CN108468214A - A kind of fluorescent fiber element base fiber containing multistage hole of the high fastness of high load and preparation method thereof - Google Patents
A kind of fluorescent fiber element base fiber containing multistage hole of the high fastness of high load and preparation method thereof Download PDFInfo
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- D—TEXTILES; PAPER
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
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- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
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Abstract
The present invention provides a kind of fluorescent fiber element base fiber containing multistage hole of the high fastness of high load and preparation method thereof, and specific preparation method is：Native cellulose is dissolved in lithium bromide water solution and forms cellulose solution, rare earth ion aqueous solution is added, after mixing, carbazyl methylated cellulose aqueous solution is added, heating stirring forms the cellulose gel glueballs containing rare earth ion, washing, it is dry, obtain porous fluorescent fiber element ball；Porous fluorescent fiber element ball and crosslinking agent are added in cellulose acetate solution, sealing, heating stirring obtains transparent spinning dope, porous fluorescent fiber cellulose fiber is prepared through electrostatic spinning；Fibroin aqueous solution is sprayed on the surface of porous fluorescent fiber cellulose fiber, baking and curing film forming obtains product.Fiber prepared by the present invention is embedded to the porous fluorescent microsphere of high load amount as functional material in cellulose acetate fibre, then fibroin film is adhered on surface, and fiber, which is prepared, has multi-stage pore structure, luminescent properties excellent.
Description
Technical field
The invention belongs to textile material technical fields, and in particular to a kind of fluorescence containing multistage hole of the high fastness of high load
Cellulose-based fiber and preparation method thereof.
Background technology
High molecular fluorescent material consists of two parts, i.e. polymer, small light-emitting molecules or luminophore.Fluorescence chromophores
In all contain conjugated double bond pi bond system, altogether often system be affected to fluorescence, the usual bigger delocalized electron of conjugated system more holds
Easy excitated, fluorescence more easy tos produce.There are two types of preparation methods for fluorescent material：Doping type and chemical bond mould assembly, wherein doping type is
By small light-emitting molecules such as naphthalimide derivative, fluorescein derivative, acridine derivatives, Rhodamine Derivatives and rare earth compoundings
It is equably doped in PVA, PAA, PMMA, polyethers or all kinds of fiber polymers and the shapes such as microballoon, film, fiber, gel is prepared
The fluorescent material of state.However, with the crisis of petroleum resources and going deep into for environmental-friendly, sustainable development idea, being based on can
Regenerated resources are that the natural polymer functional material of raw material is greatly developed, for natural polymer is compared to synthesis macromolecule,
Resourceful, cheap and easy to get, renewable, biodegradable, good biocompatibility, and containing largely through base or amido, be easy into
Row is modified.
A kind of preparation method of cellulose-based fluorescent film disclosed in Chinese patent CN 101434707B, by sodium hydroxide and
The mixed aqueous solution of urea is cooled to -12~-13 DEG C in advance, and cellulose is added and obtains cellulose solution after mixing, is cast, through sulphur
After the coagulating bath freezing film of acid, processing 30min or more in the solution of organic fluorescent dye is immersed, it is dry, obtain cellulose base
Fluorescent film.The preparation method is all physical process, is not chemically reacted, technical process is simple, easy to operate, can be used for wrapping
The fields such as dress, information technology, anti-fake and optical material, but there are the leakage problems of organic fluorescent dye.
Different from doping type, chemical bond mould assembly is by chemical bonding or polymerisation, by chromophore with chemical bonds
The high-molecular luminous material obtained in macromolecule has not easily to fall off, the equal Uniform of chromophore's distribution, stable content, luminescent properties
With light guide advantage of good performance, in fluorescence chemical sensor, photoelectric material, nonlinear optical device, optical resin, biological skill
Art, special textile etc. are widely used.Chinese patent CN 102702558B are disclosed to be based on cellulose nanometer fento film
Cellulose nanometer fento water slurry ultrasound deaeration is obtained casting solution, in polytetrafluoro by the fluorescent optical sensor for matrix and its application
Solvent is evaporated in ethylene mold and obtains cellulose nanometer microfibre film, by cellulose nanometer microfibre film in added up to 1-
Under the action of (3- dimethyl aminopropyls) -3- ethyls carbon diamines/N- hydroxysuccinimides, by the positions C-6 on cellulose membrane surface
Carboxyl reacted with the aminated compounds of bromophenyl after, obtain the cellulose nanometer fento with Suzuki reactivities site
Film, under nitrogen protection, using tetrakis triphenylphosphine palladium as catalyst, by can Suzuki the reaction monomers (boron of aryl/alkenyl
Acid or borate, chlorine, bromine, iodo aromatic hydrocarbon or alkene) fluorescent conjugated polymer that reacts preparation under reflux, it will be fluorescence conjugated
The cellulose nanometer fento film with Suzuki reactivities site is added in the solution of polymer, under nitrogen protection, is added
Tetrakis triphenylphosphine palladium, unstressed configuration substance in back flow reaction to solution, is dried to obtain highly sensitive fluorescent optical sensor.Party's legal system
Standby fluorescence sense film is easy to carry about with one, and can realize scene to nitro-aromatic explosive in the UV lamp, quickly, visually examine
It surveys.By the above-mentioned prior art it is found that cellulose can realize high load capacity by physical absorption fluorescent material, but conjugation
Low, the conjugation of chemical graft is high, but load capacity is small, therefore, how while improving load capacity, improve fluorescent material and
The binding strength of cellulose, it appears very necessary.
Invention content
The technical problem to be solved in the present invention is to provide a kind of fluorescent fiber elements containing multistage hole of the high fastness of high load
Base fiber and preparation method thereof, the present invention are fine as functional material embedment cellulose acetate using the porous fluorescent microsphere of high load amount
In dimension, then fibroin film is adhered on surface, and fluorescent material content height in fiber is prepared, and binding strength is strong, and with multistage
Pore space structure, luminescent properties are excellent.
In order to solve the above technical problems, the technical scheme is that：
A kind of fluorescent fiber element base fiber containing multistage hole of the high fastness of high load, containing for the high fastness of high load are more
Cellulose in the fluorescent fiber element base fiber of grade hole includes the cellulose of unmodified cellulose and modification, the modification
Cellulose includes carbazyl methylcellulose and cellulose acetate, the fluorescent fiber containing multistage hole of the high fastness of high load
Fluorescent light source is rare earth ion in plain base fiber, in the fluorescent fiber element base fiber containing multistage hole of the high fastness of high load
Multi-stage pore structure is made of porous fluorescent fiber element ball and porous fibre, the high fastness of high load containing the glimmering of multistage hole
Fiber optics element base fiber surface contains fibroin film.
The present invention also provides a kind of preparation method of the fluorescent fiber element base fiber containing multistage hole of the high fastness of high load,
Include the following steps：
(1) native cellulose is dissolved in lithium bromide water solution and forms cellulose solution, rare earth ion aqueous solution is added,
After mixing, carbazyl methylated cellulose aqueous solution is added, heating stirring forms the cellulose gel glueballs containing rare earth ion,
Washing, it is dry, obtain porous fluorescent fiber element ball；
(2) the porous fluorescent fiber element ball and crosslinking agent prepared step (2) is added in cellulose acetate solution, sealing,
Heating stirring obtains transparent spinning dope, and porous fluorescent fiber cellulose fiber is prepared through electrostatic spinning；
(3) fibroin aqueous solution, baking and curing are sprayed in the surface for the porous fluorescent fiber cellulose fiber for preparing step (2)
Film forming, obtains the fluorescent fiber element base fiber containing multistage hole of the high fastness of high load.
As a preferred embodiment of the above technical solution, in the step (1), native cellulose is cotton pulp or cotton linter.
As a preferred embodiment of the above technical solution, in the step (1), rare earth ion aqueous solution be europium ion, cerium ion or
Person's erbium ion.
As a preferred embodiment of the above technical solution, in the step (1), cellulose, rare earth ion and carbazyl Methyl cellulose
The mass ratio of element is 30-50:20-30：30-50.
As a preferred embodiment of the above technical solution, in the step (1), the temperature of heating stirring is 50-80 DEG C, and the time is
2-6h。
As a preferred embodiment of the above technical solution, in the step (2), crosslinking agent is glutaraldehyde.
As a preferred embodiment of the above technical solution, in the step (2), it is 1 that the solvent of transparent spinning dope, which is volume ratio,:1
DMF and acetone mixed solution.
As a preferred embodiment of the above technical solution, in the step (2), the solid content of transparent spinning dope is 100-120g/
L, the content of porous fluorescent fiber element ball is 5-8wt% wherein in solid content, and the content of crosslinking agent is 3-5wt%, remaining is vinegar
Acid cellulose.
As a preferred embodiment of the above technical solution, in the step (3), the fluorescence containing multistage hole of the high fastness of high load is fine
The content of fibroin is 0.5-2wt% in the plain base fiber of dimension.
Compared with prior art, the invention has the advantages that：
(1) by high load amount in the fluorescent fiber element base fiber containing multistage hole of the high fastness of high load prepared by the present invention
Porous fluorescent microsphere be embedded in cellulose acetate fibre as functional material, then fibroin film is adhered on surface, wherein height is negative
The porous fluorescent microsphere of carrying capacity be rare earth ion complex and cellulose macromolecule and modified cellulose macromolecular with covalent bond
Form be connected, and form three-dimensional net structure, can be in heating ring wherein modified cellulose is carbazyl methylcellulose
Thermal gels are formed under border, cellulose macromolecule and rare earth ion complex are coated, promote the close connection of the two, and pass through control
Gel micro-ball is prepared in the solid content of ratio and solution system between three, then through being dried to obtain porous fluorescent fiber
Plain ball contains very high rare earth ion load capacity in the porous fluorescent fiber element ball, and bond strength is high, by the fluorescence of porous structure
Cellulose balls are added in cellulose acetate, and porous structure is conducive to the infiltration of cellulose acetate, and through glutaraldehyde cross-linking agent
Effect is conducive to the set fastness for improving fluorescent fiber element ball and cellulose acetate, and during spinning, fluorescent fiber
Plain ball can be used as skeleton, and cellulose acetate macromolecular is promoted to be reset around fluorescent fiber element ball, improve the fiber after spinning
Mechanical strength, in addition, most afterwards through fibroin surface modification, the glutaraldehyde cross-linking on fibroin and surface can also add
The binding strength of strong fibroin and cellulose acetate, is prepared the fiber of the multistage hole of the high fastness of high load.
(2) by rare earth ion in the fluorescent fiber element base fiber containing multistage hole of the high fastness of high load prepared by the present invention
Cellulose and its derivates are firmly coated on, keep the fluorescent fiber of preparation environmentally protective, it is safe and non-toxic, can be degradable, and
Preparation method is simple, need not use expensive equipment, and since rare earth ion and silk all have luminescent effect, what is also contained is more
Grade pore space structure, advantageously forms colorful fluorescent effect, and therefore, fiber excellent combination property prepared by the present invention has very
Good researching value and market prospects.
Specific implementation mode
Below in conjunction with specific embodiment, the present invention will be described in detail, herein illustrative examples and explanation of the invention
For explaining the present invention, but it is not as a limitation of the invention.
Embodiment 1：
(1) it is 30 according to the mass ratio of cellulose, rare earth ion and carbazyl methylcellulose:20：30, cotton pulp is natural
Cellulose dissolution forms the cellulose solution of 10wt% in the lithium bromide water solution of 10wt%, and it is water-soluble that europium rare earth ion is added
Carbazyl methylated cellulose aqueous solution is added after mixing in liquid, and the heating stirring 2h at 50 DEG C is formed containing rare earth ion
Cellulose gel glueballs washs, dry, obtains the porous fluorescent fiber element ball that grain size is 200 μm.
(2) porous fluorescent fiber element ball and glutaraldehyde cross-linking agent are added in cellulose acetate solution, sealing, at 50 DEG C
Heating stirring 10h, obtains transparent spinning dope, wherein the solvent of transparent spinning dope is that volume ratio is 1:1 DMF and acetone
Mixed solution, the solid content of transparent spinning dope is 100g/L, and the content of porous fluorescent fiber element ball is wherein in solid content
The content of 5wt%, crosslinking agent are 3wt%, remaining is cellulose acetate, and voltage 10kV, it is 15cm, spinning solution to receive distance
Propulsion rate is 0.5mL/h, and porous fluorescent fiber cellulose fiber is prepared through electrostatic spinning.
(3) the fibroin aqueous solution that the surface of porous fluorescent fiber cellulose fiber is sprayed to 2wt% is dried solid at 60 DEG C
It is melted into film, obtains the fluorescent fiber element base fiber containing multistage hole of the high fastness of high load, wherein containing for the high fastness of high load is more
The content of fibroin is 0.5wt% in the fluorescent fiber element base fiber of grade hole.
Embodiment 2：
(1) it is 50 according to the mass ratio of cellulose, rare earth ion and carbazyl methylcellulose:30：50, by cotton linter day
Right cellulose dissolution forms the cellulose solution of 20wt% in the lithium bromide water solution of 20wt%, and it is water-soluble that cerium mischmetal ion is added
Carbazyl methylated cellulose aqueous solution is added after mixing in liquid, and the heating stirring 6h at 80 DEG C is formed containing rare earth ion
Cellulose gel glueballs washs, dry, obtains the porous fluorescent fiber element ball that grain size is 500 μm.
(2) porous fluorescent fiber element ball and glutaraldehyde cross-linking agent are added in cellulose acetate solution, sealing, at 60 DEG C
Heating stirring 12h, obtains transparent spinning dope, wherein the solvent of transparent spinning dope is that volume ratio is 1:1 DMF and acetone
Mixed solution, the solid content of transparent spinning dope is 120g/L, and the content of porous fluorescent fiber element ball is wherein in solid content
The content of 8wt%, crosslinking agent are 5wt%, remaining is cellulose acetate, and voltage 15kV, it is 20cm, spinning solution to receive distance
Propulsion rate is 1mL/h, and porous fluorescent fiber cellulose fiber is prepared through electrostatic spinning.
(3) the fibroin aqueous solution that the surface of porous fluorescent fiber cellulose fiber is sprayed to 5wt% is dried solid at 60 DEG C
It is melted into film, obtains the fluorescent fiber element base fiber containing multistage hole of the high fastness of high load, wherein containing for the high fastness of high load is more
The content of fibroin is 2wt% in the fluorescent fiber element base fiber of grade hole.
Embodiment 3：
(1) it is 40 according to the mass ratio of cellulose, rare earth ion and carbazyl methylcellulose:25：40, cotton pulp is natural
Cellulose dissolution forms the cellulose solution of 12wt% in the lithium bromide water solution of 15wt%, and it is water-soluble that erbium rare earth ion is added
Carbazyl methylated cellulose aqueous solution is added after mixing in liquid, and the heating stirring 4h at 60 DEG C is formed containing rare earth ion
Cellulose gel glueballs washs, dry, obtains the porous fluorescent fiber element ball that grain size is 400 μm.
(2) porous fluorescent fiber element ball and glutaraldehyde cross-linking agent are added in cellulose acetate solution, sealing, at 55 DEG C
Heating stirring 11h, obtains transparent spinning dope, wherein the solvent of transparent spinning dope is that volume ratio is 1:1 DMF and acetone
Mixed solution, the solid content of transparent spinning dope is 110g/L, and the content of porous fluorescent fiber element ball is wherein in solid content
The content of 6wt%, crosslinking agent are 4wt%, remaining is cellulose acetate, and voltage 13kV, it is 18cm, spinning solution to receive distance
Propulsion rate is 0.7mL/h, and porous fluorescent fiber cellulose fiber is prepared through electrostatic spinning.
(3) the fibroin aqueous solution that the surface of porous fluorescent fiber cellulose fiber is sprayed to 4wt% is dried solid at 60 DEG C
It is melted into film, obtains the fluorescent fiber element base fiber containing multistage hole of the high fastness of high load, wherein containing for the high fastness of high load is more
The content of fibroin is 1wt% in the fluorescent fiber element base fiber of grade hole.
Embodiment 4：
(1) it is 35 according to the mass ratio of cellulose, rare earth ion and carbazyl methylcellulose:23：40, by cotton linter day
Right cellulose dissolution forms the cellulose solution of 15wt% in the lithium bromide water solution of 13wt%, and it is water-soluble that europium rare earth ion is added
Carbazyl methylated cellulose aqueous solution is added after mixing in liquid, and the heating stirring 4h at 75 DEG C is formed containing rare earth ion
Cellulose gel glueballs washs, dry, obtains the porous fluorescent fiber element ball that grain size is 350 μm.
(2) porous fluorescent fiber element ball and glutaraldehyde cross-linking agent are added in cellulose acetate solution, sealing, at 55 DEG C
Heating stirring 11h, obtains transparent spinning dope, wherein the solvent of transparent spinning dope is that volume ratio is 1:1 DMF and acetone
Mixed solution, the solid content of transparent spinning dope is 110g/L, and the content of porous fluorescent fiber element ball is wherein in solid content
The content of 6wt%, crosslinking agent are 4wt%, remaining is cellulose acetate, and voltage 13kV, it is 19cm, spinning solution to receive distance
Propulsion rate is 0.8mL/h, and porous fluorescent fiber cellulose fiber is prepared through electrostatic spinning.
(3) the fibroin aqueous solution that the surface of porous fluorescent fiber cellulose fiber is sprayed to 4wt% is dried solid at 60 DEG C
It is melted into film, obtains the fluorescent fiber element base fiber containing multistage hole of the high fastness of high load, wherein containing for the high fastness of high load is more
The content of fibroin is 1.2wt% in the fluorescent fiber element base fiber of grade hole.
Embodiment 5：
(1) it is 30 according to the mass ratio of cellulose, rare earth ion and carbazyl methylcellulose:30：30, by cotton linter day
Right cellulose dissolution forms the cellulose solution of 10wt% in the lithium bromide water solution of 20wt%, and it is water-soluble that erbium rare earth ion is added
Carbazyl methylated cellulose aqueous solution is added after mixing in liquid, and the heating stirring 6h at 50 DEG C is formed containing rare earth ion
Cellulose gel glueballs washs, dry, obtains the porous fluorescent fiber element ball that grain size is 230 μm.
(2) porous fluorescent fiber element ball and glutaraldehyde cross-linking agent are added in cellulose acetate solution, sealing, at 50 DEG C
Heating stirring 12h, obtains transparent spinning dope, wherein the solvent of transparent spinning dope is that volume ratio is 1:1 DMF and acetone
Mixed solution, the solid content of transparent spinning dope is 100g/L, and the content of porous fluorescent fiber element ball is wherein in solid content
The content of 8wt%, crosslinking agent are 3wt%, remaining is cellulose acetate, and voltage 15kV, it is 15cm, spinning solution to receive distance
Propulsion rate is 1mL/h, and porous fluorescent fiber cellulose fiber is prepared through electrostatic spinning.
(3) the fibroin aqueous solution that the surface of porous fluorescent fiber cellulose fiber is sprayed to 2wt% is dried solid at 60 DEG C
It is melted into film, obtains the fluorescent fiber element base fiber containing multistage hole of the high fastness of high load, wherein containing for the high fastness of high load is more
The content of fibroin is 0.5wt% in the fluorescent fiber element base fiber of grade hole.
Embodiment 6：
(1) it is 50 according to the mass ratio of cellulose, rare earth ion and carbazyl methylcellulose:20：50, cotton pulp is natural
Cellulose dissolution forms the cellulose solution of 20wt% in the lithium bromide water solution of 10wt%, and it is water-soluble that europium rare earth ion is added
Carbazyl methylated cellulose aqueous solution is added after mixing in liquid, and the heating stirring 2h at 80 DEG C is formed containing rare earth ion
Cellulose gel glueballs washs, dry, obtains the porous fluorescent fiber element ball that grain size is 480 μm.
(2) porous fluorescent fiber element ball and glutaraldehyde cross-linking agent are added in cellulose acetate solution, sealing, at 60 DEG C
Heating stirring 10h, obtains transparent spinning dope, wherein the solvent of transparent spinning dope is that volume ratio is 1:1 DMF and acetone
Mixed solution, the solid content of transparent spinning dope is 120g/L, and the content of porous fluorescent fiber element ball is wherein in solid content
The content of 5wt%, crosslinking agent are 5wt%, remaining is cellulose acetate, and voltage 10kV, it is 20cm, spinning solution to receive distance
Propulsion rate is 0.8mL/h, and porous fluorescent fiber cellulose fiber is prepared through electrostatic spinning.
(3) the fibroin aqueous solution that the surface of porous fluorescent fiber cellulose fiber is sprayed to 5wt% is dried solid at 60 DEG C
It is melted into film, obtains the fluorescent fiber element base fiber containing multistage hole of the high fastness of high load, wherein containing for the high fastness of high load is more
The content of fibroin is 1.7wt% in the fluorescent fiber element base fiber of grade hole.
After testing, the hole of the fluorescent fiber element base fiber containing multistage hole for the high fastness of high load that prepared by embodiment 1-6
Diameter range, fluorescence intensity, the result of washable intensity are as follows：
As seen from the above table, the fluorescent fiber element base fiber containing multistage hole for the high fastness of high load that prepared by the present invention has
Multi-stage pore structure, fluorescence intensity is good, and conjugation is high, and fluorescent material is without leakage.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology can all carry out modifications and changes to above-described embodiment without violating the spirit and scope of the present invention.Cause
This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as
At all equivalent modifications or change, should by the present invention claim be covered.
Claims (10)
1. a kind of fluorescent fiber element base fiber containing multistage hole of high fastness of high load, it is characterised in that：The high load is high
Cellulose in the fluorescent fiber element base fiber containing multistage hole of fastness includes the cellulose of unmodified cellulose and modification,
The cellulose of the modification includes carbazyl methylcellulose and cellulose acetate, the hole containing multistage of the high fastness of high load
Fluorescent fiber element base fiber in fluorescent light source be rare earth ion, the fluorescent fiber containing multistage hole of the high fastness of high load
Multi-stage pore structure is made of porous fluorescent fiber element ball and porous fibre in plain base fiber, and containing for the high fastness of high load is more
The fluorescent fiber element base fiber surface of grade hole contains fibroin film.
2. a kind of preparation method of the fluorescent fiber element base fiber containing multistage hole of high fastness of high load, which is characterized in that packet
Include following steps：
(1) native cellulose is dissolved in lithium bromide water solution and forms cellulose solution, rare earth ion aqueous solution, mixing is added
After uniformly, carbazyl methylated cellulose aqueous solution is added, heating stirring forms the cellulose gel glueballs containing rare earth ion, washs,
It is dry, obtain porous fluorescent fiber element ball；
(2) the porous fluorescent fiber element ball and crosslinking agent prepared step (2) is added in cellulose acetate solution, seals, heating
Stirring, obtains transparent spinning dope, porous fluorescent fiber cellulose fiber is prepared through electrostatic spinning；
(3) by step (2) prepare porous fluorescent fiber cellulose fiber surface spray fibroin aqueous solution, baking and curing at
Film obtains the fluorescent fiber element base fiber containing multistage hole of the high fastness of high load.
3. a kind of preparation of the fluorescent fiber element base fiber containing multistage hole of the high fastness of high load according to claim 2
Method, it is characterised in that：In the step (1), native cellulose is cotton pulp or cotton linter.
4. a kind of preparation of the fluorescent fiber element base fiber containing multistage hole of the high fastness of high load according to claim 2
Method, it is characterised in that：In the step (1), rare earth ion aqueous solution is europium ion, cerium ion or erbium ion.
5. a kind of preparation of the fluorescent fiber element base fiber containing multistage hole of the high fastness of high load according to claim 2
Method, it is characterised in that：In the step (1), the mass ratio of cellulose, rare earth ion and carbazyl methylcellulose is:30-
50:20-30：30-50.
6. a kind of preparation of the fluorescent fiber element base fiber containing multistage hole of the high fastness of high load according to claim 2
Method, it is characterised in that：In the step (1), the temperature of heating stirring is 50-80 DEG C, time 2-6h.
7. a kind of preparation of the fluorescent fiber element base fiber containing multistage hole of the high fastness of high load according to claim 2
Method, it is characterised in that：In the step (2), crosslinking agent is glutaraldehyde.
8. a kind of preparation of the fluorescent fiber element base fiber containing multistage hole of the high fastness of high load according to claim 2
Method, it is characterised in that：In the step (2), it is 1 that the solvent of transparent spinning dope, which is volume ratio,:1 DMF and acetone it is mixed
Close solution.
9. a kind of preparation of the fluorescent fiber element base fiber containing multistage hole of the high fastness of high load according to claim 2
Method, it is characterised in that：In the step (2), the solid content of transparent spinning dope is 100-120g/L, wherein more in solid content
The content of hole fluorescent fiber element ball is 5-8wt%, and the content of crosslinking agent is 3-5wt%, remaining is cellulose acetate.
10. a kind of system of the fluorescent fiber element base fiber containing multistage hole of the high fastness of high load according to claim 2
Preparation Method, it is characterised in that：In the step (3), in the fluorescent fiber element base fiber containing multistage hole of the high fastness of high load
The content of fibroin is 0.5-2wt%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112323162A (en) * | 2020-10-30 | 2021-02-05 | 汕头市欣和健康管理有限公司 | High-efficiency slow-release microcapsule cellulose fiber prepared from wormwood |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101338189A (en) * | 2008-08-27 | 2009-01-07 | 吉林大学 | High voltage electrospinning method for preparing multi-fluorescence-encoded micro-beads |
| CN102166483A (en) * | 2011-03-04 | 2011-08-31 | 嘉兴学院 | Method for preparing molecular imprinted nanofiber membrane for detecting rhodamine B |
| CN103088554A (en) * | 2011-10-31 | 2013-05-08 | 中国科学院合肥物质科学研究院 | Porous membrane mixed by 1,4-dihydroxy anthraquinone and cellulose, preparation method and usage |
| CN103536958A (en) * | 2013-09-29 | 2014-01-29 | 武汉大学 | Modified cellulose nanofiber membrane based on layer-by-layer self-assembly of lysozyme and silk protein based as well as preparation and application thereof |
| CN105925260A (en) * | 2016-04-28 | 2016-09-07 | 东华大学 | Nano-grade luminescent material loading rare earth metal ions, and preparation method thereof |
| CN106084257A (en) * | 2016-06-06 | 2016-11-09 | 东华大学 | A kind of composite aquogel and preparation method thereof |
| CN107163933A (en) * | 2017-06-30 | 2017-09-15 | 云南师范大学 | A kind of even porous rare earth composite material of emitting red light, preparation method and application |
-
2018
- 2018-01-22 CN CN201810057067.7A patent/CN108468214A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101338189A (en) * | 2008-08-27 | 2009-01-07 | 吉林大学 | High voltage electrospinning method for preparing multi-fluorescence-encoded micro-beads |
| CN102166483A (en) * | 2011-03-04 | 2011-08-31 | 嘉兴学院 | Method for preparing molecular imprinted nanofiber membrane for detecting rhodamine B |
| CN103088554A (en) * | 2011-10-31 | 2013-05-08 | 中国科学院合肥物质科学研究院 | Porous membrane mixed by 1,4-dihydroxy anthraquinone and cellulose, preparation method and usage |
| CN103536958A (en) * | 2013-09-29 | 2014-01-29 | 武汉大学 | Modified cellulose nanofiber membrane based on layer-by-layer self-assembly of lysozyme and silk protein based as well as preparation and application thereof |
| CN105925260A (en) * | 2016-04-28 | 2016-09-07 | 东华大学 | Nano-grade luminescent material loading rare earth metal ions, and preparation method thereof |
| CN106084257A (en) * | 2016-06-06 | 2016-11-09 | 东华大学 | A kind of composite aquogel and preparation method thereof |
| CN107163933A (en) * | 2017-06-30 | 2017-09-15 | 云南师范大学 | A kind of even porous rare earth composite material of emitting red light, preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| 江泽慧等: "《中国林业工程》", 31 May 2002, 济南出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112323162A (en) * | 2020-10-30 | 2021-02-05 | 汕头市欣和健康管理有限公司 | High-efficiency slow-release microcapsule cellulose fiber prepared from wormwood |
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