CN109825108A - A kind of red reactive dyes and its method that cotton fiber is contaminated in non-aqueous media - Google Patents
A kind of red reactive dyes and its method that cotton fiber is contaminated in non-aqueous media Download PDFInfo
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Abstract
The invention discloses a kind of red reactive dyes, structure is shown in formula I:Wherein, R1、R2It is each independently selected from hydrogen, substituted or unsubstituted C1‑C4Alkyl；X is F, Cl or Br；R3、R4It is each independently selected from C1‑C4Alkoxy, halogen, hydroxyl, sulfonic group；D1、D2It is each independently selected from substituted-phenyl；The red reactive dyes of the invention solubility with higher and to cotton fiber affinity with higher in non-aqueous media, can be to contaminate on higher dye-uptake onto cotton fiber；Meanwhile corresponding part does not anchor at the hydrolised dye on fiber and is very easy to cleaning.
Description
Technical field
The invention belongs to technical field of fine, it is related to a kind of red reactive dyes, preparation method and its non-aqueous
The method of cotton fiber is contaminated in medium.
Background technique
Reactive dye are the preferred dyestuffs of cotton fiber dyeing, have more excellent every fastness.Existing commercial activity dye
Material is thus a large amount of colorful wastewaters to be generated after dyeing in water to cotton fiber dyeing, not to the protection of water environment
Benefit.China is printing and dyeing big country, every year because the dyeing waste water total amount that dyeing generates accounts for the 1/4 of industrial wastewater total amount.It is existing commercial
Reactive dye cannot adapt to the dyeing condition in non-aqueous media completely, and main performance is that dye-uptake is not high, cause larger amount of work
Property dyestuff rests in dyeing medium.
In view of this, it is necessary to develop a kind of reactive dye that cotton fiber can be contaminated in non-aqueous media.
Summary of the invention
The first purpose of the invention is to provide a kind of red reactive dyes.
A second object of the present invention is to provide a kind of preparation methods of red reactive dyes.
Third object of the present invention is to provide the sides that a kind of red reactive dyes contaminate cotton fiber in non-aqueous media
Method.
To achieve the goals above, The technical solution adopted by the invention is as follows:
The first aspect of the invention provides a kind of red reactive dyes, and structure is shown in formula I:
Wherein, R1、R2It is each independently selected from hydrogen, substituted or unsubstituted C1-C4Alkyl；
X is F, Cl or Br；
R3、R4It is each independently selected from C1-C4Alkoxy, halogen, hydroxyl, sulfonic group；
D1、D2It is each independently selected from substituted-phenyl；
Compound shown in Formulas I at least contains 2 sulfonic groups, preferably 3~8 sulfonic groups, and each sulfonic group is independent of one another, respectively
From the form for free acid form or (preferably) sulfonate.
Currently preferred compound is, in Formulas I, D1、D2It is each independently selected from one kind of following substituent group:
The most preferred compound of the present invention is with one kind of flowering structure:
The second aspect of the invention provides a kind of preparation method of red reactive dyes, comprising the following steps:
Step 1: paraphenetidine -3- sulfonic acid is soluble in water, salt acid for adjusting pH < 3 that concentration is 30%, cryosel is added dropwise
0-5 DEG C of temperature of bath control, excessive sodium nitrite is configured to the aqueous solution that concentration is 30%, is slowly added dropwise into above-mentioned p-aminophenyl
In methyl ether -3- sulfonic acid solutions, after being added dropwise completely, keeps 0-5 DEG C of temperature and pH < 3 to react, sulfamic acid, the product of generation is added
It is the water slurry of paraphenetidine -3- sulfonic acid diazonium salt for compound 1；
Step 2: J acid is soluble in water, the molar ratio of J acid and paraphenetidine -3- sulfonic acid is 1:1, is 30% with concentration
Hydrochloric acid adjust pH=5-6, ice salt bath control 0-5 DEG C of reaction temperature, above compound 1 i.e. paraphenetidine-is slowly added dropwise
The water slurry of 3- sulfonic acid diazonium salt keeps 0-5 DEG C of temperature and pH=5-6 to react, and the product of generation is the water-soluble of compound 2
Liquid；
Step 3: Cyanuric Chloride is soluble in water, the molar ratio of Cyanuric Chloride and paraphenetidine -3- sulfonic acid is 1:1, cold
But to 0-5 DEG C, the aqueous solution of compound 2 is added dropwise to wherein, during which controls pH value of solution=5-6, keeps 0-5 DEG C of temperature and pH=
5-6 reaction, the product of generation are the aqueous solution of compound 3；
Step 4: H acid is soluble in water, the molar ratio of H acid and paraphenetidine -3- sulfonic acid is 1:1, then is with concentration
10% NaOH aqueous solution adjusts pH=7, this solution is added drop-wise in the aqueous solution of above compound 3, during which control reaction temperature
30-35 DEG C of degree, and the NaOH aqueous solution that concentration is 5% is constantly added dropwise and controls reactant pH=5-6, kept for 30-35 DEG C of temperature
It is reacted with pH=5-6, the product of generation is the aqueous solution of compound 4；
Step 5: 2,4- diamino benzene sulfonic acids are soluble in water, equimolar 2,3-, bis- bromo propionyl chloro is instilled, during which constantly
The sodium bicarbonate solution that concentration is 10% is added dropwise, adjusts pH=5-6, drop finishes, and keeps pH=5-6 reaction, and the product of generation is to change
Close the aqueous solution of object 5；
Step 6: the aqueous solution of compound 5 is cooled to 0-5 DEG C, salt acid for adjusting pH < 3 for being 30% with concentration are slowly dripped
Add excessive nitrite sodium water solution, drop finishes, insulation reaction, and sulfamic acid is added, and the product of generation is the aqueous suspension of compound 6
Liquid；
Step 7: at room temperature, the water slurry of the compound 6 of the 6th step preparation to be added drop-wise to the compound of the 4th step preparation
In 4 aqueous solution, during which, pH=4-6 is adjusted with the NaOH that concentration is 5%, is stirred to react, products therefrom is compound I-1's
Aqueous solution obtains solid powder by the way of freeze-drying.
The second aspect of the invention provides a kind of preparation method of red reactive dyes, comprising the following steps:
The first step, Cyanuric Chloride is soluble in water, is cooled to 0-5 DEG C, adjusts pH=5-6 with the NaOH that concentration is 5%；Etc. rubbing
Your the H acid of ratio is soluble in water, and the NaOH that concentration is 10% is added and makes it dissolve pH < 7, under conditions of temperature is 0-5 DEG C, by H acid
Solution is slowly dropped in the water slurry of above-mentioned Cyanuric Chloride, during which, the NaOH that concentration is 5% is constantly added dropwise and adjusts pH=
5-6, insulation reaction, the product of generation are the aqueous solution of compound 7；
Under conditions of temperature is 0-5 DEG C, the water that compound 1 is paraphenetidine -3- sulfonic acid diazonium salt is hanged for second step
Supernatant liquid is slowly dropped in the aqueous solution of above compound 7, during which, the NaOH that concentration is 5% is constantly added dropwise and adjusts pH=5-
6, insulation reaction, the product of generation is the aqueous solution of compound 8；
Third step, γ acid is soluble in water, and γ acid and H acid are equimolar ratio, and the NaOH that concentration is 10% is added dropwise and makes it dissolve
The solution is warming up to 30-35 DEG C, γ acid solution is slowly added dropwise in the aqueous solution of above compound 8, during which, no by pH < 7
The NaOH that concentration is 5% is added dropwise disconnectedly to adjust pH=4-6, insulation reaction, the product of generation is the aqueous solution of compound 9；
The water slurry of compound 6 is added dropwise to the water of above compound 9 under conditions of temperature is 30-35 DEG C by the 4th step
In solution, during which, the NaOH that concentration is 5% is added dropwise constantly to adjust pH=4-6, insulation reaction, the product of generation is chemical combination
The aqueous solution of object I-2, obtains solid powder by the way of freeze-drying.
The second aspect of the invention provides a kind of preparation method of red reactive dyes, comprising the following steps:
The first step, meta position ester -4- sulfonic acid is soluble in water, and salt acid for adjusting pH < 3 that concentration is 30% are added dropwise, are cooled to 0-5
DEG C, excessive sodium nitrite insulation reaction is added dropwise, sulfamic acid is added, the product of generation is the water slurry of compound 10；
Second step when room temperature, the water slurry of above compound 10 is added dropwise in the aqueous solution of compound 9, during which, no
The NaOH that concentration is 5% being added dropwise disconnectedly to adjust pH=4-6, insulation reaction, the product of generation is the aqueous solution of compound I-3,
Solid powder is obtained by the way of freeze-drying.
The second aspect of the invention provides a kind of preparation method of red reactive dyes, comprising the following steps:
The first step, J acid is soluble in water, and the hydrochloric acid that concentration is 30% is added dropwise to adjust pH=5-6, by the water-soluble of compound 8
Liquid is warming up to 30-35 DEG C, and J acid solution is slowly added dropwise wherein, and during which, it is 5% NaOH to adjust pH that concentration, which is constantly added dropwise,
=5-6, insulation reaction, the product of generation are the aqueous solution of compound 11；
The water slurry of compound 10 is slowly dropped in the aqueous solution of above compound 11, the phase by second step at room temperature
Between, the NaOH that concentration is 5% is added dropwise constantly to adjust pH=5-6, insulation reaction, the product of generation is the water of compound I-4
Solution obtains solid powder by the way of freeze-drying.
The third aspect of the invention provides the side that a kind of red reactive dyes contaminate cotton fiber in non-aqueous media
Method, comprising the following steps:
It will be dissolved in the non-aqueous media containing the red reactive dyes by pretreated cotton fabric, sufficiently dissolve, rise
Then temperature is added solvent B, keeps the temperature after being then warming up to 90~100 DEG C again, be cooled to room temperature to keeping the temperature after 50~60 DEG C, take out
Cotton fabric is simultaneously extracted, and dyeing processes are obtained；
The non-aqueous media refers to a kind of mixture (solvent M) of binary organic solvent, one of component be polarity compared with
Big organic solvent, that is, solvent A, can dissolve the red reactive dyes, another component be the lesser organic solvent of polarity i.e.
Solvent B cannot dissolve the red reactive dyes；Solvent A and solvent B dissolve each other, and the two can dissolve each other in any proportion.Mixed
In bonding solvent, the effect of solvent B is to reduce solvent A to the solubility of red reactive dyes of the present invention；
The mass ratio of the cotton fabric and the red reactive dyes is (25~40): 1.
The cotton fabric, solvent A, solvent B bath raio be 1:5~25:5~25.
The mass ratio of the cotton fabric and the red reactive dyes is 33.3:1.
The cotton fabric refers to the pure cotton fabric of various institutional frameworks, pure cotton mercerization style and mixes with the cotton of other fiber blends
Textile fabric.
The solvent A is at least one of DMF, DMSO, N-Methyl pyrrolidone.
The solvent B is at least one of petroleum ether, tetrachloro-ethylene (PCE), carbon tetrachloride.
It is described by its processing method of pretreated cotton fabric the following steps are included:
Cotton fabric is immersed in Na2CO3In solution, then the cotton fabric loading after swelling is furnished with and is used to support sample steel mesh
Centrifuge tube in be centrifuged, to after the cotton fabric correct amount after centrifugation drying until cotton fabric moisture content is less than 2%.
Due to the adoption of the above technical scheme, the present invention has the following advantages and beneficial effects:
Its structure of red reactive dyes of the invention is made of parent dye, linker and active group.With existing activity
Unlike dyestuff, a) in dye molecule, the type and number of active group；B) the sulfonic acid group number in dye molecule
It is more than existing reactive dye.The red reactive dyes of reactive dye with this feature, that is, of the invention are in non-aqueous media
Solubility with higher and to cotton fiber affinity with higher, can be to contaminate on higher dye-uptake onto cotton fiber；Together
When, cleaning is very easy to again to the hydrolised dye not anchored at partially on fiber.
It is emphasized that all intermediates required for production each dyestuff of the invention and chemicals are all at home
It is easy to get in the market outside, does not need custom-made, manufacturing equipment required for these dyestuffs is also that DYE PRODUCTION enterprise is general
Standard device, synthesizing all kinds of reactions involved in these dyestuffs is the production common unit process of azo dyes.The present invention discloses
Dye structure in have relatively large number of sulfonic acid group so that they have very big affinity to water, thus in water to cotton fibre
Do not have higher dye-uptake when the dyeing of dimension, is only applicable in non-aqueous media of the present invention to cotton fiber dyeing, tool
There is 92% or more dye-uptake.
Specific embodiment
In order to illustrate more clearly of the present invention, below with reference to preferred embodiment, the present invention is described further.Ability
Field technique personnel should be appreciated that following specifically described content is illustrative and be not restrictive, this should not be limited with this
The protection scope of invention.
Raw materials used in the embodiment of the present invention is industrial goods, and some is aqueous filter cake.
Embodiment 1
Step 1: the diazotising of paraphenetidine -3- sulfonic acid
Paraphenetidine -3- sulfonic acid (20.3g, 0.1mol, Zhejiang Longsheng Dye Chemical Co., Ltd, 99.22%) is used
The dissolution of 200mL water, is added dropwise salt acid for adjusting pH < 3 that concentration is 30%, and ice salt bath controls 0-5 DEG C of temperature.Sodium nitrite (8.3g,
0.12mol, Jinan Kun Feng Chemical Co., Ltd., 99.5%) it is configured to the aqueous solution that concentration is 30%, it is slowly added dropwise into above-mentioned right
In aminoanisole -3- sulfonic acid solutions, after being added dropwise completely, 0-5 DEG C of temperature and pH < 3 are kept, react 15-30min.Excessive Asia
Nitric acid is destroyed with sulfamic acid (the bright big chemical Science and Technology Co., Ltd. in Shandong, 99.5%), and sulfamic acid, the production of generation is added
Object is the water slurry of paraphenetidine -3- sulfonic acid diazonium salt, and structure is shown in compound 1.
Step 2: the coupling of paraphenetidine -3- sulfonic acid diazonium salt and J acid
J acid (2- amino -5- naphthols -7- sulfonic acid) (23.9g, 0.1mol, Zhejiang Longsheng Dye Chemical Co., Ltd, wet filter
Cake, solid content 90.76%) it is dissolved with 250mL water, pH=5-6, ice salt bath control reaction temperature are adjusted with the hydrochloric acid that concentration is 30%
The above compound 1 i.e. water slurry of paraphenetidine -3- sulfonic acid diazonium salt is slowly added dropwise in 0-5 DEG C of degree, keeps temperature 0-5
DEG C and pH=5-6, react 2h, the product of generation is the aqueous solution of compound 2.
Step 3: the condensation of compound 2 and Cyanuric Chloride
Cyanuric Chloride (18.8g, 0.1mol, Zhejiang Longsheng Dye Chemical Co., Ltd, 98%) and 200mL water (include 1%
Emulsifier TX-100, the eternally happy Chemical Co., Ltd. in Nantong, 98%) it is sufficiently mixed, it is cooled to 0-5 DEG C.The change that second step is obtained
The aqueous solution for closing object 2 is added dropwise to wherein, during which controls pH value of solution=5-6, keeps 0-5 DEG C of temperature and pH=5-6, reacts 2h, raw
At product be compound 3 aqueous solution.
Step 4: the condensation of compound 3 and H acid
H acid (1- amino-8-naphthol -3,6- disulfonic acid) (32.0g, 0.1mol, Zhejiang Longsheng Dye Chemical Co., Ltd,
Wet cake, solid content 85.48%) it is dissolved with 300mL water, then the adjusting of NaOH the aqueous solution pH=7, at this time H that are 10% with concentration
Acid is completely dissolved, this solution is added drop-wise in the aqueous solution of the compound 3 of third step acquisition, is during which controlled reaction temperature 30-35
DEG C, and the NaOH aqueous solution that concentration is 5% is constantly added dropwise and controls reactant pH=5-6, keep 30-35 DEG C of temperature and pH=5-
6,2h is reacted, the product of generation is the aqueous solution of compound 4.
Step 5: the condensation of 2,4- diamino benzene sulfonic acid and 2,3 dibromo propionyl chloride
2,4- diamino benzene sulfonic acids (18.8g, 0.1mol, Zhejiang Longsheng Dye Chemical Co., Ltd, wet cake, solid content
82.13%) it is dissolved with 200ml water, then instills 2,3-, bis- bromo propionyl chloro (25.0g, 0.1mol, lark prestige section in this solution
Skill Co., Ltd, 98%), the sodium bicarbonate solution that concentration is 10% is during which constantly added dropwise, adjusts pH=5-6, drop finishes, and keeps
PH=5-6, reacts 2-3h, and the product of generation is the aqueous solution of compound 5.
Step 6: the diazotising of compound 5
The aqueous solution for the compound 5 that 5th step obtains is cooled to 0-5 DEG C, salt acid for adjusting pH < 3 for being 30% with concentration,
Sodium nitrite (8.3g, 0.12mol) aqueous solution is slowly added dropwise, drop finishes, insulation reaction 30-45min, excessive nitrous acid amino
Sulfonic acid (the bright big chemical Science and Technology Co., Ltd. in Shandong, 99.5%) destroys, and the product of generation is the water slurry of compound 6.
Step 7: the synthesis of compound I-1
Compound I-1 is by compound 6 with compound 4 through being coupled.
At room temperature, the water slurry for the compound 6 that the 6th step obtains is added drop-wise to the water-soluble of the compound 4 of the 4th step acquisition
In liquid, during which, pH=4-6 is adjusted with the NaOH that concentration is 5%, is stirred to react 2-3h, products therefrom is red reactive dyes
The aqueous solution of compound I-1, structure are shown in compound I-1, maximum absorption wavelength λ=510nm in water.Using freeze-drying
Mode obtains solid powder (freeze-drying temperature is -20~0 DEG C, sublimation drying 48h), purified treated element
Analysis result: theoretical value (%) C, 36.11；H,2.25；N,10.80；Experiment value (%) C, 36.32；H,2.27；N,10.69；
ESI(m/z)1297.8(M+H).Cotton is contaminated in non-aqueous media, makes cotton fiber in gorgeous red, dye-uptake 93.7%.
Embodiment 2
The first step, the condensation of Cyanuric Chloride and H acid
Cyanuric Chloride (9.2g, 0.05mol, Zhejiang Longsheng Dye Chemical Co., Ltd, 98%) and 100mL water (include 1%
Emulsifier TX-100, the eternally happy Chemical Co., Ltd. in Nantong, 98%) mixing, it is cooled to 0-5 DEG C, is adjusted with the NaOH that concentration is 5%
PH=5-6.H acid (16.0g, 0.05mol, Zhejiang Longsheng Dye Chemical Co., Ltd, wet cake, solid content 85.48%) and water
(200mL) mixing is added the NaOH that concentration is 10% and makes it dissolve (pH < 7).The H acid solution is slowly dropped at 0-5 DEG C
It states in the water slurry of Cyanuric Chloride, during which, the NaOH that concentration is 5% is constantly added dropwise and adjusts pH=5-6, insulation reaction 2-
3h, the product of generation are the aqueous solution of compound 7.
Second step, the coupling of compound 1 and compound 7
The synthetic method of compound 1 is shown in embodiment 1.
At 0-5 DEG C, by the compound 1 prepared in embodiment 1 the i.e. water slurry of paraphenetidine -3- sulfonic acid diazonium salt
It is slowly dropped in the aqueous solution of above compound 7, during which, the NaOH that concentration is 5% is constantly added dropwise and adjusts pH=5-6, protects
Temperature reaction 2-3h, the product of generation are the aqueous solution of compound 8.
Third step, γ acid and compound 8 are condensed
γ acid (12.0g, 0.05mol, Zhejiang Longsheng Dye Chemical Co., Ltd, wet cake, solid content 95.36%) with
The mixing of 100ml water is added dropwise the NaOH that concentration is 10% and makes it dissolve (pH < 7), which is warming up to 30-35 DEG C, and γ acid is molten
Liquid is slowly added dropwise in the aqueous solution of above compound 8, and during which, it is 5% NaOH to adjust pH=4- that concentration, which is constantly added dropwise,
6, insulation reaction 2-3h, the product of generation are the aqueous solution of compound 9.
4th step, the synthesis of compound I-2
Compound I-2 is coupled by compound 9 and compound 6, there is the synthetic method detailed in Example of related compounds 6
1。
Under conditions of temperature is 30-35 DEG C, the water slurry of the compound 6 prepared in embodiment 1 is added dropwise to above-mentionedization
In the aqueous solution for closing object 9, during which, it is 5% NaOH to adjust pH=4-6, insulation reaction 2-3h that concentration, which is constantly added dropwise, is generated
Product be compound I-2 aqueous solution.Maximum absorption wavelength λ=515nm of the solution.It is (cold by the way of freeze-drying
Freezing drying temperature is -20~0 DEG C, sublimation drying 48h) solid powder is obtained, purified elemental analysis result: reason
By value (%): C, 36.11；H,2.25；N,10.80；Experiment value (%): C, 36.01；H,2.21；N,10.59；ESI(m/z):
1297.8(M+H).Cotton is contaminated in non-aqueous media, makes cotton fiber in gorgeous red, dye-uptake 94.8%.
Embodiment 3
The first step, the diazotising of meta position ester -4- sulfonic acid
Meta position ester -4- sulfonic acid (18.0g, 0.05mol, Zhejiang Longsheng Dye Chemical Co., Ltd provide, wet cake, admittedly contain
56.5%) amount is mixed with 150mL water, salt acid for adjusting pH < 3 that concentration is 30% are added dropwise, are cooled to 0-5 DEG C, sodium nitrite is added dropwise
(4.2g, 0.06mol), insulation reaction 2h.Excessive nitrous acid is destroyed with sulfamic acid, and the product of generation is the water of compound 10
Suspension.
Second step, the synthesis of compound I-3
Compound I-3 is coupled by compound 10 and compound 9, has the synthetic method of related compounds 9 to be detailed in implementation
Example 2.
When room temperature, the water slurry of above compound 10 is added dropwise to the aqueous solution of the compound 9 prepared in embodiment 2
In, during which, the NaOH that concentration is 5% is added dropwise constantly to adjust pH=4-6, insulation reaction 2-3h, the product of generation is chemical combination
The aqueous solution of object I-3, maximum absorption wavelength λ=508nm of the solution.Use freeze-drying mode (freeze-drying temperature for-
20~0 DEG C, sublimation drying 48h) solid powder is obtained, purified elemental analysis result: theoretical value (%) C,
33.01；H,2.15；N,9.62；Experiment value (%) C, 33.21；H,2.10；N,9.47；ESI(m/z)1455.7(M+H).Non-
Cotton is contaminated in aqueous medium, makes cotton fiber in gorgeous red, dye-uptake 92.8%.
Embodiment 4
The first step, the synthesis of compound 11
Compound 11 is condensed by J acid and compound 8, there is the synthetic method detailed in Example 2 of related compounds 8.
J acid (23.9g, 0.1mol, Zhejiang Longsheng Dye Chemical Co., Ltd, wet cake, solid content 90.76%) with
The mixing of 250mL water is added dropwise the hydrochloric acid that concentration is 30% to adjust pH=5-6, and is completely dissolved J acid.It will be prepared in embodiment 2
The aqueous solution of compound 8 be warming up to 30-35 DEG C, J acid solution is slowly added dropwise wherein, during which, it is 5% that concentration, which is constantly added dropwise,
NaOH to adjust pH=5-6, insulation reaction 2-3h, the product of generation is the aqueous solution of compound 11.
Second step, the synthesis of compound I-4
Compound I-4 is coupled by compound 11 and compound 10, has the synthetic method of related compounds 10 to be detailed in
Embodiment 3.
At room temperature, the water slurry of the compound 10 prepared in embodiment 3 is slowly dropped to the water of above compound 11
In solution, during which, it is 5% NaOH to adjust pH=5-6 that concentration, which is constantly added dropwise, and the product of insulation reaction 2-3h, generation are
The aqueous solution of compound I-4, maximum absorption wavelength λ=500nm of the solution.(the freeze-drying temperature by the way of freeze-drying
Degree is -20~0 DEG C, sublimation drying 48h) obtain solid powder, purified elemental analysis result: theoretical value (%)
C,33.01；H,2.15；N,9.62；；Experiment value (%) C, 33.51；H,2.20；N,9.38；ESI(m/z)1455.7(M+H).?
Cotton is contaminated in non-aqueous media, makes cotton fiber in gorgeous red, dye-uptake 98%.
Comparative example 1
By commercially available commercial dye (active red M-3BE, C.I. REACTIVE Red 195, Zhejiang Longsheng Dye Chemical Co., Ltd)
Cotton, dye-uptake 70.23% are contaminated in non-aqueous media using same method.Active red M-3BE structure is as follows:
Colouring method
The pretreatment of cotton fabric:
Cotton fabric (commercially available bleaching plain cloth) 10g is immersed in the Na that concentration is 20g/L2CO330min in solution, then will swelling
Cotton fabric afterwards is fitted into equipped with being used to support in the centrifuge tube of sample steel mesh, is centrifuged 3.5min with revolving speed 1400rpm.After centrifugation
Fabric correct amount after be put into baking oven be dried to cotton fabric moisture content be 2% until.
Dyeing:
Above-mentioned process pretreated cotton fabric (commercially available bleaching plain cloth) 1g is weighed, (being accurate to ± 0.0002g) is by coloration
3% weighs 30mg (being accurate to ± 0.0002g).By bath raio (cotton fabric/DMSO/PCE (tetrachloro-ethylene)=1:5~25:5~25)
The mixed liquor for measuring 5mL DMSO/PCE, is added in the vial equipped with 30mg dyestuff, dissolves dyestuff sufficiently, is formed molten
Liquid 1.
It is added in a dye tank by solution 1 and by pretreated cotton fabric as experimental group, another dye tank only adds
Solution 1 does not put cotton fabric as control experiment, and 25 DEG C heat up, and the rate of 1 DEG C/min is warming up to 55 DEG C, 10min are kept the temperature, to two
5~20ml PCE is all added in a dye tank, is then warming up to 95 DEG C again with the rate of 1 DEG C/min, keeps the temperature 2h, is then cooled to room
Temperature is taken out cotton fabric and is extracted.
The measurement of dye-uptake:
Be separately added into 10ml methanol in two dye tanks, make contaminate tank in solvent be uniformly mixed (DMSO and PCE are immiscible,
The not upper dyestuff contaminated is at DMSO layers), the dye liquor in tank is contaminated by two respectively and is poured into 50ml volumetric flask, and constant volume is in 50ml, then
The mixed solution in 2ml blank control group dye tank is measured, n times is diluted, surveys absorbance A0, then survey again in the dye tank containing cotton
The absorbance A of dye liquor1(some need to be diluted this dye liquor as the case may be).The calculation formula of dye-uptake is as follows:
Dye-uptake=(A0(n+1)-A1)/(A0(n+1)) × 100%
A0The absorbance value tested after the mixed solution in tank dilutes n times is contaminated for blank control group；
A1The absorbance value tested after the mixed solution in tank dilutes n times is contaminated for experimental group；
N is extension rate.
The above is only presently preferred embodiments of the present invention, is not intended to limit the present invention in any form, though
So the present invention has been disclosed as a preferred embodiment, and however, it is not intended to limit the invention, any technology people for being familiar with this patent
Member without departing from the scope of the present invention, when the technology contents using above-mentioned prompt make it is a little change or be modified to
The equivalent embodiment of equivalent variations, but anything that does not depart from the technical scheme of the invention content, it is right according to the technical essence of the invention
Any simple modification, equivalent change and modification made by above embodiments, in the range of still falling within the present invention program.
Claims (10)
1. a kind of red reactive dyes, it is characterised in that: structure is shown in formula I:
Wherein, R1、R2It is each independently selected from hydrogen, substituted or unsubstituted C1-C4Alkyl；
X is F, Cl or Br；
R3、R4It is each independently selected from C1-C4Alkoxy, halogen, hydroxyl, sulfonic group；
D1、D2It is each independently selected from substituted-phenyl；
Compound shown in Formulas I at least contains 2 sulfonic groups.
2. red reactive dyes according to claim 1, it is characterised in that: in Formulas I, D1、D2It is each independently selected from following
One kind of substituent group:
3. red reactive dyes according to claim 2, it is characterised in that: the red reactive dyes structure is as follows:
4. a kind of preparation method of red reactive dyes as claimed in claim 3, it is characterised in that: the following steps are included:
Step 1: paraphenetidine -3- sulfonic acid is soluble in water, salt acid for adjusting pH < 3 that concentration is 30%, ice salt bath control is added dropwise
0-5 DEG C of temperature processed, excessive sodium nitrite is configured to the aqueous solution that concentration is 30%, is slowly added dropwise into above-mentioned p-aminophenyl first
In ether -3- sulfonic acid solutions, after being added dropwise completely, keeps 0-5 DEG C of temperature and pH < 3 to react, sulfamic acid is added, the product of generation is
Compound 1 is the water slurry of paraphenetidine -3- sulfonic acid diazonium salt；
Step 2: J acid is soluble in water, the molar ratio of J acid and paraphenetidine -3- sulfonic acid is 1:1, the salt for being 30% with concentration
Acid for adjusting pH=5-6, ice salt bath control 0-5 DEG C of reaction temperature, above compound 1 i.e. paraphenetidine -3- sulphur are slowly added dropwise
The water slurry of sour diazonium salt keeps 0-5 DEG C of temperature and pH=5-6 to react, and the product of generation is the aqueous solution of compound 2；
Step 3: Cyanuric Chloride is soluble in water, the molar ratio of Cyanuric Chloride and paraphenetidine -3- sulfonic acid is 1:1, is cooled to
0-5 DEG C, the aqueous solution of compound 2 is added dropwise to wherein, during which controls pH value of solution=5-6, keeps 0-5 DEG C of temperature and pH=5-6
Reaction, the product of generation are the aqueous solution of compound 3；
Step 4: H acid is soluble in water, the molar ratio of H acid and paraphenetidine -3- sulfonic acid is 1:1, then with concentration is 10%
NaOH aqueous solution adjusts pH=7, this solution is added drop-wise in the aqueous solution of above compound 3, during which controls reaction temperature 30-35
DEG C, and the NaOH aqueous solution that concentration is 5% is constantly added dropwise and controls reactant pH=5-6, keep 30-35 DEG C of temperature and pH=5-
6 reactions, the product of generation are the aqueous solution of compound 4；
Step 5: 2,4- diamino benzene sulfonic acids are soluble in water, equimolar 2,3-, bis- bromo propionyl chloro is instilled, is during which constantly added dropwise
The sodium bicarbonate solution that concentration is 10% adjusts pH=5-6, and drop finishes, and keeps pH=5-6 reaction, and the product of generation is compound 5
Aqueous solution；
Step 6: the aqueous solution of compound 5 is cooled to 0-5 DEG C, salt acid for adjusting pH < 3 for being 30% with concentration were slowly added dropwise
Sodium nitrite in aqueous solution is measured, drop finishes, insulation reaction, and sulfamic acid is added, and the product of generation is the water slurry of compound 6；
Step 7: at room temperature, the water slurry of the compound 6 of the 6th step preparation is added drop-wise to the compound 4 of the 4th step preparation
In aqueous solution, during which, pH=4-6 is adjusted with the NaOH that concentration is 5%, is stirred to react, products therefrom is the water-soluble of compound I-1
Liquid obtains solid powder by the way of freeze-drying.
5. a kind of preparation method of red reactive dyes as claimed in claim 3, it is characterised in that: the following steps are included:
The first step, Cyanuric Chloride is soluble in water, is cooled to 0-5 DEG C, adjusts pH=5-6 with the NaOH that concentration is 5%；Equimolar ratio
H acid it is soluble in water, the NaOH that concentration is 10% is added and makes it dissolve pH < 7, under conditions of temperature is 0-5 DEG C, by H acid solution
It is slowly dropped in the water slurry of above-mentioned Cyanuric Chloride, during which, the NaOH that concentration is 5% is constantly added dropwise and adjusts pH=5-6,
Insulation reaction, the product of generation are the aqueous solution of compound 7；
Compound 1 is the water slurry of paraphenetidine -3- sulfonic acid diazonium salt under conditions of temperature is 0-5 DEG C by second step
It is slowly dropped in the aqueous solution of above compound 7, during which, the NaOH that concentration is 5% is constantly added dropwise and adjusts pH=5-6, protects
Temperature reaction, the product of generation are the aqueous solution of compound 8；
Third step, γ acid is soluble in water, and γ acid and H acid are equimolar ratio, and the NaOH that concentration is 10% is added dropwise and makes it dissolve pH < 7,
The solution is warming up to 30-35 DEG C, γ acid solution is slowly added dropwise in the aqueous solution of above compound 8, during which, is constantly dripped
Add the NaOH that concentration is 5% to adjust pH=4-6, insulation reaction, the product of generation is the aqueous solution of compound 9；
The water slurry of compound 6 is added dropwise to the aqueous solution of above compound 9 under conditions of temperature is 30-35 DEG C by the 4th step
In, during which, the NaOH that concentration is 5% is added dropwise constantly to adjust pH=4-6, insulation reaction, the product of generation is compound I-2
Aqueous solution, solid powder is obtained by the way of freeze-drying.
6. a kind of preparation method of red reactive dyes as claimed in claim 3, it is characterised in that: the following steps are included:
The first step, meta position ester -4- sulfonic acid is soluble in water, and salt acid for adjusting pH < 3 that concentration is 30% are added dropwise, and is cooled to 0-5 DEG C, drop
Add excessive sodium nitrite insulation reaction, sulfamic acid is added, the product of generation is the water slurry of compound 10；
Second step when room temperature, the water slurry of above compound 10 is added dropwise in the aqueous solution of compound 9, during which, constantly
The NaOH that concentration is 5% is added dropwise to adjust pH=4-6, insulation reaction, the product of generation is the aqueous solution of compound I-3, is used
The mode of freeze-drying obtains solid powder.
7. a kind of preparation method of red reactive dyes as claimed in claim 3, it is characterised in that: the following steps are included:
The first step, J acid is soluble in water, and the hydrochloric acid that concentration is 30% is added dropwise to adjust pH=5-6, by the aqueous solution liter of compound 8
J acid solution is slowly added dropwise wherein to 30-35 DEG C for temperature, and during which, it is 5% NaOH to adjust pH=5- that concentration, which is constantly added dropwise,
6, insulation reaction, the product of generation is the aqueous solution of compound 11；
The water slurry of compound 10 is slowly dropped in the aqueous solution of above compound 11 by second step at room temperature, during which,
The NaOH that concentration is 5% is added dropwise constantly to adjust pH=5-6, insulation reaction, the product of generation is the water-soluble of compound I-4
Liquid obtains solid powder by the way of freeze-drying.
8. a kind of method that described in any item red reactive dyes of claims 1 to 3 contaminate cotton fiber in non-aqueous media, special
Sign is: the following steps are included:
It will be dissolved in the non-aqueous media containing the red reactive dyes by pretreated cotton fabric, sufficiently dissolve, be warming up to
It is kept the temperature after 50~60 DEG C, solvent B is then added, is kept the temperature after being then warming up to 90~100 DEG C again, be cooled to room temperature, taken out cotton and knit
Object is simultaneously extracted, and dyeing processes are obtained；
The non-aqueous media refers to a kind of mixture of binary organic solvent, and one of component is the biggish organic solvent of polarity
That is solvent A can dissolve the red reactive dyes, another component is the lesser organic solvent of polarity i.e. solvent B, Bu Nengrong
Solve the red reactive dyes；
The mass ratio of the cotton fabric and the red reactive dyes is (25~40): 1；
The cotton fabric, solvent A, solvent B bath raio be 1:5~25:5~25.
9. the method that red reactive dyes according to claim 8 contaminate cotton fiber in non-aqueous media, it is characterised in that: institute
Stating solvent A is at least one of DMF, DMSO, N-Methyl pyrrolidone；
The solvent B is at least one of petroleum ether, tetrachloro-ethylene, carbon tetrachloride.
10. the method that red reactive dyes according to claim 8 contaminate cotton fiber in non-aqueous media, it is characterised in that:
It is described by its processing method of pretreated cotton fabric the following steps are included:
Cotton fabric is immersed in Na2CO3In solution, then by after swelling cotton fabric be packed into equipped be used to support sample steel mesh from
It is centrifuged in heart pipe, to drying after the cotton fabric correct amount after centrifugation until cotton fabric moisture content is less than 2%.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115368753A (en) * | 2022-08-11 | 2022-11-22 | 南通大学 | PH color-changing reactive dye for sweat detection and preparation method thereof |
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| DE2748966A1 (en) * | 1977-11-02 | 1979-05-03 | Hoechst Ag | HYDRO-SOLUBLE COLORS, PROCESS FOR THEIR PRODUCTION, THEIR USE AS FIBER-REACTIVE COLORS FOR COLORING AND PRINTING FIBER MATERIALS AND FIBER MATERIALS DYED WITH THEM |
| US5200511A (en) * | 1991-04-27 | 1993-04-06 | Basf Aktiengesellschaft | Cholorotriazine dyes with two azo chromophores exhibiting further reactive groups |
| CN1167785A (en) * | 1996-04-24 | 1997-12-17 | 希巴特殊化学控股公司 | Fibre-reactive dyes, their preparation and their use |
| CN107419553A (en) * | 2016-05-23 | 2017-12-01 | 海宁绿宇纺织科技有限公司 | A kind of colouring method of silicon substrate non-aqueous media suitable for reactive dye |
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| DE2748966A1 (en) * | 1977-11-02 | 1979-05-03 | Hoechst Ag | HYDRO-SOLUBLE COLORS, PROCESS FOR THEIR PRODUCTION, THEIR USE AS FIBER-REACTIVE COLORS FOR COLORING AND PRINTING FIBER MATERIALS AND FIBER MATERIALS DYED WITH THEM |
| US5200511A (en) * | 1991-04-27 | 1993-04-06 | Basf Aktiengesellschaft | Cholorotriazine dyes with two azo chromophores exhibiting further reactive groups |
| CN1167785A (en) * | 1996-04-24 | 1997-12-17 | 希巴特殊化学控股公司 | Fibre-reactive dyes, their preparation and their use |
| CN107419553A (en) * | 2016-05-23 | 2017-12-01 | 海宁绿宇纺织科技有限公司 | A kind of colouring method of silicon substrate non-aqueous media suitable for reactive dye |
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| CN115368753A (en) * | 2022-08-11 | 2022-11-22 | 南通大学 | PH color-changing reactive dye for sweat detection and preparation method thereof |
| CN115368753B (en) * | 2022-08-11 | 2023-08-15 | 南通大学 | PH color-changing reactive dye for sweat detection and preparation method thereof |
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