CN112852130B - Polylactic acid composite material with fluorescence and photothermal conversion functions and preparation method thereof - Google Patents
Polylactic acid composite material with fluorescence and photothermal conversion functions and preparation method thereof Download PDFInfo
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- CN112852130B CN112852130B CN202110134678.9A CN202110134678A CN112852130B CN 112852130 B CN112852130 B CN 112852130B CN 202110134678 A CN202110134678 A CN 202110134678A CN 112852130 B CN112852130 B CN 112852130B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention discloses a polylactic acid composite material with fluorescence and photothermal conversion functions, which comprises fluorescence bio-based polyester modified lignin, zinc oxide, silver particles and polylactic acid, wherein the addition amount of the fluorescence bio-based polyester modified lignin is 5% of the mass of a polylactic acid matrix, the addition amount of the zinc oxide is 10% of the mass of the polylactic acid matrix, and the addition amount of the silver particles is 5% of the mass of the polylactic acid matrix. Compared with polylactic acid/pure lignin composite materials, the fluorescence property of the polylactic acid composite material provided by the invention is greatly improved, the polylactic acid composite material can be used in the field of anti-counterfeiting materials, has a photothermal conversion effect, and widens the application range of polylactic acid in the fields of fluorescence anti-counterfeiting and photothermal conversion thermal fabrics.
Description
Technical Field
The invention relates to a polylactic acid composite material with fluorescence and photothermal conversion functions and a preparation method thereof, belonging to the technical field of composite materials.
Background
In recent years, with the rapid development of world socioeconomic and scientific civilizations, fossil energy sources such as: coal, petroleum and other human resources depend on the reduction of living resources year by year, and the alternative energy sources are few. The widespread use of these fossil energy sources and petroleum-based products produces waste that is difficult to degrade, severely pollutes the environment and interferes with people's normal lives. Therefore, the search for biodegradable bio-based energy sources and polymer materials is becoming a research hotspot. Compared with fossil energy and petroleum-based materials, bio-based materials can undergo a biodegradation process after use, thus having great advantages over petroleum-based materials and reducing the dependence of people on petroleum-based polymers. Polylactic acid is a bio-based material polymer prepared by ring-opening polymerization of lactic acid prepared from corn starch, is a material with biodegradability and biocompatibility, and can be completely degraded into an environment-friendly product. Polylactic acid is mainly applied to the fields of agriculture, medical treatment, packaging and the like, but due to the single functionality, the application of polylactic acid in other fields is limited to a great extent. Therefore, how to overcome the limitation of single function of polylactic acid is a difficult problem to prepare the multifunctional polylactic acid composite material.
The lignin is a natural polymer resource on the earth, and has excellent biodegradable characteristics, biocompatibility and the like. However, 98% of the lignin is used as fuel for combustion to obtain energy, which generates a large amount of greenhouse gas carbon dioxide and wastes the lignin resource. Therefore, the reasonable and efficient application of the lignin has positive significance to the environment and the economy. Due to the benzene ring structure of lignin, the lignin is generally used as a reinforcing agent of a polymer and simultaneously endows the polymer with good biocompatibility, but the single property of the lignin limits the wide application of the lignin in other fields.
Disclosure of Invention
The purpose is as follows: in order to overcome the defect that polylactic acid and lignin have single functions in the prior art, the invention provides a polylactic acid composite material with fluorescence and photothermal conversion functions and a preparation method thereof.
Researches show that a conjugated compound (thiazole picolinic acid, TPA) generated by the dehydration reaction of citric acid and cysteine has biocompatibility and good fluorescence property, and the esterification reaction of the conjugated compound and lignin not only maintains the biodegradability of the lignin, but also endows the lignin with excellent fluorescence property. The zinc oxide and the silver are used as semiconductors and noble metal materials, have certain absorption capacity on sunlight and have photothermal conversion performance. Therefore, the fluorescent bio-based polyester modified lignin can be compounded with zinc oxide, silver particles and polylactic acid to prepare the polylactic acid composite material with the functions of fluorescence and photothermal conversion.
The technical scheme is as follows: in order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a polylactic acid composite material with fluorescence and photothermal conversion functions comprises fluorescence bio-based polyester modified lignin, zinc oxide, silver particles and polylactic acid, wherein the addition amount of the fluorescence bio-based polyester modified lignin is 5% of the mass of a polylactic acid matrix, the addition amount of the zinc oxide is 10% of the mass of the polylactic acid matrix, and the addition amount of the silver particles is 5% of the mass of the polylactic acid matrix.
Further, the addition amount of the zinc oxide is 10% of the mass of the polylactic acid matrix.
Furthermore, the shape of the zinc oxide is flaky or columnar.
A preparation method of a polylactic acid composite material with fluorescence and photothermal conversion functions comprises the following steps:
(1) mixing lignin powder with citric acid, cysteine and deionized water, and performing ultrasonic and ball milling to obtain fluorescent bio-based polyester modified lignin;
adding Zn (NO)3)2·6H2Dissolving O in deionized water, adding triethanolamine or hexamethylenetetramine into the solution, stirring, then placing into an autoclave, reacting for 1.5-3h at the temperature of 150-;
FeCl is added3·6H2Adding O and polyvinylpyrrolidone into the ethylene glycol solution, and stirring vigorously; then AgNO is added 3Adding the mixture into glycol solution to be stirred and mixed; the two solutions are mixed homogeneously, the solution is transferred into a high-pressure kettle after mixing is finished, the temperature is kept at 150-170 ℃ for 1.5-3h, then the solution is naturally cooled, the obtained solution is cleaned by acetone and ethanol, and the obtained solution is subjected to high-speed centrifugation, so that silver particles can be separated from the ethylene glycol solution;
(2) adding a proper amount of fluorescent bio-based polyester modified lignin, a zinc oxide sample and silver particles into a dichloromethane solution of polylactic acid, stirring, and then casting and volatilizing to form a film to prepare the polylactic acid composite material with the functions of fluorescence and photothermal conversion.
Further, the molar ratio of citric acid to cysteine is 1: 1.
Further, the preparation process of the zinc oxide sample comprises the following steps:
Zn(NO3)2·6H2mixing O and deionized water in a mass ratio of 1:6, adding triethanolamine, and stirring at room temperature to obtain a mixed solution A, wherein the volume ratio of the deionized water to the triethanolamine is 2: 1; and then the mixed solution A is put into an autoclave for reaction at the temperature of 150-.
Further, the preparation process of the zinc oxide sample comprises the following steps:
Zn(NO3)2·6H2Mixing O and deionized water in a mass ratio of 1:6, adding hexamethylenetetramine in a volume ratio of 12:1, and stirring at room temperature to obtain a mixed solution B; and then the mixed solution B is put into an autoclave for reaction at the temperature of 150-.
Further, AgNO3With polyvinylpyrrolidone and FeCl3·6H2The mass ratio of O is 1: 630: 617.
further, in the step (2), the mass of the modified lignin is 5% of the mass of the polylactic acid matrix, the mass of the zinc oxide sample is 10% of the mass of the polylactic acid matrix, and the mass of the silver particles is 5% of the mass of the polylactic acid matrix.
Has the advantages that: compared with polylactic acid/pure lignin composite materials, the fluorescence property of the polylactic acid composite material provided by the invention is greatly improved, the polylactic acid composite material can be used in the field of anti-counterfeiting materials, has a photothermal conversion effect, and widens the application range of polylactic acid in the fields of fluorescence anti-counterfeiting and photothermal conversion thermal fabrics.
The fluorescent bio-based polyester is conjugated on the lignin matrix by applying a green chemical method on the basis of insolubilizing the lignin, so that the fluorescent property of the lignin is realized, and meanwhile, the photo-thermal conversion performance of the material is greatly improved under the synergistic effect of the added zinc oxide and silver particles; the finally obtained polylactic acid composite material has the functions of fluorescence and photothermal conversion, and opens up a new direction for the multifunctional application of polylactic acid.
Drawings
FIG. 1 is a fluorescence spectrum of the polylactic acid composite material of example 1;
FIG. 2 is a fluorescence spectrum of the polylactic acid composite materials of examples 1 and 2;
FIG. 3 is a fluorescence spectrum of the polylactic acid composite materials of examples 1 and 3;
fig. 4 is a graph showing the photothermal conversion effect of the polylactic acid composite materials of examples 2 and 3.
Detailed Description
The present invention will be further described with reference to the following examples and the accompanying drawings.
Example 1
(1) Preparation of fluorescent bio-based polyester modified lignin
Mixing lignin powder with citric acid, cysteine and deionized water to form an aqueous solution, and performing ultrasonic treatment by using an ultrasonic instrument; then, the completely dissolved solutions were poured into 4 zirconia ball milling pots, respectively, for ball milling. After the ball milling was completed, the sample was freeze-dried for 48 h.
(2) Preparation of polylactic acid composite material with fluorescence function
Dissolving 1.5g of dried polylactic acid in 20mL of dichloromethane solution, preparing two groups of solutions according to the formula, stirring at room temperature to obtain clear and transparent solutions, adding 0.075g of Lignin into one sample, adding 0.075g of fluorescent bio-based polyester modified Lignin into the other sample, and volatilizing the solvent at room temperature to obtain the polylactic acid/pure Lignin composite material (PLA/Lignin) and the polylactic acid composite material (PLA/FL) with the fluorescent function.
Example 2
(1) Preparation of fluorescent bio-based polyester modified lignin
Mixing lignin powder with citric acid, cysteine and deionized water to form an aqueous solution, and performing ultrasonic treatment by using an ultrasonic instrument; then, the completely dissolved solutions were poured into 4 zirconia ball milling pots, respectively, for ball milling. After the ball milling was completed, the sample was freeze-dried for 48 h.
(2) Preparation of polylactic acid composite material with fluorescence and photothermal conversion functions
Dissolving 1.5g of dried polylactic acid in 20mL of dichloromethane solution, stirring at room temperature to obtain a clear and transparent solution, adding 0.075g of fluorescent bio-based polyester modified lignin, 0.15g of rod-shaped (one-dimensional 1D) zinc oxide and 0.075g of silver particles, continuing stirring for 12h, pouring the solution into a flat glass dish, casting to form a film, and volatilizing the solvent at room temperature to obtain the polylactic acid composite material (PLA/FL/1 DZnO/Ag) with the functions of fluorescence and photothermal conversion.
Example 3
(1) Preparation of fluorescent bio-based polyester modified lignin
Mixing lignin powder with citric acid, cysteine and deionized water to form an aqueous solution, and performing ultrasonic treatment by using an ultrasonic instrument; then, the completely dissolved solutions were poured into 4 zirconia ball milling pots, respectively, for ball milling. After the ball milling was completed, the sample was freeze-dried for 48 h.
(2) Preparation of polylactic acid composite material with fluorescence and photothermal conversion functions
Dissolving 1.5g of dried polylactic acid in 20mL of dichloromethane solution, stirring at room temperature to obtain a clear and transparent solution, adding 0.075g of fluorescent bio-based polyester modified lignin, 0.15g of flaky (two-dimensional 2D) zinc oxide and 0.075g of silver particles, continuing stirring for 12h, pouring the solution into a flat glass dish, casting to form a film, and volatilizing the solvent at room temperature to obtain the polylactic acid composite material (PLA/FL/2 DZnO/Ag) with the functions of fluorescence and photothermal conversion.
Comparative example 1
Comparative example 1 the polylactic acid/pure lignin composite prepared in example 1 was used.
As shown in fig. 1, the composite material is prepared from pure lignin, fluorescent bio-based polyester modified lignin and polylactic acid with the same content, and the polylactic acid composite material containing the fluorescent bio-based polyester modified lignin shows excellent fluorescence property, and compared with the composite material of polylactic acid and pure lignin, the fluorescence property is greatly improved. Referring to fig. 2 and 3, on the basis of adding the fluorescent bio-based polyester modified lignin, after adding the rod-shaped or sheet-shaped zinc oxide and the silver particles, the fluorescence performance of the composite material is further improved compared with that of the fluorescent bio-based polyester modified lignin/polylactic acid composite material.
In addition, due to the good absorption performance of zinc oxide on ultraviolet band and the existence of surface plasma resonance effect of silver particles, the polylactic acid composite material is endowed with excellent photo-thermal conversion performance, and in a thermal infrared imaging diagram as shown in FIG. 4, the photo-thermal conversion performance is actually realizedThe polylactic acid composite materials of examples 2 and 3 were exposed to 1 sun (i.e., an irradiation intensity of 1 kW m)-2The simulated light source) is respectively raised to 62.1 ℃ and 67.1 ℃ within 3min, and the temperature is greatly improved compared with the 30.8 ℃ of a pure polylactic acid material, thereby proving that the polylactic acid composite material has good photo-thermal conversion performance. Meanwhile, as shown in fig. 4, the photothermal conversion performance of the polylactic acid composite material containing the flake (2D) zinc oxide is superior to that of the polylactic acid composite material containing the columnar (1D) zinc oxide, because the flake zinc oxide has a higher specific surface area for light absorption and conversion into heat, and can have a better photothermal conversion effect under the synergistic effect with the silver particles.
The invention conjugates the fluorescent bio-based polyester on the lignin matrix, thereby not only realizing the high-valued application of the lignin in the field of fluorescent materials, but also maintaining the biocompatibility of the lignin. After the zinc oxide with different dimensionality and morphology is prepared into a composite material together with the fluorescent bio-based polyester modified lignin, the silver particles and the polylactic acid, the polylactic acid is endowed with excellent fluorescence performance and excellent photo-thermal conversion performance, the application field of the polylactic acid is greatly expanded, and the development concept of the current green bio-based functional material is met.
The above description is only of the preferred embodiments of the present invention, and it should be noted that: it will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles of the invention and these are intended to be within the scope of the invention.
Claims (6)
1. The polylactic acid composite material with the functions of fluorescence and photothermal conversion is characterized by comprising fluorescent bio-based polyester modified lignin, zinc oxide, silver particles and polylactic acid, wherein the addition amount of the fluorescent bio-based polyester modified lignin is 5% of the mass of a polylactic acid matrix, the addition amount of the zinc oxide is 10% of the mass of the polylactic acid matrix, and the addition amount of the silver particles is 5% of the mass of the polylactic acid matrix;
the zinc oxide is flaky or rod-shaped;
the preparation method of the fluorescent bio-based polyester modified lignin comprises the following steps: mixing lignin powder with citric acid, cysteine and deionized water, and performing ultrasonic and ball milling to obtain the lignin powder;
the preparation method of the zinc oxide comprises the following steps: adding Zn (NO)3)2·6H2Dissolving O in deionized water, adding triethanolamine or hexamethylenetetramine into the solution, stirring, then loading into an autoclave, reacting at the temperature of 150 ℃ and 170 ℃ for 1.5-3h, collecting a product, washing with deionized water, and collecting after freeze drying;
The preparation method of the silver particles comprises the following steps: FeCl is added3·6H2Adding O and polyvinylpyrrolidone into the ethylene glycol solution, stirring vigorously, and adding AgNO3Adding the solution into an ethylene glycol solution, stirring and mixing, carrying out homogeneous phase mixing on the two solutions, transferring the solution into a high-pressure kettle after mixing is finished, preserving heat at the temperature of 150 ℃ and 170 ℃ for 1.5-3h, naturally cooling, cleaning the obtained solution with acetone and ethanol, and carrying out high-speed centrifugation on the obtained solution to separate silver particles from the ethylene glycol solution.
2. The method for preparing the polylactic acid composite material with the functions of fluorescence and photothermal conversion as claimed in claim 1, which is characterized by comprising the following steps:
(1) mixing lignin powder with citric acid, cysteine and deionized water, and performing ultrasonic and ball milling to obtain fluorescent bio-based polyester modified lignin;
adding Zn (NO)3)2·6H2Dissolving O in deionized water, adding triethanolamine or hexamethylenetetramine into the solution, stirring, then placing into an autoclave, reacting for 1.5-3h at the temperature of 150-;
FeCl is added3·6H2Adding O and polyvinylpyrrolidone into the ethylene glycol solution, stirring vigorously, and adding AgNO 3Adding into ethylene glycol solution, stirring, mixing, homogenizing, transferring into high-pressure autoclave, keeping at 150-170 deg.C for 1.5-3h, naturally cooling, cleaning with acetone and ethanol,centrifuging the obtained solution at high speed to separate silver particles from the glycol solution;
(2) adding a proper amount of fluorescent bio-based polyester modified lignin, a zinc oxide sample and silver particles into a dichloromethane solution of polylactic acid, stirring, and then casting and volatilizing to form a film to prepare the polylactic acid composite material with the functions of fluorescence and photothermal conversion;
in the step (2), the mass of the modified lignin is 5% of the mass of the polylactic acid matrix, the mass of the zinc oxide sample is 10% of the mass of the polylactic acid matrix, and the mass of the silver particles is 5% of the mass of the polylactic acid matrix.
3. The method for preparing a polylactic acid composite material with both fluorescence and photothermal conversion functions as claimed in claim 2, wherein the molar ratio of citric acid to cysteine is 1: 1.
4. The preparation method of the polylactic acid composite material with the fluorescence and photothermal conversion functions as claimed in claim 2, wherein the preparation process of the zinc oxide sample comprises the following steps:
Zn(NO3)2·6H2Mixing O and deionized water in a mass ratio of 1:6, adding triethanolamine, and stirring at room temperature to obtain a mixed solution A, wherein the volume ratio of the deionized water to the triethanolamine is 2: 1; and then the mixed solution A is put into an autoclave for reaction at the temperature of 150-.
5. The preparation method of the polylactic acid composite material with the fluorescence and photothermal conversion functions as claimed in claim 2, wherein the preparation process of the zinc oxide sample comprises the following steps:
Zn(NO3)2·6H2mixing O and deionized water in a mass ratio of 1:6, adding hexamethylenetetramine in a volume ratio of 12:1, and stirring at room temperature to obtain a mixed solution B; then the mixed solution B is put into an autoclave to react for 2 hours at 160 ℃, the product is collected, washed by deionized water and freeze-driedAnd collecting the sample for later use, wherein the sample is in a sheet shape.
6. The method for preparing the polylactic acid composite material with the functions of fluorescence and photothermal conversion as claimed in claim 2, wherein AgNO is used3With polyvinylpyrrolidone and FeCl3·6H2The mass ratio of O is 1: 630: 617.
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| WO2017028643A1 (en) * | 2015-08-19 | 2017-02-23 | 中国科学院深圳先进技术研究院 | Photothermal shape memory composite material, component, and preparation method thereof |
| US10099191B1 (en) * | 2017-06-22 | 2018-10-16 | Tripod Technology Corporation | Method of making colloidal metal nanoparticles |
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| CN102983009A (en) * | 2012-11-06 | 2013-03-20 | 南京大学昆山创新研究院 | Flexible photo-anode of dye-sensitized solar cell based on zinc oxide nano-sheet and preparation of flexible photo-anode of dye-sensitized solar cell based on zinc oxide nano-sheet |
| WO2017028643A1 (en) * | 2015-08-19 | 2017-02-23 | 中国科学院深圳先进技术研究院 | Photothermal shape memory composite material, component, and preparation method thereof |
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