CN108341920A - A kind of high intensity water dispersible rare earth fluoride up-conversion luminescent material and preparation method thereof - Google Patents
A kind of high intensity water dispersible rare earth fluoride up-conversion luminescent material and preparation method thereof Download PDFInfo
- Publication number
- CN108341920A CN108341920A CN201810115648.1A CN201810115648A CN108341920A CN 108341920 A CN108341920 A CN 108341920A CN 201810115648 A CN201810115648 A CN 201810115648A CN 108341920 A CN108341920 A CN 108341920A
- Authority
- CN
- China
- Prior art keywords
- rare earth
- luminescent material
- conversion luminescent
- water dispersible
- preparation
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
-
- 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
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- 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
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7772—Halogenides
-
- 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
- C08K3/16—Halogen-containing compounds
-
- 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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/182—Metal complexes of the rare earth metals, i.e. Sc, Y or lanthanide
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- Luminescent Compositions (AREA)
Abstract
The present invention relates to anti-fake material technical fields, disclose a kind of preparation method of high intensity water dispersible rare earth fluoride up-conversion luminescent material.This method prepares aqueous polyurethane by nucleophilic addition prepolymerization reaction（WPU）Performed polymer；Then, in the aqueous solution of rare-earth salts, using WPU performed polymers as ligand, after hydro-thermal reaction, centrifugation, cleaning, drying process, rare earth fluoride up-conversion luminescent material is obtained.The up-conversion luminescent material being prepared using method provided by the invention is in the rodlike micro-crystal of bifurcated, while having the characteristics that crystallinity is high, shining that strong, water dispersible is good, is very suitable for adding it in water-based ink system for anti-fake.
Description
Technical field
The present invention relates to anti-fake material technical fields, more particularly, to a kind of high intensity water dispersible rare earth fluoride
Up-conversion luminescent material and preparation method thereof.
Background technology
With the fast development of market economy and information technology, forgery means are more and more superb, and the four of counterfeit and shoddy goods
It is cruel to have seriously endangered people's health and safety.Some traditional counterfeit protection measures are constantly cracked by criminal, and emerging is anti-fake
Technology constantly moves towards greenization, intelligence, popular.Radio frequency（RFID）Label, microlens array is anti-fake, DNA, sound
The living things feature recognitions such as line, human eye iris, the materials such as stimuli responsive (optical electrical/magnetic response, physical/chemical stimulation) or technology are answered
It transports and gives birth to.Embedded photoluminescent material has anti-counterfeiting power strong, and preparation process is simple, and cost is relatively low, need not put into a large amount of equipment,
And can be perfectly combined with package design, packaging structure, information technology and artificial intelligence, push product and its packaging to new development
Highly, therefore increasingly favored by researchers.
Up-conversion luminescent material refers to absorbing two or more lower photons of energy, launches the higher light of single energy
Son, that is, photon energy of the photon energy absorbed less than transmitting.Since rear-earth-doped up-conversion luminescent material has low toxicity, fluorescence
Long lifespan, good light stability, luminescent spectrum band are narrow, inanimate object autofluorescence is interfered, anti-Stokes displacement is big, light penetration depth
The advantages such as strong, it is considered to be one of most potential embedded photoluminescent material, biomedicine, solar cell, solid state laser,
The fields such as sensor, Three-dimensional Display, living imaging, anti-fake have broad application prospects.Wherein, the sound of rare earth fluoride matrix
Sub- energy is low, can effectively reduce radiationless transition loss, improve luminous efficiency, be the emphasis and hot spot of upper study on the transformation.
In order to expand the application of up-conversion luminescent material, it is a kind of and its important to add it in water-based ink system
Means, thus up-conversion luminescent material must have a preferable water dispersible, and with the binder compatibility in ink system compared with
It is good.However, existing up-conversion uses oil/water two-phase synthesis, itself water dispersible is bad, the solvent-based ink of preparation
Environmental-protecting performance is poor, and the ligand of up-conversion surface sealing end, keeps it poor with the compatibility of ink adhesive, causes anti-fake
Ink is unstable, and placement has been layered, and ink printability is poor, to influence its anti-counterfeiting performance.Therefore, rare earth fluoride is studied
The preparation method of up-conversion luminescent material improves its luminous intensity and water dispersible, has great society to entire anti-fake industry
It can realistic meaning and economic benefit.
Aqueous polyurethane（WPU）It is that conventional urethane is replaced with water（PU）In organic solvent develop as decentralized medium
The macromolecule resin come, has many advantages, such as environment nontoxic, nonflammable, not easy to pollute, can be brought as ink vehicle fabulous
Cementability, wearability and glossiness etc. have shown that excellent application value in environment-friendly ink.But it is not yet found that about will
WPU performed polymers prepare the report of rare earth fluoride up-conversion luminescent material using one step hydro thermal method as ligand.
Invention content
In response to the problems existing in the prior art, the purpose of the present invention is to provide a kind of high intensity water dispersible rare earth fluorides
The preparation method of up-conversion luminescent material.This method prepares rare earth using WPU performed polymers as organic ligand, using one step hydro thermal method
Converting luminescent material of fluoride optimizes its application and environmental-protecting performance, to expand application of the up-conversion in anti-counterfeit field
Provide a new technological approaches.
The purpose of the present invention is to provide a kind of high intensity water dispersible rare earth fluoride up-conversion luminescent materials.
The present invention is achieved by the following technical solutions：
A kind of preparation method of high intensity water dispersible rare earth fluoride up-conversion luminescent material, includes the following steps：
S1. feedstock processing：The raw materials such as diisocyanate, polyalcohol, chain extender and acetone are dried except water process；
The preparation of S2.WPU performed polymers：The raw material in step S1 is taken, the matter of the diisocyanate, polyalcohol, chain extender is adjusted
It is respectively 35% ~ 45%, 40% ~ 55%, 9% ~ 16% to measure score, after catalyst and acetone is added, passes through nucleophilic addition prepolymerization reaction, system
It is standby to obtain WPU performed polymers；
S3. hydrothermal synthesis：The WPU performed polymers of step S2 are added into rare earth salt aqueous solution, aqueous slkali and Fluorine source is then added, stirs
It after mixing uniformly, is transferred in hydrothermal reaction kettle, carries out hydro-thermal reaction；
S4. sample post-processes：By the material obtained by step S3 to get water dispersible rare earth fluoride after centrifugation, cleaning, drying
Up-conversion luminescent material.
The present invention is in a creative way using the good WPU performed polymers of water dispersible as organic ligand, using one step hydro thermal method system
Standby rare earth fluoride up-conversion luminescent material, obtained rare earth fluoride up-conversion luminescent material are in the rodlike micro-crystal of bifurcated,
Have the characteristics that crystallinity is high, the strong and water dispersible that shines is good.
Further, in step S1, the polyalcohol is polycarbonate glycol, and the chain extender is the hydrophilic expansion of carboxylic acid type
Chain agent.
Further, in step S2, the reaction condition of the WPU performed polymers is：40 ~ 70 DEG C of reaction temperature, reaction time 6
~10 h。
Further, in step S2, the catalyst is dibutyl tin dilaurate, and addition is total solids content
0.1%~1%。
Further, in step S2, the volume fraction of the acetone is 10 ~ 30%.
Further, in step S3, WPU 1 ~ 15g of performed polymer of step S2 is added into 1mmol rare earth salt aqueous solutions, add
Enter aqueous slkali 0.3 ~ 2 mL and 0.1714 ~ 0.6857g of Fluorine source, after stirring evenly, is transferred in hydrothermal reaction kettle, regulation system pH
Value reacts 7 ~ 24 h to 7 ~ 8 at a temperature of 140 ~ 220 DEG C.
Further, in step S3, the molar ratio of carboxyl and the rare-earth salts is 0.5 ~ 8.7 in the WPU performed polymers:1；
The aqueous slkali is ammonium hydroxide, and the content of the aqueous slkali is the 0.5 ~ 2% of system total volume；
The Fluorine source is sodium fluoride, and F ion and the molar ratio of rare-earth salts are 4 ~ 16 in the Fluorine source:1；
The deionized water that reaction medium is 100% in the hydrothermal system.
Further, in step S3, the rare-earth salts be rare earth nitrades or Rare Earths salt, the rare earth include yttrium,
Ytterbium, erbium and thulium.
Further, in step S4, the material obtained by step S3 is transferred in centrifuge, under the conditions of 8000 r/min
It is centrifuged, collects solid precipitation, then cleaned fixed precipitation 5 times using ethyl alcohol and deionized water, vacuum is dry at 80 DEG C
Dry 12 h.
Further, the vacuum drying is vacuumized in vacuum drying chamber, the Pa of final vacuum≤133.
A kind of upper conversion that the preparation method of above-mentioned high intensity water dispersible rare earth fluoride up-conversion luminescent material obtains
Luminescent material.
Compared with prior art, the invention has the advantages that：
The present invention using the good WPU performed polymers of water dispersible as organic ligand, is prepared dilute in a creative way using one step hydro thermal method
Native converting luminescent material of fluoride, since the N on the carboxylic group and carbamate groups on WPU molecular weight possesses one
It to lone pair electrons, can be chelated with rare-earth ion coordination, by scientific design WPU molecular chain structures, control itself and rare earth
The chelating of ion and release influence crystal nucleation and growth, to control the synthesis of up-conversion luminescent material.It is carried using the present invention
The up-conversion luminescent material that the method for confession is prepared is in the rodlike micro-crystal of bifurcated, while having crystallinity height, luminous strong, water
The characteristics of good dispersion.
The present invention independently synthesizes WPU performed polymers, using it as organic ligand, through hydro-thermal reaction, centrifugation, cleaning, drying etc.
Rare earth fluoride up-conversion luminescent material is obtained after processing, is very suitable for adding it in water-based ink system for anti-fake.
The rare earth fluoride up-conversion luminescent material that the method for the present invention is prepared is used to be added to using WPU as binder as pigment
When in water-based ink, since the water dispersible of the up-conversion luminescent material blocked with WPU is good, and with the compatibility of WPU binders
It is good, can preferably be coated by WPU resins, form stable dispersion, to promoted the environment-friendly type of ink, printability,
Stability and anti-counterfeiting performance have apparent meaning, can be widely applied to anti-counterfeit field.
Description of the drawings
Fig. 1 is that the embodiment of the present invention 1 ~ 3 obtains the XRD diagram of rare earth fluoride up-conversion luminescent material；
Fig. 2 is that the embodiment of the present invention 1 ~ 3 obtains the fluorescence spectra and digital photograph figure of rare earth fluoride up-conversion luminescent material
（Add near infrared light optical filter）；
Fig. 3 is the SEM figures that the embodiment of the present invention 1 ~ 3 obtains rare earth fluoride up-conversion luminescent material；
Wherein, a is the rare earth fluoride up-conversion luminescent material that embodiment 1 is prepared（NaYF4:Er/Tm）；B is embodiment 2
The rare earth fluoride up-conversion luminescent material being prepared（NaYF4:Yb/Er）；C is the rare earth fluorination that embodiment 3 is prepared
Object up-conversion luminescent material（NaYF4:Yb/Tm）.
Specific implementation mode
It is further illustrated the present invention with reference to specific embodiment.Following embodiments only for illustration, Bu Nengli
Solution is limitation of the present invention.Unless stated otherwise, the raw material and equipment used in following embodiments, which are this field, routinely to be made
Raw material and equipment.
Embodiment 1
The present embodiment provides a kind of preparation method of high intensity water dispersible rare earth fluoride up-conversion luminescent material, including it is following
Step：
S1. feedstock processing：The raw materials such as diisocyanate, polycarbonate glycol, carboxylic acid type hydrophilic chain extender, acetone are done
It is dry to remove water process；
The preparation of S2.WPU performed polymers：The raw material in step S1 is taken, the diisocyanate, polycarbonate glycol, carboxylic are adjusted
The mass fraction of acid type hydrophilic chain extender is respectively 40%, 47%, 13%, and dibutyl tin dilaurate and acetone is added, is warming up to 40
~ 70 DEG C of 7 h of reaction are to get WPU performed polymers；
Wherein, the volume fraction of the acetone is 22%, and the addition of the dibutyl tin dilaurate is total solids content
0.15%；
S3. hydrothermal synthesis：The WPU performed polymers in 4 g steps S2 are added into the aqueous solution of 1mmol Rare Earths salts, ammonia is added
0.5143 g of 0.75 mL of water and sodium fluoride, regulation system pH value to 7 ~ 8 react 15 h at a temperature of 180 DEG C；
Wherein, the rare earth is yttrium, erbium, thulium, and the molar ratio of Y3+, Er3+, Tm3+ are 88：10：2, carboxylic in the WPU performed polymers
The molar ratio of base and rare-earth salts is 3:1, the molar ratio of fluorine ion and rare-earth salts is 12 in the Fluorine source:1, in the hydrothermal system
The deionized water that reaction medium is 100%；
S4. sample post-processes：Material obtained by step S3 is transferred in centrifuge, carried out under the conditions of 8000 r/min from
The heart collects solid precipitation, then cleans 5 times fixed precipitation using ethyl alcohol and deionized water, 12 h are dried in vacuo at 80 DEG C.
Wherein, the vacuum drying is vacuumized in vacuum drying chamber, the Pa of final vacuum≤133.
Embodiment 2
The preparation method of high intensity water dispersible rare earth fluoride up-conversion luminescent material provided in this embodiment is with reference to embodiment
1, difference from example 1 is that：In step S2, the diisocyanate, polycarbonate glycol, carboxylic acid type parent are adjusted
The mass fraction of water chain extender is respectively 40%, 51%, 9%；In step S3, the rare earth is yttrium, ytterbium, erbium, Y3+, Yb3+, Er3+
Molar ratio be 78：20：2, the molar ratio of carboxyl and rare-earth salts is 2 in the WPU performed polymers:1, the addition of the ammonium hydroxide is
0.5 mL。
Embodiment 3
The preparation method of high intensity water dispersible rare earth fluoride up-conversion luminescent material provided in this embodiment is with reference to embodiment
1, difference from example 1 is that：In step S2, the diisocyanate, polycarbonate glycol, carboxylic acid type parent are adjusted
The mass fraction of water chain extender is respectively 40%, 49%, 11%；In step S3, the rare earth is yttrium, ytterbium, thulium, Y3+, Yb3+, Tm3+
Molar ratio be 78：20：2, the molar ratio of carboxyl and rare-earth salts is 2.5 in the WPU performed polymers:1, the addition of the ammonium hydroxide
For 0.625 mL.
Embodiment 4
The preparation method of high intensity water dispersible rare earth fluoride up-conversion luminescent material provided in this embodiment is with reference to embodiment
1, difference from example 1 is that：In step S2, the diisocyanate, polycarbonate glycol, carboxylic acid type parent are adjusted
The mass fraction of water chain extender is respectively 35%, 55%, 10%；In step S3, the WPU performed polymers addition is 15 g, described
The molar ratio of carboxyl and rare-earth salts is 8.7 in WPU performed polymers:1, the addition of the ammonium hydroxide is 2 mL, and the sodium fluoride adds
It is 0.1714 g to enter amount.
Embodiment 5
The preparation method of high intensity water dispersible rare earth fluoride up-conversion luminescent material provided in this embodiment is with reference to embodiment
1, difference from example 1 is that：In step S2, the diisocyanate, polycarbonate glycol, carboxylic acid type parent are adjusted
The mass fraction of water chain extender is respectively 45%, 40%, 15%；In step S3, the WPU performed polymers addition is 1 g, the WPU
The molar ratio of carboxyl and rare-earth salts is 0.87 in performed polymer:1, the addition of the ammonium hydroxide is 0.3 mL, and the sodium fluoride adds
It is 0.6857 g to enter amount.
Embodiment 6
The preparation method of high intensity water dispersible rare earth fluoride up-conversion luminescent material provided in this embodiment is with reference to embodiment
1, difference from example 1 is that：In step S2, the addition of the dibutyl tin dilaurate is total solids content
0.1%, the volume fraction of the acetone is 10%；In step S3, the hydrothermal temperature is 140 DEG C, and the time is 24 h.
Embodiment 7
The preparation method of high intensity water dispersible rare earth fluoride up-conversion luminescent material provided in this embodiment is with reference to embodiment
1, difference from example 1 is that：In step S2, the diisocyanate, polycarbonate glycol, carboxylic acid type parent are adjusted
The mass fraction of water chain extender is respectively 39%, 45%, 16%；The molar ratio of carboxyl and rare-earth salts is 3.7 in the WPU performed polymers:
1, the addition of the ammonium hydroxide is 1 mL, and the addition of the dibutyl tin dilaurate is the 1% of total solids content, described third
The volume fraction of ketone is 30%；In step S3, the hydrothermal temperature is 220 DEG C, and the time is 7 h.
The method provided respectively embodiment 1 ~ 3 is prepared rare earth fluoride up-conversion luminescent material and carries out XRD, fluorescence
Spectrum, digital photograph figure and SEM figure detections, wherein fluorescence spectrum is the fluorescence spectrum under being excited using 980 nm near infrared lights
Figure, is shown in Fig. 1 ~ 3 in specific testing result.
As shown in Figure 1, the standard card of all diffraction maximum positions and relative intensity and hexagonal phase NaYF4（JCPDS 28-
1192）Substantially it coincide, illustrates the hexagonal phase structure that the material of synthesis is pure.In addition, the diffraction maximum of three kinds of materials is sharp and strong
Degree is higher, illustrates that crystallinity is higher, crystalline quality is good.
As shown in Figure 2, NaYF4:The emission peak positions of Er/Tm up-conversion luminescent materials be respectively 521 nm, 541 nm and
654 nm, corresponding transition of electronic energy are respectively 2H11/2 4I15/2,4S3/2 4I15/2 and 4F9/2 4I15/2；
NaYF4:The emission peak positions of Yb/Er up-conversion luminescent materials are respectively 410 nm, 521 nm, 541 nm and 654 nm, right
The transition of electronic energy answered is respectively 2H9/2 4I15/2,2H11/2
4I15/2,4S3/2 4I15/2 and 4F9/2 4I15/2；NaYF4:The emission peak positions of Yb/Tm up-conversion luminescent materials point
Not Wei 475 nm, 644 nm and 693 nm, corresponding transition of electronic energy is respectively 1G4
3H6,1G4 3F4 and 3F3 3H6.
By the digital photograph figure in Fig. 2（Add near infrared light optical filter）It is found that turning on 1 ~ 3 gained rare earth fluoride of embodiment
Change the red, green, blue three coloured light that luminescent material emits high intensity under the excitation of 980nm near infrared lights.
As seen from Figure 3, the up-conversion luminescent material being prepared using method provided by the invention is rodlike in bifurcated
Micro-crystal, preferably, plane of crystal is smooth, clear-cut for dispersibility in water, illustrates crystallinity height, with XRD diagram result
Unanimously.
There is crystallinity height, hair using the rare earth fluoride up-conversion luminescent material that method provided by the invention is prepared
The features such as light intensity, water dispersible are good is very suitable for being added into water-based ink system for field of anti-counterfeit technology.Work as the present invention
The rare earth fluoride up-conversion luminescent material that method is prepared is added to as pigment using WPU as in the water-based ink of binder
When, it, can be compared with since the water dispersible of the up-conversion luminescent material blocked with WPU is good, and good with the compatibility of WPU binders
It is coated by WPU resins well, forms stable dispersion, to promoting the environment-friendly type of ink, printability, stability and anti-fake
Performance has apparent meaning, can be widely applied to anti-counterfeit field.
The present invention illustrates the detailed process equipment and processing step of the present invention, people in the art by above-described embodiment
Member is not it should be appreciated that the present invention is limited by above-described embodiment, and the above embodiments and description only describe the present invention
Principle, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, this is to this field
It is it will be apparent that these changes and improvements all fall within the protetion scope of the claimed invention for technical staff.
Claims (10)
1. a kind of preparation method of high intensity water dispersible rare earth fluoride up-conversion luminescent material, which is characterized in that including with
Lower step：
S1. feedstock processing：The raw materials such as diisocyanate, polyalcohol, chain extender and acetone are dried except water process；
The preparation of S2.WPU performed polymers：The raw material in step S1 is taken, the matter of the diisocyanate, polyalcohol, chain extender is adjusted
It is respectively 35% ~ 45%, 40% ~ 55%, 9% ~ 16% to measure score, after catalyst and acetone is added, passes through nucleophilic addition prepolymerization reaction, system
It is standby to obtain WPU performed polymers；
S3. hydrothermal synthesis：The WPU performed polymers of step S2 are added into rare earth salt aqueous solution, aqueous slkali and Fluorine source is then added, stirs
After mixing uniformly, it is transferred in hydrothermal reaction kettle and carries out hydro-thermal reaction；
S4. sample post-processes：By the material obtained by step S3 to get water dispersible rare earth fluoride after centrifugation, cleaning, drying
Up-conversion luminescent material.
2. the preparation method of high intensity water dispersible rare earth fluoride up-conversion luminescent material according to claim 1, special
Sign is, in step S1, the polyalcohol is polycarbonate glycol, and the chain extender is carboxylic acid type hydrophilic chain extender.
3. the preparation method of high intensity water dispersible rare earth fluoride up-conversion luminescent material according to claim 1, special
Sign is, in step S2, the reaction condition of the WPU performed polymers is：40 ~ 70 DEG C of reaction temperature, 6 ~ 10 h of reaction time.
4. the preparation method of high intensity water dispersible rare earth fluoride up-conversion luminescent material according to claim 3, special
Sign is, in step S2, the catalyst is dibutyl tin dilaurate, and addition is the 0.1% ~ 1% of total solids content.
5. the preparation method of high intensity water dispersible rare earth fluoride up-conversion luminescent material according to claim 3, special
Sign is, in step S2, the volume fraction of the acetone is 10 ~ 30%.
6. the preparation method of high intensity water dispersible rare earth fluoride up-conversion luminescent material according to claim 1, special
Sign is, in step S3, WPU 1 ~ 15g of performed polymer of step S2 are added into 1mmol rare earth salt aqueous solutions, be added aqueous slkali and
Fluorine source after stirring evenly, is transferred in hydrothermal reaction kettle, regulation system pH value to 7 ~ 8, at a temperature of 140 ~ 220 DEG C react 7 ~
24 h。
7. the preparation method of high intensity water dispersible rare earth fluoride up-conversion luminescent material according to claim 6, special
Sign is, in step S3, the molar ratio of carboxyl and the rare-earth salts is 0.5 ~ 8.7 in the WPU performed polymers:1；
The aqueous slkali is ammonium hydroxide, and the content of the aqueous slkali is the 0.5 ~ 2% of system total volume；
The Fluorine source is sodium fluoride, and the molar ratio of fluorine ion and rare-earth salts is 4 ~ 16 in the Fluorine source:1；
The deionized water that reaction medium is 100% in the hydrothermal system.
8. the preparation method of high intensity water dispersible rare earth fluoride up-conversion luminescent material according to claim 6, special
Sign is, in step S3, the rare-earth salts is rare earth nitrades or Rare Earths salt, and the rare earth includes yttrium, ytterbium, erbium and thulium.
9. the preparation method of high intensity water dispersible rare earth fluoride up-conversion luminescent material according to claim 1, special
Sign is, in step S4, the material obtained by step S3 is transferred in centrifuge, is centrifuged under the conditions of 8000 r/min,
Solid precipitation is collected, fixed precipitation is cleaned 5 times using ethyl alcohol and deionized water then, 12 h are dried in vacuo at 80 DEG C.
10. according to the preparation of any one of the claim 1 ~ 9 high intensity water dispersible rare earth fluoride up-conversion luminescent material
The up-conversion luminescent material that method obtains.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810115648.1A CN108341920B (en) | 2018-02-06 | 2018-02-06 | High-strength water-dispersible rare earth fluoride up-conversion luminescent material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810115648.1A CN108341920B (en) | 2018-02-06 | 2018-02-06 | High-strength water-dispersible rare earth fluoride up-conversion luminescent material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108341920A true CN108341920A (en) | 2018-07-31 |
| CN108341920B CN108341920B (en) | 2021-05-25 |
Family
ID=62958936
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810115648.1A Active CN108341920B (en) | 2018-02-06 | 2018-02-06 | High-strength water-dispersible rare earth fluoride up-conversion luminescent material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108341920B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110591035A (en) * | 2019-07-09 | 2019-12-20 | 武汉大学 | Rapid self-healing polyurethane elastomer with up-conversion fluorescent response and preparation method thereof |
| CN111704794A (en) * | 2020-06-29 | 2020-09-25 | 深圳市象形科技有限公司 | Anti-seismic barrier foam and preparation method thereof |
| CN115011175A (en) * | 2022-05-05 | 2022-09-06 | 浙江理工大学 | Rare earth pigment photocuring color paste and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100259156A1 (en) * | 2007-11-22 | 2010-10-14 | Merck Patent Gesellschaft | Surface-modified phosphors |
| CN101864313A (en) * | 2009-12-08 | 2010-10-20 | 中国科学院苏州纳米技术与纳米仿生研究所 | Method for preparing luminous nanocrystals with monodispersity, hydrophily and biocompatibility |
| CN105131806A (en) * | 2015-10-13 | 2015-12-09 | 厦门大学 | Waterborne fluorescent polyurethane coating and preparation method thereof through prepolymer mixing |
| CN107312439A (en) * | 2017-07-24 | 2017-11-03 | 合肥思敬齐化工材料有限责任公司 | A kind of aqueous polyurethane coating of anti-neutron irradiation and preparation method thereof |
-
2018
- 2018-02-06 CN CN201810115648.1A patent/CN108341920B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100259156A1 (en) * | 2007-11-22 | 2010-10-14 | Merck Patent Gesellschaft | Surface-modified phosphors |
| CN101864313A (en) * | 2009-12-08 | 2010-10-20 | 中国科学院苏州纳米技术与纳米仿生研究所 | Method for preparing luminous nanocrystals with monodispersity, hydrophily and biocompatibility |
| CN105131806A (en) * | 2015-10-13 | 2015-12-09 | 厦门大学 | Waterborne fluorescent polyurethane coating and preparation method thereof through prepolymer mixing |
| CN107312439A (en) * | 2017-07-24 | 2017-11-03 | 合肥思敬齐化工材料有限责任公司 | A kind of aqueous polyurethane coating of anti-neutron irradiation and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110591035A (en) * | 2019-07-09 | 2019-12-20 | 武汉大学 | Rapid self-healing polyurethane elastomer with up-conversion fluorescent response and preparation method thereof |
| CN111704794A (en) * | 2020-06-29 | 2020-09-25 | 深圳市象形科技有限公司 | Anti-seismic barrier foam and preparation method thereof |
| CN115011175A (en) * | 2022-05-05 | 2022-09-06 | 浙江理工大学 | Rare earth pigment photocuring color paste and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108341920B (en) | 2021-05-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108341920A (en) | A kind of high intensity water dispersible rare earth fluoride up-conversion luminescent material and preparation method thereof | |
| Wang et al. | Carbon dot powders with cross-linking-based long-wavelength emission for multicolor imaging of latent fingerprints | |
| CN102942933B (en) | In-water-phase monodisperse sodium yttrium tetrafluoride multi-color luminescent nanoparticle and preparation method thereof | |
| EP1633680B1 (en) | Synthesis of nanoparticles comprising metal (iii) vanadate | |
| CN109762206A (en) | Photochromic adjustable fluorescence oxidation nanometer cellophane of one kind and preparation method thereof | |
| CN110408396B (en) | Na L uF based on lanthanide ion doping4/Y2O3Dual-mode fluorescent material, anti-counterfeiting ink, and preparation method and application thereof | |
| CN101101291A (en) | Three-D nano hole Eu coordinate polymer type zinc ion fluorescent probe and its preparation method and uses | |
| CN104498037B (en) | Conversion nano granule and preparation method thereof on the water solublity that a kind of PAMAM modifies | |
| CN103215037A (en) | Method for synthesizing upconversion fluorescence hollow nanosphere based on sodium polyacrylate microsphere template synthesis | |
| CN104371715B (en) | A kind of water solublity molybdenum trioxide up-conversion nano material and preparation method thereof | |
| CN106350057A (en) | Preparation method of fluorescent hybrid nanoparticles | |
| CN107603623B (en) | Small-size β -NaREF4Preparation method of fluorescent powder | |
| CN112391167A (en) | Rare earth doped ternary metal fluoride NaCaLnF6And preparation method of heterogeneous isomorphic material thereof | |
| CN106497560A (en) | Controllable carbon point based compound nano material of luminescent properties and preparation method and application | |
| CN110951479B (en) | Preparation method of PEG (polyethylene glycol) coated porous rare earth phosphate fluorescent nano material | |
| CN102925155B (en) | Near infrared fluorescent probe substrate material of rare earth ion nano alkali metal rare earth fluoride and preparation method of near infrared fluorescent probe substrate material | |
| CN106905959B (en) | A kind of preparation method of the fluoride nano crystal containing manganese | |
| CN103540318B (en) | Preparation method of rare earth complex grafted luminescent titanium dioxide mesoporous microsphere | |
| CN105754585B (en) | A kind of nanocrystalline preparation method of the Coated with Oleic Acid rare earth calcirm-fluoride of High Efficiency Luminescence | |
| CN107529514B (en) | Preparation method and application of fluorine ion-doped carbon dots | |
| CN108250843B (en) | Water-based rare earth up-conversion fluorescent ink, preparation method and anti-counterfeiting application thereof | |
| Yang et al. | Facile synthesize of upconversion β-NaYF4 capped with waterborne polyurethane prepolymer for packaging anti-counterfeiting | |
| CN108130081B (en) | Ytterbium and erbium co-doped gadolinium vanadate green upconversion luminescence nanocrystal and preparation method thereof | |
| CN109266349B (en) | Preparation method and application of water-soluble rare earth up-conversion nanoparticles | |
| CN106832341A (en) | A kind of fluorescence chitin hydrogel and its preparation method and application |
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 |