CN108084992A - A kind of fluorescent fiber element and preparation method thereof - Google Patents
A kind of fluorescent fiber element and preparation method thereof Download PDFInfo
- Publication number
- CN108084992A CN108084992A CN201711279495.6A CN201711279495A CN108084992A CN 108084992 A CN108084992 A CN 108084992A CN 201711279495 A CN201711279495 A CN 201711279495A CN 108084992 A CN108084992 A CN 108084992A
- Authority
- CN
- China
- Prior art keywords
- solution
- cellulose
- fluorescent
- fiber element
- parts
- 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.)
- Pending
Links
Classifications
-
- 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
- C09K11/07—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials having chemically interreactive components, e.g. reactive chemiluminescent compositions
-
- 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
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- 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
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
-
- 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
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
-
- 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
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
-
- 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
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
Abstract
The invention discloses a kind of fluorescent fiber elements and preparation method thereof, in terms of mass fraction, the raw material for preparing of the fluorescent fiber element includes 0.01~10 part of cellulose, 10 1000 parts of organic ligand solution, 5 2000 parts of metal ion solutions and 25 100 parts of fluorescent dye solutions；It is 1 in mass ratio by organic ligand and organic solvent that the organic ligand solution, which is,：(20 100) prepare and obtain；It is 1 in mass ratio by metal center and organic solvent that the metal ion solution, which is,：(10 20) prepare and obtain；The fluorescent dye solution is by fluorescent dye and dye solvent in mass ratio 1：(50 100) prepare and obtain.Fluorescent fiber element prepared by the present invention is that have good optical activity, the embedded photoluminescent material of fluorescence relaxation, can avoid the reunion of dye molecule, reduces the release of its thermal relaxation.
Description
Technical field
The invention belongs to pulp technology for making paper, and in particular to a kind of fluorescent fiber element and preparation method thereof.
Background technology
Fluoroscopic examination have the characteristics that high sensitivity, response when to it is short, the range of linearity is wide, easy to operate, biotechnology,
It is widely used in the fields such as flow cytometer, medical diagnosis, sequencing, evidence obtaining and genetic analysis.At present, molecule is utilized
Fluorescence can carry out cell imaging and unimolecule spectral investigation, have for the development of biology, medicine and laser technology important
Meaning.
Metal organic framework compound (Metal-Organic Frameworks) MOFs is by inorganic metal center (metal
Ion or metal cluster) it is connected with each other with the organic ligand of bridging by self assembly, one kind of formation has periodic network structure
Crystalline state porous material.MOFs is a kind of hybrid inorganic-organic materials, also referred to as coordination polymer (coordination
Polymer), it is both different from inorganic porous material, also different from general organic coordination compound.Have concurrently inorganic material rigidity and
The flexible characteristic of organic material.MOFs has good structure and can modify to be led with the characteristic of easy functionalization as materials chemistry
The new research hotspot in domain, the metal organic framework compound of many three-dimensional structures are similar to traditional point in structure and in nature
Son sieve inorganic porous material, has good adsorption property to gas and fluid organic material.
It is to embody its good optically active necessary condition that monodisperse status, which is presented, in dye molecule.Even if dye molecule exists
Can also it reunite under the concentration of very little, due to being stimulated, energy is easy to discharge by thermal relaxation dye molecule after reunion, because
This, assembles dye molecule also as a new research hotspot in recent years in the molecular sieve pore passage of rule.
The content of the invention
It is an object of the invention to provide a kind of fluorescent fiber element and preparation method thereof, to overcome existing in the prior art ask
Topic, fluorescent fiber element prepared by the present invention are that have good optical activity, the embedded photoluminescent material of fluorescence relaxation, can avoid dyestuff
The reunion of molecule reduces the release of its thermal relaxation.
In order to achieve the above objectives, the present invention adopts the following technical scheme that：
A kind of fluorescent fiber element, in terms of mass fraction, the raw material for preparing of the fluorescent fiber element includes 0.01~10 part
Cellulose, 10-1000 parts of organic ligand solution, 5-2000 parts of metal ion solutions and 25-100 parts of fluorescent dye solutions；
It is 1 in mass ratio by organic ligand and organic solvent that the organic ligand solution, which is,：(20-100) preparation obtains；
It is 1 in mass ratio by metal center and organic solvent that the metal ion solution, which is,：(10-20) preparation obtains；
The fluorescent dye solution is by fluorescent dye and dye solvent in mass ratio 1：(50-100) preparation obtains.
Further, the cellulose be Cellulose nanocrystal palpus, it is nano cellulose crystal, Nano bacteria cellulose, micro-
One or more of fibrillated fibers element, microcrystalline cellulose；
Further, the metal center is zinc nitrate hexahydrate, four nitric hydrate zinc, zinc nitrate, chromic nitrate or acetic acid
One or more of copper；
The organic ligand is 1,4- terephthalic acid (TPA)s, 1,3,5- trimesic acids, 2,3,5,6- Pyromellitic Acids or 1,
The one or more of 4,5,8- naphthalenetetracarbacidic acidic anhydride solutions；
The organic solvent is n,N-Dimethylformamide, n,N-dimethylacetamide, N-Methyl pyrrolidone or anhydrous
One or more of ethyl alcohol.
Further, the fluorescent dye is one kind of rhodamine B, methyl orange or methylene blue；The dye solvent is
Chloroformic solution, the dichloromethane solution of rhodamine B, the dichloromethane solution of the dichloromethane solution of methyl orange or methylene blue
It is a kind of.
A kind of preparation method of above-mentioned fluorescent fiber element, comprises the following steps：
1) organic ligand solution is made in organic ligand dissolving in organic solvent, it is molten that cellulose is added to organic ligand
In liquid, ultrasonic disperse is uniform, obtains precursor solution；
2) by metal center dissolving in organic solvent, stir to being completely dissolved, obtain metal ion solution；
3) metal ion solution in step 2) is added in the precursor solution of step 1), then is mixed solution and turns
It moves on in reaction vessel, using being reacted by the way of heating/pressurization, by metal ion and organic ligand with in-situ synthesis original
Position synthesis on cellulose, obtains cellulose and the compound of metal organic framework compound；
4) fluorescent dye is dissolved in dye solvent and fluorescent dye solution is made, the cellulose that step 3) is obtained and gold
Belong to organic framework compounds compound be immersed in fluorescent dye solution, then filter, and with organic solvent washing for several times after
Fluorescent fiber element is made in drying.
Further, the whipping temp in step 2) is 0 DEG C -120 DEG C, and stir speed (S.S.) is 5 revs/min -7000 revs/min
Clock.
Further, heating is specially temperature requirement room temperature to 120 degrees Celsius in step 3)；Pressurization is specially pressure requirements
0.1-5.0MPa。
Further, the reaction time is 4-24h in step 3).
Further, soaking temperature is 5 DEG C -200 DEG C in step 4), soaking time 4-72h.
Further, washing times are 2-10 times in step 4), and drying temperature is 85-105 DEG C.
Compared with prior art, the present invention has technique effect beneficial below：
In the present invention by the way that organic ligand, metal center and cellulose are once combined, preparation process is simplified, is reduced
Preparation energy consumption, develops a kind of new high-efficiency fluorescence cellulose.Nitric hydrate zinc, organic ligand are dissolved in organic solvent
In, the compatibility of the two is improved, and can make final product that there is superior adsorptivity；Cellulose and organic ligand are being had
Solvent is mutually scattered, can ensure good contact between cellulose and organic ligand.
In the preparation, the preparation process of fluorescent fiber element includes heating, pressurization, heating/pressurization three kinds of modes of combination；Heating
Or pressuring method can make to combine as soon as possible between the metal organic framework compound of organic ligand and metal center composition and fiber,
And it is trans associated with heating/pressurization, reaction can further be promoted faster to carry out；Metal organic framework compound and cellulose
Between combination include：Non-covalent bond (ester bond (- COO-), ehter bond (- O-), amino (- NH-), carbonnitrogen bond (- C-N-)) with
And Zn and organoligand coordination key, the combination of non-covalent bond and coordinate bond then so that the two is even closer, can more be suitable for spy
The demand of different industry.
Description of the drawings
Fig. 1 is the XRD spectrum of 9 fluorescence speciality paper of embodiment；
Fig. 2 is the XRD spectrum of 9 fluorescence speciality paper of embodiment；
Fig. 3 is the TGA collection of illustrative plates of 9 fluorescence speciality paper of embodiment；
Fig. 4 is the SEM image of 9 fluorescence speciality paper of embodiment；
Fig. 5 is the SEM image of 9 fluorescence speciality paper of embodiment；
Fig. 6 is the luminescence generated by light collection of illustrative plates of 9 fluorescence speciality paper of embodiment.
Specific embodiment
Embodiments of the present invention are described in further detail below：
A kind of fluorescent fiber element, the fluorescent fiber element are had by cellulose that parts by weight are 0.01~10 part, 10-1000 parts
Machine ligand solution, 5-2000 part metal ion solution and 25-100 parts of fluorescent dye solutions；The component and content of cellulose such as table 1
It is shown：
The component and content of 1 cellulose of table
The component and content of organic ligand solution are as shown in table 2：
The component and content of 2 organic ligand solution of table
The component and content of metal ion solution are as shown in table 3：
The component and content of 3 metal ion solution of table
The component and content of fluorescent dye solution are as shown in table 4：
The component and content of 4 fluorescent dye solution of table
A kind of preparation method of fluorescent fiber element, comprises the following steps：
1) organic ligand solution is made in organic ligand dissolving in organic solvent, it is molten that cellulose is added to organic ligand
In liquid, ultrasonic disperse is uniform, obtains precursor solution；
2) by metal center dissolving in organic solvent, stir to being completely dissolved, obtain metal ion solution；
3) metal ion solution in step 2) is added in the precursor solution of step 1), then is mixed solution and turns
It moves on in reaction vessel, using being reacted by the way of heating/pressurization, by metal ion and organic ligand with in-situ synthesis original
Position synthesis on cellulose, obtains cellulose and the compound of metal organic framework compound；
4) fluorescent dye is dissolved in dye solvent and fluorescent dye solution is made, the cellulose that step 3) is obtained and gold
The compound for belonging to organic framework compounds is immersed in fluorescent dye, is then filtered, and is dried afterwards for several times with organic solvent washing
Fluorescent fiber element is made.
The present invention is described in further detail with reference to embodiment：
Embodiment 1
1) 0.5 part of Isosorbide-5-Nitrae-terephthalic acid (TPA) is dissolved in 10 parts of n,N-Dimethylformamide and organic ligand solution is made,
0.01 part of Cellulose nanocrystal must be added in organic ligand solution, ultrasonic disperse is uniform, obtains precursor solution；
2) 0.5 part of zinc nitrate hexahydrate is dissolved in 5 parts of n,N-Dimethylformamide, in 5 revs/min of stir speed (S.S.)s, 0
It is stirred under DEG C whipping temp to being completely dissolved, obtains metal ion solution；
3) metal ion solution in step 2) is added in the precursor solution of step 1), then is mixed solution and turns
It moves on in reaction vessel, using being reacted by the way of heating/pressurization, 25-120 DEG C of calefactive interzone, pressure 0.1MPa reacts
4h, by metal ion and organic ligand with in-situ synthesis fabricated in situ on Cellulose nanocrystal palpus.Obtain cellulose nanometer
The compound of whisker and metal organic framework compound.
4) 0.5 part of fluorescent dyes rhodamine B is dissolved in 25 parts of chloroforms and fluorescent dye solution is made.Step 3) is obtained
Cellulose nanocrystal must be immersed in 4h in fluorescent dye with the compound of metal organic framework compound, then use glass filter
Filtering, and the i.e. obtained fluorescent fiber of 85 DEG C of drying is plain after wash 2 times with n,N-Dimethylformamide.
Embodiment 2
1) by 4 part 1,3,5- trimesic acids, which are dissolved in 80 parts of absolute ethyl alcohols, is made organic ligand solution, and 0.1 part is received
Rice cellulose crystals are added in organic ligand solution, and ultrasonic disperse is uniform, obtains precursor solution；
2) 4 part of four nitric hydrate zinc is dissolved in 40 parts of absolute ethyl alcohols, in 100 revs/min of stir speed (S.S.)s, 25 DEG C of stirrings
At a temperature of stir to being completely dissolved, obtain metal ion solution；
3) metal ion solution in step 2) is added in the precursor solution of step 1), then is mixed solution and turns
It moves on in reaction vessel, using being reacted by the way of heating/pressurization, 25-120 DEG C of calefactive interzone, pressure 0.2MPa reacts
8h, by metal ion and organic ligand with in-situ synthesis fabricated in situ on nano cellulose crystal.Obtain nano-cellulose
The compound of crystal and metal organic framework compound.
4) 0.6 part of fluorescent dye methylene blue is dissolved in 30 parts of chloroforms and fluorescent dye solution is made.Step 3) is obtained
To nano cellulose crystal and the compound of metal organic framework compound be immersed in 8h in fluorescent dye, then filtered with glass
Device filters, and the i.e. obtained fluorescent fiber of 90 DEG C of drying is plain after wash 3 times with absolute ethyl alcohol.
Embodiment 3
1) by 5 parts of 2,4,5,6- Pyromellitic Acids be dissolved in 100 parts of DMAC N,N' dimethyl acetamides be made organic ligand it is molten
1 part of Nano bacteria cellulose is added in organic ligand solution by liquid, and ultrasonic disperse is uniform, obtains precursor solution；
2) 10 parts of zinc nitrates are dissolved in 200 parts of absolute ethyl alcohols, in 300 revs/min of stir speed (S.S.)s, 35 DEG C of whipping temps
Lower stirring obtains metal ion solution to being completely dissolved；
3) metal ion solution in step 2) is added in the precursor solution of step 1), then is mixed solution and turns
It moves on in reaction vessel, using being reacted by the way of heating/pressurization, 25-120 DEG C of calefactive interzone, pressure 0.25MPa reacts
10h, by metal ion and organic ligand with in-situ synthesis fabricated in situ on Nano bacteria cellulose.Obtain bacteria nano fibre
Dimension element and the compound of metal organic framework compound.
4) 0.7 part of fluorescent dye methyl orange is dissolved in 42 parts of chloroforms and fluorescent dye solution is made.Step 3) is obtained
Nano bacteria cellulose and the compound of metal organic framework compound be immersed in 12h in fluorescent dye, then filtered with glass
Device filters, and the i.e. obtained fluorescent fiber of 90 DEG C of drying is plain after wash 4 times with absolute ethyl alcohol.
Embodiment 4
1) by 6 parts of Isosorbide-5-Nitraes, 5,8- naphthalenetetracarbacidic acidics, which are dissolved in 150 parts of n,N-dimethylacetamide, is made organic ligand solution,
2 parts of fento celluloses are added in organic ligand solution, ultrasonic disperse is uniform, obtains precursor solution；
2) 15 parts of zinc nitrates are dissolved in 300 parts of n,N-dimethylacetamide, in 700 revs/min of stir speed (S.S.)s, 45 DEG C
It is stirred under whipping temp to being completely dissolved, obtains metal ion solution；
3) metal ion solution in step 2) is added in the precursor solution of step 1), then is mixed solution and turns
It moves on in reaction vessel, using being reacted by the way of heating/pressurization, 25-120 DEG C of calefactive interzone, pressure 0.3MPa reacts
12h, by metal ion and organic ligand with in-situ synthesis fabricated in situ on fento cellulose.Obtain fento cellulose
With the compound of metal organic framework compound.
4) 0.75 part of fluorescent dye methylene blue is dissolved in 45 parts of chloroforms and fluorescent dye solution is made.Step 3) is obtained
To fento cellulose and the compound of metal organic framework compound be immersed in 16h in fluorescent dye, then filtered with glass
Device filters, and the i.e. obtained fluorescent fiber of 92 DEG C of drying is plain after wash 4 times with absolute ethyl alcohol.
Embodiment 5
1) 6 parts of 1,4,5,8 naphthalenetetracarboxylic acids are dissolved in 200 parts of N,N-dimethylformamides, absolute ethyl alcohols and are made organic
3 parts of microcrystalline celluloses are added in organic ligand solution by ligand solution, and ultrasonic disperse is uniform, obtains precursor solution；
2) 20 parts of zinc nitrates are dissolved in 400 parts of n,N-Dimethylformamide, in absolute ethyl alcohol, are stirred at 1000 revs/min
Rate is mixed, is stirred under 50 DEG C of whipping temps to being completely dissolved, obtains metal ion solution；
3) metal ion solution in step 2) is added in the precursor solution of step 1), then is mixed solution and turns
It moves on in reaction vessel, using being reacted by the way of heating/pressurization, 25-120 DEG C of calefactive interzone, pressure 0.35MPa reacts
14h, by metal ion and organic ligand with in-situ synthesis fabricated in situ on microcrystalline cellulose.Obtain microcrystalline cellulose and gold
Belong to the compound of organic framework compounds.
4) 0.8 fluorescent dyes rhodamine B is dissolved in 56 parts of dichloromethane and fluorescent dye solution is made.Step 3) is obtained
To microcrystalline cellulose and the compound of metal organic framework compound be immersed in 20h in fluorescent dye, then use glass filter
Filtering, and the i.e. obtained fluorescent fiber of 94 DEG C of drying is plain after wash 5 times with absolute ethyl alcohol.
Embodiment 6
1) by 7 part 1,3,5- trimesic acids, which are dissolved in 350 parts of n,N-Dimethylformamide, is made organic ligand solution,
5 parts of Cellulose nanocrystal palpuses, nano cellulose crystal, Nano bacteria celluloses are added in organic ligand solution, ultrasound point
It dissipates uniformly, obtains precursor solution；
2) 40 parts of copper acetates are dissolved in 400 parts of absolute ethyl alcohols, in 2000 revs/min of stir speed (S.S.)s, 50 DEG C of stirring temperature
The lower stirring of degree obtains metal ion solution to being completely dissolved；
3) metal ion solution in step 2) is added in the precursor solution of step 1), then is mixed solution and turns
It moves on in reaction vessel, using being reacted by the way of heating/pressurization, 25-120 DEG C of calefactive interzone, pressure 0.38MPa reacts
16h, by metal ion and organic ligand with in-situ synthesis fabricated in situ Cellulose nanocrystal palpus, nano cellulose crystal,
On Nano bacteria cellulose.Obtain Cellulose nanocrystal palpus, nano cellulose crystal, Nano bacteria cellulose and the organic bone of metal
The compound of frame compound.
4) 0.8 part of fluorescent dye methylene blue is dissolved in 60 parts of dichloromethane and fluorescent dye solution is made.By step
3) Cellulose nanocrystal palpus, nano cellulose crystal, Nano bacteria cellulose and the metal organic framework compound obtained is answered
It closes object and is immersed in 20h in fluorescent dye, then filtered with glass filter, and 96 DEG C of drying i.e. system after wash 6 times with absolute ethyl alcohol
Obtain fluorescent fiber element.
Embodiment 7
1) 8 parts of 1,4- terephthalic acid (TPA)s, 2,3,5,6- Pyromellitic Acids are dissolved in 400 parts of N,N-dimethylformamides
Organic ligand solution is made, 6 parts of Cellulose nanocrystals palpuses, nano cellulose crystals are added in organic ligand solution, ultrasound
It is uniformly dispersed, obtains precursor solution；
2) 60 parts of zinc nitrate hexahydrates, four nitric hydrate zinc, zinc nitrate are dissolved in 600 parts of n,N-dimethylacetamide,
In absolute ethyl alcohol, stirred under 3000 revs/min of stir speed (S.S.)s, 70 DEG C of whipping temps to being completely dissolved, it is molten to obtain metal ion
Liquid；
3) metal ion solution in step 2) is added in the precursor solution of step 1), then is mixed solution and turns
It moves on in reaction vessel, using being reacted by the way of heating/pressurization, 25-120 DEG C of calefactive interzone, pressure 0.4MPa reacts
18h, by metal ion and organic ligand with in-situ synthesis fabricated in situ in Cellulose nanocrystal palpus, nano cellulose crystal
On.Obtain the compound of Cellulose nanocrystal palpus, nano cellulose crystal and metal organic framework compound.
4) 0.9 part of fluorescent dye methylene blue is dissolved in 73 parts of dichloromethane and fluorescent dye solution is made.By step
3) compound of the Cellulose nanocrystal palpus, nano cellulose crystal and the metal organic framework compound that obtain is immersed in fluorescence dye
In material for 24 hours, then filtered with glass filter, and that fluorescent fiber is made is plain for 98 DEG C of drying after washing 7 times with absolute ethyl alcohol.
Embodiment 8
1) by 9 parts of 1,4- terephthalic acid (TPA)s, 1,3,5- trimesic acids, 2,3,5,6- Pyromellitic Acids, 1,4,5,8- naphthalenes
It is molten that tetracarboxylic acid anhydride is dissolved in 900 parts of N,N-dimethylformamides, DMAC N,N' dimethyl acetamide, absolute ethyl alcohols obtained organic ligand
Liquid, by 8 parts of Cellulose nanocrystal palpuses, nano cellulose crystal, Nano bacteria cellulose, fento cellulose, microcrystalline celluloses
It is added in organic ligand solution, ultrasonic disperse is uniform, obtains precursor solution；
2) 80 parts of zinc nitrate hexahydrates, four nitric hydrate zinc, zinc nitrate, chromic nitrate, copper acetate are dissolved in 1600 parts of N,
Dinethylformamide, n,N-dimethylacetamide, in absolute ethyl alcohol, in 4000 revs/min of stir speed (S.S.)s, 80 DEG C of whipping temps
Lower stirring obtains metal ion solution to being completely dissolved；
3) metal ion solution in step 2) is added in the precursor solution of step 1), then is mixed solution and turns
It moves on in reaction vessel, using being reacted by the way of heating/pressurization, 25-120 DEG C of calefactive interzone, pressure 0.44MPa reacts
20h, by metal ion and organic ligand with in-situ synthesis fabricated in situ Cellulose nanocrystal palpus, nano cellulose crystal,
Nano bacteria cellulose, fento cellulose, on microcrystalline cellulose.Obtain Cellulose nanocrystal palpus, nano cellulose crystal, thin
Bacterium nano-cellulose, fento cellulose, the compound of microcrystalline cellulose and metal organic framework compound.
4) 0.9 part of fluorescent dyes rhodamine B is dissolved in 90 parts of dichloromethane and fluorescent dye solution is made.By step 3)
Obtained Cellulose nanocrystal palpus, nano cellulose crystal, Nano bacteria cellulose, fento cellulose, microcrystalline cellulose with
The compound of metal organic framework compound is immersed in 28h in fluorescent dye, is then filtered with glass filter, and uses absolute ethyl alcohol
Fluorescent fiber element is made in 100 DEG C of drying after washing 8 times.
Embodiment 9
1) 9.99995 parts of 2,3,5,6- Pyromellitic Acids are dissolved in 990 parts of N,N-dimethylformamides and are made organic
10 parts of microcrystalline celluloses are added in organic ligand solution by ligand solution, and ultrasonic disperse is uniform, obtains precursor solution；
2) 100 parts of zinc nitrate hexahydrates are dissolved in 1900 parts of n,N-Dimethylformamide, in 5000 revs/min of stirrings
Rate stirs to being completely dissolved under 100 DEG C of whipping temps, obtains metal ion solution；
3) metal ion solution in step 2) is added in the precursor solution of step 1), then is mixed solution and turns
It moves on in reaction vessel, using being reacted by the way of heating/pressurization, 25-120 DEG C of calefactive interzone, pressure 0.46MPa reacts
22h, by metal ion and organic ligand with in-situ synthesis fabricated in situ on microcrystalline cellulose.Obtain microcrystalline cellulose and gold
Belong to the compound of organic framework compounds.
4) 1 part of fluorescent dye methyl orange is dissolved in 99 parts of dichloromethane and fluorescent dye solution is made.Step 3) is obtained
To microcrystalline cellulose and the compound of metal organic framework compound be immersed in 34h in fluorescent dye, then use glass filter
Filtering, and the i.e. obtained fluorescent fiber of 102 DEG C of drying is plain after wash 9 times with absolute ethyl alcohol.
As shown in Fig. 1 fluorescent fiber elements XRD, wherein the absworption peak at 2 θ=15.5 ° is metal organic framework compound
Characteristic absorption peak, 2 θ=25 ° and 34.5 ° are the characteristic absorption peaks of cellulose.Illustrate cellulose and metal organic framework compound
Form compound.
Fig. 2 is the FTIR collection of illustrative plates of fluorescent fiber element, in general, flexural vibrations peak of the ester function base there are three feature,
In-C=O- a key characteristic peak about in 1740cm-1, the characteristic peak of another-C-O-C- key is about in 1140cm-1With
1300cm-1.Just as Figure 2 shows, the absworption peak of-C=O- keys appears in 1740cm-1, 1336cm-1The absworption peak at place may
It is the stretching vibration peak of asymmetry-C-O-C-.As Figure 2 shows, 3624cm-1It may be the vibration peak of cellulose alcoholic extract hydroxyl group.
474cm-1Place is-Zn-O- key feature stretching vibrations.Further explanation cellulose and metal organic framework compound form compound
Object.
As shown in Fig. 3 fluorescence speciality papers TGA, fluorescent fiber element has the thermal weight loss of four-stage：During 100 DEG C of first stage
Heated to dry out, 200 DEG C -300 DEG C of second stage is the thermal weight loss of rhodamine B, and it is fiber that the phase III, which is 300 DEG C -350 DEG C,
The thermal weight loss of element, fourth stage are the partial pyrolysis of 350 DEG C of -470 DEG C of metal organic framework compounds.Above-mentioned data illustrate this
Fluorescent fiber element has excellent thermal.
As shown in Fig. 4 and Fig. 5 fluorescent fiber element SEM images, the size of metal organic framework compound reaches nanoscale, and
It is uniformly dispersed in cellulose surface.
As shown in Fig. 6 fluorescent fiber element fluorescence spectrums, the luminescence generated by light of fluorescent fiber element is very capable, illustrates fluorescent dye
Exist with single dimer form, existed in the form of dimer or polymer, therefore fluorescent quenching will not occur easily, had
Good photoluminescence stability.
Embodiment 10
1) by 9.99995 parts of 1,4- terephthalic acid (TPA)s, 1,3,5- trimesic acids, 2,3,5,6- Pyromellitic Acids, 1,4,
5,8- naphthalenetetracarbacidic acidic acid anhydrides, which are dissolved in 990 parts of N,N-dimethylformamides, DMAC N,N' dimethyl acetamide, absolute ethyl alcohols, is made organic
Ligand solution, by 10 parts of Cellulose nanocrystal palpuses, nano cellulose crystal, Nano bacteria cellulose, fento cellulose, crystallites
Cellulose is added in organic ligand solution, and ultrasonic disperse is uniform, obtains precursor solution；
2) 100 parts of zinc nitrate hexahydrates, four nitric hydrate zinc, zinc nitrate, chromic nitrate, copper acetate are dissolved in 1900 parts of N,
Dinethylformamide, n,N-dimethylacetamide, in absolute ethyl alcohol, in 7000 revs/min of stir speed (S.S.)s, 105 DEG C of stirring temperature
The lower stirring of degree obtains metal ion solution to being completely dissolved；
3) metal ion solution in step 2) is added in the precursor solution of step 1), then is mixed solution and turns
It moves on in reaction vessel, using being reacted by the way of heating/pressurization, 25-120 DEG C of calefactive interzone, pressure 0.5MPa reacts
For 24 hours, by metal ion and organic ligand with in-situ synthesis fabricated in situ Cellulose nanocrystal palpus, nano cellulose crystal,
Nano bacteria cellulose, fento cellulose, on microcrystalline cellulose.Obtain Cellulose nanocrystal palpus, nano cellulose crystal, thin
Bacterium nano-cellulose, fento cellulose, the compound of microcrystalline cellulose and metal organic framework compound.
4) 1 part of fluorescent dyes rhodamine B is dissolved in 99 parts of dichloromethane and fluorescent dye solution is made.Step 3) is obtained
Cellulose nanocrystal palpus, nano cellulose crystal, Nano bacteria cellulose, fento cellulose, microcrystalline cellulose and the gold arrived
The compound for belonging to organic framework compounds is immersed in 48h in fluorescent dye, is then filtered with glass filter, and is washed with absolute ethyl alcohol
Fluorescent fiber element is made in 105 DEG C of drying after washing 10 times.
Claims (10)
1. a kind of fluorescent fiber element, which is characterized in that in terms of mass fraction, the raw material for preparing of the fluorescent fiber element includes 0.01
~10 parts of cellulose, 10-1000 parts of organic ligand solution, 5-2000 parts of metal ion solutions and 25-100 parts of fluorescent dyes are molten
Liquid；
It is 1 in mass ratio by organic ligand and organic solvent that the organic ligand solution, which is,：(20-100) preparation obtains；
It is 1 in mass ratio by metal center and organic solvent that the metal ion solution, which is,：(10-20) preparation obtains；
The fluorescent dye solution is by fluorescent dye and dye solvent in mass ratio 1：(50-100) preparation obtains.
2. a kind of fluorescent fiber element according to claim 1, which is characterized in that the cellulose is Cellulose nanocrystal
One or more of palpus, nano cellulose crystal, Nano bacteria cellulose, fento cellulose, microcrystalline cellulose.
3. a kind of fluorescent fiber element according to claim 1, which is characterized in that the metal center is six nitric hydrates
One or more of zinc, four nitric hydrate zinc, zinc nitrate, chromic nitrate or copper acetate；
The organic ligand is 1,4- terephthalic acid (TPA)s, 1,3,5- trimesic acids, 2,3,5,6- Pyromellitic Acids or 1,4,5,
The one or more of 8- naphthalenetetracarbacidic acidic anhydride solutions；
The organic solvent is n,N-Dimethylformamide, n,N-dimethylacetamide, N-Methyl pyrrolidone or absolute ethyl alcohol
One or more of.
4. a kind of fluorescent fiber element according to claim 1, which is characterized in that the fluorescent dye is rhodamine B, methyl
One kind of orange or methylene blue；The dye solvent is chloroformic solution, the dichloromethane solution of rhodamine B, the dichloro of methyl orange
One kind of the dichloromethane solution of dichloromethane or methylene blue.
5. a kind of preparation method of claim 1-4 any one of them fluorescent fiber element, which is characterized in that including following step
Suddenly：
1) organic ligand solution is made in organic ligand dissolving in organic solvent, cellulose is added to organic ligand solution
In, ultrasonic disperse is uniform, obtains precursor solution；
2) by metal center dissolving in organic solvent, stir to being completely dissolved, obtain metal ion solution；
3) metal ion solution in step 2) is added in the precursor solution of step 1), then is mixed solution and is transferred to
In reaction vessel, using being reacted by the way of heating/pressurization, metal ion and organic ligand are closed in situ with in-situ synthesis
Into the compound on cellulose, obtaining cellulose and metal organic framework compound；
4) fluorescent dye is dissolved in dye solvent and fluorescent dye solution is made, the cellulose that step 3) obtains and metal are had
The compound of machine framework compound is immersed in fluorescent dye solution, is then filtered, and is dried afterwards for several times with organic solvent washing
Fluorescent fiber element is made.
A kind of 6. preparation method of fluorescent fiber element according to claim 5, which is characterized in that the stirring temperature in step 2)
It spends for 0 DEG C -120 DEG C, stir speed (S.S.) is 5 revs/min -7000 revs/min.
7. the preparation method of a kind of fluorescent fiber element according to claim 5, which is characterized in that heating is specific in step 3)
It is temperature requirement room temperature to 120 degrees Celsius；Pressurization is specially pressure requirements 0.1-5.0MPa.
A kind of 8. preparation method of fluorescent fiber element according to claim 5, which is characterized in that reaction time in step 3)
For 4-24h.
A kind of 9. preparation method of fluorescent fiber element according to claim 5, which is characterized in that soaking temperature in step 4)
For 5 DEG C -200 DEG C, soaking time 4-72h.
A kind of 10. preparation method of fluorescent fiber element according to claim 5, which is characterized in that washing time in step 4)
Number is 2-10 times, and drying temperature is 85-105 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711279495.6A CN108084992A (en) | 2017-12-06 | 2017-12-06 | A kind of fluorescent fiber element and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711279495.6A CN108084992A (en) | 2017-12-06 | 2017-12-06 | A kind of fluorescent fiber element and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108084992A true CN108084992A (en) | 2018-05-29 |
Family
ID=62174180
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711279495.6A Pending CN108084992A (en) | 2017-12-06 | 2017-12-06 | A kind of fluorescent fiber element and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108084992A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109355931A (en) * | 2018-11-14 | 2019-02-19 | 东华大学 | A kind of preparation method of the multifunctional dyeing fluorescence cotton fabric based on MOF |
| CN110698728A (en) * | 2019-09-09 | 2020-01-17 | 中国科学院金属研究所 | Cellulose/nano inorganic particle composite pigment and preparation method and application thereof |
-
2017
- 2017-12-06 CN CN201711279495.6A patent/CN108084992A/en active Pending
Non-Patent Citations (3)
| Title |
|---|
| KHANJANI SOMAYEH等: "Ultrasound-promoted coating of MOF-5 on silk fiber and study of adsorptive removal and recovery of hazardous anionic dye "congo red"", 《ULTRASONICS SONOCHEMISTRY》 * |
| YANG QIANG等: "Surface modification of PCC filled cellulose paper by MOF-5 (Zn3(BDC)2) metal-organic frameworks for use as soft gas adsorption composite materials", 《CELLULOSE》 * |
| 王悦辉等: "不同电性的纳米银对甲基橙光谱学性质的影响", 《物理化学学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109355931A (en) * | 2018-11-14 | 2019-02-19 | 东华大学 | A kind of preparation method of the multifunctional dyeing fluorescence cotton fabric based on MOF |
| CN110698728A (en) * | 2019-09-09 | 2020-01-17 | 中国科学院金属研究所 | Cellulose/nano inorganic particle composite pigment and preparation method and application thereof |
| CN110698728B (en) * | 2019-09-09 | 2022-02-01 | 中国科学院金属研究所 | Cellulose/nano inorganic particle composite pigment and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Dissolution of highly molecular weight cellulose isolated from wheat straw in deep eutectic solvent of Choline/L-Lysine hydrochloride | |
| CN109763333B (en) | Method for preparing metal organic framework through modified carrier | |
| CN104772048B (en) | Inorganic-organic hybrid film that a kind of inorganic filler is combined with dopamine and its production and use | |
| JP5781321B2 (en) | Protein-adsorbing cellulose nonwoven fabric | |
| CN108142420A (en) | A kind of anti-biotic material and preparation method thereof | |
| CN113750968B (en) | Water-insoluble cyclodextrin-based metal organic framework material and preparation method thereof | |
| CN110227357B (en) | Flexible tailorable nanocellulose/covalent organic framework composite membrane and preparation method thereof | |
| CN106179200A (en) | A kind of preparation method and applications of magnetic porous carbon based on native cellulose | |
| CN108084992A (en) | A kind of fluorescent fiber element and preparation method thereof | |
| CN101708436A (en) | Molecular sieve composite membrane | |
| CN105600793A (en) | Method for preparing silicon oxide nanofiber | |
| CN114632430B (en) | Covalent organic polymer material nanosheet composite matrix membrane for gas separation and preparation method thereof | |
| CN109224879A (en) | A kind of preparation method of CHA molecular screen membrane | |
| CN106220530A (en) | A kind of diphenyl diimide/carbon nano-tube hybridization material and preparation method and application | |
| CN110975833A (en) | Preparation method and application of silicon dioxide/cellulose composite porous material | |
| CN114753186B (en) | Paper deacidification composite material with high-stability suspension dispersion in fluorocarbon medium and preparation method and application thereof | |
| CN109825037A (en) | A kind of modified carbon nano-tube epoxy resin-base composite material | |
| CN108103832B (en) | Photochromic specialty paper and preparation method thereof | |
| Zhang et al. | Self-assembly of porous cellulose fibers and the incorporation of graphene carbon quantum dots for stable luminescence | |
| CN110218330A (en) | A kind of selfreparing modified silicon rubber and preparation method thereof | |
| CN109971125A (en) | A kind of carbon fiber/epoxy resin composite material and its preparation method and application with selfreparing | |
| CN108049239B (en) | Photochromic filler special paper and preparation method thereof | |
| CN109046231B (en) | Method for preparing mesoporous copper bismuth silicate nano composite material by ultrasonic-assisted hydrothermal synthesis method and application | |
| CN108102106A (en) | A kind of photochromic fibre element and preparation method thereof | |
| CN113582158B (en) | Micron carbon sphere material, 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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180529 |
|
| RJ01 | Rejection of invention patent application after publication |