CN112480479B - Preparation method of nanocellulose-based fluorescent film - Google Patents

Preparation method of nanocellulose-based fluorescent film Download PDF

Info

Publication number
CN112480479B
CN112480479B CN202011371906.6A CN202011371906A CN112480479B CN 112480479 B CN112480479 B CN 112480479B CN 202011371906 A CN202011371906 A CN 202011371906A CN 112480479 B CN112480479 B CN 112480479B
Authority
CN
China
Prior art keywords
nano
cellulose
ccnc
suspension
acid solution
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202011371906.6A
Other languages
Chinese (zh)
Other versions
CN112480479A (en
Inventor
王玮
姜帅
孙旭
张胜文
白绘宇
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangnan University
Original Assignee
Jiangnan University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jiangnan University filed Critical Jiangnan University
Priority to CN202011371906.6A priority Critical patent/CN112480479B/en
Publication of CN112480479A publication Critical patent/CN112480479A/en
Application granted granted Critical
Publication of CN112480479B publication Critical patent/CN112480479B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
    • 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
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
    • C09K11/7795—Phosphates
    • 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
    • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2301/04—Oxycellulose; Hydrocellulose
    • 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
    • C08K3/32—Phosphorus-containing compounds

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Luminescent Compositions (AREA)

Abstract

The invention discloses a preparation method of a nano cellulose-based fluorescent film, belonging to the field of modification of high polymer materials. The preparation method comprises the following steps: (1) dissolving lanthanum salt and europium salt in a solvent, dropwise adding a phosphate ethylene glycol solution, carrying out reflux reaction at 100-4:Eu3+(ii) a (2) The LaPO obtained in the step (1) is used4:Eu3+Adding the mixture into a carboxylated nano-cellulose water suspension, and uniformly dispersing to obtain a uniform and stable suspension; wherein, the LaPO4:Eu3+The addition amount of (A) is 1-10 wt% of the carboxylated nano-cellulose; (3) and (3) carrying out suction filtration on the suspension obtained in the step (2) until no water drops, then flatly paving the suspension to form a film, and finally carrying out hot pressing treatment to obtain the nano cellulose based fluorescent film. The nano cellulose-based fluorescent film has deep red fluorescence under near ultraviolet excitation (254nm), high luminous intensity, high luminous efficiency, and better light transmittance and flexibility.

Description

Preparation method of nanocellulose-based fluorescent film
Technical Field
The invention relates to a preparation method of a nano cellulose-based fluorescent film, belonging to the field of modification of high polymer materials.
Background
The current problems of resource shortage, environmental pollution and the like restrict the sustainable development of economy, so that a green natural renewable novel material becomes a research hotspot, and cellulose is a renewable natural environment-friendly material and has great development value due to abundant reserves, biodegradability, no toxicity and no harm.
The nano-cellulose has the characteristics of wide source, abundant reserves, degradability, high crystallinity, high Young modulus, hyperfine structure, huge specific surface area and the like, and is widely researched and applied. The nano cellulose film has good light transmission and flexibility, is compounded with a fluorescent material by taking the nano cellulose film as a carrier to obtain the composite film with the fluorescent property, and has potential application in the fields of photoelectric materials, biomedicine, package anti-counterfeiting and the like. However, most of the currently used organic fluorescent dyes have poor stability and are difficult to stably use for a long time.
The rare earth element has a unique 4f electronic layer structure, so that the rare earth element has particularly rich electronic energy level transitions and has extremely wide application in the photoelectron industry. The rare earth phosphate luminescent material has high luminous intensity, high luminous efficiency, good stability efficiency, good thermal stability and chemical stability, and can be widely applied to various lighting and display devices. However, the rare earth element nanoparticles have high specific surface area and are easy to agglomerate, so that the rare earth element nanoparticles are difficult to uniformly disperse in solvents such as water, ethanol and the like, and are difficult to uniformly disperse in a polymer matrix in a nanometer size finally, and the fluorescence property of the rare earth element nanoparticles is reduced.
The patent (CN105672014A) mentions a preparation method of magnetic nano-fiber paper, and mentions a forming process of cellulose paper, and particularly, a 10-50 wt% nano-cellulose aqueous solution is used for dispersing Fe3O4Then, vacuum filtration and hot pressing are carried out to obtain a filter membrane to form the paper, but a plurality of silane coupling agents, surfactants and the like are required to be added in the preparation process, and the process is complex.
Disclosure of Invention
In order to solve at least one of the above problems, the present invention provides a method for preparing a nanocellulose-based fluorescent film, which has deep red fluorescence under near ultraviolet excitation (254nm), high luminous intensity, high luminous efficiency, and good light transmittance and flexibility. The method is simple and feasible, is easy to operate, and the prepared nano cellulose-based fluorescent film has potential application in the fields of photoelectric materials, biomedicine, package anti-counterfeiting and the like.
The first object of the present invention is to provide a method for preparing a nanocellulose-based fluorescent membrane, comprising the following steps:
(1) dissolving lanthanum salt and europium salt in a solvent, dropwise adding a phosphate ethylene glycol solution, carrying out reflux reaction at 100-4:Eu3+；
(2) The rare earth nano fluorescent particle LaPO obtained in the step (1)4:Eu3+Adding the mixture into a carboxylated nano-cellulose water suspension, and uniformly dispersing to obtain a uniform and stable suspension; wherein the solid content of the carboxylated nano-cellulose water suspension is 0.5-2 wt%; the rare earth nano fluorescent particle LaPO4:Eu3+The addition amount of (A) is 1-10 wt% of the carboxylated nano-cellulose;
(3) and (3) carrying out suction filtration on the suspension obtained in the step (2) until no water drops, then flatly paving the suspension to form a film, and finally carrying out hot pressing treatment to obtain the nano cellulose based fluorescent film.
In one embodiment, the lanthanum salt in the step (1) is one or more of lanthanum nitrate, lanthanum sulfate and lanthanum chloride; the europium salt is one or more of europium nitrate and europium chloride, and the phosphate is one or more of monopotassium phosphate, dipotassium phosphate, sodium dihydrogen phosphate and disodium phosphate.
In one embodiment, the solvent in step (1) is ethylene glycol.
In one embodiment, the phosphate glycol solution of step (1) has a pH of 1.5 to 2.5; the concentration of phosphate in the phosphate glycol solution is 1.5-2.5 mol/L.
In one embodiment, the volume ratio of the solvent to the phosphate glycol solution in step (1) is 4: 1.
in one embodiment, the centrifugation and washing in step (1) is specifically washing with acetone for 2-10 times; the centrifugation speed is 15000rpm and the centrifugation time is 30 min.
In one embodiment, the temperature of the drying in step (1) is room temperature (20-30 ℃), and the drying time is 0.5-2 h.
In one embodiment, the dropping process of the phosphate ethylene glycol solution in step (1) requires high-speed stirring, and the phosphate ethylene glycol solution is added while stirring, wherein the specific high-speed stirring speed is 1000-2000 rpm.
In one embodiment, the molar ratio of lanthanum salt to europium salt added in step (1) is 90-97.5: 2.5 to 10 are further preferably 92.5: 7.5.
in one embodiment, the solid-to-liquid ratio of the rare earth salt (lanthanum salt and europium salt) to the solvent in step (1) is 0.03 to 0.05mol L-1。
In one embodiment, the step (2) of dispersing uniformly is ultrasonic dispersing, and ultrasonic parameters are set as follows: the ultrasonic power is 200-1000W, and the ultrasonic time is 10-30 min.
In one embodiment, the rare earth nano fluorescent particle LaPO in the step (2)4:Eu3+The amount of (b) added was 7.5 wt% of the carboxylated nanocellulose.
In one embodiment, the preparation method of the carboxylated nanocellulose in the step (2) comprises the following steps:
heating the mixed acid solution of the hydrochloric acid solution and the nitric acid solution to 110 ℃ below 100 ℃, adding the nano-cellulose, and carrying out reflux reaction for 3-5h at 110 ℃ below 100 ℃; centrifuging to obtain precipitate after the reaction is finished; then dialyzing the precipitate with water to neutrality; and then ultrasonic dispersion and concentration are carried out to obtain the carboxylated nano-cellulose.
In one embodiment, the concentration of the hydrochloric acid solution and the concentration of the nitric acid solution in the preparation method of the carboxylated nano-cellulose are both 4 mol/L.
In one embodiment, the volume ratio of the hydrochloric acid solution to the nitric acid solution in the preparation method of the carboxylated nanocellulose is 5-8: 2-5; more preferably 6: 4.
in one embodiment, the amount ratio of the nanocellulose to the mixed acid solution in the preparation method of the carboxylated nanocellulose is 4 g: 200 mL.
In one embodiment, the centrifugation in the preparation method of the carboxylated nanocellulose is 6000r/min for 6 min.
In one embodiment, the ultrasonic dispersion in the preparation method of the carboxylated nanocellulose is ultrasonic treatment for 10min at 250w power by a cell crusher.
In one embodiment, the carboxylated nanocellulose is prepared by a process wherein the concentration is carried out to a solids content of 1 wt%.
In one embodiment, the suction filtration in the step (3) is vacuum filtration, and the specific parameters are that a mixed fiber filter membrane with the pore diameter of 0.15 μm is adopted, the vacuum degree is-0.09 MPa to-0.1 MPa, and the filtration is carried out for 4-6h until no water drops.
In one embodiment, the pressure of the hot pressing treatment in the step (3) is 10MPa, the temperature is 80 ℃, and the time is 30-60 min.
In one embodiment, the flat film formation in step (3) is to form a film by clamping the suspension which is filtered to be in a non-dripping state between two flat PTFE sheets.
The second purpose of the invention is to provide a deep red light emitting nano cellulose based fluorescent film obtained by the method of the invention.
The third purpose of the invention is to apply the nano cellulose-based fluorescent film in the fields of photoelectric materials, biomedicine or package anti-counterfeiting.
The invention has the beneficial effects that:
(1) the invention can prepare the rare earth nano fluorescent particle LaPO which can be stably dispersed in water4:Eu3+Using LaPO4:Eu3+And the cellulose-based fluorescent film has a hydrogen bond effect and an electrostatic effect with hydroxyl groups of the nano-cellulose, is loaded on a molecular chain of the nano-cellulose through simple ultrasonic blending, has a simple preparation process and a good effect, and has a deep red fluorescent emission, high luminous intensity and better light transmission under the excitation of ultraviolet light (254 nm).
(2) LaPO of the invention4:Eu3+Uniformly dispersed in the nano-cellulose matrix, avoiding the intermolecular aggregation and improving the relative luminous brightness.
(3) The transmittance of the nano cellulose-based fluorescent film at 600nm is more than 72.5%; the tensile strength of CCNC-7.5 is up to 163MPa, and the water contact angle is up to 90 degrees; excellent washing resistance and high luminous intensity.
Drawings
FIG. 1 shows fluorescence emission spectra of CNC, CCNC-2.5, CCNC-5, CCNC-7.5, CCNC-10, CCNC-15; the inset is a picture of CCNC-7.5 illuminating at an ultraviolet lamp.
FIG. 2 is a graph showing the transmittance of CNC, CCNC-2.5, CCNC-5, CCNC-7.5, CCNC-10, CCNC-15.
FIG. 3 shows the transmittance at 600nm of a fluorescent film and E-LaPO4:7.5％Eu3+The relationship between the contents.
FIG. 4 shows the results of the mechanical property tests of CNC, CCNC-2.5, CCNC-5, CCNC-7.5, CCNC-10 and CCNC-15.
FIG. 5 shows the results of water contact angle measurements for CNC, CCNC-2.5, CCNC-5, CCNC-7.5, CCNC-10, CCNC-15.
FIG. 6 shows the result of the water-washing resistance test of CCNC-7.5.
Fig. 7 is CCNC 8: 2. CCNC 7: 3. CCNC 5: 5. CCNC 6: zeta potential diagram of 4.
FIG. 8 shows the rare earth nano-fluorescent particles LaPO obtained by different media4:Eu3+Fluorescence emission spectrum of (1).
FIG. 9 shows Eu in different concentrations3+Ion-doped rare earth nano fluorescent particle LaPO4:Eu3+Fluorescence emission spectrum of (1).
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:
1. fluorescence Spectroscopy (PL) characterisation: after being air-dried at room temperature, LaPO4, Eu3+ powder is fully and uniformly ground and filled between double-layer quartz plates, an FS-5 type fluorescence spectrometer is adopted to test the excitation spectrum and the emission spectrum of a sample at room temperature, and an excitation light source is an Xe lamp; the fluorescent film is horizontally clamped between 2 quartz plates, an excitation spectrum and an emission spectrum of a sample at room temperature are tested by adopting an FS-5 type fluorescence spectrometer, and an excitation light source is an Xe lamp.
2. And (3) visible light transmittance analysis: the fluorescent film is cut into a strip shape with the length of 1.0cm and the width of 3.5cm, the visible light transmittance of a sample is measured by a TU-1901 type spectrophotometer, the scanning wavelength is 400-800 nm, and the scanning interval is 1.0 nm.
3. And (3) mechanical property analysis: cutting the fluorescent film into a dumbbell shape with the effective length of 25mm and the width of 4mm, testing the mechanical property of the fluorescent film by adopting a 2967X type double-upright-column table system according to the GB/T1040.2-2006 standard, fixing the stretching speed at 5mm/min, and testing each group of samples for 3 times to obtain an average value.
4. Water contact angle test: the water contact angle of the fluorescent film is tested by adopting an OCA 40 type dynamic contact angle instrument, the dosage of each water drop is fixed to be 1.5 mu L, the state of the water drop on the surface of the fluorescent film is observed after the water drop is dripped for 1s, the water contact angle is calculated by utilizing the self-contained software of the system, and an average value is obtained by measuring 5 points of each fluorescent film.
5. Zeta potential test: after the aqueous suspension of CCNC at a concentration of 1.0% by weight was ultrasonically dispersed for 10min, the Zeta potential value of the suspension at 25 ℃ was measured using a Zeta PALS type potential analyzer, and each group of samples was measured 3 times to take an average value.
6. Washing resistance: soaking in pure water at room temperature for 5 min.
Example 1
A preparation method of a nano cellulose-based fluorescent film specifically comprises the following steps:
(1) preparation of carboxylated nanocellulose:
adding a mixed acid solution of a 4mol/L hydrochloric acid solution and a 4mol/L nitric acid solution (the volume ratio of the hydrochloric acid solution to the nitric acid solution is 6: 4) with the total volume of 200mL into a three-neck flask, heating to 105 ℃, adding 4g of nano-cellulose, and carrying out reflux reaction at 105 ℃ for 4 hours; centrifuging at 6000r/min for 6min to remove acid solution after reaction, taking down precipitate, dispersing with water, transferring into dialysis bag, and dialyzing with water to neutrality; then, carrying out ultrasonic treatment for 10min under the power of 250W by using a cell crusher to obtain a transparent carboxylated nano cellulose (CCNC) water suspension with blue light, and then concentrating the transparent carboxylated nano cellulose (CCNC) water suspension by using a rotary evaporator until the solid content is 1.0 wt% for later use; notation CCNC 6: 4;
(2) rare earth nano fluorescent particle LaPO4:Eu3+The preparation of (1):
the total molar amount of La (NO) was 5mmol3)3·6H2O、Eu(NO3)3·6H2O dissolved in 100ml ethylene glycol, La (NO)3)3·6H2O、Eu(NO3)3·6H2The molar ratio of O is 92.5: 7.5 dropwise addition with stirring at 2000rpm5mL KH2PO4After the dropwise addition of the ethylene glycol solution (the concentration is 2mol/L), heating to 120 ℃ and refluxing for 3 hours; cooling after the reaction is finished, centrifuging at a high speed of 15000r/min for 30min to obtain white precipitate, repeatedly centrifuging and washing with acetone for three times, and air drying at room temperature to obtain the rare earth nano fluorescent particle LaPO4:Eu3+(ii) a Recording as follows: E-LaPO4:7.5％Eu3+；
(3) Preparing a nano cellulose-based fluorescent film:
the rare earth nano fluorescent particle LaPO obtained in the step (2)4:Eu3+Adding the mixture into 40mL of carboxylated nano-cellulose water suspension with the concentration of 1.0 wt% obtained in the step (1), and uniformly dispersing by ultrasonic to obtain uniform and stable suspension; wherein the rare earth nano fluorescent particle LaPO4:Eu3+The addition amount of (A) is 7.5 wt% of the carboxylated nanocellulose; and then, carrying out suction filtration on the obtained uniform and stable suspension liquid by using a mixed fiber filter membrane with the aperture of 0.15 mu m under the vacuum degree of-0.1 mPa until the dispersion liquid is in a non-dripping state, clamping the suspension liquid between two flat PTFE plates, carrying out vacuum drying at 45 ℃ for 30min, and carrying out hot pressing at 80 ℃ for 15min to obtain the nano cellulose-based fluorescent membrane, wherein the label is CCNC-7.5.
Example 2
Adjusting the rare earth nanophosphor LaPO in step (3) of example 14:Eu3+The amount of the modified nanocellulose was 2.5, 5, 10, 15 wt% based on the carboxylated nanocellulose, and the nanocellulose-based fluorescent films were obtained and were designated as CCNC-2.5, CCNC-5, CCNC-10, and CCNC-15.
Comparative example 1
Omitting the rare earth nano fluorescent particle LaPO in example 14:Eu3+Directly forming a film by using the nano-cellulose to obtain a nano-cellulose film, and recording the nano-cellulose film as CNC.
The films obtained in examples 1 and 2 and comparative example 1 were subjected to performance tests, and the test results were as follows:
FIG. 1 shows fluorescence emission spectra of CNC, CCNC-2.5, CCNC-5, CCNC-7.5, CCNC-10, CCNC-15. As can be seen from fig. 1: under the excitation of 254nm ultraviolet light, no fluorescence emission peak appears in an emission spectrum of CCNC, and the CCNC is known not to have photoluminescence performance; nano meterE-LaPO4:7.5％Eu3+After the particles are introduced, more obvious Eu appears in the emission spectra of CCNC-2.5, CCNC-5, CCNC-7.5, CCNC-10 and CCNC-153+Characteristic emission peak, the position and the shape of the emission peak are all equal to those of E-LaPO4:7.5％Eu3+The fluorescent nanoparticles are completely consistent, and the strongest emission peak is positioned near 690nm, which indicates that the introduction of E-LaPO4:7.5％Eu3+The nano fluorescent particles can successfully endow the nano cellulose membrane with better fluorescence performance; as shown in the inset, the colorless and transparent CCNC-7.5 emitted bright red light under the UV lamp. Furthermore, it was found that with E-LaPO4:7.5％Eu3+The content is increased, and the intensity of each fluorescence emission peak of the corresponding fluorescent film is continuously increased, but the increasing trend is gradually slowed down.
FIG. 2 is a graph showing the transmittance of CNC, CCNC-2.5, CCNC-5, CCNC-7.5, CCNC-10, CCNC-15. FIG. 3 is the transmittance at 600nm of the film and E-LaPO4:7.5％Eu3+The relationship between the contents. As can be seen from fig. 2 and 3: CCNC has excellent light transparency, and the transmittance at 600nm is as high as 80.5 percent; random nano E-LaPO4:7.5％Eu3+The particle content increases and the visible light transmittance of the corresponding phosphor film continues to decrease, but is found in E-LaPO4:7.5％Eu3+When the particle content is not more than 7.5 wt%, the light transmittance of the fluorescent film is reduced slowly, and the transmittances of CCNC-2.5, CCNC-5.0 and CCNC-7.5 at 600nm are 77.9%, 75.2% and 72.5% in sequence, along with E-LaPO4:7.5％Eu3+When the content reaches 10.0 wt%, the light transmittance of the fluorescent film begins to be greatly reduced, and the transmittances of CCNC-10.0 and CCNC-15.0 at 600nm are respectively reduced to 60.7 percent and 52.8 percent, so that the light transparency is poor.
FIG. 4 shows the results of the mechanical property tests of CNC, CCNC-2.5, CCNC-5, CCNC-7.5, CCNC-10 and CCNC-15. As can be seen from fig. 4: the tensile strength of CCNC is 145MPa, and E-LaPO is introduced4:7.5％Eu3+The tensile strength of the fluorescent film is increased and tends to be continuously and remarkably increased (2.5-7.5 wt%) and then continuously and rapidly reduced (7.5-15.0 wt%), wherein the tensile strength of the CCNC-7.5 film is the highest and is 163MPa, which is 12.5% higher than that of a CCNC pure film.
FIG. 5 shows the results of water contact angle measurements for CNC, CCNC-2.5, CCNC-5, CCNC-7.5, CCNC-10, CCNC-15. As can be seen from fig. 5: the water contact angle of CCNC is lower, only 65 degrees, which is in accordance with the stronger hydrophilic property of cellulose; with the introduction of rice E-LaPO4:7.5％Eu3+The content is increased, the water contact angle of the fluorescent film is gradually increased, when the content of the fluorescent nanoparticles reaches 7.5 wt%, the water contact angle value of the CCNC-7.5 film is increased to 90 degrees, and the hydrophobicity is obviously improved.
FIG. 6 shows the result of the water-washing resistance test of CCNC-7.5. As can be seen from fig. 6: compared with an unwashed CCNC-7.5 membrane, after 1 time of water washing, the fluorescence emission peak intensity of the CCNC-7.5 membrane is slightly reduced, but the reduction amplitude is weak; after 2 times and 3 times of water washing, the fluorescence emission peak intensity of the CCNC-7.5 membrane basically does not change any more, which indicates that most of E-LaPO4:7.5％Eu3+The particles can be firmly combined in the CCNC matrix, and the CCNC-7.5 has better water washing resistance.
Example 3
The volumes of the hydrochloric acid solution and the nitric acid solution in step (1) of example 1 were adjusted to 8: 2. 7: 3. 5: 5, otherwise in accordance with example 1, a nanocellulose suspension with a concentration of 1.0% by weight is obtained, denoted as CCNC 8: 2. CCNC 7: 3. CCNC 5: 5.
mixing the CCNC 8: 2. CCNC 7: 3. CCNC 5: 5. CCNC 6: 4, the performance test is carried out, and the test result is shown in figure 7. The Zeta potential value of the corresponding suspension tends to increase and then decrease as the part of nitric acid in the mixed acid increases, wherein the ratio of CCNC 6: the Zeta potential of the aqueous suspension of 4 was the highest negative and was-52.0 mV, indicating that CCNC 6: the dispersing property of 4 is the best.
Comparative example 2
The solvent ethylene glycol of the step (1) in the example 1 is adjusted to be water, and the rest is kept consistent with the example 1, so that the rare earth nano fluorescent particle LaPO is obtained4:Eu3+。
The obtained rare earth nano fluorescent particle LaPO4:Eu3+The performance test was performed and the test results are shown in fig. 8. As can be seen from fig. 8: the luminous intensity is higher by adopting the ethylene glycol as a medium.
Example 4
Preparation of La (NO) in step (2) of example 13)3·6H2O、Eu(NO3)3·6H2The molar ratio of O is 97.5: 2.5, 95: 5: 92.5: 7.5 (example 1) 90: 10, otherwise in accordance with the examples, to obtain LaPO4:Eu3+Recorded as Eu3+2.5、Eu 3+5、Eu3+7.5、Eu3+10。
The obtained seed LaPO4:Eu3+The performance test was performed and the test results are shown in fig. 9. As can be seen from fig. 9: all LaPOs were excited under 254nm UV4:Eu3+The position and the shape of the emission peak are basically consistent with those of Eu3+The doping concentration is increased, the emission peak intensity is in the trend of increasing firstly and then decreasing, and the optimal La (NO)3)3·6H2O、Eu(NO3)3·6H2The molar ratio of O is 92.5: 7.5.
although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (5)

1. A method of preparing a nanocellulose-based fluorescent membrane, comprising the steps of:
(1) dissolving lanthanum salt and europium salt in ethylene glycol, dropwise adding phosphate ethylene glycol solution, carrying out reflux reaction at 100-4:Eu3+(ii) a The addition molar ratio of the lanthanum salt to the europium salt is 90-95: 5-10;
(2) the rare earth nano fluorescent particle LaPO obtained in the step (1)4:Eu3+Adding the mixture into a carboxylated nano-cellulose water suspension, and uniformly dispersing to obtain a uniform and stable suspension; wherein the solid content of the carboxylated nano-cellulose water suspension is 0.5-2 wt%; the rare earth nano fluorescent particle LaPO4:Eu3+The addition amount of (A) is 7.5 wt% of the carboxylated nanocellulose;
the preparation method of the carboxylated nano-cellulose comprises the following steps:
heating the mixed acid solution of the hydrochloric acid solution and the nitric acid solution to 110 ℃ below 100 ℃, adding the nano-cellulose, and carrying out reflux reaction for 3-5h at 110 ℃ below 100 ℃; centrifuging to obtain precipitate after the reaction is finished; then dialyzing the precipitate with water to neutrality; then ultrasonic dispersion and concentration are carried out to obtain carboxylated nano-cellulose; the volume ratio of the hydrochloric acid solution to the nitric acid solution is 5-8: 2-5; the concentration of the hydrochloric acid solution and the concentration of the nitric acid solution are both 4 mol/L;
(3) and (3) carrying out suction filtration on the suspension obtained in the step (2) until no water drops, then flatly paving the suspension to form a film, and finally carrying out hot pressing treatment to obtain the nano cellulose based fluorescent film.
2. The method according to claim 1, wherein the pressure of the hot pressing treatment in the step (3) is 10MPa, the temperature is 80 ℃, and the time is 30-60 min.
3. The method as claimed in claim 1 or 2, wherein the lanthanum salt in step (1) is one or more of lanthanum nitrate, lanthanum sulfate and lanthanum chloride; the europium salt is one or more of europium nitrate and europium chloride, and the phosphate is one or more of monopotassium phosphate, dipotassium phosphate, sodium dihydrogen phosphate and disodium phosphate.
4. The nanocellulose-based fluorescent membrane prepared by the method of any one of claims 1-3.
5. The application of the nano cellulose-based fluorescent film as claimed in claim 4 in the field of photoelectric materials or package anti-counterfeiting.
CN202011371906.6A 2020-11-30 2020-11-30 Preparation method of nanocellulose-based fluorescent film Active CN112480479B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011371906.6A CN112480479B (en) 2020-11-30 2020-11-30 Preparation method of nanocellulose-based fluorescent film

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011371906.6A CN112480479B (en) 2020-11-30 2020-11-30 Preparation method of nanocellulose-based fluorescent film

Publications (2)

Publication Number Publication Date
CN112480479A CN112480479A (en) 2021-03-12
CN112480479B true CN112480479B (en) 2022-02-01

Family

ID=74937273

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011371906.6A Active CN112480479B (en) 2020-11-30 2020-11-30 Preparation method of nanocellulose-based fluorescent film

Country Status (1)

Country Link
CN (1) CN112480479B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113308937A (en) * 2021-05-28 2021-08-27 陕西科技大学 Cell culture paper and preparation method and application thereof
CN116144078B (en) * 2023-01-28 2024-04-12 齐鲁工业大学(山东省科学院) Double-emission circularly polarized fluorescent composite film and preparation method and application thereof
CN116716106A (en) * 2023-06-16 2023-09-08 珠海惠友电子有限公司 Preparation method of gadolinium phosphate and rare earth doped gadolinium phosphate fluorescent powder

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19539315A1 (en) * 1995-10-23 1997-04-24 Hoechst Ag UV-active regenerated cellulose fibers
CN102464981B (en) * 2010-11-19 2013-07-17 北京林业大学 Lignin-based carbon nanomaterial having fluorescent performance and preparation method thereof
TWI538985B (en) * 2013-11-13 2016-06-21 國立高雄應用科技大學 Reddish-orange phosphor material and manufacturing method thereof
CN104130429A (en) * 2014-05-06 2014-11-05 上海大学 Preparation method of transparent nano-cellulose paper with fluorescence properties
CN104844833B (en) * 2015-04-15 2017-05-24 华南农业大学 Red light conversion film and preparation method and application thereof
CN106718422A (en) * 2017-01-10 2017-05-31 厦门大学 A kind of preparation method of degradable multifunctional fibre element agricultural film
CN106883854B (en) * 2017-02-20 2019-10-29 陕西科技大学 Rare earth based quantum dot composite nano fiber element and its preparation method and application
CN110564010A (en) * 2019-09-19 2019-12-13 华南理工大学 Fluorescent material, preparation method of fluorescent material and anti-counterfeiting film

Also Published As

Publication number Publication date
CN112480479A (en) 2021-03-12

Similar Documents

Publication Publication Date Title
CN112480479B (en) Preparation method of nanocellulose-based fluorescent film
You et al. Transparent sunlight conversion film based on carboxymethyl cellulose and carbon dots
Ma et al. One-step ultrasonic synthesis of fluorescent N-doped carbon dots from glucose and their visible-light sensitive photocatalytic ability
CN109762206A (en) Photochromic adjustable fluorescence oxidation nanometer cellophane of one kind and preparation method thereof
Wan et al. High‐efficiency solid‐state luminescence from hydrophilic carbon dots with aggregation‐induced emission characteristics
CN112226231A (en) Multicolor fluorescent carbon quantum dot and preparation method and application thereof
CN113913186B (en) Carbon dot-based room-temperature phosphorescent composite material capable of stably emitting afterglow and preparation method, application and use method thereof
Corsini et al. Highly emissive fluorescent silica-based core/shell nanoparticles for efficient and stable luminescent solar concentrators
Cao et al. Transparent, luminescent, and highly organized monolayers of zeolite L
Hu et al. Surface passivated carbon nanodots prepared by microwave assisted pyrolysis: effect of carboxyl group in precursors on fluorescence properties
CN109438727B (en) Fluorescent response self-healing hydrogel and preparation method thereof
CN112458795B (en) Photochromic fluorescent nano-paper based on lanthanide metal organic framework and preparation method thereof
CN107686727A (en) Yellow carbon quantum dot fluorescent material and preparation method and application
CN106497561B (en) Method for preparing graphene quantum dot yellow fluorescent powder or mixture thereof and method for preparing white light LED device
CN109369962A (en) A kind of imitative clam shell feature is cellulose nano-fibrous/preparation method of black phosphorus alkene composite membrane
CN104086927B (en) A kind of flexible rare-earth transparent luminous film and its preparation method
CN108264579A (en) A kind of hydrogel material containing big ring rare earth compounding, preparation method and application
Zhang et al. Aggregation-induced white emission of lanthanide metallopolymer and its coating on cellulose nanopaper for white-light softening
CN112300787A (en) Preparation method of ultraviolet fluorescent anti-counterfeiting film based on carbon quantum dots
CN117247775B (en) Luminescent composite nano material and preparation method and application thereof
Chatterjee et al. In situ formation of luminescent CdSe QDs in a metallohydrogel: a strategy towards synthesis, isolation, storage and re-dispersion of the QDs
Alharbi et al. Photoluminescent cellulose nanofibers-reinforced alginate hydrogel with color-tunable and self-healing properties for authentication applications
CN109233807A (en) A kind of rare-earth compound luminescent hydrogel material and the preparation method and application thereof
Shen et al. Synthesis of silica/rare-earth complex hybrid luminescence materials with cationic surfactant and their photophysical properties
CN115466357B (en) Anisotropic rare earth hybridized luminous hydrogel and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant