CN109355931A - A kind of preparation method of the multifunctional dyeing fluorescence cotton fabric based on MOF - Google Patents
A kind of preparation method of the multifunctional dyeing fluorescence cotton fabric based on MOF Download PDFInfo
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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
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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
- D06P1/52—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 synthetic macromolecular substances
- D06P1/5264—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds
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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
- 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
- D06P3/58—Material containing hydroxyl groups
- D06P3/60—Natural or regenerated cellulose
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Abstract
The preparation method of the present invention relates to a kind of multifunctional dyeing fluorescence cotton fabric based on MOF.This method comprises: prepared by Zn-MOF preliminary finish cotton fabric, the multifunctional dyeing fluorescence cotton fabric preparation based on Zn-MOF.This method technological operation is simple, high-efficient, is not necessarily to special installation, and low raw-material cost is easy to get, and is suitable for industrialized production；The multifunctional dyeing fluorescence cotton fabric fluorescence property based on Zn-MOF of preparation is excellent, while having antibacterial deodourizing, anti-mould and anti-moth, uvioresistant and the multiple performances such as fire-retardant.
Description
Technical field
The invention belongs to the preparation field of fluorescence cotton fabric, in particular to a kind of multifunctional dyeing fluorescence cotton based on MOF
The preparation method of fabric.
Background technique
As important one kind in cotton fabric product, the type for enriching cotton fabric has extremely important fluorescence cotton fabric
Meaning.Currently, common fluorescent fabric product is substantially chemical fibre product, such as terylene, acrylic fibers, polyamide fibre, and has excellent
The cotton fabric of fluorescent effect is but rarely reported.At the same time, it is applied again with fluorescence for the fluorchrome of cotton fabric dyeing process in the market
Based on material.The cotton fabric of pigment dyeing often has that colour fastness to rubbing and feel are bad, selects fluorescent dye to cotton
Textile dyeing can be very good to solve the problems, such as this, and feel is better than fluorescent paint dyed cotton fabric, and fastness is excellent, but be applicable in
It is but extremely rare in the fluorescent dye kind of cotton fabric dyeing process.
In recent years, with the metal organic framework compound (Metal-Organic of high-specific surface area and porosity
Frameworks, MOF), especially Zn-MOF, since controllable, material can be loaded with pore structure and size adjustable for it
Post-processing, structure can modify cutting and be easy to the characteristics such as functionalization, arouse widespread concern.MOF is as a kind of novel
Hybrid inorganic-organic materials, researchers are carried on surface of cotton fabric (Cellulose, 2012,19 (5): 1771-
1779；RSC Adv,2016,6(48):42324-42333；Bioengineering,2018,5(1):14；Ind Eng Chem
Res, 2018,57 (28): 9151-9161), show good application prospect.It is anti-that the cotton fabric of load MOF can be used for it
Numerous fabric functional fields such as bacterium deodorization, anti-mould and anti-moth, radiation protection, antistatic, uvioresistant, crease-resistant, fire-retardant and fluorescence.Although
The cotton fabric of load MOF has a extensive future, but is also faced with some problems, such as since interface cohesion not enough securely leads to machine
Tool performance and mechanical stability difference etc..In addition, the excellent rare earth ion of fluorescent dye or fluorescence property is wrapped in MOF
As a kind of high-efficiency fluorescence sensor application in sensing or detection cation, anion, small molecule, steam and easy explosive etc.
Aspect also has become one of direction that researchers are mainly studied (Chem-Eur J, 2015,21 (27): 9748-
9752；ACS Appl Mater Inter,2017,9(29):24671-24677；J Mater Chem C,2017,5(19):
4661-4669).But as most compounds, the application of powdered MOF be also required to face its dissolve melting property difference and
The disadvantages of machinability is poor.Therefore, how to overcome problem above, develop a kind of fluorescent dyeing based on MOF and efficient
Stable fluorescence cotton fabric has important practical value.
Currently, the method that surface of cotton fabric synthesis MOF is mainly used has: solvent-thermal process method, hydrothermal synthesis method, microwave close
Cheng Fa, ultrasonic, ion thermal synthesis method, electrochemical synthesis and mechanosynthesis etc. (2018, Hebei industrial technology, 35
(1):72-76)。
Summary of the invention
The preparation of technical problem to be solved by the invention is to provide a kind of multifunctional dyeing fluorescence cotton fabric based on MOF
Method, to overcome, the cotton fabric fluorescent effect of carried metal organic framework compounds in the prior art is bad, illumination mode is single
And the defects of Zn-MOF and cotton fabric room machine performance and poor mechanical stability.
It is proposed of the invention innovative by Zn-MOF by fluorescent dye and rare earth ion package and high-efficient carrier in
Surface of cotton fabric comprehensively utilizes the mutual synergistic effect between Zn-MOF composite construction Subjective and Objective, improves its luminous efficiency, changes
Its single illumination mode, while brittle Zn-MOF and flexible cotton fabric room machine are effectively solved by way of LBL self-assembly
The problem of performance and mechanical stability difference, to realize extensive use of the fluorescent dye on cotton fabric, this is fluorescence cotton fabric
Exploitation provide a kind of new preparation method for being different from traditional dyeing process.Zn-MOF is passed through LBL self-assembly by the present invention
Mode deposit to surface of cotton fabric, be compared with other methods, equipment is simple, and reaction temperature is low, and energy consumption is small, take water as a solvent,
Liquid waste processing difficulty is low.
The present invention prepares a kind of cotton fabric with multiple performance based on Zn-MOF.The present invention be prepared based on
The multifunctional dyeing fluorescence cotton fabric of Zn-MOF is except having the function of antibacterial deodourizing, anti-mould and anti-moth, uvioresistant and fire-retardant etc. traditional
It arranges outside characteristic and conventional color development, tinctorial property, also there is good thermal stability, fluorescent stability and higher hair
Light efficiency, fluorescence property are excellent.
A kind of preparation method of multifunctional dyeing fluorescence cotton fabric based on MOF of the invention, comprising:
(1) cotton fabric is successively used to zinc salt solution, polybasic carboxylic acid aqueous solution preliminary finish, above-mentioned preliminary finish is repeated, obtains
Zn-MOF preliminary finish cotton fabric, wherein the molar ratio of zinc salt and polybasic carboxylic acid is 1:1-1:5；
(2) by preliminary finish cotton fabric dip dyeing in fluorescent dye solution in step (1), fabric rinsing is taken out, is dried,
Zn-MOF dyed cotton fabric is obtained, then impregnates the cotton fabric in rare earth salt aqueous solution, takes out fabric washing, drying obtains
To the multifunctional dyeing fluorescence cotton fabric based on Zn-MOF；
Or impregnate preliminary finish cotton fabric in step (1) in rare earth salt aqueous solution, fabric washing is taken out, drying obtains
To the fluorescence cotton fabric based on Zn-MOF, then by the cotton fabric in fluorescent dye solution dip dyeing, take out fabric rinsing,
It dries, obtains the multifunctional dyeing fluorescence cotton fabric based on Zn-MOF；
Wherein, the dosage of fluorescent dye is 0.02%-10.0%owf, and the concentration of rare earth salt aqueous solution is 0.001-
0.1mol/L。
Zinc salt is at least one of zinc acetate, zinc chloride, zinc nitrate and zinc sulfate in the step (1).
Polybasic carboxylic acid is terephthalic acid (TPA), trimesic acid, Pyromellitic Acid, 2- amino to benzene two in the step (1)
Formic acid, 2,5- dihydric para-phthalic acid, 4- oxo -1,4- dihydro -2,6- pyridinedicarboxylic acid, pyridine -2,6- dicarboxylic acids, fourth two
At least one of acid, glutaric acid, citric acid, butane tetracarboxylic acid and biphenyl dicarboxylic acid.
Cotton fabric is successively used to zinc salt solution, polybasic carboxylic acid aqueous solution preliminary finish specifically: by cotton in the step (1)
Fabric impregnates in zinc salt solution, takes out cotton fabric washing, then drying impregnates cotton fabric in polybasic carboxylic acid solution,
Cotton fabric washing is taken out, drying, wherein zinc salt solution concentration is 0.2-1.2mol/L, and polybasic carboxylic acid concentration of aqueous solution is 0.1-
0.6mol/L。
The dipping bath ratio is 1:5-1:50, and dipping temperature is 70-75 DEG C, and dip time is 2-10min.
The washing temperature is room temperature；Drying temperature is 80-120 DEG C, and drying time is 10-30min.
The number that above-mentioned preliminary finish is repeated in the step (1) is 1-16 times.
Cotton fabric is pre-processed with zinc salt solution and with the technique item of polybasic carboxylic acid aqueous solution preliminary finish in the step (1)
Part is identical.
Fluorescent dye is rhodamine 6G, crystal violet, rhodamine B, acridine orange, Safranine O, calcein in the step (2)
At least one of with methylene blue；The solvent of fluorescent dye solution is chloroform.
Rare-earth salts is at least one of europium salt, samarium salt, terbium salt and dysprosium salt in the step (2).
The europium salt is at least one of acetic acid europium, Europium chloride, europium nitrate and europium sulfate.
The samarium salt is at least one of acetic acid samarium, samarium trichloride, samaric nitrate and samarium sulphate.
The terbium salt is at least one of acetic acid terbium, terbium chloride, terbium nitrate and sulfuric acid terbium.
The dysprosium salt is at least one of acetic acid dysprosium, dysprosium chloride, dysprosium nitrate and dysprosium sulfate.
Dip dyeing bath raio is 1:5-1:50 in the step (2), and dip dyeing temperature is 20-40 DEG C, dipping dye
The color time is 12-48h.
Rinsing is carried out in chloroform in the step (2).
Dipping bath ratio is 1:5-1:50 in the step (2), and dipping temperature is 20-40 DEG C, and dip time is 6-
24h。
Drying temperature is 80-120 DEG C in the step (2), and drying time is 10-45min.
The present invention due to Zn-MOF can by simple alternate cycles impregnation method uniform load in surface of cotton fabric, from
And Zn-MOF cotton fabric is made to show wide application prospect in various fields, such as be used for antibacterial, uvioresistant and fire-retardant neck
Domain.Further, since Zn-MOF has porosity and big specific surface area, fluorescent dye and excellent fluorescence can be introduced inside it
The rare earth ion of performance, to assign its new fluorescent characteristic.Fluorescent dye and rare earth ion are combined and are introduced into Zn-MOF simultaneously
It is carried on cotton fabric, can be assigned using the synergistic effect between zinc ion, polybasic carboxylic acid, fluorescent dye and rare earth ion
The excellent fluorescence property of cotton fabric is given, the fields such as high-performance apparel, anti-fake, detection and security information can be applied to.The present invention
Based on the principle provide it is a kind of it is easy to operate, raw material is cheap is easy to get, suitable for the multifunctional dyeing based on MOF of large-scale production
The preparation method of fluorescence cotton fabric.During the preparation process, cotton fabric impregnates in the aqueous solution of zinc salt, fabric and zinc ion physics
Absorption combines, and impregnates, makes polynary in the aqueous solution of polybasic carboxylic acid under process conditions identical with zinc salt solution later
The compound to be formed with specific skeleton structure and composition is complexed in carboxylic acid and the zinc ion of fabric surface load, repeats above step
After certain number, Zn-MOF preliminary finish cotton fabric is obtained by way of LBL self-assembly.Zn-MOF preliminary finish cotton fabric passes through
The chloroform dye liquor of fluorescent dye dip dyeing at a certain temperature, obtains Zn-MOF dyed cotton fabric, then by the dyeing
Cotton fabric is impregnated in rare earth salt aqueous solution at a certain temperature, and (or Zn-MOF preliminary finish cotton fabric is impregnated at a certain temperature
In rare earth salt aqueous solution, obtain the fluorescence cotton fabric based on Zn-MOF, then by the fluorescence cotton fabric fluorescent dye trichlorine
Dip dyeing under certain temperature in dichloromethane.).After arrangement, while providing cotton fabric certain function and color, original is utilized
Expect the synergistic effect between several persons, can be further improved the fluorescence efficiency of fluorescence cotton fabric, finally obtains a kind of efficient, steady
It is fixed, lasting with antibacterial deodourizing, anti-mould and anti-moth, uvioresistant and flame retardant property the multifunctional dyeing fluorescence cotton based on Zn-MOF
Fabric.The preparation method is not limited solely to cotton fabric, by non-cotton fabric by that can also apply the present invention after certain processing
Obtain the non-cotton fabric of multifunctional dyeing fluorescence based on Zn-MOF.
Beneficial effect
(1) fluorescent dye and rare earth ion are combined and are introduced into Zn-MOF by the present invention, pass through zinc ion, polynary carboxylic
Synergistic effect between acid, fluorescent dye and rare earth ion, can be improved the multifunctional dyeing fluorescence cotton based on Zn-MOF
The luminous efficiency of fabric.
(2) zinc salt, polybasic carboxylic acid used in preparation process of the present invention and rare-earth salts are nontoxic, reduce at waste liquid
The difficulty and resource input of reason, reduce the discharge of waste water.
(3) preparation process of the present invention is easy to operate, high production efficiency, is not necessarily to special installation, and low raw-material cost is easy to get,
Suitable for industrialized production.
(4) the multifunctional dyeing fluorescence cotton fabric prepared by the present invention based on Zn-MOF have antibacterial deodourizing, anti-mould and anti-moth,
Uvioresistant and the multiple performances such as fire-retardant, and these performances can be supported on cotton fabric well by Zn-MOF, washed, rubbed
Performance can still be kept for a long time afterwards.
(5) the multifunctional dyeing fluorescence cotton fabric prepared by the present invention based on Zn-MOF is a kind of excellent new and effective glimmering
Luminescent material has good thermal stability, fluorescent stability and higher luminous efficiency, can be in high-performance apparel, anti-fake, detection
There is extraordinary application prospect with fields such as security informations.
(6) it is suitable for other non-cotton fabrics.
Detailed description of the invention
Fig. 1 is scanning electron microscope (SEM) figure of the multifunctional dyeing fluorescence cotton fabric based on Zn-MOF prepared by embodiment 1.
Fig. 2 is X-ray diffraction (XRD) figure of the multifunctional dyeing fluorescence cotton fabric based on Zn-MOF prepared by embodiment 1.
Fig. 3 is the fluorogram of the multifunctional dyeing fluorescence cotton fabric based on Zn-MOF prepared by embodiment 1, excitation wavelength
For 281nm (λex=281nm).
Fig. 4 is the fluorogram of the multifunctional dyeing cotton fabric based on Zn-MOF prepared by comparative example 3, and excitation wavelength is
281nm(λex=281nm).
Fig. 5 is the fluorogram of the Multifunction fluorescent cotton fabric based on Zn-MOF prepared by comparative example 4, and excitation wavelength is
281nm(λex=281nm).
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Zinc acetate as used in the following examples, zinc chloride, zinc nitrate, zinc sulfate, terephthalic acid (TPA), equal benzene front three
Acid, Pyromellitic Acid, citric acid, butane tetracarboxylic acid, rhodamine 6G, crystal violet, rhodamine B, acridine orange, Zang Hong O, three chloromethanes
Alkane, acetic acid europium, Europium chloride, samarium trichloride, terbium nitrate and dysprosium sulfate etc. are commercial goods.
Embodiment 1
(1) the aqueous terephthalic acid solution B of the zinc acetate aqueous solution A and 0.4mol/L of 0.8mol/L are prepared respectively.Cotton is knitted
Object impregnates 5min, bath raio 1:50 at 70-75 DEG C in solution A, and room temperature is washed, and dries 30min at 80 DEG C；Later with it is molten
It impregnates, washes in solution B under the identical process conditions of liquid A, drying.After repeating above step 8 times, Zn-MOF preliminary finish is obtained
Cotton fabric.
(2) chloroform soln C, the bath raio 1:50 of rhodamine 6G dosage 4.0%owf are prepared, by Zn-MOF at 20 DEG C
Preliminary finish cotton fabric dip dyeing in solution C takes out after 48 hours, rinses, dries in chloroform, obtains Zn-MOF dye
Color cotton fabric.It prepares the acetic acid europium aqueous solution D of 0.1mol/L, Zn-MOF dyed cotton fabric is impregnated 12 in solution D at 20 DEG C
It is taken out after hour, bath raio 1:50, washing, dries 45min at 80 DEG C, obtain the multifunctional dyeing fluorescence cotton based on Zn-MOF and knit
Object.The multifunctional dyeing fluorescence cotton fabric based on Zn-MOF is all larger than the bacteriostasis rate of staphylococcus aureus and Escherichia coli
99%, uvioresistant performance UPF are 50+, and washable, resistance to unlubricated friction, moisture-proof fastness of rubbing are 4-5 grade, and limit oxygen index LOI is 21；This
Cotton fabric is resistant to 400 DEG C or more of high temperature, and fluorescence lifetime 1.023ms has good stability, and fluorescence quantum yield is
32.36%, luminous efficiency is higher, and ultraviolet light (281nm), which irradiates lower cotton fabric, becomes bright-coloured jewel from the pale pink under daylight
Red, be protected from light storage 90 days it is unchanged, can satisfy application requirement.
Fig. 1 shows: the Zn-MOF uniform fold of synthesis is on the surface of the fluorescent staining cotton fabric of preparation, and Zn-MOF shape
For needle shape.
Fig. 2 shows: the XRD spectra of the compound of surface of cotton fabric covering and the XRD spectra of known in the literature Zn-MOF
Unanimously, it can illustrate that the compound is target product Zn-MOF.
Fig. 3 shows: in the fluorogram of the multifunctional dyeing fluorescence cotton fabric based on Zn-MOF 589nm, 614nm,
Occurs strong absorption peak at 649nm and 696nm, the characteristic peak of these absorption peaks and rhodamine 6G and acetic acid europium is almost the same, position
It sets and slightly offsets, wherein the characteristic peak of 580nm of rhodamine 6G or so is influenced by the characteristic peak of the 593nm of acetic acid europium or so, is made
The characteristic peak for obtaining the two is overlapped, and the absorption peak strength of 589nm and 696nm is caused to increase, compared with Fig. 5, acetic acid europium feature peak intensity
Degree increases obviously, and position is slightly offset, this shows to generate strong collaboration between the rhodamine 6G introduced, acetic acid europium and Zn-MOF
Effect, so that the fluorescence intensity of the cotton fabric increases, luminous efficiency is improved.
Embodiment 2
(1) the trimesic acid aqueous solution B of the solder(ing)acid A and 0.4mol/L of 0.6mol/L are prepared respectively.Cotton is knitted
Object impregnates 5min, bath raio 1:50 at 70-75 DEG C in solution A, and room temperature is washed, and dries 25min at 90 DEG C；Later in it is molten
It impregnates, washes in solution B under the identical process conditions of liquid A, drying.After repeating above step 8 times, Zn-MOF preliminary finish is obtained
Cotton fabric.
(2) chloroform soln C, the bath raio 1:50 of crystal violet dosage 2.0%owf are prepared, it is at 25 DEG C that Zn-MOF is pre-
Finishing of cotton textiles dip dyeing in solution C takes out after 36 hours, rinses, dries in chloroform, obtains Zn-MOF dyeing
Cotton fabric.The Europium chloride aqueous solution D of 0.05mol/L is prepared, it is small that Zn-MOF dyed cotton fabric is impregnated to 12 in solution D at 25 DEG C
When after take out, bath raio 1:50, washing dries 30min at 90 DEG C, obtains the multifunctional dyeing fluorescence cotton based on Zn-MOF and knit
Object.The multifunctional dyeing fluorescence cotton fabric based on Zn-MOF is all larger than the bacteriostasis rate of staphylococcus aureus and Escherichia coli
99%, uvioresistant performance UPF are 50+, and washable, resistance to unlubricated friction, moisture-proof fastness of rubbing are 4-5 grade, and limit oxygen index LOI is 21；This
Cotton fabric is resistant to 400 DEG C or more of high temperature, and fluorescence lifetime 1.002ms has good stability, and fluorescence quantum yield is
28.13%, luminous efficiency is higher, and ultraviolet light (281nm), which irradiates lower cotton fabric, becomes bright-coloured orchid purple from the lavender under daylight
Color, be protected from light storage 90 days it is unchanged, can satisfy application requirement.
Embodiment 3
(1) the Pyromellitic Acid aqueous solution B of the zinc nitrate aqueous solution A and 0.1mol/L of 0.4mol/L are prepared respectively.Cotton is knitted
Object impregnates 8min, bath raio 1:20 at 70-75 DEG C in solution A, and room temperature is washed, and dries 20min at 100 DEG C；Later in
It impregnates, washes in solution B under the identical process conditions of solution A, drying.After repeating above step 12 times, it is pre- to obtain Zn-MOF
Finishing of cotton textiles.
(2) the samarium trichloride aqueous solution C of 0.01mol/L is prepared, soaks Zn-MOF preliminary finish cotton fabric in solution C at 30 DEG C
Stain is taken out after 18 hours, bath raio 1:20, washing, dries 20min at 100 DEG C, obtains the fluorescence cotton fabric based on Zn-MOF.Match
The chloroform soln D of rhodamine B dosage 1.0%owf processed, bath raio 1:20 knit the fluorescence cotton based on Zn-MOF at 30 DEG C
Object dip dyeing in solution D takes out after 24 hours, rinses, dries in chloroform, obtains based on the multi-functional of Zn-MOF
Fluorescent staining cotton fabric.The multifunctional dyeing fluorescence cotton fabric based on Zn-MOF is to staphylococcus aureus and Escherichia coli
Bacteriostasis rate is all larger than 99%, and uvioresistant performance UPF is 50+, and washable, resistance to unlubricated friction, moisture-proof fastness of rubbing are 4-5 grades, and limit oxygen refers to
Number LOI is 21；This cotton fabric is resistant to 400 DEG C or more of high temperature, and fluorescence lifetime 1.008ms has good stability, fluorescence volume
Sub- yield be 30.18%, luminous efficiency is higher, be protected from light storage 90 days it is unchanged, can satisfy application requirement.
Embodiment 4
(1) the aqueous citric acid solution B of the zinc sulfate solution A and 0.2mol/L of 0.4mol/L are prepared respectively.Cotton fabric in
8min, bath raio 1:20 are impregnated at 70-75 DEG C in solution A, room temperature is washed, and dries 20min at 100 DEG C；Later in solution A
It impregnates, washes in solution B under identical process conditions, drying.After repeating above step 12 times, Zn-MOF preliminary finish cotton is obtained
Fabric.
(2) chloroform soln C, the bath raio 1:20 of acridine orange dosage 0.5%owf are prepared, it is at 35 DEG C that Zn-MOF is pre-
Finishing of cotton textiles dip dyeing in solution C takes out after 18 hours, rinses, dries in chloroform, obtains Zn-MOF dyeing
Cotton fabric.The terbium nitrate aqueous solution D of 0.01mol/L is prepared, it is small that Zn-MOF dyed cotton fabric is impregnated to 15 in solution D at 35 DEG C
When after take out, bath raio 1:20, washing dries 20min at 100 DEG C, obtains the multifunctional dyeing fluorescence cotton based on Zn-MOF and knit
Object.The multifunctional dyeing fluorescence cotton fabric based on Zn-MOF is all larger than the bacteriostasis rate of staphylococcus aureus and Escherichia coli
99%, uvioresistant performance UPF are 50+, and washable, resistance to unlubricated friction, moisture-proof fastness of rubbing are 4-5 grade, and limit oxygen index LOI is 21；This
Cotton fabric is resistant to 400 DEG C or more of high temperature, and fluorescence lifetime 0.876ms has good stability, and fluorescence quantum yield is
27.96%, luminous efficiency is higher, be protected from light storage 90 days it is unchanged, can satisfy application requirement.
Embodiment 5
(1) the butane tetracarboxylic aqueous acid B of the zinc nitrate aqueous solution A and 0.1mol/L of 0.2mol/L are prepared respectively.Cotton is knitted
Object impregnates 10min, bath raio 1:10 at 70-75 DEG C in solution A, and room temperature is washed, and dries 10min at 120 DEG C；Later in
It impregnates, washes in solution B under the identical process conditions of solution A, drying.After repeating above step 16 times, it is pre- to obtain Zn-MOF
Finishing of cotton textiles.
(2) the dysprosium sulfate aqueous solution C of 0.001mol/L is prepared, at 40 DEG C by Zn-MOF preliminary finish cotton fabric in solution C
Dipping takes out after 24 hours, bath raio 1:10, washing, dries 10min at 120 DEG C, obtains the fluorescence cotton fabric based on Zn-MOF.
The chloroform soln D of Safranine O dosage 0.1% (owf), bath raio 1:10 are prepared, by the fluorescence cotton based on Zn-MOF at 40 DEG C
Fabric dip dyeing in solution D takes out in 12 hours, rinses, dries in chloroform, obtains more function based on Zn-MOF
It can fluorescent staining cotton fabric.The multifunctional dyeing fluorescence cotton fabric based on Zn-MOF is to staphylococcus aureus and Escherichia coli
Bacteriostasis rate be all larger than 99%, uvioresistant performance UPF is 50+, and washable, resistance to unlubricated friction, moisture-proof fastness of rubbing are 4-5 grades, limit oxygen
Index LOI is 21；This cotton fabric is resistant to 400 DEG C or more of high temperature, and fluorescence lifetime 0.885ms has good stability, fluorescence
Quantum yield is 28.04%, and luminous efficiency is higher, be protected from light storage 90 days it is unchanged, can satisfy application requirement.
Comparative example 1
The chloroform soln A of rhodamine 6G dosage 4.0%owf, bath raio 1:50 are prepared, by common cotton fabric at 20 DEG C
Dip dyeing takes out after 48 hours in solution A, rinses in chloroform, dries, and obtains dyed cotton fabric.The dyed cotton is knitted
Washable, resistance to unlubricated friction, the moisture-proof of object fastness of rubbing are 3-4 grades, and limit oxygen index LOI is 18, and fluorescence property is very poor, almost without glimmering
Optical phenomenon, be protected from light storage 90 days it is unchanged.
Comparative example 2
The acetic acid europium water solution A of 0.1mol/L is prepared, is taken after common cotton fabric is impregnated 12 hours in solution A at 20 DEG C
Out, bath raio 1:50 is washed, and is dried 45min at 80 DEG C, is obtained rare-earth salt processing cotton fabric.The rare-earth salt processing cotton fabric
Washable, resistance to unlubricated friction, moisture-proof fastness of rubbing are 3-4 grades, and limit oxygen index LOI is 18, and fluorescence lifetime is extremely short, only 0.028ms,
Stability is very poor, and fluorescence quantum yield 1.79%, luminous efficiency is very poor, be protected from light storage 90 days it is unchanged.
Comparative example 3
(1) the aqueous terephthalic acid solution B of the zinc acetate aqueous solution A and 0.4mol/L of 0.8mol/L are prepared respectively.Cotton is knitted
Object impregnates 5min, bath raio 1:50 at 70-75 DEG C in solution A, and room temperature is washed, and dries 30min at 80 DEG C；Later with it is molten
It impregnates, washes in solution B under the identical process conditions of liquid A, drying.After repeating above step 8 times, Zn-MOF preliminary finish is obtained
Cotton fabric.
(2) chloroform soln C, the bath raio 1:50 of rhodamine 6G dosage 4.0%owf are prepared, by Zn-MOF at 20 DEG C
Preliminary finish cotton fabric dip dyeing in solution C takes out after 48 hours, rinses, dries in chloroform, obtains based on Zn-
The multifunctional dyeing cotton fabric of MOF.The multifunctional dyeing cotton fabric based on Zn-MOF is to staphylococcus aureus and large intestine bar
The bacteriostasis rate of bacterium is all larger than 99%, and uvioresistant performance UPF is 50+, and washable, resistance to unlubricated friction, moisture-proof fastness of rubbing are 4-5 grades, the limit
Oxygen index (OI) LOI is 21；This cotton fabric is resistant to 400 DEG C or more of high temperature, and compared with Example 1, fluorescence lifetime is very short, only
0.198ms, stability is very poor, and fluorescence quantum yield is only 5.78%, poor light emission efficiency, and ultraviolet light (281nm) irradiates lower cotton
Fabric becomes bright-coloured bluish violet from the pale pink under daylight, be protected from light storage 90 days it is unchanged.
Fig. 4 shows: occur absorption peak at 579nm in the fluorogram of the multifunctional dyeing cotton fabric based on Zn-MOF,
This is almost the same with the characteristic peak of the common cotton rhodamine 6G dyeing of known in the literature, and position is slightly offset, and illustrates rhodamine
There is certain synergistic effect between 6G and Zn-MOF.
Comparative example 4
(1) the aqueous terephthalic acid solution B of the zinc acetate aqueous solution A and 0.4mol/L of 0.8mol/L are prepared respectively.Cotton is knitted
Object impregnates 5min, bath raio 1:50 at 70-75 DEG C in solution A, and room temperature is washed, and dries 30min at 80 DEG C；Later with it is molten
It impregnates, washes in solution B under the identical process conditions of liquid A, drying.After repeating above step 8 times, Zn-MOF preliminary finish is obtained
Cotton fabric.
(2) the acetic acid europium aqueous solution C of 0.1mol/L is prepared, impregnates Zn-MOF dyed cotton fabric in solution C at 20 DEG C
It takes out, bath raio 1:50, washes after 12 hours, dry 45min at 80 DEG C, obtain the Multifunction fluorescent cotton based on Zn-MOF and knit
Object.The Multifunction fluorescent cotton fabric based on Zn-MOF is all larger than the bacteriostasis rate of staphylococcus aureus and Escherichia coli
99%, uvioresistant performance UPF are 50+, and washable, resistance to unlubricated friction, moisture-proof fastness of rubbing are 4-5 grade, and limit oxygen index LOI is 21；This
Cotton fabric is resistant to 400 DEG C or more of high temperature, and compared with Example 1, fluorescence lifetime is shorter, be 0.499ms, stability compared with
Difference, fluorescence quantum yield 14.65%, luminous efficiency is poor, and ultraviolet light (281nm) irradiates lower cotton fabric by the light powder under daylight
Discoloration be dark violet red, be protected from light storage 90 days it is unchanged.
Fig. 5 shows: in the fluorogram of the Multifunction fluorescent cotton fabric based on Zn-MOF in 587nm, 611nm, 648nm and
Occurring stronger absorption peak at 694nm, this is almost the same with the characteristic peak of known in the literature acetic acid europium, and position is slightly offset,
Compared with Fig. 3, intensity is smaller, illustrates there is synergistic effect between acetic acid europium and Zn-MOF.
Claims (10)
1. a kind of preparation method of the multifunctional dyeing fluorescence cotton fabric based on MOF, comprising:
(1) cotton fabric is successively used to zinc salt solution, polybasic carboxylic acid aqueous solution preliminary finish, above-mentioned preliminary finish is repeated, obtains Zn-
MOF preliminary finish cotton fabric, wherein the molar ratio of zinc salt and polybasic carboxylic acid is 1:1-1:5；
(2) by preliminary finish cotton fabric dip dyeing in fluorescent dye solution in step (1), fabric rinsing is taken out, dries, obtains
Then Zn-MOF dyed cotton fabric impregnates the cotton fabric in rare earth salt aqueous solution, take out fabric washing, and drying obtains base
In the multifunctional dyeing fluorescence cotton fabric of Zn-MOF；
Or impregnate preliminary finish cotton fabric in step (1) in rare earth salt aqueous solution, fabric washing is taken out, drying obtains base
In the fluorescence cotton fabric of Zn-MOF, then by the cotton fabric, dip dyeing, taking-up fabric rinsing dry in the air in fluorescent dye solution
It is dry, obtain the multifunctional dyeing fluorescence cotton fabric based on Zn-MOF；
Wherein, the dosage of fluorescent dye is 0.02%-10.0%owf, and the concentration of rare earth salt aqueous solution is 0.001-0.1mol/L.
2. the method according to claim 1, wherein zinc salt is zinc acetate, zinc chloride, nitre in the step (1)
At least one of sour zinc and zinc sulfate；Polybasic carboxylic acid is terephthalic acid (TPA), trimesic acid, Pyromellitic Acid, 2- amino pair
Phthalic acid, 2,5- dihydric para-phthalic acid, 4- oxo -1,4- dihydro -2,6- pyridinedicarboxylic acid, pyridine -2,6- dicarboxylic acids,
At least one of succinic acid, glutaric acid, citric acid, butane tetracarboxylic acid and biphenyl dicarboxylic acid.
3. the method according to claim 1, wherein successively using zinc salt water-soluble cotton fabric in the step (1)
Liquid, polybasic carboxylic acid aqueous solution preliminary finish specifically: cotton fabric is impregnated in zinc salt solution, cotton fabric washing is taken out, dries,
Then cotton fabric is impregnated in polybasic carboxylic acid aqueous solution, takes out cotton fabric washing, drying, wherein zinc salt solution concentration is
0.2-1.2mol/L, polybasic carboxylic acid concentration of aqueous solution are 0.1-0.6mol/L.
4. according to the method described in claim 3, dipping temperature is equal it is characterized in that, dipping bath ratio is 1:5-1:50
It is 70-75 DEG C, dip time is 2-10min.
5. according to the method described in claim 3, it is characterized in that, the washing temperature is room temperature；Drying temperature is 80-
120 DEG C, drying time is 10-30min.
6. the method according to claim 1, wherein cotton fabric zinc salt solution is pre- whole in the step (1)
It manages identical with the process conditions of polybasic carboxylic acid aqueous solution preliminary finish；The number for repeating above-mentioned preliminary finish is 1-16 times.
7. the method according to claim 1, wherein fluorescent dye is rhodamine 6G, crystallization in the step (2)
At least one of purple, rhodamine B, acridine orange, Safranine O, calcein and methylene blue；The solvent of fluorescent dye solution is three
Chloromethanes；Rare-earth salts is at least one of europium salt, samarium salt, terbium salt and dysprosium salt.
8. the method according to the description of claim 7 is characterized in that the europium salt is acetic acid europium, Europium chloride, europium nitrate and sulfuric acid
At least one of europium；Samarium salt is at least one of acetic acid samarium, samarium trichloride, samaric nitrate and samarium sulphate；Terbium salt is acetic acid terbium, chlorine
Change at least one of terbium, terbium nitrate and sulfuric acid terbium；Dysprosium salt is at least one in acetic acid dysprosium, dysprosium chloride, dysprosium nitrate and dysprosium sulfate
Kind.
9. the method according to claim 1, wherein dip dyeing bath raio is 1:5-1 in the step (2):
50, dip dyeing temperature is 20-40 DEG C, and the dip dyeing time is 12-48h；Rinsing is carried out in chloroform.
10. the method according to claim 1, wherein dipping bath ratio is 1:5-1:50 in the step (2),
Dipping temperature is 20-40 DEG C, and dip time is 6-24h；Drying temperature is 80-120 DEG C, and drying time is 10-
45min。
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