CN109679582B - Liquid photo-thermal conversion material and preparation method and application thereof - Google Patents
Liquid photo-thermal conversion material and preparation method and application thereof Download PDFInfo
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- 229910052740 iodine Inorganic materials 0.000 claims abstract description 41
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
- G01J1/00—Photometry, e.g. photographic exposure meter
- G01J1/42—Photometry, e.g. photographic exposure meter using electric radiation detectors
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- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
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- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Photometry And Measurement Of Optical Pulse Characteristics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a liquid photo-thermal conversion material and a preparation method and application thereof. The material of the invention is formed by doping iodine into a micromolecule material containing unsaturated carbon-carbon double bonds; the mass percentage of iodine doping in the unsaturated carbon-carbon double bond-containing micromolecule material is 0.1-1000%. The preparation method comprises the following steps of the method (1) or (2): (1) exposing the micromolecular material containing unsaturated carbon-carbon double bonds in iodine vapor, and smoking to obtain the product; (2) directly contacting a micromolecular material containing unsaturated carbon-carbon double bonds with a solid iodine simple substance, and heating for reaction to obtain the iodine-containing composite material. The method is applied to the field of preparing the photo-thermal conversion material. The invention has simple preparation, cheap and easily obtained materials, mass preparation of photo-thermal products and wide applicability of the method, and the material form of the material is liquid, has the unique advantages of liquid materials, such as flexibility, self-repairability, adulteration and long circulation in organisms, and can integrate a plurality of functional intelligent materials by combining the photo-thermal capability.
Description
Technical Field
The invention relates to a liquid photo-thermal conversion material and a preparation method and application thereof, belonging to the field of photo-thermal conversion materials.
Background
The photothermal conversion material is a material capable of absorbing light and converting the light into heat, has photothermal conversion capability, mostly has the characteristic of black color, has the characteristic of multiband absorption, is one of important research points in the field of light energy utilization, and attracts the wide attention of numerous researchers. The photothermal conversion can enrich the utilization forms of light energy and improve the utilization efficiency of the light energy, is one of the forms with the highest utilization rate of the light energy at present, and plays a significant role in the fields of seawater desalination, analysis and detection, cancer diagnosis and treatment and the like. At present, the key and difficult point of research in the field of photothermal conversion is to develop a novel photothermal conversion material, on one hand, the requirement of increasing an absorption waveband and efficiently utilizing energy is met; on the other hand, the material performance is required to be improved, and the novel application of the photothermal conversion is finally expanded.
The currently developed photothermal conversion materials can be mainly divided into five types, namely carbon-based photothermal conversion materials, metal-based photothermal conversion materials, semiconductor-based photothermal conversion materials, near-infrared dye small molecules and conjugated polymers. All of which are solid and often suffer from problems in specific applications. Firstly, when the solid material is used, phenomena such as serious abrasion and even breakage often occur due to poor deformation performance, so that the use is inconvenient, and meanwhile, the device is easy to damage, the resources are wasted and the environment is polluted. Secondly, when the solid material is mixed and doped with other materials, phase separation is easy to occur due to the bean effect, so that the mixed and doped performance is poor. Therefore, many researchers at present try to avoid the disadvantages of solid materials by making the solid materials into micron and nanometer particles and dispersing the micron and nanometer particles in liquid. Although this method has some effect, it still does not completely circumvent all the disadvantages of solid materials. On the one hand, the dispersion of the solid in the liquid dilutes the concentration of the photothermal conversion material, reducing the photothermal conversion performance. On the other hand, in the long circulation in vivo, the micro-and nano-particles are easily aggregated at the internal organs and capillaries and hardly reach the diseased site all over, which reduces the long-term effect of the photothermal conversion material for in vivo disease detection and treatment, and the micro-and nano-particles are difficult to be removed by metabolism in vivo, reducing the in vivo long-term biocompatibility of the material. Therefore, the dependence of the photothermal conversion material on the solid morphology greatly limits the applications of the current photothermal conversion material in many fields, and the development and preparation of the new photothermal conversion material still face a serious challenge.
Compared to solid materials, liquid materials have five significant advantages: firstly, the liquid material has flexibility, and can generate large deformation under the action of a tiny external force; secondly, the liquid material has self-repairability, and the dispersed liquid drops are mutually fused after being contacted to form large liquid drops; thirdly, the liquid material has excellent doping and doped capabilities, and the functional material added into the liquid material is easy to process, modify or dissolve and disperse to form a multifunctional aggregate; fourthly, the liquid material is easier to absorb or discharge from the body in the organism, and has less influence on the healthy physiological metabolism of the organism; fifthly, the intrinsic liquid material can form a high-concentration even pure single substance system without being diluted by other liquids. Based on the advantages of the liquid material, the photo-thermal conversion material is expanded to the liquid field, and the advantages of the photo-thermal conversion material can be more fully exerted. Therefore, the development of liquid photothermal conversion materials is beneficial to promoting the practical application of photothermal conversion research in clinical medicine.
Disclosure of Invention
The invention aims to provide a liquid photo-thermal conversion material and a preparation method and application thereof, and the invention carries out specific iodine doping on a micromolecule liquid material containing unsaturated carbon-carbon double bonds, so that the light absorption wavelength of the material is expanded from a short-wave ultraviolet region to a visible light region or even a near infrared region, and the material has the capability of light absorption and light conversion into heat in a corresponding waveband; in addition, through the treatment of different small molecule materials and the change of the amount of the dopant, liquid photothermal conversion materials with different photothermal conversion capabilities can be obtained.
The invention provides a liquid photo-thermal conversion material, which is formed by doping iodine into a micromolecule material containing unsaturated carbon-carbon double bonds;
the mass percentage of iodine doping in the unsaturated carbon-carbon double bond-containing micromolecular material is 0.1-1000%.
In the invention, the mass percentage of iodine doping in the unsaturated carbon-carbon double bond-containing micromolecular material can be 50%, 45-55%, 40-60%, 0.1-50%, 50-1000% or 0.1-500%.
In the above materials, the small molecule material containing unsaturated carbon-carbon double bonds is selected from at least one of methyl oleate, ethyl oleate, propyl oleate, butyl oleate, amyl oleate, isopropyl oleate, oleyl ricinoleate, oleic acid, glyceryl oleate, sorbitan monooleate, glyceryl trioleate, oleyl chloride, erucic acid, triolenyl phosphate, methyl arachidonic acid, arachidic acid, octadecenoic acid, palmitoleic acid, decyl oleate, linoleic acid, linolenic acid, terpinolene, tert-butylcyclopentadiene, carene, hexene, p-menthene, cyclooctadiene, phellandrene, cyclohexene, heptene, octene and nonene.
In the above materials, the material is in a liquid state;
the light absorption wavelength of the material can be 200-1800 nm.
In the above material, the viscosity of the material may be 1.0 to 30.0 mPas.
In the above material, the conductivity of the material can be 0.0001 to 1S/m.
The invention also provides a preparation method of the liquid photothermal conversion material, which comprises the following steps of the method (1) or (2):
(1) exposing the micromolecular material containing unsaturated carbon-carbon double bonds in iodine vapor, and smoking to obtain the liquid photo-thermal conversion material;
(2) and directly contacting the unsaturated carbon-carbon double bond-containing micromolecule material with a solid iodine simple substance, and heating for reaction to obtain the liquid photo-thermal conversion material.
In the method (1) of the preparation method, the smoking temperature may be 0 to 200 ℃, specifically 65 ℃, and the time may be 1 second to 1 week, specifically 1, 3, 6, 12, 24h, 1 to 48h, or 1 to 72 h;
the vapor pressure of the iodine vapor may be 0.01 to 20kPa, specifically 0.75Pa, 0.01 to 0.75kPa, 0.75 to 20kPa, or 0.05 to 10 kPa.
In the method (2) of the above preparation method, the temperature of the heating reaction may be 0 to 200 ℃ and the time may be 1 second to 1 week.
In the method (2) of the preparation method, the solid iodine simple substance accounts for 0.1-1000% by mass of the unsaturated carbon-carbon double bond-containing small molecular material, and specifically may be 50%, 0.1-50%, 50-1000% or 0.1-500%.
The invention further provides application of the liquid photothermal conversion material in the field of preparation of photothermal conversion materials.
In the above application, the photothermal conversion material comprises an anti-icing coating and/or a light intensity detector; the method can be particularly applied to the preparation of cable protection, pipeline protection, bridge buildings or vehicles anti-icing layers and the preparation of light intensity detectors for the rapid determination of illumination intensity.
According to the invention, the liquid photothermal conversion material is used for preparing the ice-covering-proof coating, and the surface of the ice-covering-proof coating can be subjected to photothermal conversion under sunlight, so that a certain ice melting effect is realized, and ice adsorption is reduced; the liquid photo-thermal conversion material can expand with heat and contract with cold under light, is used for preparing the simple light intensity detector,
the invention has the following advantages:
compared with the traditional photothermal conversion material, the photothermal conversion material has simple preparation process, cheap and easily obtained materials, mass preparation of photothermal products and wide applicability of the method, and the material form of the material is liquid, so the material has the unique advantages of liquid materials, such as flexibility, self-repairability, adulteration and long circulation in organisms, and can be integrated with a plurality of functional intelligent materials by combining the photothermal capacity of the material. In addition, the subsequent combination of the thermal response material is expected to realize the wider application of converting from photo-thermal to other energy, and has great application prospect.
Drawings
FIG. 1 is a diagram of materials for iodine doping of oleic acid (a) and ethyl oleate (b) for different lengths in example 1 of the present invention.
FIG. 2 is data of UV-VIS-NIR absorption of oleic acid (a) and ethyl oleate (b) with iodine doping for different durations in example 1 of the present invention.
FIG. 3 is the IR spectrum absorbance data of oleic acid (a) and ethyl oleate (b) obtained by iodine doping for different durations in example 1 of the present invention.
FIG. 4 is Raman scattering spectra data of oleic acid (a) and ethyl oleate (b) doped with iodine for different durations in example 1 of the present invention.
FIG. 5 is a graph showing the viscosity change of ethyl oleate doped with iodine for various periods of time in example 1 of the present invention.
FIG. 6 is data of the conductivity change of ethyl oleate doped with iodine for different periods of time in example 1 of the present invention.
FIG. 7 is an example of the application of the iodine doped oleic acid and ethyl oleate anti-icing coating of example 2 of the present invention.
FIG. 8 shows the temperature data of iodine doped with oleic acid and ethyl oleate under illumination, respectively, in example 2 of the present invention.
FIG. 9 is a diagram illustrating an example of a product application of the iodine doped ethyl oleate light intensity detector in embodiment 3 of the present invention.
FIG. 10 is the light intensity detection data of the iodine doped ethyl oleate light intensity detector product in example 1 of the present invention.
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Examples 1,
Fumigating iodine (1 second-1 week, specifically 0, 1, 3, 6, 12, 24h) oleic acid and ethyl oleate (0.001 mL-10 h) at a certain temperature (0-200 deg.C, specifically 65 deg.C) and vapor pressure of iodine vapor (0.01-20 kPa, specifically 0.75Pa)6mL) to obtain a liquid photothermal conversion material with a certain iodine doping amount (the iodine doping mass percentage content is 0.1-1000%, specifically 50%).
The physical diagram of the liquid photothermal conversion material obtained above is shown in fig. 1.
Of iodine
As shown in FIGS. 2-4, the light absorption wavelength of the liquid photothermal conversion material can be 200-1800 nm.
As can be seen from FIG. 5, the viscosity of the liquid photothermal conversion material can be 1.0 to 30.0 mPas.
As shown in FIG. 6, the liquid photothermal conversion material has an electrical conductivity of 0.0001 to 1S/m.
Example 2 preparation and application of anti-icing coating of micromolecule liquid photothermal conversion material
Under a certain temperature (0-200 ℃, specifically 65 ℃) and the vapor pressure of iodine vapor (0.01-20 kPa, specifically 0.75Pa), respectively soaking oleic acid and ethyl oleate in a substrate with a certain thickness (0.001 mm-10 cm) for 1 second-1 week, specifically 0, 1, 3, 6, 12, 24h) for different iodine smoking time lengths (1 second-1 week, specifically 0, 1, 3, 6, 12, 24h) to obtain the ice-covering-proof coating with the photo-thermal conversion capability, as shown in FIG. 7. The material has a certain iodine doping amount (the mass percentage content of iodine doping is 0.1-1000%, and can be 50%). Substrates for the coating include paper, wood board, rubber, Polydimethylsiloxane (PDMS), Ecoflex products, and the like.
And (3) acquiring the photothermal conversion heating data of the coating under the irradiation of one sunlight illumination intensity by using a Fluke Tix 660 infrared camera through a CROWNTECH SOLARBEAM-02-3A sunlight simulator. The room temperature was controlled at 25 ± 5 ℃ in the photothermal conversion test, and the temperature-raising property of the coating was measured under illumination with a light intensity of one sunlight illumination intensity, and the obtained data is shown in fig. 8. The result shows that the photo-thermal performance of the substrate is obviously improved after the substrate is treated by the micromolecule liquid photo-thermal conversion material.
The method has the advantages of simple preparation process, readily available materials, low cost, large-scale preparation, application in important fields of cable protection, pipeline protection, bridge construction, anti-icing of vehicles and the like, and huge application market. The coating can be obviously heated after being irradiated by sunlight, the surface temperature can be increased, the surface friction coefficient can be changed, the ice layer is effectively prevented from being accumulated on the surface of an object, the artificial energy supplement is not needed, and an effective solution is provided for the difficult problems encountered in the daily production and life of human beings.
Example 3 preparation and application of light intensity Detector for liquid photothermal conversion Material
Fumigating iodine (1 second to 1 week, specifically 0, 1, 3, 6, 12, 24h) at a certain temperature (0-200 ℃, specifically 65 ℃) with ethyl oleate (0.001mL to 10%6mL) was packaged in a self-contained apparatus to obtain a light intensity detector capable of detecting the intensity of light, as shown in fig. 9. The homemade device includes a display portion and a light receiving portion. The display part is a tubular object (material: glass, quartz, metal, polymer material, length: 0.001-1000m, outer diameter: 0.001-100 cm, inner diameter: 0.001-100 cm) with a certain specification. The light receiving part is a specially made bottle-shaped object (material: glass, quartz, metal, polymer material, length: 0.001-1000m, outer diameter: 0.001-100 cm, inner diameter: 0.001-100 cm) with a certain specification. After the photo-thermal conversion micromolecule liquid black material is irradiated, the temperature is increased, so that the density and the volume are changed, the corresponding irradiation intensity can be obtained by quantitatively analyzing the volume change condition, and the specific data is shown in figure 10. Due to the fact thatThe liquid photo-thermal conversion material is expected to be applied to rapid determination of illumination intensity, and innovative application of the photo-thermal conversion material is widened.
Claims (9)
1. A liquid photothermal conversion material, characterized in that: the material is formed by doping iodine into a micromolecule material containing unsaturated carbon-carbon double bonds;
the mass percentage of iodine doping in the unsaturated carbon-carbon double bond-containing small molecular material is 0.1-50%;
the small molecular material containing unsaturated carbon-carbon double bonds is selected from at least one of methyl oleate, ethyl oleate, propyl oleate, butyl oleate, amyl oleate, isopropyl oleate, oleyl ricinoleate, oleic acid, glyceryl oleate, sorbitan monooleate, glyceryl trioleate, oleyl chloride, erucic acid, trioleyl phosphate, methyl arachidonic acid, octadecenoic acid, palmitoleic acid, decyl oleate, linoleic acid, linolenic acid, terpinolene, tert-butylcyclopentadiene, carene, hexene, p-menthene, cyclooctadiene, phellandrene, cyclohexene, heptene, octene and nonene;
the preparation method of the liquid photothermal conversion material comprises the following steps of the method (1) or (2):
(1) exposing the micromolecular material containing unsaturated carbon-carbon double bonds in iodine vapor, and smoking to obtain the liquid photo-thermal conversion material;
(2) and directly contacting the unsaturated carbon-carbon double bond-containing micromolecule material with a solid iodine simple substance, and heating for reaction to obtain the liquid photo-thermal conversion material.
2. The material of claim 1, wherein: the material is liquid in nature;
the light absorption wavelength of the material is 200-1800 nm;
the viscosity of the material is 1.0-30.0 mPas.
3. The material according to claim 1 or 2, characterized in that: the conductivity of the material is 0.0001-1S/m.
4. A method for producing the liquid photothermal conversion material described in any one of claims 1 to 3, comprising the steps of the following method (1) or (2):
(1) exposing the micromolecular material containing unsaturated carbon-carbon double bonds in iodine vapor, and smoking to obtain the liquid photo-thermal conversion material;
(2) and directly contacting the unsaturated carbon-carbon double bond-containing micromolecule material with a solid iodine simple substance, and heating for reaction to obtain the liquid photo-thermal conversion material.
5. The method of claim 4, wherein: in the method (1), the smoking temperature is 0-200 ℃, and the time is 1 second-1 week;
the vapor pressure of the iodine vapor is 0.01 to 1000 Pa.
6. The method of claim 4, wherein: in the method (2), the heating reaction is carried out at a temperature of 0-200 ℃ for 1 second-1 week.
7. The production method according to claim 4 or 6, characterized in that: in the method (2), the solid iodine simple substance accounts for 0.1-50% of the unsaturated carbon-carbon double bond-containing small molecular material by mass.
8. Use of the liquid photothermal conversion material according to any of claims 1 to 3 for the production of photothermal conversion materials.
9. Use according to claim 8, characterized in that: the photothermal conversion material includes an anti-icing coating and/or a light intensity detector.
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| CN103951850A (en) * | 2014-05-05 | 2014-07-30 | 付国东 | Optothermal response system, resin material and optothermal response smart glass |
| CN107556562A (en) * | 2017-09-04 | 2018-01-09 | 三维天工（北京）科技有限公司 | The preparation method of customizable optical-thermal conversion material and application |
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| CN103951850A (en) * | 2014-05-05 | 2014-07-30 | 付国东 | Optothermal response system, resin material and optothermal response smart glass |
| CN107556562A (en) * | 2017-09-04 | 2018-01-09 | 三维天工（北京）科技有限公司 | The preparation method of customizable optical-thermal conversion material and application |
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