N; the prepared PNIPAm/PPy composite hydrogel has a PNIPAm characteristic peak at 1000 cm-1The characteristic functional group C = N-H of PPy appeared here, indicating that PNIPAm/PPy composite hydrogel was successfully prepared.
FIG. 2 is an SEM image of the PPy, PNIPAm, PNIPAm/PPy composite hydrogel prepared in this example; wherein a is PPy, b is PNIPAm, and c-d are PNIPAm/PPy and an enlarged image thereof; as can be seen from FIG. 2, the prepared PPy is in a microspherical structure, the prepared PNIPAm hydrogel is in a network structure, the average particle size of PPy microspheres in the PNIPAm/PPy composite hydrogel is 400-800 nm, and the PPy microspheres grow and are attached to the surface of the PNIPAm network structure.
And (3) performing phase transition time test on the prepared PNIPAm/PPy composite hydrogel: the prepared PNIPAm/PPy composite hydrogel is packaged into laminated glass as shown in figure 3, and the phase transition time of the composite hydrogel is tested under the irradiation of a xenon lamp (simulated sunlight). The test result shows that the phase change of the PNIPAm/PPy composite hydrogel can be realized within 3 min, and the phase change of the PNIPAm hydrogel serving as the comparative example gradually occurs after 10 min.
Example 2
(1) Dissolving 0.05 g PVP with molecular weight of 58000 in 50mL of pure water, stirring at 40 deg.C for 30 min to form stable micelle, and stirring at 65 deg.C for N2Adding 0.8g of PNIPAm and 0.016 g of cross-linking agent BIS under the atmosphere, uniformly stirring, heating to 60 ℃, adding 0.032 g of initiator KPS after the temperature is stable, heating and stirring at 60 ℃ for 6 h, stopping reaction, naturally cooling to room temperature to obtain PNIPAm hydrogel, and performing vacuum freeze drying to obtain solid PNIPAm;
(2) dissolving 0.5 g PVP with the molecular weight of 58000 into 50mL of pure water, stirring uniformly to form a gel, adding 0.69 mL of pyrrole and 2.25 g of KPS into the mixed solution, reacting for 3 hours in an ice water bath (<5 ℃) to obtain a soluble PPy solution, and carrying out vacuum freeze drying to obtain PPy powder.
(3) And (3) adding 10mL of the PPy solution prepared in the step (2) into 50mL of the PNIPAm hydrogel obtained in the step (1), ultrasonically stirring for 0.5 h at a low temperature (<5 ℃), dialyzing for 60 h by using a 1000 Da dialysis bag, removing residual initiator crosslinking agent to obtain a PNIPAm/PPy composite hydrogel system, and performing vacuum freeze drying to obtain the PNIPAm/PPy composite hydrogel.
And (3) performing phase transition time test on the prepared PNIPAm/PPy composite hydrogel: the prepared PNIPAm/PPy composite hydrogel is packaged into laminated glass as shown in figure 3, and the phase transition time of the composite hydrogel is tested under the irradiation of a xenon lamp (simulated sunlight). The test result shows that the phase change of the PNIPAm/PPy composite hydrogel can be realized within 4min, and the phase change of the PNIPAm hydrogel obtained in the step (1) gradually occurs after 12 min.
Example 3
(1) Dissolving 0.1 g PVP with molecular weight of 58000 in 50mL pure water, stirring at 50 deg.C for 30 min to form stable micelle, and stirring at 70 deg.C for N2Adding 0.5 g NIPAm and 0.005 g crosslinking agent BIS under atmosphere,stirring uniformly, heating to 70 ℃, adding 0.02g of initiator KPS after the temperature is stable, heating and stirring at 70 ℃ for 5 hours, stopping reaction, naturally cooling to room temperature to obtain PNIPAm hydrogel, and performing vacuum freeze drying to obtain solid PNIPAm. (ii) a
(2) Dissolving 0.8g of PVP with the molecular weight of 58000 into 50mL of pure water, stirring uniformly to form a gel, adding 0.35 mL of pyrrole and 1.85 g of KPS, reacting for 1h in an ice water bath (at the temperature of less than 5 ℃) to obtain a soluble PPy solution, and carrying out vacuum freeze drying to obtain PPy powder;
(3) and (3) adding 10mL of the PPy solution prepared in the step (2) into 100mL of the PNIPAm hydrogel obtained in the step (1), ultrasonically stirring for 1h at a low temperature (<5 ℃), dialyzing for 72 h by using a 1000 Da dialysis bag, removing the residual initiator crosslinking agent to obtain a PNIPAm/PPy composite hydrogel system, and freeze-drying in vacuum to obtain the PNIPAm/PPy composite hydrogel.
And (3) performing phase transition time test on the prepared PNIPAm/PPy composite hydrogel: the prepared PNIPAm/PPy composite hydrogel is packaged into laminated glass as shown in figure 3, and the phase transition time of the composite hydrogel is tested under the irradiation of a xenon lamp (simulated sunlight). The test result shows that the phase change of the PNIPAm/PPy composite hydrogel can be realized within 5 min, and the phase change of the PNIPAm hydrogel obtained in the step (1) gradually occurs after 10 min.
Example 4
In this embodiment, a PNIPAm/PPy composite hydrogel laminated glass device is constructed as shown in fig. 3, and the PNIPAm/PPy composite hydrogel is encapsulated in the laminated glass device, and the specific encapsulation steps are as follows:
(1) ultrasonically cleaning two glass plates with length of 20 mm, width of 20 mm and thickness of 1.2 mm for 10 min by using acetone, ethanol and deionized water2Drying for later use;
(2) fixing one of the glass substrate frames by using a transparent 3M double-sided adhesive tape with the thickness of 1 mm, curing for 12-24 h at room temperature, reserving a gap of 1 mm in the middle of the tail part of the glass substrate, and reserving gaps of 1 mm in the edge part of the top part of the glass substrate respectively, so that the hydrogel can be conveniently injected and the air of the laminated glass can be conveniently discharged;
(3) pressing the other glass substrate on the glass substrate adhered with the 3M adhesive tape, and sealing a gap of 1 mm reserved at the bottom by using epoxy resin when the glass substrate is firmly adhered, so as to prevent liquid from being reserved from the bottom;
(4) sucking a proper amount of the prepared composite hydrogel by using an injector, injecting the hydrogel from a gap reserved at the top, and continuously sealing the gap by using epoxy resin after the injection is finished. And repeatedly checking to see whether bubbles are remained or not, and if not, indicating that the assembly of the laminated glass device for packaging the PNIPAm/PPy composite hydrogel is finished.
The phase transition time test of the PNIPAm/PPy composite hydrogel prepared in the embodiment 1-3 is carried out by using a laminated glass device for encapsulating the PNIPAm/PPy composite hydrogel: the phase transition time of the composite hydrogel was tested under irradiation of a xenon lamp (simulated sunlight). The test result shows that the PNIPAm/PPy composite hydrogel can realize phase change within 3-5 min, and the PNIPAm hydrogel obtained in the step (1) gradually undergoes phase change after 10-12 min. Therefore, the prepared PNIPAm/PPy composite hydrogel has relatively excellent photoresponse characteristic, can realize thermochromism in a short time, and achieves the effect of adjusting the indoor temperature.
Example 5
In this example, the PNIPAm/PPy composite hydrogel laminated glass device constructed in example 3 was assembled into an energy saving device as shown in fig. 4. Simulating sunlight by using a xenon lamp to perform irradiation for 20min, performing heat preservation and fixation treatment by using heat insulation foam, placing PNIPAm/PPy composite hydrogel laminated glass (PNIPAm/PPy group) on the surface of a test tube opening, wherein the distance between the xenon lamp and the laminated glass is 0.2-0.5 m, and recording the change condition of the water temperature in the test tube by using an infrared thermal imager under the irradiation condition of the xenon lamp. Meanwhile, the laminated glass encapsulating the PNIPAm hydrogel (PNIPAm group) and the laminated glass not encapsulating the hydrogel (Blank group) were used as control groups, respectively.
FIG. 5 is a graph of temperature change; FIG. 6 is a graph of infrared imaging after various times; as can be seen from FIGS. 5 and 6, the water temperature in the test tubes of each group showed a clear trend of temperature change from 3 min, and the PNIPAm/PPy group showed a slower rise in water temperature than the PNIPAm group and Blank group, which was 0.9 deg.C lower than the PNIPAm group at 10 min, and which was lower than the Blank group at 20minThe temperature was 3.5 ℃ lower and the temperature of the PNIPAm/PPy group rose relatively slowly with time. After the irradiation is stopped, the temperature of the PNIPAm/PPy group is slowly decreased, so that the good heat preservation and insulation effect of the PNIPAm/PPy composite hydrogel is reflected. The PNIPAm/PPy composite hydrogel can generate phase change under the irradiation condition after 3 min, and the light transmittance is reduced after the phase change, so that the temperature of water is lower than that of a PNIPAm group and a Blank group, and the rising speed of the water temperature in a test tube can be obviously reduced. Therefore, the PNIPAm/PPy composite hydrogel can be applied to an intelligent window to effectively adjust the indoor temperature, and has the effects of energy conservation and heat preservation. In summer, the PPy in the PNIPAm/PPy composite hydrogel absorbs near infrared to accelerate the phase change of the PNIPAm and reduce the indoor temperature in summer. Because the PPy solution has near infrared light with the wavelength of 1064 nm, the PPy solution has low power (0.5W/m)2) The solar energy can still reach a higher temperature (40.6 ℃) after being irradiated for 10 min under the light intensity, so that the solar energy can be absorbed in winter, the light energy is converted into heat, a heat wall is formed to block the loss of the indoor temperature, the loss of the indoor temperature is prevented to a certain extent, the heat insulation effect is achieved, and the purposes of being warm in winter and cool in summer are achieved. The PNIPAm/PPy composite hydrogel can be used as a thermochromic material layer to be applied to the fields of intelligent response, intelligent glass, flexible devices, aerospace and the like according to the characteristics of the PNIPAm/PPy composite hydrogel.
The above examples are only for illustrating the technical idea and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered in the protection scope of the present invention.
Claims (10)
1. The PNIPAm/PPy composite hydrogel is characterized in that the PPy in the composite hydrogel is microspherical, the average particle size is 400-800 nm, and the PNIPAm is in a network shape; the PPy grows on the surface of the network-shaped PNIPAm in a microsphere form.
2. A preparation method of PNIPAm/PPy composite hydrogel is characterized by comprising the following steps:
(1) stirring PVP in pure water to form PVP micelles, adding PNIPAm and BIS in an inert atmosphere, uniformly mixing, adding KPS, and carrying out polymerization reaction for a period of time to obtain PNIPAm hydrogel;
(2) PVP is stirred in pure water to form PVP micelles, pyrrole and KPS are added and mixed evenly, and a soluble PPy solution is obtained through low-temperature reaction;
(3) and (3) adding the PPy solution prepared in the step (2) into the PNIPAm hydrogel obtained in the step (1), ultrasonically stirring uniformly at a low temperature, dialyzing to obtain a PNIPAm/PPy composite hydrogel system, and carrying out vacuum freeze drying to obtain the PNIPAm/PPy composite hydrogel.
3. The method according to claim 2, wherein the PVP, pure water, PNIPAm, BIS and KPS in step (1) are used in the following amounts: 0.02-0.1 g: 50mL of: 0.5-1 g: 0.005-0.16 g: 0.02-0.032 g.
4. The preparation method according to claim 2, wherein the stirring temperature in the step (1) is 35-50 ℃ for dissolution, and the stirring time is 30-60 min; the temperature of the polymerization reaction is 60-70 ℃, and the time is 4-6 h.
5. The method according to claim 2, wherein the PVP, pure water, pyrrole and KPS in step (2) are used in the following amount relationship: 0.2-0.8 g: 50mL of: 0.35-0.69 mL: 1.85-2.7 g.
6. The preparation method according to claim 2, wherein the low-temperature reaction in the step (2) is carried out in an environment of less than 5 ℃ for 1-3 h.
7. The preparation method of claim 2, wherein the volume ratio of the PPy solution to the PNIPAm hydrogel in the step (3) is 1: 1-10.
8. The preparation method according to claim 2, wherein the low temperature in the step (3) is a temperature <5 ℃, and the time of the ultrasonic treatment is 0.5-1 h; and the dialysis is carried out for 48-72 h by using a 1000 Da dialysis bag.
9. The method according to claim 2, wherein the PVP is PVP-K30, molecular weight is 44000-54000.
10. The PNIPAm/PPy composite hydrogel as claimed in claim 1, which is used in the field of thermochromic materials.
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