CN112521635A - Preparation method of thermal gel with near-infrared photothermal conversion response - Google Patents
Preparation method of thermal gel with near-infrared photothermal conversion response Download PDFInfo
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- CN112521635A CN112521635A CN202011598598.0A CN202011598598A CN112521635A CN 112521635 A CN112521635 A CN 112521635A CN 202011598598 A CN202011598598 A CN 202011598598A CN 112521635 A CN112521635 A CN 112521635A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2329/00—Characterised by the use of homopolymers or 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 an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2371/02—Polyalkylene oxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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Abstract
A preparation method of thermal gel with near-infrared photothermal conversion responsiveness belongs to the technical field of intelligent materials. The invention mixes the hydroxyl-containing hydrophilic polymer and the transition metal acetate to prepare the hydroxyl-containing hydrophilic polymer/transition metal acetate thermal gel with inherent near-infrared photo-thermal response characteristic. The thermal gel with the near-infrared absorption performance can be synthesized by a mixing heating mode, and the gel has a reversible phenomenon. The preparation method is simple in preparation process, does not need to carry out additional chemical modification or mix with additional reagents on the hydroxyl-containing hydrophilic polymer, does not need complex equipment, and is wide in application scene.
Description
Technical Field
The invention relates to a preparation method of thermal gel with near-infrared photothermal conversion responsiveness, and belongs to the technical field of intelligent materials.
Background
As one of the most promising smart materials, stimulus-responsive gels are characterized by the ability to respond to external stimuli, such as temperature, ionic strength, light, pH, electric/magnetic fields, and the like. Among these, thermal gels attract considerable interest because they undergo a physical sol-gel transition once the temperature exceeds a critical point. Currently, the most common strategy for preparing thermogel systems is to incorporate a thermosensitive polymer into the system. For example, an aqueous solution of an amphiphilic block copolymer consisting of hydrophilic polyethylene glycol and hydrophobic polypropylene oxide, polyglycolide or poly epsilon-caprolactone and the like can be self-assembled into a polymer micelle, and can cause reversible sol-gel transformation after being heated. However, this approach has two inherent disadvantages: (1) it usually requires a cumbersome polymer synthesis, which is time consuming; (2) the sol-gel transition is hardly induced by remote stimuli such as light, electricity and magnetism, which makes it difficult to accurately and remotely control the properties of the thermal gel.
In order to achieve controllability by remote stimulation, one possible approach is to introduce an energy-converting additive into the polymer matrix, which additive can convert remote energy into localized heat. Near Infrared (NIR) light-induced photothermal conversion agents such as metal nanoparticles, graphene, and the like. However, this physical doping strategy faces such a challenge due to the poor solubility of the photothermal conversion agent in the polymer matrix: an increase in doping percentage typically causes phase separation, while a decrease in doping percentage decreases the light-to-heat conversion efficiency. Thus, it remains a challenge to produce thermal gels with inherent NIR photoresponse without cumbersome polymer synthesis.
Disclosure of Invention
The invention aims to overcome the defects and provide a preparation method of the thermal gel with near-infrared photothermal conversion response, and the prepared thermal gel shows high photothermal conversion efficiency and reversible sol-gel conversion behavior. The resulting thermal gel can be prepared with precise control of gel properties by remote stimulation with Near Infrared (NIR) light, with an in situ sol-gel transition occurring as the temperature is increased.
According to the technical scheme, the preparation method of the thermal gel with near-infrared photothermal conversion response comprises the step of mixing the hydroxyl-containing hydrophilic polymer with the transition metal acetate to prepare the hydroxyl-containing hydrophilic polymer/transition metal acetate thermal gel with the inherent NIR photothermal response characteristic.
Further, the steps are as follows: dissolving a hydroxyl-containing hydrophilic polymer in deionized water under the conditions of room temperature and magnetic stirring, and stirring at high temperature to obtain a uniform transparent solution; after cooling to room temperature, adding transition metal acetate serving as a light response additive into the solution, and uniformly mixing to form a transparent reaction solution; preparing a hollow double-layer container by using a transparent plate, injecting a reaction solution and sealing by using glue to prepare the hydroxyl-containing hydrophilic polymer/transition metal acetate thermal gel.
Further, the hydrophilic polymer containing hydroxyl is polyethylene glycol, polytetrahydrofuran or polyoxypropylene glycol.
Further, the transition metal acetate is specifically Cu (OAc)2、Cr2(OAc)3Or Fe (OAc)2。
Further, the transparent plate is polycarbonate or polymethyl methacrylate.
The method comprises the following specific steps:
(1) at room temperature, stirring at 350-; heating to 80-100 ℃, continuously stirring for 1-3h at 350-450r/min to obtain uniform transparent solution, and cooling to room temperature;
(2) adding transition metal acetate into the solution obtained in the step (1), wherein the molar weight of metal ions is less than that of the hydroxyl-containing hydrophilic polymer; stirring for 2 h at 300 r/min, and uniformly mixing to form a transparent solution, namely a hydroxyl-containing hydrophilic polymer/transition metal acetate thermal gel reaction solution;
(3) using a transparent plate to prepare a hollow double-layer container, injecting the reaction solution obtained in the step (2) and sealing with glue to complete the sample preparation.
Further, the molar weight ratio of the hydroxyl-containing hydrophilic polymer to the metal ions in the step (2) is 5-40: 1.
Further, when the hydrophilic polymer containing hydroxyl groups is a polyethylene glycol PVA, the molecular weight of the PVA is 6 to 8 ten thousand.
Further, taking PVA/Cu (OAc)2Thermal gelation, preparation of hollow double-layer vessel using transparent plate and injection of reaction solution and sealing with glue complete sample preparation.
With PVA/Cu (OAc)2Thermosol for example, the present invention is prepared by simply mixing hydrophilic polyvinyl alcohol (PVA) and copper acetate [ Cu (OAc) ] in deionized water2 ]A new NIR light-responsive thermal gel was prepared. Blue PVA/Cu (OAc) after irradiation with NIR light2The solution turned rapidly to a green gel and the temperature rose sharply, but in the absence of NIR light it recovered its original blue sol state.
During irradiation, copper ions (Cu)2+) Absorbs NIR light and converts it to heat, promoting Cu2+Hydrolysis to copper hydroxide [ Cu (OH)2]. Subsequently, PVA and Cu (OH)2The clusters co-aggregate into cage complexes, driven primarily by hydrophobic interactions, in which the flexible chains of PVA project hydroxyl groups to the outside, while Cu OH)2The clusters are located in the center of the entangled chains. Thus, these clathrate complexes gradually form a three-dimensional thermal gel network. The invention does not need chemical modification of PVA and additional reagent, PVA/Cu (OAc)2Thermal gels exhibit high photothermal conversion efficiency and reversible sol-gel transition behavior.
Unlike other reported PVA-based hydrogels, the latter require cumbersome modifications to PVA or additional harsh basic conditions, namely PVA/Cu (OAc)2Thermal gels are directly induced by NIR light without additional chemical modification of PVA orAdditional reagents were incorporated.
The invention has the beneficial effects that: the thermal gel with the near-infrared absorption performance can be synthesized by a mixing heating mode, and the gel has a reversible phenomenon. The preparation method is simple in preparation process, does not need to carry out additional chemical modification or mix with additional reagents on the hydroxyl-containing hydrophilic polymer, does not need complex equipment, and is wide in application scene.
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FIG. 1 is a graph of a thermogel UV-visible near-IR spectrophotometer test prepared in example 1.
Detailed Description
Example 1
Adding PVA into deionized water according to the mass concentration of 10%, and continuously stirring for 2 h at 95 ℃ to obtain a uniform transparent solution. After cooling to room temperature, Cu (OAc) was added2Stirred for 2 h, then a blue solution was formed (in which the molar ratio of hydroxyl groups to copper ions was 20: 3). The molecular weight of the PVA particles is 7 ten thousand.
After a long-range illumination for 300s by means of NIR illumination, stable PVA/Cu (OAc) is obtained2Green thermal gel. Moreover, this green thermal gel gradually returned to its original blue sol state again in the absence of irradiation.
The spectral absorption values of the thermal gel prepared in example 1 in the near infrared region are shown in FIG. 1. As shown in FIG. 1, 300-780 nm is the visible light region, and 800-2000 nm is the near infrared region, which is the concentrated region of solar energy. As can be seen from the figure, the sample has higher spectral absorption performance in the region, and the change is more obvious. The combination of the gel change characteristics means that the gel has obvious light responsiveness in the area.
Claims (9)
1. A preparation method of thermal gel with near-infrared photothermal conversion responsiveness is characterized in that: hydroxyl-containing hydrophilic polymers are mixed with transition metal acetates to prepare hydroxyl-containing hydrophilic polymer/transition metal acetate thermal gels with intrinsic NIR photothermal response characteristics.
2. The method of making a thermal gel having near-infrared photothermal conversion responsiveness according to claim 1, characterized by the steps of: dissolving a hydroxyl-containing hydrophilic polymer in deionized water under the conditions of room temperature and magnetic stirring, and stirring at high temperature to obtain a uniform transparent solution; after cooling to room temperature, adding transition metal acetate serving as a light response additive into the solution, and uniformly mixing to form a transparent reaction solution; preparing a hollow double-layer container by using a transparent plate, injecting a reaction solution and sealing by using glue to prepare the hydroxyl-containing hydrophilic polymer/transition metal acetate thermal gel.
3. The method of preparing a thermal gel having near-infrared photothermal conversion responsiveness according to claim 1, wherein: the hydrophilic polymer containing hydroxyl is polyethylene glycol, polytetrahydrofuran or polyoxypropylene glycol.
4. The method of preparing a thermal gel having near-infrared photothermal conversion responsiveness according to claim 1, wherein: the transition metal acetate is Cu (OAc)2、Cr2(OAc)3Or Fe (OAc)2。
5. The method of preparing a thermal gel having near-infrared photothermal conversion responsiveness according to claim 1, wherein: the transparent plate is polycarbonate or polymethyl methacrylate.
6. The method of preparing a thermal gel having near-infrared photothermal conversion responsiveness according to claim 1, characterized by the steps of:
(1) at room temperature, stirring at 350-; heating to 80-100 ℃, continuously stirring for 1-3h at 350-450r/min to obtain uniform transparent solution, and cooling to room temperature;
(2) adding transition metal acetate into the solution obtained in the step (1), wherein the molar weight of metal ions is less than that of the hydroxyl-containing hydrophilic polymer; stirring for 2 h at 300 r/min, and uniformly mixing to form a transparent solution, namely a hydroxyl-containing hydrophilic polymer/transition metal acetate thermal gel reaction solution;
(3) using a transparent plate to prepare a hollow double-layer container, injecting the reaction solution obtained in the step (2) and sealing with glue to complete the sample preparation.
7. The method of preparing a thermal gel having near-infrared photothermal conversion responsiveness according to claim 6, wherein: the molar weight ratio of the hydroxyl-containing hydrophilic polymer to the metal ions in the step (2) is 5-40: 1.
8. The method of preparing a thermal gel having near-infrared photothermal conversion responsiveness according to claim 6, wherein: when the hydrophilic polymer containing hydroxyl is polyethylene glycol PVA, the molecular weight of the PVA is 6-8 ten thousand.
9. The method of preparing a thermal gel having near-infrared photothermal conversion responsiveness according to claim 6, wherein: taking hydroxyl-containing hydrophilic polymer/transition metal acetate thermal gel, preparing a hollow double-layer container by using a transparent plate, injecting the thermal gel reaction solution, and sealing with glue to complete sample preparation.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105885065A (en) * | 2016-05-13 | 2016-08-24 | 西南交通大学 | Preparation method of electrical stimulation-near infrared dual response high strength hydrogel |
| CN106893120A (en) * | 2017-03-06 | 2017-06-27 | 乌鲁木齐诺西辰环境工程有限公司 | A kind of preparation method of strain-responsive conductive hydrogel |
| CN109503862A (en) * | 2017-09-15 | 2019-03-22 | 天津大学 | A kind of near-infrared response type nano composite supramolecular hydrogel and preparation method thereof |
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2020
- 2020-12-30 CN CN202011598598.0A patent/CN112521635A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105885065A (en) * | 2016-05-13 | 2016-08-24 | 西南交通大学 | Preparation method of electrical stimulation-near infrared dual response high strength hydrogel |
| CN106893120A (en) * | 2017-03-06 | 2017-06-27 | 乌鲁木齐诺西辰环境工程有限公司 | A kind of preparation method of strain-responsive conductive hydrogel |
| CN109503862A (en) * | 2017-09-15 | 2019-03-22 | 天津大学 | A kind of near-infrared response type nano composite supramolecular hydrogel and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| ZHANG HAO ET AL.: "A simple PVA/Cu(OAc)2 thermogel with an inherent near-infrared light response and its applications in smart windows and photoresistors", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
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Application publication date: 20210319 |