CN105862451B - A kind of fluorescent silk fiber based on BODIPY class dyestuffs and preparation method thereof - Google Patents
A kind of fluorescent silk fiber based on BODIPY class dyestuffs and preparation method thereof Download PDFInfo
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- CN105862451B CN105862451B CN201610319896.9A CN201610319896A CN105862451B CN 105862451 B CN105862451 B CN 105862451B CN 201610319896 A CN201610319896 A CN 201610319896A CN 105862451 B CN105862451 B CN 105862451B
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- 239000000835 fiber Substances 0.000 title claims abstract description 92
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 23
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 17
- 239000000243 solution Substances 0.000 claims abstract description 17
- 239000010457 zeolite Substances 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 239000007864 aqueous solution Substances 0.000 claims abstract description 10
- 230000008961 swelling Effects 0.000 claims abstract description 9
- 239000000975 dye Substances 0.000 claims description 35
- 239000007850 fluorescent dye Substances 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- LIQLLTGUOSHGKY-UHFFFAOYSA-N [B].[F] Chemical group [B].[F] LIQLLTGUOSHGKY-UHFFFAOYSA-N 0.000 claims description 18
- WVIICGIFSIBFOG-UHFFFAOYSA-N pyrylium Chemical compound C1=CC=[O+]C=C1 WVIICGIFSIBFOG-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- 238000001723 curing Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 238000007493 shaping process Methods 0.000 claims description 8
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 150000004676 glycans Chemical class 0.000 claims 1
- 229920001661 Chitosan Polymers 0.000 abstract description 3
- 238000009941 weaving Methods 0.000 abstract description 3
- 230000006641 stabilisation Effects 0.000 abstract description 2
- 238000011105 stabilization Methods 0.000 abstract description 2
- 230000021615 conjugation Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000002096 quantum dot Substances 0.000 description 3
- 150000003839 salts Chemical group 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 230000035800 maturation Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 238000006862 quantum yield reaction Methods 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 241000255789 Bombyx mori Species 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- 230000002895 hyperchromatic effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000004224 protection Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009261 transgenic effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/0004—General aspects of dyeing
- D06P1/0012—Effecting dyeing to obtain luminescent or phosphorescent dyeings
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/46—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing natural macromolecular substances or derivatives thereof
- D06P1/48—Derivatives of carbohydrates
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/673—Inorganic compounds
- D06P1/67333—Salts or hydroxides
- D06P1/6735—Salts or hydroxides of alkaline or alkaline-earth metals with anions different from those provided for in D06P1/67341
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/02—Material containing basic nitrogen
- D06P3/04—Material containing basic nitrogen containing amide groups
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Molecular Biology (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The present invention provides a kind of fluorescent silk fiber based on BODIPY class dyestuffs and preparation method thereof, it is that the silk fiber of swelling is impregnated in the aqueous solution containing zeolite to be pre-processed, in hydrophilic BODIPY fluorochromes and low molecular chitosan solution is impregnated in respectively repeatedly, most it is heating and curing through decatize to obtain fluorescent silk fiber afterwards.The fluorescent silk fiber fluorescent stabilization based on BODIPY class dyestuffs of this method preparation, intensity is high, color is uniform, it can mass produce, and the good mechanical property of the silk fiber prepared, pliability is high, can operate with the numerous areas such as weaving, biologic medical, false proof.
Description
Technical field：
The invention belongs to textile material technical field, and in particular to a kind of fluorescent silk fiber based on BODIPY class dyestuffs
And preparation method thereof.
Background technology：
It is well known that the color of natural silk is white or yellow, with the continuous progress of science and technology, people pass through function
It is modified to be extended for the color of silk red, green, orange etc., in addition can also have the work(such as fluorescence, UV resistance, antibacterial
Effect, not only expands utilization of the silk in field of textiles, also starts to be related to the fields such as biomedicine, authentication.
At present, the method for fluorescent natural silk mainly has three kinds：Transgenic engineering, silk post processing and feeding method, its transfer base
Because engineering and feeding method have many out of contior factors, and process is complicated, cost is high, efficiency is low, after traditional silk
Method for sorting is that silk is dyed by dyestuff, and because the conjugation of dyestuff and silk is not high, the content of Wastewater Dyes reaches,
Very big pollution is caused to environment.A kind of stretch-proof, the strong red fluorescence of uvioresistant disclosed in Chinese patent CN 103275702B
The preparation method of silk, it is light yellow by being obtained after mixing silk, gold chloride and sodium hydroxide through Muffle furnace heating response
Silk, handling to obtain the silk fiber with strong red fluorescence through freeze-day with constant temperature.Method prepared by this method is easy, but passes through
The structure of silk is destroyed after Muffle furnace heats, and mechanicalness reduces, and use range is restricted.Chinese patent
A kind of silk fiber knitted fabric obtains the colouring method of iridescent disclosed in CN103225217A, and the silk fiber after scouringing and bleaching is knitted
Thing first through soaking with after modifier treatment, is handled, finally using excessive through cationic fluorescent dyestuff and the dyeing of levelling agent heating and thermal insulation
Flowing water is washed, and is routinely soaped, and polyurethanes environmental protection color fixing agent fixation and drying obtain the silk fiber of iridescent.This method is logical
Fluorescent dye is attached to the surface of silk fabric by hyperchromatic method, is fabric acquisition iridescent, but this dyeing
Prepare that the performance of fluorescent fiber is unstable, the conjugation of fluorescent dye and silk fiber is not high, and performance is unstable during use.
With the continuous maturation of nanometer technique, nanometer technique is widely used in silk fiber material by researcher.In
A kind of preparation method for the fluorescent natural silk for assembling quantum dot nano particle, is with silkworm disclosed in state patent CN 101275362A
Silk is matrix, connects one layer of high-molecular organic material on silk surface by electrostatic adsorption, passes through the organic polymer material
Material adsorbs quantum dot nano-particle again, then adsorbs organic polymer by quantum dot nano-particle, obtains one or many quantum
Point cladding should silk fiber, this method prepare fluorescent silk fiber fluorescent material and silk fiber conjugation not
Height, and fluorescence intensity inequality is easily caused, influence using effect.
The content of the invention：
The technical problem to be solved in the present invention is to provide a kind of fluorescent silk fiber and its system based on BODIPY class dyestuffs
Preparation Method, it is the effect being crosslinked by micron order zeolite adsorption and low-molecular weight chitoglycan, by water miscible BODIPY classes dyestuff
The inside and surface of silk fiber are attached to, fluorescent dye is firmly coated on silk fiber and obtains excellent glimmering of fluorescence property
Light silk fiber.The fluorescent silk fiber fluorescent stabilization of this method preparation, intensity is high, color is uniform, can mass produce, and
The good mechanical property of the silk fiber of preparation, pliability is high, can operate with the numerous areas such as weaving, biologic medical, false proof.
In order to solve the above technical problems, the technical scheme is that：
A kind of fluorescent silk fiber based on BODIPY class dyestuffs, it is characterised in that described based on BODIPY class dyestuffs
Fluorescent silk fiber includes natural silk fiber, zeolite, hydrophilic fluorescent dye and low-molecular weight chitoglycan, and the natural silk is fine
The color of dimension can be that white, yellow or colour, the zeolite are Mn oxide modified zeolite, and the hydrophilic fluorescent dye is water
Dissolubility BODIPY class dyestuffs.
As the preferred of above-mentioned technical proposal, the particle diameter of the Mn oxide modified zeolite is 50-100 microns, the water
Dissolubility BODIPY classes dyestuff is the pyrylium dyes of quaternary fluorine boron two or the pyrylium dyes of sulfonate type fluorine boron two.
The present invention also provides a kind of preparation method of the fluorescent natural silk based on BODIPY class dyestuffs, it is characterised in that：Including
Following steps：
(1) natural silk fiber is impregnated in warm water after degumming process and vibrates swelling, then be impregnated in containing the water-soluble of zeolite
In liquid, ultrasound, washing, the natural silk fiber that naturally dry is pre-processed are taken out；
(2) the natural silk fiber for the pretreatment for preparing step (1), with bath raio 1:40, hydrophilic fluorescent dye is submerged initially in,
Take out, be then immersed in low-molecular weight chitoglycan solution, take out, then immerse hydrophilic fluorescent dye, take out, be finally immersed in low molecule amount
Chitosan solution, take out drying and obtain the silk fiber of fluorescent staining；
(3) silk fiber for the fluorescent staining for preparing step (2) is heating and curing through alcohol steam individual composition, water
Wash away except surface combines material loosely, drying and shaping obtains the fluorescent silk fiber based on BODIPY class dyestuffs.
As the preferred of above-mentioned technical proposal, in the step (1), the temperature of the warm water is 30-45 DEG C, the vibration
Time be 10-30min.
As the preferred of above-mentioned technical proposal, in the step (1), the quality of zeolite point in the aqueous solution containing zeolite
Number is 0.5-5%.
As the preferred of above-mentioned technical proposal, in the step (1), the ultrasonic frequency is 200-300W, ultrasonic
Time is 30-60min.
As the preferred of above-mentioned technical proposal, in the step (2), the concentration of hydrophilic fluorescent dye is 5-15g/ml.
As the preferred of above-mentioned technical proposal, in the step (1), the mass fraction of low-molecular weight chitoglycan solution is 2-
3%, the relative molecular weight of the low-molecular weight chitoglycan is less than 20000.
As the preferred of above-mentioned technical proposal, in the step (3), the volume ratio of ethanol and water is 1 in alcohol steam:
1, the time of individual composition is 15-20min.
As the preferred of above-mentioned technical proposal, in the step (3), the temperature that is heating and curing is 70-100 DEG C, and the time is
5-10min。
Compared with prior art, the invention has the advantages that：
(1) zeolite is a kind of hydrous alumino silicates mineral of framework construction, and crystals have the empty island of many uniform pore diameters
The very big hole with inner surface, there is excellent absorption property.The present invention selects micron-sized zeolite as raw material, after swelling
The surface of silk fiber and the silk macromolecular of inside between gap become big, acted on through sonic oscillation, micron-sized zeolite meeting
Into the surface and inside of silk fiber, prepared for absorption fluorescent material.
(2) present invention selects water miscible BODIPY classes dyestuff as fluorescent dye, BODIPY classes dyestuff and traditional water
The fluorescent dyes such as dissolubility rhodamine are compared, and the fluorescence quantum yield of BODIPY class dyestuffs is high, and fluorescence spectrum half-peak breadth is narrower, has
Excellent photostability, and chemical modification is easily carried out, the pyrylium dyes of quaternary fluorine boron two and sulfonate type that the present invention selects
The technology maturation of the pyrylium dyes of fluorine boron two, optical stability is good, water-soluble good.
(3) low-molecular weight chitoglycan solution is also added in the present invention, contains abundant parent in the chitosan of low molecule amount
It water base group, can be crosslinked with the macromolecular in silk fiber, firmly be attached to the inside and surface of silk fiber.
(4) fluorescent silk fiber for preparing of the present invention, the suction-operated of zeolite is first passed through by hydrophilic BODIPY class dyestuffs
Be adsorbed in the inside and surface of silk fiber, then the crosslinked action by low-molecular weight chitoglycan and silk fiber, by zeolite and
The fixing of dye of BODIPY classes improves the conjugation of BODIPY classes dyestuff and silk fiber in the inside of silk fiber and surface, because
The fluorescence intensity of this fluorescent silk fiber prepared is high, and good light stability, color is uniform, can mass produce, and prepare
The good mechanical property of silk fiber, pliability is high, can operate with the numerous areas such as weaving, biologic medical, false proof.
Embodiment：
The present invention is described in detail below in conjunction with specific embodiment, 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) white natural silk fiber is impregnated in vibration swelling 10min in 30 DEG C of warm water after degumming process, then
It is impregnated in the aqueous solution for 50 microns of the Mn oxide modified zeolite that mass fraction is 0.5%, it is ultrasonic under 200W power
30min, take out washing, the natural silk fiber that naturally dry is pre-processed.
(2) the natural silk fiber for the pretreatment for preparing step (1), with bath raio 1:40, it is submerged initially in 5g/ml quaternary ammonium salt
The pyrylium dyes of type fluorine boron two, take out, be then immersed in the low-molecular weight chitoglycan solution that mass fraction is 2%, take out, then immerse
The 5g/ml pyrylium dyes of quaternary fluorine boron two, take out, be finally immersed in the low-molecular weight chitoglycan solution that mass fraction is 2%,
Take out drying and obtain the silk fiber of fluorescent staining；
(3) silk fiber for the fluorescent staining for preparing step (2) is 1 through volume ratio:1 alcohol steam individual composition
15min, be heating and curing at 70 DEG C 5min, and washing removes surface and combines material loosely, and drying and shaping obtains being based on BODIPY classes
The fluorescent silk fiber of dyestuff.
Embodiment 2：
(1) the natural silk fiber of yellow is impregnated in vibration swelling 30min in 45 DEG C of warm water after degumming process, then
It is impregnated in the aqueous solution for 100 microns of the Mn oxide modified zeolite that mass fraction is 5%, it is ultrasonic under 300W power
60min, take out washing, the natural silk fiber that naturally dry is pre-processed.
(2) the natural silk fiber for the pretreatment for preparing step (1), with bath raio 1:40, it is submerged initially in 15g/ml sulfonic acid
The pyrylium dyes of salt form fluorine boron two, take out, be then immersed in the low-molecular weight chitoglycan solution that mass fraction is 3%, take out, then immerse
The 15g/ml pyrylium dyes of sulfonate type fluorine boron two, take out, it is molten to be finally immersed in the low-molecular weight chitoglycan that mass fraction is 3%
Liquid, take out drying and obtain the silk fiber of fluorescent staining；
(3) silk fiber for the fluorescent staining for preparing step (2) is 1 through volume ratio:1 alcohol steam individual composition
20min, be heating and curing at 100 DEG C 10min, and washing removes surface and combines material loosely, and drying and shaping obtains being based on BODIPY
The fluorescent silk fiber of class dyestuff.
Embodiment 3：
(1) colored natural silk fiber is impregnated in vibration swelling 20min in 35 DEG C of warm water after degumming process, then
It is impregnated in the aqueous solution for 70 microns of the Mn oxide modified zeolite that mass fraction is 1%, it is ultrasonic under 250W power
40min, take out washing, the natural silk fiber that naturally dry is pre-processed.
(2) the natural silk fiber for the pretreatment for preparing step (1), with bath raio 1:40, it is submerged initially in 10g/ml quaternary ammonium
The pyrylium dyes of salt form fluorine boron two, take out, be then immersed in the low-molecular weight chitoglycan solution that mass fraction is 2.5%, take out, then soak
Enter the 10g/ml pyrylium dyes of quaternary fluorine boron two, take out, be finally immersed in the low-molecular weight chitoglycan that mass fraction is 2.5%
Solution, take out drying and obtain the silk fiber of fluorescent staining；
(3) silk fiber for the fluorescent staining for preparing step (2) is 1 through volume ratio:1 alcohol steam individual composition
15min, be heating and curing at 80 DEG C 7min, and washing removes surface and combines material loosely, and drying and shaping obtains being based on BODIPY classes
The fluorescent silk fiber of dyestuff.
Embodiment 4：
(1) white natural silk fiber is impregnated in vibration swelling 25min in 40 DEG C of warm water after degumming process, then
It is impregnated in the aqueous solution for 60 microns of the Mn oxide modified zeolite that mass fraction is 2%, it is ultrasonic under 300W power
30min, take out washing, the natural silk fiber that naturally dry is pre-processed.
(2) the natural silk fiber for the pretreatment for preparing step (1), with bath raio 1:40, it is submerged initially in 9g/ml sulfonate
The pyrylium dyes of type fluorine boron two, take out, be then immersed in the low-molecular weight chitoglycan solution that mass fraction is 2.5%, take out, then immerse
The 9g/ml pyrylium dyes of sulfonate type fluorine boron two, take out, it is molten to be finally immersed in the low-molecular weight chitoglycan that mass fraction is 2.5%
Liquid, take out drying and obtain the silk fiber of fluorescent staining；
(3) silk fiber for the fluorescent staining for preparing step (2) is 1 through volume ratio:1 alcohol steam individual composition
20min, be heating and curing at 100 DEG C 5min, and washing removes surface and combines material loosely, and drying and shaping obtains being based on BODIPY classes
The fluorescent silk fiber of dyestuff.
Embodiment 5：
(1) colored natural silk fiber is impregnated in vibration swelling 30min in 30 DEG C of warm water after degumming process, then
It is impregnated in the aqueous solution for 100 microns of the Mn oxide modified zeolite that mass fraction is 4%, it is ultrasonic under 200W power
60min, take out washing, the natural silk fiber that naturally dry is pre-processed.
(2) the natural silk fiber for the pretreatment for preparing step (1), with bath raio 1:40, it is submerged initially in 15g/ml quaternary ammonium
The pyrylium dyes of salt form fluorine boron two, take out, be then immersed in the low-molecular weight chitoglycan solution that mass fraction is 3%, take out, then immerse
The 15g/ml pyrylium dyes of sulfonate type fluorine boron two, take out, it is molten to be finally immersed in the low-molecular weight chitoglycan that mass fraction is 3%
Liquid, take out drying and obtain the silk fiber of fluorescent staining；
(3) silk fiber for the fluorescent staining for preparing step (2) is 1 through volume ratio:1 alcohol steam individual composition
20min, be heating and curing at 70 DEG C 10min, and washing removes surface and combines material loosely, and drying and shaping obtains being based on BODIPY classes
The fluorescent silk fiber of dyestuff.
Embodiment 6：
(1) the natural silk fiber of white, yellow or colour is impregnated in 35 DEG C of warm water and vibrated after degumming process
20min is swelled, then is impregnated in the aqueous solution for 50 microns of the Mn oxide modified zeolite that mass fraction is 5%, in 300W work(
Ultrasonic 50min under rate, take out washing, the natural silk fiber that naturally dry is pre-processed.
(2) the natural silk fiber for the pretreatment for preparing step (1), with bath raio 1:40, it is submerged initially in 5g/ml quaternary ammonium salt
The pyrylium dyes of type fluorine boron two, take out, be then immersed in the low-molecular weight chitoglycan solution that mass fraction is 3%, take out, then immerse
The 5g/ml pyrylium dyes of sulfonate type fluorine boron two, take out, be finally immersed in the low-molecular weight chitoglycan solution that mass fraction is 3%,
Take out drying and obtain the silk fiber of fluorescent staining；
(3) silk fiber for the fluorescent staining for preparing step (2) is 1 through volume ratio:1 alcohol steam individual composition
20min, be heating and curing at 80 DEG C 10min, and washing removes surface and combines material loosely, and drying and shaping obtains being based on BODIPY classes
The fluorescent silk fiber of dyestuff.
After testing, the fluorescence quantum yield, glimmering of the fluorescent silk fiber based on BODIPY class dyestuffs prepared by embodiment 1-6
It is luminous intensity, mechanical strength, as follows with the result of natural silk fiber：
As seen from the above table, the fluorescent silk fiber fluorescence intensity based on BODIPY class dyestuffs that prepared by the present invention is high, and light is steady
It is qualitative good, and good mechanical property.
The above-described embodiments merely illustrate the principles and effects of the present invention, not for the limitation present invention.It is any ripe
Know the personage of this technology all can carry out modifications and changes under the spirit and scope without prejudice to the present invention to above-described embodiment.Cause
This, those of ordinary skill in the art is complete without departing from disclosed spirit and institute under technological thought such as
Into all equivalent modifications or change, should by the present invention claim be covered.
Claims (9)
1. a kind of fluorescent silk fiber based on BODIPY class dyestuffs, it is characterised in that described based on the glimmering of BODIPY class dyestuffs
Light silk fiber includes natural silk fiber, zeolite, hydrophilic fluorescent dye and low-molecular weight chitoglycan, the natural silk fiber
Color can be white, yellow or colour, the zeolite be Mn oxide modified zeolite, and the hydrophilic fluorescent dye is water-soluble
Property BODIPY class dyestuffs, the particle diameter of the Mn oxide modified zeolite is 50-100 microns, the water-soluble BODIPY classes dyestuff
For the pyrylium dyes of quaternary fluorine boron two or the pyrylium dyes of sulfonate type fluorine boron two.
A kind of 2. preparation method of the fluorescent natural silk based on BODIPY class dyestuffs, it is characterised in that：Comprise the following steps：
(1) natural silk fiber is impregnated in warm water after degumming process and vibrates swelling, then be impregnated in the aqueous solution containing zeolite
In, ultrasound, take out washing, the natural silk fiber that naturally dry is pre-processed；
(2) the natural silk fiber for the pretreatment for preparing step (1), with bath raio 1:40, hydrophilic fluorescent dye is submerged initially in, is taken
Go out, be then immersed in low-molecular weight chitoglycan solution, take out, then immerse hydrophilic fluorescent dye, take out, be finally immersed in low molecule amount shell
Glycan solution, take out drying and obtain the silk fiber of fluorescent staining；
(3) silk fiber for the fluorescent staining for preparing step (2) is heating and curing, washing is gone through alcohol steam individual composition
Except surface combines material loosely, drying and shaping obtains the fluorescent silk fiber based on BODIPY class dyestuffs.
A kind of 3. preparation method of fluorescent natural silk based on BODIPY class dyestuffs according to claim 2, it is characterised in that：
In the step (1), the temperature of the warm water is 30-45 DEG C, and the time of the vibration is 10-30min.
A kind of 4. preparation method of fluorescent natural silk based on BODIPY class dyestuffs according to claim 2, it is characterised in that：
In the step (1), the mass fraction of zeolite is 0.5-5% in the aqueous solution containing zeolite.
A kind of 5. preparation method of fluorescent natural silk based on BODIPY class dyestuffs according to claim 2, it is characterised in that：
In the step (1), the ultrasonic frequency is 200-300W, and the ultrasonic time is 30-60min.
A kind of 6. preparation method of fluorescent natural silk based on BODIPY class dyestuffs according to claim 2, it is characterised in that：
In the step (2), the concentration of hydrophilic fluorescent dye is 5-15g/ml.
A kind of 7. preparation method of fluorescent natural silk based on BODIPY class dyestuffs according to claim 2, it is characterised in that：
In the step (1), the mass fraction of low-molecular weight chitoglycan solution is 2-3%, and the relative of the low-molecular weight chitoglycan is divided
Son amount is less than 20000.
A kind of 8. preparation method of fluorescent natural silk based on BODIPY class dyestuffs according to claim 2, it is characterised in that：
In the step (3), the volume ratio of ethanol and water is 1 in alcohol steam:1, the time of individual composition is 15-20min.
A kind of 9. preparation method of fluorescent natural silk based on BODIPY class dyestuffs according to claim 2, it is characterised in that：
In the step (3), the temperature being heating and curing is 70-100 DEG C, time 5-10min.
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| CN106835673A (en) * | 2017-03-27 | 2017-06-13 | 广西科技大学 | A kind of UV resistance zinc oxide silk composite fiber and preparation method thereof |
| FR3065970B1 (en) * | 2017-05-02 | 2020-12-11 | Crime Science Tech | USE OF 4-BORA-3A, 4A-DIAZA-S-INDACENES FOR THE MANUFACTURE OF FLUORESCENT FIBERS |
| CN108277644B (en) * | 2018-01-23 | 2019-09-13 | 福州大学 | A kind of flexible fluorescent cloth and preparation method thereof based on cotton |
| CN109667168A (en) * | 2018-12-25 | 2019-04-23 | 潍坊苏瑞新材料科技有限公司 | A kind of Multifunctional floating mountain flour with extremely strong dispersion level dyeing effect |
| CN109722922A (en) * | 2018-12-25 | 2019-05-07 | 潍坊苏瑞新材料科技有限公司 | A kind of alkalescent ground pumice with excellent upper dye and colour fixation |
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| CN103225217A (en) * | 2013-04-28 | 2013-07-31 | 佛山市名洲纺织有限公司 | Silk fiber knitted fabric dyeing method for achieving fluorescent color |
| CN105568718A (en) * | 2016-01-12 | 2016-05-11 | 西安交通大学 | Method for preparing fluorescence silk fibers from small soluble organic molecule |
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| CN101338189A (en) * | 2008-08-27 | 2009-01-07 | 吉林大学 | High voltage electrospinning method for preparing multi-fluorescence-encoded micro-beads |
| CN103225217A (en) * | 2013-04-28 | 2013-07-31 | 佛山市名洲纺织有限公司 | Silk fiber knitted fabric dyeing method for achieving fluorescent color |
| CN105568718A (en) * | 2016-01-12 | 2016-05-11 | 西安交通大学 | Method for preparing fluorescence silk fibers from small soluble organic molecule |
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