CN114249858A - Visual polymer thermometer with temperature memory function and preparation method thereof - Google Patents

Visual polymer thermometer with temperature memory function and preparation method thereof Download PDF

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CN114249858A
CN114249858A CN202210053202.7A CN202210053202A CN114249858A CN 114249858 A CN114249858 A CN 114249858A CN 202210053202 A CN202210053202 A CN 202210053202A CN 114249858 A CN114249858 A CN 114249858A
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polymer
temperature
thermometer
monomer
sensitive
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CN114249858B (en
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张洪吉
宋雨方
秦旭东
马丕明
周世嘉
王金刚
孙双霜
王晓蓉
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Jiangsu Dynamic Chemical Co ltd
Jiangnan University
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Jiangnan University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/106—Esters of polycondensation macromers
    • C08F222/1063—Esters of polycondensation macromers of alcohol terminated polyethers
    • 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

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Abstract

The invention discloses a visible polymer thermometer with a temperature memory function and a preparation method thereof, belonging to the field of polymer temperature sensors. The method comprises the following steps: (1) hydrophilic monomer, hydrophobic monomer, LCST type temperature sensitive monomer or LCST type temperature sensitive polymer chain and triple or multiple hydrogen bond unit derivative are polymerized in the presence of initiator to prepare LCST type temperature sensitive polymer material containing triple and multiple hydrogen bond units; (2) the aqueous solution/dispersion of the material or the hydrogel prepared by further crosslinking has programmable memory temperature and is used by a polymer thermometer with adjustable memory time. The low critical solution temperature of the high polymer material, namely the measurement temperature, is adjusted by adjusting the proportion of the hydrophilic and hydrophobic monomers, the temperature response and the memory time are adjusted by adjusting the proportion of the LCST type temperature-sensitive monomers or LCST type temperature-sensitive high molecular chains or derivatives of triple or multiple hydrogen bond units, and the high polymer thermometer can quickly erase thermal history and be repeatedly used.

Description

Visual polymer thermometer with temperature memory function and preparation method thereof
Technical Field
The invention relates to a visible polymer thermometer with a temperature memory function and a preparation method thereof, belonging to the field of polymer temperature sensors.
Background
Temperature plays an important role in a series of life and scientific problems, such as the decay process of food with the release of heat resulting in temperature rise, human body fever resulting in body temperature rise above normal body temperature, water absorption of energy resulting in temperature rise, etc., which occur with temperature change.
The traditional mercury or red liquid thermometer can measure the temperature change of an object by the principle of expansion and contraction, but when the mercury thermometer is removed from the measured object, the temperature reading is quickly restored to the room temperature, and the process is not memorized by the thermometer. The related workers find that when the external temperature changes, the high molecular polymer changes correspondingly due to the inherent phase transition property (such as glass transition, melting, liquid crystal and solubility changes), so that the polymer is widely applied to the development of the high molecular temperature sensor. Most of the currently developed polymer thermometers are homo-polymers or copolymers containing temperature-sensitive monomers, and can be used for designing and manufacturing polymer thermometers due to the unique temperature stimulus responsiveness of the temperature-sensitive monomers, but when the external temperature returns to the initial state, the phase change of the polymer material also returns to the initial state, for example, when the external temperature rises, the molecular chains curl and shrink along with the phase change, and the polymer aqueous solution changes from a transparent state to a white turbid state, so that the temperature change can be visually observed; however, when the temperature stimulus is removed, it rapidly returns to a transparent state, during which time the change in temperature is not recorded. At present, although such a polymer thermometer can visually sense a temperature change, it lacks a function of memorizing the temperature change.
Disclosure of Invention
In order to solve the problems in the prior art, the applicant of the present invention provides a visual polymer thermometer with a temperature memory function and a preparation method thereof.
The invention prepares the Temperature-sensitive polymer material containing multiple hydrogen bond units by performing polycondensation or chain polymerization on hydrophilic monomers, hydrophobic monomers, LCST (Lower Critical Solution Temperature) type Temperature-sensitive monomers (homopolymers or copolymers of which have a Lower Critical Solution Temperature, namely LCST phenomenon) or Temperature-sensitive polymer chains, functional monomers and derivatives of triple or multiple hydrogen bond units in the presence of an initiator or a catalyst by a method of bulk polymerization/Solution polymerization/suspension polymerization/emulsion polymerization, dissolves/disperses the prepared polymer material in water or a cosolvent of water/organic solvent to prepare the polymer Solution with adjustable memory Temperature and memory time based on the LCST phenomenon, or prepares the polymer hydrogel with adjustable memory Temperature and memory time by a method of physical or chemical crosslinking, both can be used as a polymer thermometer.
The mechanism of the visual polymer thermometer with the temperature memory function designed based on the LCST phenomenon and the triple/multiple hydrogen bond system is as follows: when the external temperature is higher than the minimum eutectic temperature of a designed polymer thermometer, the hydrophilicity and hydrophobicity of an LCST-type temperature-sensitive polymer chain are changed, the temperature-sensitive chain segment of the LCST-type temperature-sensitive polymer chain is changed from a stretching state (a polymer aqueous solution/hydrogel is transparent) when hydrophilic to a curling and shrinking state (the polymer aqueous solution/hydrogel is opaque and forms a hydrophobic region) when hydrophobic, the shrinkage of the temperature-sensitive chain segment is close to the distance between multiple hydrogen bond units of a side group in the polymer chain, and the formation of the hydrophobic region promotes the association between the multiple hydrogen bond units, so that a strong multiple hydrogen bond cross-linking structure is formed between the temperature-sensitive chain segments which are curled and shrunk due to heating. When the polymer thermometer is removed from the measured object, the temperature is reduced, so that the temperature-sensitive chain segment becomes hydrophilic again, however, a dimer structure formed by association among multiple hydrogen bond units can form a dynamic physical cross-linking point to limit the relaxation speed of the polymer chain, so that the process of the temperature-sensitive chain from a curling and shrinking state (opaque state) to an expanding state (transparent state) is slowed down, and the measured temperature is memorized by the polymer thermometer. Because the duration of memory depends on the chain relaxation speed, the cross-linking degree can be regulated and controlled by adjusting the density of the temperature-sensitive monomer and the triple or multiple hydrogen bond units, the higher the multiple hydrogen bond cross-linking density is, the slower the dimer dissociation speed is, the longer the chain relaxation time is, and the longer the memory time is. In addition, as shown in fig. 2, the polymer thermometer with the memory function can also adjust the phase transition temperature thereof by adjusting the proportion of hydrophilic and hydrophobic monomers in the molecular chain for detecting different temperature intervals.
The invention provides a visual polymer thermometer with a temperature memory function and a preparation method thereof, wherein the method comprises the following steps:
(1) preparing a temperature-sensitive high polymer material containing multiple hydrogen bond units by performing polycondensation or chain polymerization on a hydrophilic monomer, a hydrophobic monomer, an LCST (lower-temperature-sensitive styrene) type temperature-sensitive monomer or an LCST type temperature-sensitive high molecular chain, a functional monomer and a derivative of the triple or multiple hydrogen bond units in the presence of an initiator or a catalyst;
(2) dissolving or dispersing the polymer material prepared in the step (1) to prepare a polymer solution with adjustable memory temperature and memory time, or preparing a polymer hydrogel with adjustable memory temperature and memory time by a physical or/and chemical crosslinking method, wherein the polymer solution and the polymer hydrogel can be used as a polymer thermometer.
In one embodiment, the hydrophilic monomer is a mono-, di-, or multi-functional hydrophilic monomer (containing a hydrophilic group such as-OH, -CHO, -COOH, -NH2, etc.) containing a polar group for adjusting the low critical solution temperature of the polymer thermometer. Such as one or more of acrylic acid, methacrylic acid, N-dimethylacrylamide, N-methylenebisacrylamide, allylpolyethylene glycol and the like, and the amount thereof is more than or equal to 0 wt% (the percentage of the total mass fraction of the added monomers, the same applies below).
In one embodiment, the hydrophobic monomer (containing nonpolar groups such as longer hydrocarbon chains) is one or more of butyl methacrylate, butyl acrylate, methyl methacrylate, etc., and is used for adjusting the low critical eutectic temperature of the high molecular thermometer, and the dosage of the hydrophobic monomer is more than or equal to 0 wt% (percentage of the total mass fraction).
In one embodiment, the LCST-type temperature-sensitive monomer or polymer chain refers to a temperature-sensitive monomer whose homopolymer or copolymer has a low critical solution temperature, and is used for adjusting the memory time of a polymer thermometer, such as N-isopropylacrylamide (NIPA), 2-methyl-2-acrylic acid-2- (2-methoxyethoxy) ethyl ester (MEO)2MA), polyethylene glycol methacrylate (POEGMA), 2-ethyl-2-oxazole, one or more of PEO (polyethylene oxide)/PPO (polypropylene oxide) derivatives, 2- (dimethylamino) ethyl methacrylate, 2- (2-methoxyethoxy) ethyl 2-methyl-2-acrylate and the like, wherein the using amount of the one or more is more than or equal to 5 wt% (accounting for the percentage of the total mass fraction).
In one embodiment, the functional monomer is a monomer containing a reactive group, such as-COOH, -OH, -NH2Isoactive groups, can be openedThe hydrogel type polymer thermometer is prepared by adding crosslinking monomer to react with crosslinking sites on alkene functional monomer, and the dosage of the hydrogel type polymer thermometer is more than or equal to 0 wt% (accounting for the percentage of the total mass fraction).
In one embodiment, the derivative containing triple or multiple hydrogen bond units is a derivative of monomers containing 3 or more proton donors or acceptors, such as 2-ureido-4 [1H ] -pyrimidone methyl methacrylate, N-acryloyl glycinamide, thymine, adenine, uracil, and the like, and is used for adjusting the length of the memory time of the high molecular thermometer (the memory time can be adjusted and controlled between 1 minute and 6 months), and the dosage of the derivative is more than or equal to 5 wt% (in percentage of the total mass fraction).
The hydrophilic monomer, the hydrophobic monomer, the LCST type temperature-sensitive monomer (the homopolymer or the copolymer of the monomer has LCST phenomenon), the functional monomer and the derivative of the triple or multiple hydrogen bond units are prepared into the polymer thermometer by one of polymerization methods of bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization and the like through a polymerization mechanism of polycondensation or chain polymerization.
The polycondensation or chain polymerization in the step (1) may be any of bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, and the like.
The dissolving or dispersing of the step (2) is dissolving or dispersing in water or a water/organic solvent cosolvent.
The polymer hydrogel with adjustable memory temperature and memory time in the step (2) can be prepared by firstly preparing a polymer material solution and then adding a cross-linking agent to obtain the polymer hydrogel, or directly adding the cross-linking agent in the process of preparing the polymer material to obtain the hydrogel.
The memory temperature is adjustable, and the LCST can be controlled by adjusting the use amounts of the hydrophilic monomer and the hydrophobic monomer, wherein the adjustable temperature range is 0 ℃ to 100 ℃. Increasing the proportion of hydrophilic monomers increases the LCST of the thermometer, in contrast to increasing the proportion of hydrophobic monomers which decreases the LCST.
The memory time is adjustable by adjusting the dosage of LCST type temperature-sensitive monomers and derivatives containing triple or multiple hydrogen bond units. The adjustable time range is 1 minute to 6 months. The memory time of the polymer thermometer can be improved by increasing the dosage of the LCST type temperature-sensitive monomer and the derivative containing triple or multiple hydrogen bond units. When the dosage of the derivative of the multiple hydrogen bond units is fixed, the dosage of the LCST type temperature-sensitive monomer is increased, more hydrophobic areas can be formed, the association among the multiple hydrogen bond units is improved, and a denser dynamic network is formed to improve the memory time. When the dosage of the LCST type temperature-sensitive monomer is fixed, the dosage of the derivative containing triple or multiple hydrogen bond units is increased, the association among the multiple hydrogen bond units can be improved, and a denser dynamic network is formed to improve the memory time.
The utility model discloses a visual, it is realized through the solubility change of macromolecular chain, when the measuring temperature is higher than the LSCT of macromolecular thermometer, the polymer chain is changed into hydrophobic state by hydrophilic state, the macromolecular chain is the state of stretching in aqueous when hydrophilic state, the absorptivity of macromolecular thermometer to the visible light scope is extremely low to be transparent state this moment, the polymer chain shrink is globular when hydrophobic state, the absorptivity of macromolecular thermometer to the visible light scope increases to be opaque state this moment, the change of transmissivity produces huge difference in the vision before and after the macromolecular thermometer is measured, the operator can audio-visual observation.
The repeated use is realized by destroying the association among the triple or multiple hydrogen bond units to accelerate the relaxation speed of the polymer chain, the triple or multiple hydrogen bond dimers are dissociated under the acidic or alkaline condition, the formed physical cross-linking points disappear, the polymer chain is rapidly relaxed and recovered to the stretched state, and then the polymer chain is soaked in deionized water to remove free hydrogen ions and hydroxyl ions. When the polymer thermometer is reused, the triple or multiple hydrogen bond dimer structure is formed again due to the hydrophobization to suppress the relaxation rate of the polymer chain.
The second purpose of the invention is to provide the visible polymer thermometer with the temperature memory function prepared by the method.
The third purpose of the invention is to provide a method for reusing the visible polymer thermometer with temperature memory function. The memory thermal history of the polymer thermometer produced after use can be erased.
The method for reusing is to soak the used polymer thermometer in an acidic solution with pH less than 1 or an alkaline solution with pH more than 10 to accelerate the dissociation of triple or multiple hydrogen bond dimers, so that the polymer chains of the triple or multiple hydrogen bond dimers are quickly relaxed and restored to a stretched state, and then remove free hydrogen ions and hydroxyl ions (such as soaking in deionized water) so as to reuse the polymer thermometer.
The visible polymer thermometer with the temperature memory function has higher application value in the fields of medical use, production and processing, food transportation and the like, such as medical thermometers, temperature detection in the process of food storage and transportation and the like.
The invention has the beneficial technical effects that:
the invention creatively introduces triple or multiple hydrogen bond units into the LCST type temperature-sensitive polymer chain, controls the formation and dissociation of multiple hydrogen bond dimers in the material through the temperature change of the temperature-sensitive polymer, realizes the memory of the temperature change through regulating and controlling the relaxation speed of the polymer, can visually identify the temperature change, and can program the memory time and the memory temperature without external equipment. The polymer thermometer with the memory function has the advantages of simple preparation method and high temperature detection speed, is suitable for various scenes, and can not cause damage to human bodies and the environment even if the polymer thermometer is damaged, so the polymer thermometer with the memory function has great application value in a plurality of fields such as medical thermometers, temperature detection in food storage and transportation processes and the like.
The designed high molecular thermometer can be reused, and the heat history memorized by the high molecular thermometer after use can be erased.
Drawings
FIG. 1 is a graph showing the change in transmittance before, after and after one week for water having a temperature of 38 ℃ measured by a polymer thermometer prepared in example 1 of the present invention.
FIG. 2 is a graph showing UV-visible spectrums of polymer hydrogel type thermometers having different measured temperatures (LCST) according to examples 2 to 6 of the present invention.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of better illustrating the invention and is not intended to limit the invention thereto.
The test method comprises the following steps:
the memory duration testing method comprises the following steps: and recording the change of the transmittance of 200-800nm wavelength within one week of the measured polymer thermometer by using an ultraviolet-visible spectrophotometer, wherein the data acquisition frequency is 5 minutes/time. The time required for the transmittance to return from the value measured by the polymer thermometer to about 50% at a wavelength of 500nm was taken as the memory time.
LCST test method: and recording a relation curve of the transmittance of the polymer thermometer at the wavelength of 700nm and the temperature change by using an ultraviolet-visible spectrophotometer, and taking the corresponding temperature when the transmittance is 50 percent as a low critical solution temperature, namely a measurable lowest temperature.
Example 1
A visual polymer thermometer with temperature memory function and a preparation method thereof, taking LCST type polymer hydrogel temperature as an example, the thermometer can detect the temperature of 38 ℃ and above, and the temperature memory time is a week (the 500nm transmittance is about 50%), the method comprises the following steps:
1) 149.83mg of N-isopropylacrylamide (temperature-sensitive monomer), 100.20mg of N, N-dimethylacrylamide (hydrophilic monomer), 107.154mg of 2-ureido-4 [1H ] -pyrimidone methyl methacrylate (multiple hydrogen bond unit), 21.45mg of N, N-methylene bisacrylamide (cross-linking agent), 10.73mg of ammonium persulfate (initiator) and 5ml of dimethyl sulfoxide (solvent) are uniformly mixed, dissolved and injected into a mold, the mold is placed in a forced air drying oven to react for 3 hours at 85 ℃, and after the reaction is finished, the dimethyl sulfoxide is replaced by deionized water to obtain the temperature-sensitive polymer hydrogel containing the multiple hydrogen bond unit;
(2) the polymer hydrogel can be directly used as a polymer thermometer, placed on the surface of an object to be measured, and used for measuring water at 38 ℃, as shown in fig. 1, an ultraviolet-visible split photometer is used for recording the change of transmittance (200 + 800nm, wherein 400 + 800nm is the visible light range) before and after the test, as shown in fig. 2, the polymer thermometer before the test is in a transparent state (500nm, transmittance is 82.9%), the polymer thermometer after the test for 120s is in an opaque state (500nm, transmittance is 9.3%), and the polymer thermometer after one week is in a semitransparent state (500nm, transmittance is 52.6%).
The application comprises the following steps: the polymer hydrogel can be directly used as a medical polymer thermometer for detecting the change of the body temperature of a patient. The polymer hydrogel is pasted on the forehead of a patient, and when the body temperature of the patient is higher than 38 ℃, the polymer thermometer is changed from a transparent state to a white opaque state, so that nursing staff can find the body temperature change of the patient in time. When the body temperature of the patient is reduced from 38 ℃ to the normal body temperature, the polymer hydrogel thermometer starts to be slowly converted from the opaque state to the transparent state, and medical personnel can calculate the time for the patient to return to the normal body temperature by measuring the change of the transparency of the polymer hydrogel thermometer and combining the transmittance change curve of the graph in figure 1.
Example 2
A visual polymer thermometer with temperature memory function and a preparation method thereof, taking LCST type polymer solution thermometer as an example, the thermometer can detect the temperature above 50 ℃, and the temperature memory time is one week (the 500nm transmittance is about 50%), the method comprises the following steps:
(1) adding 134.61mg of N-isopropylacrylamide, 121.352mg of N, N-dimethylacrylamide, 107.154mg of 2-ureido-4 [1H ] -pyrimidone methyl methacrylate, 10.73mg of ammonium persulfate and 5ml of dimethyl sulfoxide into a three-neck flask provided with an oil bath pot, a condenser pipe and a stirring device, starting stirring, reacting for 3 hours at 85 ℃, and removing a solvent to obtain a temperature-sensitive high polymer material containing multiple hydrogen bond units;
(2) dissolving the polymer material in deionized water to prepare a polymer solution with the mass fraction of 20 wt%, packaging the obtained polymer solution in a glass tube to obtain a polymer thermometer, measuring hot water at 50 ℃, recording the change of the transmittance (400 plus 800nm and visible light range) of the polymer thermometer by using an ultraviolet-visible split photometer, wherein the polymer thermometer is in a transparent state (500nm and the transmittance is 87.5%) before the test, the polymer thermometer is in an opaque state (500nm and the transmittance is 6.3%) after the test is carried out for 30s, and the polymer thermometer is in a semitransparent state (500nm and the transmittance is 51.4%) after one week.
Example 3
A visual polymer thermometer with temperature memory function and a preparation method thereof, taking LCST type polymer hydrogel thermometer as an example, the thermometer can detect the temperature of more than 55 ℃, and the temperature memory time is a week (the 500nm transmittance is about 50%), the method comprises the following steps:
(1) uniformly mixing 134.61mg of N-isopropylacrylamide, 142.885mg of N, N-dimethylacrylamide, 107.154mg of 2-ureido-4 [1H ] -pyrimidone methyl methacrylate, 21.45mg of N, N-methylene bisacrylamide, 10.73mg of ammonium persulfate and 5ml of dimethyl sulfoxide, dissolving, injecting into a mold, placing in a forced air drying oven, reacting for 3 hours at 85 ℃, and replacing the dimethyl sulfoxide by using deionized water after the reaction is finished to obtain the temperature-sensitive polymer hydrogel containing multiple hydrogen bond units;
(2) the polymer hydrogel can be directly used as a polymer thermometer, hot water at 50 ℃ is measured by using the polymer hydrogel, the change of the transmittance (400 plus 800nm and visible light range) is recorded by using an ultraviolet-visible split photometer, the polymer thermometer is in a transparent state (500nm and the transmittance is 90.4%) before the test, the polymer thermometer is in an opaque state (500nm and the transmittance is 10.2%) after the test is carried out for 30s, and the polymer thermometer is in a semitransparent state (500nm and the transmittance is 49.6%) after one week. The tested polymer hydrogel is soaked in an acid solution with the pH value less than 1 for 10 minutes and then is soaked in deionized water for 2 hours, and the transmittance of the polymer hydrogel is recovered to 89.4 percent (500nm), so that the polymer hydrogel can be used again.
Example 4
A visual polymer thermometer with temperature memory function and a preparation method thereof, taking LCST type polymer hydrogel thermometer as an example, the thermometer can detect the temperature above 65 ℃, and the temperature memory time is one month (the 500nm transmittance is about 50%), the method comprises the following steps:
(1) uniformly mixing 134.61mg of N-isopropylacrylamide, 160.541mg of N, N-dimethylacrylamide, 143.154mg of 2-ureido-4 [1H ] -pyrimidone methyl methacrylate, 21.45mg of N, N-methylene bisacrylamide, 10.73mg of ammonium persulfate and 5ml of dimethyl sulfoxide, dissolving, injecting into a mold, placing into a forced air drying oven, reacting for 3 hours at 85 ℃, and replacing the dimethyl sulfoxide by using deionized water after the reaction is finished to obtain the temperature-sensitive polymer hydrogel containing multiple hydrogen bond units;
(2) the polymer hydrogel can be directly used as a polymer thermometer to measure hot water at 50 ℃, an ultraviolet-visible split photometer is used for recording the change of the transmittance (400 + 800nm, visible light range), the polymer thermometer is in a transparent state (500nm, the transmittance is 86.5%) before the test, the polymer thermometer is in an opaque state (500nm, the transmittance is 2.1%) after the test is carried out for 30s, and the polymer thermometer is in a semitransparent state (500nm, the transmittance is 50.8%) after one month.
Example 5
A visual polymer thermometer with temperature memory function and a preparation method thereof, taking LCST type polymer hydrogel thermometer as an example, the thermometer can detect the temperature of more than 77 ℃, and the temperature memory time is one month (the 500nm transmittance is about 50%), the method comprises the following steps:
(1) evenly mixing 134.61mg of N-isopropylacrylamide, 178.6mg of N, N-dimethylacrylamide, 143.154mg of methyl 2-ureido-4 [1H ] -pyrimidone methacrylate, 21.45mg of N, N-methylene bisacrylamide, 10.73mg of ammonium persulfate and 5ml of dimethyl sulfoxide, dissolving, injecting into a mold, placing in a forced air drying oven, reacting for 3 hours at 85 ℃, and replacing the dimethyl sulfoxide by using deionized water after the reaction is finished to obtain the temperature-sensitive polymer hydrogel containing multiple hydrogen bond units;
(2) the polymer hydrogel can be directly used as a polymer thermometer to measure hot water at 50 ℃, an ultraviolet-visible split photometer is used for recording the change of the transmittance (400 + 800nm, visible light range), the polymer thermometer is in a transparent state (500nm, the transmittance is 88.4%) before the test, the polymer thermometer is in an opaque state (500nm, the transmittance is 13.3%) after the test is carried out for 30s, and the polymer thermometer is in a semitransparent state (500nm, the transmittance is 50.5%) after one month.
Example 6
A visual polymer thermometer with temperature memory function and a preparation method thereof, taking LCST type polymer hydrogel thermometer as an example, the thermometer can detect the temperature above 85 ℃, and the temperature memory time is one month (the 500nm transmittance is about 50%), the method comprises the following steps:
(1) uniformly mixing 134.61mg of N-isopropylacrylamide, 198.18mg of N, N-dimethylacrylamide, 143.154mg of 2-ureido-4 [1H ] -pyrimidone methyl methacrylate, 21.45mg of N, N-methylene bisacrylamide, 10.73mg of ammonium persulfate and 5ml of dimethyl sulfoxide, dissolving, injecting into a mold, placing in a forced air drying oven, reacting for 3 hours at 85 ℃, and replacing the dimethyl sulfoxide by using deionized water after the reaction is finished to obtain the temperature-sensitive polymer hydrogel containing multiple hydrogen bond units;
(2) the polymer hydrogel can be directly used as a polymer thermometer to measure hot water at 50 ℃, an ultraviolet-visible split photometer is used for recording the change of the transmittance (400 + 800nm, visible light range), the polymer thermometer is in a transparent state (500nm, the transmittance is 87.3%) before the test, the polymer thermometer is in an opaque state (500nm, the transmittance is 14.1%) after the test is carried out for 30s, and the polymer thermometer is in a semitransparent state (500nm, the transmittance is 50.2%) after one month.
Example 7
A visual polymer thermometer with temperature memory function and a preparation method thereof, taking LCST type polymer hydrogel thermometer as an example, the thermometer can detect the temperature above 45 ℃, and the temperature memory time is 2 hours (the 500nm transmittance is about 50%), the method comprises the following steps:
(1) 134.61mg of 2-methyl-2-acrylic acid-2- (2-methoxyethoxy) ethyl ester, 98.18mg of N, N-dimethylacrylamide, 20mg of methyl methacrylate, 34.4mg of N-acryloyl glycinamide, 21.45mg of N, N-methylene bisacrylamide, 10.73mg of azobisisobutyronitrile and 5ml of dimethyl sulfoxide are uniformly mixed, dissolved and injected into a mold, the mold is placed in a forced air drying oven to react for 6 hours at 70 ℃, and after the reaction is finished, the dimethyl sulfoxide is replaced by deionized water to obtain the thermosensitive polymer hydrogel containing multiple hydrogen bond units;
(2) the polymer hydrogel can be directly used as a polymer thermometer. The temperature of the hot water was measured at 45 ℃ and the change of the transmittance (400 plus 800nm, visible light range) was recorded by using an ultraviolet-visible spectrophotometer, and the polymer thermometer was in a transparent state (500nm, transmittance 93.1%) before the test, in an opaque state (500nm, transmittance 16.5%) after the test for 30s, and in a translucent state (500nm, transmittance 49.7%) after 2 hours.
Example 8
A visual polymer thermometer with temperature memory function and a preparation method thereof, taking LCST type polymer hydrogel thermometer as an example, the thermometer can detect the temperature above 52 ℃, and the temperature memory time is 8 hours (the 500nm transmittance is about 50%), the method comprises the following steps:
(1) uniformly mixing 143.2 mg of vinyl PEO/PPO, 98.18mg of N, N-dimethylacrylamide, 20mg of methacrylic acid, 71.56mg of uracil, 21.45mg of N, N-methylenebisacrylamide, 10.73mg of potassium persulfate and 5ml of dimethyl sulfoxide, dissolving, injecting into a mold, placing into an air-blowing drying oven, reacting for 4 hours at 80 ℃, and after the reaction is finished, replacing the dimethyl sulfoxide by using deionized water to obtain the temperature-sensitive polymer hydrogel containing multiple hydrogen bond units;
(2) the polymer hydrogel can be directly used as a polymer thermometer. The temperature of the hot water was measured at 52 ℃, the change of the transmittance (400 plus 800nm, visible light range) was recorded by using an ultraviolet-visible spectrophotometer, the polymer thermometer before the test was in a transparent state (500nm, transmittance of 97.3%), the polymer thermometer after the test was in an opaque state (500nm, transmittance of 13.8%) after 30s, and the polymer thermometer after 8 hours was in a translucent state (500nm, transmittance of 50.0%).
The above embodiments are only for embodying the inventive concept of the inventor, and any type of evolution and improvement based on the inventive concept of the invention are within the protection scope of the invention.

Claims (10)

1. A preparation method of a visual polymer thermometer with a temperature memory function is characterized by comprising the following steps:
(1) preparing a temperature-sensitive high polymer material containing multiple hydrogen bond units by performing polycondensation or chain polymerization on a hydrophilic monomer, a hydrophobic monomer, an LCST (lower-temperature-sensitive styrene) type temperature-sensitive monomer or an LCST type temperature-sensitive high molecular chain, a functional monomer and a derivative of the triple or multiple hydrogen bond units in the presence of an initiator or a catalyst;
(2) dissolving or dispersing the polymer material prepared in the step (1) to prepare a polymer solution with adjustable memory temperature and memory time, or preparing a polymer hydrogel with adjustable memory temperature and memory time by a physical or/and chemical crosslinking method, wherein the polymer solution and the polymer hydrogel can be used as a polymer thermometer.
2. The method of claim 1, wherein the derivative containing triple or multiple hydrogen bonding units is a derivative of a monomer containing 3 or more proton donors or acceptors, and is used for adjusting the memory time of the polymer thermometer.
3. The method according to claim 1, wherein the LCST-type thermo-sensitive monomer or LCST-type thermo-sensitive polymer chain is a thermo-sensitive monomer whose homopolymer or copolymer has a low critical solution temperature, and is used for adjusting the memory time of the polymer thermometer.
4. The method according to any one of claims 1 to 3, wherein the hydrophilic monomer is a monofunctional, bifunctional or polyfunctional hydrophilic monomer containing a polar group; the hydrophobic monomer is a hydrophobic monomer containing a nonpolar group.
5. A method according to any one of claims 1 to 3, wherein the functional monomer is a monomer containing a reactive group capable of reacting with the cross-linking sites on the functional monomer by the addition of a cross-linking monomer to produce a hydrogel polymer thermometer.
6. The method according to any one of claims 1 to 3, wherein the polymer hydrogel with adjustable memory temperature and memory time in step (2) is obtained by first preparing a polymer material solution and then adding a cross-linking agent to obtain the polymer hydrogel, or directly adding the cross-linking agent to obtain the hydrogel during the process of preparing the polymer material.
7. A polymer thermometer produced by the method according to any one of claims 1 to 6.
8. The method of claim 7, wherein the used thermometer is immersed in an acidic solution with a pH of less than 1 or an alkaline solution with a pH of more than 10 to accelerate dissociation of the triple or multiple hydrogen bond dimers, thereby rapidly relaxing the polymer chains to a stretched state, and then removing free hydrogen ions and hydroxyl ions to enable reuse.
9. Use of the polymer thermometer according to claim 7.
10. Use according to claim 9 for medical thermometers, temperature detection during food preservation or transport, etc.
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