CN113390521B - Temperature indicating device - Google Patents
Temperature indicating device Download PDFInfo
- Publication number
- CN113390521B CN113390521B CN202110775485.1A CN202110775485A CN113390521B CN 113390521 B CN113390521 B CN 113390521B CN 202110775485 A CN202110775485 A CN 202110775485A CN 113390521 B CN113390521 B CN 113390521B
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- Prior art keywords
- porous hollow
- hydrogel
- temperature
- reactant
- indicating device
- Prior art date
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Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
- G01K1/00—Details of thermometers not specially adapted for particular types of thermometer
- G01K1/02—Means for indicating or recording specially adapted for thermometers
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
- G01K11/00—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00
- G01K11/12—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00 using changes in colour, translucency or reflectance
- G01K11/16—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00 using changes in colour, translucency or reflectance of organic materials
Abstract
The application relates to a temperature indicating device, which utilizes porous hollow microspheres with hydrogel grafted on the surfaces, the hydrogel grafted on the porous hollow microspheres blocks a phase-change solvent containing a reactant A into the porous hollow microspheres when the temperature is lower than the response temperature, and isolates the reactant B out of the porous hollow microspheres; when the indicating device is above the critical temperature, the hydrogel volume shrinks, the pore channels of the porous hollow microspheres appear, and the phase-change solvent melts and permeates to the outside of the porous hollow microspheres to enable the reactant A and the reactant B to react and develop color. The structural design can prepare the reactant A and the reactant B into the same layer of the temperature indicating device, is simpler than the traditional multilayer structural design, and the reactant A and the reactant B are easier to react and develop, so that the temperature of a product is indicated, and the temperature indicating sensitivity is high.
Description
Technical Field
The application relates to the technical field of temperature monitoring and application, in particular to a temperature indicating device.
Background
In the handling of certain products, particularly in the medical industry, it is important to track the temperature, for example, to monitor cumulative thermal exposure and threshold thermal events of certain medical products, etc., many medical products are exposed to cumulative heat at a certain thermal intensity over time, resulting in their loss of effectiveness, and exposure to temperatures above a certain threshold limit can also cause damage to the product. In addition to medical products, other materials (e.g., perishable foods) must also be stored at a temperature, otherwise deterioration may occur at a temperature or upon a certain amount of cumulative heat exposure. To address these problems, there have been many people currently attaching temperature indicators to containers of such products to determine whether the product has reached a particularly detrimental temperature, thereby taking effective measures to avoid product damage.
The means of temperature monitoring currently on the market can be divided into electronic and non-electronic technologies. The electronic technical instrument is generally large in size, suitable for large products or whole boxes, and high in cost. In the non-electronic temperature monitor, the technical proposal of China patent application No. CN200420078916.0 mentions the capillary action principle of using a simple thermometer, and a device capable of changing color when the ambient temperature exceeds the set temperature is manufactured, the volume of the device is relatively large, the device is not applicable to relatively small volume of products, and key components of the device are fragile and not easy to use. The british Timesstrip company in the patent publication No. CN1533518A proposes a color-changing label device, the solution is gradually permeated into the observation area after the capsule filled with the solvent is crushed, so as to monitor, but the monitoring product designed in the scheme can lose efficacy within a few minutes for a short time and hours for a late time once being used, and can only measure the cold chain transportation time, but can not measure whether the cold chain environment exceeds the set dangerous temperature, and meanwhile, the product has the problems of complex structure, high cost and larger volume, so that the popularization and the application are limited.
Therefore, the application provides a cheap and convenient temperature detector which has important significance for the safety of medical products, foods and the like.
Disclosure of Invention
The application mainly solves the monitoring problems of accumulated heat exposure and specific threshold temperature of products in certain special industries, and provides a temperature indicating device.
In order to achieve the above object, the present application provides a temperature indicating device, including a base layer and a functional layer disposed on the base layer for indicating temperature, wherein the functional layer includes a plurality of porous hollow microspheres grafted with hydrogel, a phase-change solvent containing a reactant A, a reactant B, and a sol for fixing the reactant B; when the temperature indicating device is placed in a temperature environment which is lower than the volume phase transition temperature of the hydrogel, the hydrogel blocks the phase change solvent into the porous hollow microspheres and isolates the reactant B from the outside of the porous hollow microspheres, when the temperature indicating device is placed in a temperature environment which is higher than the volume phase transition temperature of the hydrogel, the hydrogel volume contracts, pore channels of the porous hollow microspheres appear, and the phase change solvent melts and permeates to the outside of the porous hollow microspheres to enable the reactant A and the reactant B to react and develop, so that the temperature of a product is indicated.
As a further improvement of the present application, the solid-liquid phase transition temperature of the phase change solvent is not higher than the volume phase transition temperature of the hydrogel, and the response temperature of the temperature indicating device is the volume phase transition temperature of the hydrogel.
As a further improvement of the application, the wall material of the porous hollow microsphere is at least one selected from polystyrene, polyaryletherketone, polyether ether ketone, polyarylene imine, polyimide, polyethylene, polystyrene-polyvinyl aniline hydrochloride copolymer, polystyrene-divinylbenzene copolymer, polylactic acid-glycolic acid copolymer, polymethyl methacrylate, glycidyl methacrylate-ethylene dimethacrylate copolymer and PVA.
As a further improvement of the present application, the hydrogel is at least one of poly (N-isopropylacrylamide), chitosan, polyacrylamide, cellulose derivatives, polyoxyethylene, polyoxypropylene, polylactic acid, polyethylene glycol, poly (epsilon-caprolactone-glycolide), poly (epsilon-caprolactone-p-dioxanone), polyester, poly (2-methyl-2-acrylic acid-2- (2-methoxyethoxy) ethyl ester-co-OEGMA, and polyhydroxyethyl methacrylate.
As a further improvement of the application, the mass percent of the hydrogel is not more than 20% of the porous hollow microsphere.
As a further improvement of the application, the mass percent of the hydrogel is not more than 10% of the porous hollow microsphere.
As a further improvement of the application, the mass percent of the hydrogel is not more than 5% of the porous hollow microsphere.
As a further improvement of the present application, the phase change solvent is at least one of tetradecane, pentadecane, hexadecane, heptadecane, octadecane, eicosane, docosyl, tetracosane, triacontane, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, octadecanol, dodecanol, tetradecanol, hexadecanol, octadecanol, eicosyl alcohol, docosyl alcohol, pentaerythritol, neopentyl glycol, tetracutol, mannitol, paraffin wax, erythritol, hydroquinone, methyl stearate, methyl palmitate, benzophenone.
As a further improvement of the present application, the reactant A is at least one of bisphenol A, bisphenol C, bisphenol S, bisphenol F, bisphenol AF, DBSP, D-8, acid phosphate, acid metal salt.
As a further development of the application, the reactant B is bromothymol blue, bromocresol green, methylyellow, methyl orange, bromocresol green, red 500, 7- [4- (diethylamino) -2-ethoxyphenyl ] -7- (2-methyl-1H-indol-3-yl) furo [3,4-B ] pyridin-5 (7H) -one, 4'- [ (9-butyl-9H-carbazol-3-yl) methylene ] bis [ N-methyl-N-phenylaniline ], 2' - (dibenzylamino) -6'- (diethylamino) fluoran, 3-bis (N-octyl-2-methylindole) o-benzolactone, 2-phenylamino-3-methyl-6-diethylfluoran, 2-phenylamino-3-methyl-6-dibutylfluoran, 6-dimethylamino-3, 3-bis (4-dimethylaminophenyl) phthalide, 10-benzoyl-3, 7-bis (dimethylamino) phenazine, 3-diethylamino-4-diethylfluoran, 2-diethylamino-6-ethylphthalan, 2-diethylamino-4' - (diethylamino-4-methylbenzan) phthalan, 2-diethylamino-4-ethyl-4-phenylphthalan 6- (N-ethyl-4-toluidinyl) -2-methylfluoran, 3- (N-ethyl-4-toluidinyl) -6-methyl-7-anilinofluoran, 3',6' -dimethoxy fluoran, 1, 2-benzo-6-diethylaminofluoran, 3- (1, 2-dimethyl-3-indolyl) -3- [ 4-diethylamino-2-methylphenyl ] phthalide, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-aza-2-benzo [ C ] furanone, 6' - (diethylamino) -1',2' -benzofluoran, 2- (2 ',4' -dimethylamino-3-methyl-6-diethylaminofluoran), N-dimethyl-4- (2- (2- (octyloxy) phenyl) -6-phenylpyridin-4-yl) aniline, 3- (4-dimethylaminophenyl) -3- (1-butyl-2-methyl-indol-3-dimethylamino) phthalide, at least one of 3-N-isopentyl-N-ethylamino-6-methyl-7-phenylaminofluoran.
As a further development of the application, the temperature indicating device further comprises a protective layer arranged outside the functional layer.
As a further improvement of the present application, the protective layer is a transparent protective film.
In order to achieve the above object, the present application further provides a method for preparing the temperature indicating device, which comprises the following steps: s1, grafting reaction: grafting hydrogel to the porous hollow microspheres to obtain hydrogel grafted porous hollow microspheres; s2, soaking the hydrogel grafted porous hollow microspheres in the step S1 into a phase-change solvent containing a reactant A, reducing the temperature after full soaking to solidify the phase-change solvent filled into the hydrogel grafted porous hollow microspheres, taking out the phase-change solvent left on the surface, removing the phase-change solvent, putting the hydrogel grafted porous hollow microspheres into water to enable the hydrogel grafted on the porous hollow microspheres to absorb water and expand and block holes of the porous hollow microspheres, and obtaining porous hollow microspheres with the phase-change solvent containing the reactant A filled in the holes; s3, preparing a functional layer: and (2) fully mixing the reactant B with the sol to obtain a first sol mixture, fully and uniformly mixing the porous hollow microspheres filled with the phase-change solvent containing the reactant A in the holes in the step (S2) with the first sol mixture to obtain a second sol mixture, and coating the second sol mixture on a substrate to form a functional layer.
As a further improvement of the application, a protective layer is provided outside the functional layer.
The application has the beneficial effects that the application provides the temperature indicating device, which utilizes the structural design of the grafted porous hollow microsphere, the hydrogel grafted on the porous hollow microsphere blocks the phase-change solvent containing the reactant A to the inside of the porous hollow microsphere and isolates the reactant B to the outside of the porous hollow microsphere. When the indicating device is at a temperature above the volume phase transition temperature of the hydrogel, the hydrogel volume contracts, the pores of the porous hollow microspheres appear, and the phase change solvent melts and permeates outside the porous hollow microspheres to enable the reactant A and the reactant B to react and develop color. Thereby indicating the product temperature. The structural design can prepare the reactant A and the reactant B which play a role in temperature indication color development into the same layer of the temperature indication device, and compared with the traditional multilayer structural design, the temperature indication device has the advantages of simplicity, thinner indicating device, small volume, easier combination reaction of the reactant A and the reactant B for color development and high temperature indication sensitivity.
Drawings
FIG. 1 is a schematic diagram of the overall structure of a temperature indicating device;
in the figure: 1. a base layer; 2. a functional layer; 3. and (3) a protective layer.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the technical solutions of the present application will be clearly and completely described below with reference to specific embodiments of the present application and the accompanying drawings. It should be apparent that the described embodiments are only some embodiments of the present application and not all embodiments are not intended to limit the scope of the present application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
In order to solve the monitoring problem of accumulated heat exposure and specific threshold temperature of products in certain special industries, the application provides a temperature indicating device, as shown in figure 1, which comprises a base layer 1 and a functional layer 2 arranged on the base layer 1 and used for indicating temperature, wherein the functional layer 2 comprises a plurality of porous hollow microspheres grafted with hydrogel, a phase-change solvent containing a reactant A, a reactant B and sol for fixing the reactant B, when the temperature indicating device is placed in an environment lower than the volume phase transition temperature of the hydrogel, the hydrogel blocks the phase-change solvent into the porous hollow microspheres, the hydrogel isolates the reactant B outside the porous hollow microspheres, when the temperature indicating device is placed in an environment higher than the volume phase transition temperature of the hydrogel, the hydrogel volume is contracted, the pore channels of the porous hollow microspheres are visualized, and the phase-change solvent is melted and permeated into the outside of the porous hollow microspheres to enable the reactant A and the reactant B to react and develop color. Thereby indicating the product temperature. When the temperature indicating device develops color, the response temperature of the temperature indicating device can be judged, the product temperature is further indicated, and when the response temperature occurs in the general temperature indicating device, the environment temperature of the product is not lower than the response temperature.
The temperature indicating device utilizes the characteristics of the porous hollow microsphere hole structure design and the grafted hydrogel with volume phase transition at a specific temperature to simultaneously prepare the reactant A and the reactant B which have the color development function into the same layer of the indicating device, and compared with the indicating device with the traditional multilayer structure design, the temperature indicating device has the advantages that the structure is simple, the reactant A and the reactant B are easier to combine and react to develop color, and the temperature indicating sensitivity is high.
In the present application, as a preferred embodiment, the wall material of the porous hollow microsphere is not limited to at least one selected from the group consisting of polystyrene, polyaryletherketone, polyetheretherketone, polyarylene imide, polyimide, polyethylene, polystyrene-polyvinylaniline hydrochloride copolymer, polystyrene-divinylbenzene copolymer, polylactic acid-glycolic acid copolymer, polymethyl methacrylate, glycidyl methacrylate-ethylene dimethacrylate copolymer, and PVA.
In the application, the grafted hydrogel has the characteristic of volume phase transition at a specific temperature, namely: when the grafted hydrogel is lower than the volume phase transition temperature, the volume of the grafted hydrogel is in an expanded state, and the hydrogel in the expanded state can completely cover the holes of the porous hollow microspheres; when the grafted hydrogel is higher than the volume phase transition temperature, the volume of the grafted hydrogel is in a contracted state, and the hydrogel after volume contraction can expose part or all of the pores of the porous hollow microsphere. As a preferred embodiment, the hydrogel may be, but is not limited to, at least one of poly (N-isopropylacrylamide), chitosan, polyacrylamide, cellulose derivatives, polyoxyethylene, polyoxypropylene, polylactic acid, polyethylene glycol, poly (epsilon-caprolactone-glycolide), poly (epsilon-caprolactone-p-dioxanone), polyester, poly (2-methyl-2-acrylic acid-2- (2-methoxyethoxy) ethyl ester-co-OEGMA), polyhydroxyethyl methacrylate. In the present application, as a preferred embodiment, the mass percentage of the hydrogel is not more than 20% of the porous hollow microspheres. Further preferably, the mass percentage of the hydrogel is not more than 10% of the porous hollow microsphere. Further preferably, the mass percentage of the hydrogel is not more than 5% of the porous hollow microsphere.
In the present application, as a preferred embodiment, the phase change solvent may be at least one of, but not limited to, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, eicosane, docosane, tetracosane, triacontane, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, decanol, dodecanol, tetradecanol, hexadecanol, octadecanol, eicosyl alcohol, docosyl alcohol, pentaerythritol, neopentyl glycol, tetracutol, mannitol, paraffin wax, erythritol, hydroquinone, methyl stearate, methyl palmitate, benzophenone.
In the present application, as a preferred embodiment, the reactant a may be at least one of bisphenol a, bisphenol C, bisphenol S, bisphenol F, bisphenol AF, DBSP, D-8, acid phosphate, acid metal salt, but not limited thereto.
In the present application, as a preferred embodiment, the reactant B may be, but is not limited to, bromothymol blue, bromocresol green, methylyellow, methyl orange, bromocresol green, red 500, 7- [4- (diethylamino) -2-ethoxyphenyl ] -7- (2-methyl-1-octyl-1H-indol-3-yl) furo [3,4-B ] pyridin-5 (7H) -one, 4'- [ (9-butyl-9H-carbazole-3-yl) methylene ] bis [ N-methyl-N-phenylaniline ], 2' - (dibenzylamino) -6'- (diethylamino) fluoran, 3-bis (N-octyl-2-methylindole) phthalide, 2-phenylamino-3-methyl-6-diethylfluoran, 2-phenylamino-3-methyl-6-dibutylfluoran, 6-dimethylamino-3, 3-bis (4-dimethylaminophenyl) phthalein, 10-benzoyl-3, 7-dimethylamino-bis (3-carbazol-3-yl) methylene ] bis [ N-methyl-phenylamine ], 2' - (dibenzamido) fluoran, 3-bis (N-octyl-2-methylindole), 2-phenylamino-3-methyl-6-diethyl fluoran, 2-phenylamino-3-diethyl fluoran, 6- (N-ethyl-4-toluidinyl) -2-methylfluoran, 3- (N-ethyl-4-toluidinyl) -6-methyl-7-anilinofluoran, 3',6' -dimethoxy fluoran, 1, 2-benzo-6-diethylaminofluoran, 3- (1, 2-dimethyl-3-indolyl) -3- [ 4-diethylamino-2-methylphenyl ] phthalide, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-aza-2-benzo [ C ] furanone, 6' - (diethylamino) -1',2' -benzofluoran, 2- (2 ',4' -dimethylamino-3-methyl-6-diethylaminofluoran), N-dimethyl-4- (2- (2- (octyloxy) phenyl) -6-phenylpyridin-4-yl) aniline, 3- (4-dimethylaminophenyl) -3- (1-butyl-2-methyl-indol-3-dimethylamino) phthalide, at least one of 3-N-isopentyl-N-ethylamino-6-methyl-7-phenylaminofluoran.
In the present application, as a preferred embodiment, as shown in fig. 1, the temperature indicating device further includes a protective layer 3 provided outside the functional layer 2. Preferably, the protective layer 3 is a transparent protective film, so as to facilitate observation of the color change of the temperature indicating device.
In order to achieve the above object, the present application further provides a method for preparing a temperature indicating device, which is applied to the temperature indicating device, and includes the following steps: s1, grafting reaction: grafting hydrogel to the porous hollow microspheres to obtain hydrogel grafted porous hollow microspheres; s2, soaking the hydrogel grafted porous hollow microspheres in the step S1 into a phase-change solvent containing a reactant A, reducing the temperature after full soaking to solidify the phase-change solvent filled into the hydrogel grafted porous hollow microspheres, taking out the phase-change solvent left on the surface, removing the phase-change solvent, putting the hydrogel grafted porous hollow microspheres into water to enable the hydrogel grafted on the porous hollow microspheres to absorb water and expand and block holes of the porous hollow microspheres, and obtaining porous hollow microspheres with the phase-change solvent containing the reactant A filled in the holes; s3, preparing a functional layer 2: and (2) fully mixing the reactant B with the sol to obtain a first sol mixture, fully and uniformly mixing the porous hollow microspheres filled with the phase-change solvent containing the reactant A in the holes in the step (S2) with the first sol mixture to obtain a second sol mixture, and coating the second sol mixture on the base layer 1 to form the functional layer.
In the present application, as a preferred embodiment, a protective layer 3 is provided outside the functional layer 2 for protecting the functional layer 2. Preferably, the protective layer 3 is a transparent protective film, so as to facilitate observation of the color change of the temperature indicating device.
In order to verify that the technical scheme of the application has excellent technical effects, the application also provides 2 groups of examples for demonstration.
Example 1
In the temperature indicating device prepared in the embodiment, the wall material of the porous hollow microsphere is polystyrene; the hydrogel grafted to the porous hollow microsphere is poly (N-isopropyl acrylamide), and the volume phase transition temperature of the hydrogel is 32 ℃; the phase change solvent is a mixed solvent of tetradecyl alcohol and decyl alcohol, and the mass percentage of the tetradecyl alcohol and the decyl alcohol is 20:1, a step of; the reactant A dissolved in the phase-change solvent is gallic acid, the mass percentage of the gallic acid to the phase-change solvent is 1%, and the melting point of the phase-change solvent containing the reactant A is about 32 ℃; reactant B was red pigment-16.
When the temperature indicating device of the embodiment is in an environment below 32 ℃, the phase change solvent is solid, and the hydrogel expands to block the holes; when the temperature indicating device of the embodiment is in an environment higher than 32 ℃, the phase-change solvent is melted, the hydrogel is shrunk, holes appear, the phase-change solvent is diffused outside the microsphere, gallic acid and the haematochrome-16 react to form red, obviously, the temperature of 32 ℃ is the corresponding temperature of the embodiment, and the temperature indicating device of the embodiment can simply and conveniently monitor the critical point of the environment temperature higher than 32 ℃.
Example 2
In the temperature indicating device prepared in the embodiment, the wall material of the porous hollow microsphere is polystyrene-divinylbenzene copolymer; the hydrogel grafted to the porous hollow microsphere is a copolymer of 2-methyl-2-acrylic acid-2- (2-methoxyethoxy) ethyl ester and OEGMA, the mass percentage of the hydrogel is 61.3% and 38.7%, and the volume phase transition temperature of the hydrogel is 38 ℃; the phase-change solvent is tetradecyl alcohol, the reactant A dissolved in the phase-change solvent is bisphenol F, the mass percentage of the bisphenol F and the phase-change solvent is 0.5%, and the melting point of the phase-change solvent containing the reactant A is about 38 ℃; reactant B was chosen for deep blue BL-63.
When the temperature indicating device of the embodiment is in an environment below 38 ℃, the phase-change solvent is solid, and the hydrogel expands to block the holes; when the temperature indicating device of the embodiment is in an environment higher than 38 ℃, the phase-change solvent is melted, the hydrogel is shrunk, holes appear, the phase-change solvent is diffused outside the microspheres, bisphenol F and deep blue BL-63 react to form blue, and obviously, the temperature of 38 ℃ is the corresponding temperature of the embodiment, and the temperature indicating device of the embodiment can simply and conveniently monitor the critical point of the environment temperature higher than 38 ℃.
In summary, the present application provides a temperature indicating device, which uses the structural design of a porous hollow microsphere grafted with hydrogel, when the temperature indicating device is placed in an environment lower than the volume phase transition temperature of the hydrogel, the hydrogel blocks the phase-change solvent containing the reactant a inside the porous hollow microsphere, the hydrogel isolates the reactant B outside the porous hollow microsphere, when the temperature indicating device is placed in an environment higher than the volume phase transition temperature of the hydrogel, the hydrogel volume shrinks, the pores of the porous hollow microsphere appear, and the phase-change solvent melts and permeates outside the porous hollow microsphere to react and develop the reactant a and the reactant B.
The structure design can prepare the reactant A and the reactant B which play a role in temperature indication and color development into the same layer of the temperature indication device, and compared with the traditional indication device with the multi-layer structure design, the structure is simple, the volume is small, the carrying is convenient, the reactant A and the reactant B are easier to combine and react to develop color, and the temperature indication sensitivity is high. The method can be applied to various temperature monitoring scenes.
Although the present disclosure describes embodiments, not every embodiment is described in terms of a single embodiment, and such description is for clarity only, and one skilled in the art will recognize that the embodiments may be combined in any suitable manner to form other embodiments that will be apparent to those skilled in the art.
The above list of detailed descriptions is only specific to practical embodiments of the present application, and they are not intended to limit the scope of the present application, and all equivalent embodiments or modifications that do not depart from the spirit of the present application should be included in the scope of the present application.
Claims (14)
1. The temperature indicating device is characterized by comprising a base layer and a functional layer which is arranged on the base layer and used for indicating temperature, wherein the functional layer comprises a plurality of porous hollow microspheres grafted with hydrogel, a phase-change solvent containing a reactant A, a reactant B and sol for fixing the reactant B; when the temperature indicating device is placed in a temperature environment which is lower than the volume phase transition temperature of the hydrogel, the hydrogel blocks the phase change solvent into the porous hollow microspheres and isolates the reactant B from the outside of the porous hollow microspheres, when the temperature indicating device is placed in a temperature environment which is higher than the volume phase transition temperature of the hydrogel, the hydrogel volume contracts, pore channels of the porous hollow microspheres appear, and the phase change solvent melts and permeates to the outside of the porous hollow microspheres to enable the reactant A and the reactant B to react and develop, so that the temperature of a product is indicated.
2. The temperature indicating device of claim 1, wherein the solid-liquid phase transition temperature of the phase change solvent is not higher than the bulk phase transition temperature of the hydrogel, and the response temperature of the temperature indicating device is the bulk phase transition temperature of the hydrogel.
3. The temperature indicating device of claim 1, wherein the wall material of the porous hollow microsphere is selected from at least one of polystyrene, polyaryletherketone, polyetheretherketone, polyaramid, polyimide, polyethylene, polystyrene-polyvinylaniline hydrochloride copolymer, polystyrene-divinylbenzene copolymer, polylactic acid-glycolic acid copolymer, polymethyl methacrylate, glycidyl methacrylate-ethylene dimethacrylate copolymer, PVA.
4. The temperature indicating device of claim 1, wherein the hydrogel is at least one of poly (N-isopropylacrylamide), chitosan, polyacrylamide, cellulose derivatives, polyoxyethylene, polyoxypropylene, polylactic acid, polyethylene glycol, poly (epsilon-caprolactone-glycolide), poly (epsilon-caprolactone-p-dioxanone), polyester, poly (2-methyl-2-acrylic acid-2- (2-methoxyethoxy) ethyl ester-co-OEGMA), and polyhydroxyethyl methacrylate.
5. The temperature indicating device of claim 1, wherein the hydrogel comprises no more than 20% by mass of the porous hollow microspheres.
6. The temperature indicating device of claim 5, wherein the hydrogel comprises no more than 10% by mass of the porous hollow microspheres.
7. The temperature indicating device of claim 6, wherein the hydrogel comprises no more than 5% by mass of the porous hollow microspheres.
8. The temperature indicating device of claim 1, wherein the phase change solvent is at least one of tetradecane, pentadecane, hexadecane, heptadecane, octadecane, eicosane, docosyl, tetracosane, triacontane, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, decanol, dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, docosyl, pentaerythritol, neopentyl glycol, tetracutol, mannitol, paraffin wax, erythritol, hydroquinone, methyl stearate, methyl palmitate, benzophenone.
9. The temperature indicating device of claim 1, wherein reactant a is at least one of bisphenol a, bisphenol C, bisphenol S, bisphenol F, bisphenol AF, DBSP developer, D-8 developer, TGSH developer, acid phosphate and its modified resin, acid metal salt.
10. The temperature indicating device of claim 1, wherein reactant B is bromothymol blue, bromocresol green, methylyellow, methyl orange, bromocresol green, red 500, 7- [4- (diethylamino) -2-ethoxyphenyl ] -7- (2-methyl-1-octyl-1H-indol-3-yl) furo [3,4-B ] pyridin-5 (7H) -one, 4' - [ (9-butyl-9H-carbazol-3-yl) methylene ] bis [ N-methyl-N-phenylaniline ], 2' - (dibenzylamino) -6' - (diethylamino) fluoran, 3-bis (N-octyl-2-methylindole) phthalide, 2-phenylamino-3-methyl-6-diethyl fluoran, 2-phenylamino-3-methyl-6-dibutyl fluoran, 6-dimethylamino-3, 3-bis (4-dimethylaminophenyl) phthalein, 10-benzoyl-3, 7-bis (dimethylamino-3-ethyl) phenone, 3' - (diethylamino) fluoran, 3-bis (N-octyl-2-methylindole) phthalein, 2-dimethylamino-3-diethyl fluoran, 2-diethylamino-4 ' -diethyl fluoran, 6- (N-ethyl-4-toluidinyl) -2-methylfluoran, 3- (N-ethyl-4-toluidinyl) -6-methyl-7-anilinofluoran, 3',6' -dimethoxy fluoran, 1, 2-benzo-6-diethylaminofluoran, 3- (1, 2-dimethyl-3-indolyl) -3- [ 4-diethylamino-2-methylphenyl ] phthalide, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-aza-2-benzo [ C ] furanone, 6' - (diethylamino) -1',2' -benzofluoran, 2- (2 ',4' -dimethylamino-3-methyl-6-diethylaminofluoran), N-dimethyl-4- (2- (2- (octyloxy) phenyl) -6-phenylpyridin-4-yl) aniline, 3- (4-dimethylaminophenyl) -3- (1-butyl-2-methyl-indol-3-dimethylamino) phthalide, at least one of 3-N-isopentyl-N-ethylamino-6-methyl-7-phenylaminofluoran.
11. The temperature indicating device of claim 1, further comprising a protective layer disposed outside the functional layer.
12. The temperature indicating device of claim 11 wherein the protective layer is a transparent protective film.
13. A method of manufacturing a temperature indicating device according to any one of claims 1 to 12, comprising the steps of:
s1, grafting reaction: grafting hydrogel to the porous hollow microspheres to obtain hydrogel grafted porous hollow microspheres;
s2, soaking the hydrogel grafted porous hollow microspheres in the step S1 into a phase-change solvent containing a reactant A, reducing the temperature after full soaking to solidify the phase-change solvent filled into the hydrogel grafted porous hollow microspheres, taking out the phase-change solvent left on the surface, removing the phase-change solvent, putting the hydrogel grafted porous hollow microspheres into water to enable the hydrogel grafted on the porous hollow microspheres to absorb water and expand and block holes of the porous hollow microspheres, and obtaining porous hollow microspheres with the phase-change solvent containing the reactant A filled in the holes;
s3, preparing a functional layer: and (2) fully mixing the reactant B with the sol to obtain a first sol mixture, fully and uniformly mixing the porous hollow microspheres filled with the phase-change solvent containing the reactant A in the holes in the step (S2) with the first sol mixture to obtain a second sol mixture, and coating the second sol mixture on a substrate to form a functional layer.
14. The method of manufacturing a temperature indicating device according to claim 13, wherein a protective layer is provided outside the functional layer.
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