CN110078648B - 4, 4' -diamino disulfonated diphenyl sulfone and preparation method and application thereof - Google Patents

4, 4' -diamino disulfonated diphenyl sulfone and preparation method and application thereof Download PDF

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CN110078648B
CN110078648B CN201910340612.8A CN201910340612A CN110078648B CN 110078648 B CN110078648 B CN 110078648B CN 201910340612 A CN201910340612 A CN 201910340612A CN 110078648 B CN110078648 B CN 110078648B
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diamino
diphenyl sulfone
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CN110078648A (en
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周雷云
刘子轩
刘卫斌
程翠云
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Shanghai Liyuan Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C315/00—Preparation of sulfones; Preparation of sulfoxides
    • C07C315/04—Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C315/00—Preparation of sulfones; Preparation of sulfoxides
    • C07C315/06—Separation; Purification; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/26—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C317/32—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C317/34—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having sulfone or sulfoxide groups and amino groups bound to carbon atoms of six-membered aromatic rings being part of the same non-condensed ring or of a condensed ring system containing that ring
    • C07C317/36—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having sulfone or sulfoxide groups and amino groups bound to carbon atoms of six-membered aromatic rings being part of the same non-condensed ring or of a condensed ring system containing that ring with the nitrogen atoms of the amino groups bound to hydrogen atoms or to carbon atoms
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
    • C09B62/503—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring the reactive group being an esterified or non-esterified hydroxyalkyl sulfonyl or mercaptoalkyl sulfonyl group, a quaternised or non-quaternised aminoalkyl sulfonyl group, a heterylmercapto alkyl sulfonyl group, a vinyl sulfonyl or a substituted vinyl sulfonyl group, or a thiophene-dioxide group
    • C09B62/507—Azo dyes
    • C09B62/513—Disazo or polyazo dyes
    • 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
    • D06P1/38—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 reactive dyes
    • D06P1/384—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 reactive dyes reactive group not directly attached to heterocyclic group

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Abstract

The invention discloses 4,4 '-diamino disulfonated diphenyl sulfone as well as a preparation method and application thereof, belonging to the technical field of chemical synthesis, and the key point of the technical scheme is that the 4, 4' -diamino disulfonated diphenyl sulfone has the following molecular structure:
Figure DDA0002040576640000011
wherein M is H or an alkali metal cation. According to the invention, the 4, 4' -diamino disulfonic diphenyl sulfone is used as an intermediate for preparing the reactive dye, so that the reactive dye with a plurality of reactive groups can be prepared, the color fixation rate is more than 85%, and the problem of low color fixation rate of the traditional reactive dye is solved.

Description

4, 4' -diamino disulfonated diphenyl sulfone and preparation method and application thereof
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to 4, 4' -diamino disulfonic diphenyl sulfone as well as a preparation method and application thereof.
Background
The reactive dye is also called reactive dye, is a novel water-soluble dye appearing in the 50 th century in 20 th century, has the remarkable characteristics of bright color, excellent application performance, convenient use, strong applicability and the like, contains active groups capable of reacting with hydroxyl in cellulose and amino in protein fiber in molecules, generates covalent bonds with the fiber during dyeing, generates a dye-fiber compound, and is widely applied to the cellulose fiber; in the 21 st century, due to environmental ecological restrictions and economic factors, the requirements on production and preparation, dyeing degree, fixation rate and dyeing wastewater of reactive dyes are higher and higher.
The common three primary colors of the existing reactive dyes are C.I. reactive red 195, C.I. reactive yellow 145 and C.I. reactive blue 194; in the prior art, patent application No. CN201710331552.4 discloses a method for preparing c.i. reactive red 195 by continuous coupling in a microchannel, wherein cyanuric chloride reacts with H acid to obtain a condensate; the primary condensate reacts with para-ester to obtain a secondary condensate, and the secondary condensate reacts with 2-naphthylamine-1, 5-disulfonic acid diazonium salt in a microchannel reactor by controlling the flow rate and the reaction residence time to obtain the product.
However, the color fixation rate of the reactive dye of the C.I. reactive red 195 is only about 70-80%, the residual dye is discharged with the wastewater, a large amount of colored wastewater is generated, the chroma is more than several thousand times, the COD value is generally 0.8-3 ten thousand ppm, the COD value of the concentrated wastewater is more than 5 ten thousand ppm, and the environmental protection treatment cost is increased; there is therefore an ongoing need to develop new reactive dyes having a high degree of fixation.
Disclosure of Invention
One of the purposes of the invention is to provide 4,4 '-diamino disulfonated diphenyl sulfone, which can be used for preparing reactive dyes with a plurality of reactive groups by taking the 4, 4' -diamino disulfonated diphenyl sulfone as an intermediate for preparing the reactive dyes, so that the color fixing rate of the reactive dyes reaches more than 85 percent, and the problem of low color fixing rate of the traditional reactive dyes is solved.
The technical purpose of the invention is realized by the following technical scheme:
a 4, 4' -diamino disulfonated diphenyl sulfone having the following molecular structure:
Figure BDA0002040576620000011
wherein M is H or an alkali metal cation.
By adopting the technical scheme, the 4, 4' -diamino disulfonic acid diphenyl sulfone is used as an intermediate for preparing the reactive dye, the reactive dye with a plurality of reactive groups can be prepared, the color fixing rate of the reactive dye reaches more than 85 percent, and the problem of low color fixing rate of the traditional reactive dye is solved.
Further, the alkali metal cation is Na or K.
The second purpose of the invention is to provide a preparation method of 4, 4' -diamino disulfonic diphenyl sulfone.
The technical purpose of the invention is realized by the following technical scheme:
a preparation method of 4, 4' -diamino disulfonated diphenyl sulfone comprises the following steps: the weight portion is:
s1: taking 40-60 parts of concentrated sulfuric acid and 30-50 parts of fuming sulfuric acid, and uniformly stirring to obtain a sulfonating agent;
s2: 24.83 parts of 4, 4' -diamino diphenyl sulfone is uniformly added into the sulfonating agent at room temperature; then heating to 80-90 ℃ and reacting for 5-7h to obtain reaction liquid;
s3: after the reaction solution is cooled to room temperature, adding the reaction solution into 300 parts of ice water by 200 parts while stirring; adjusting pH of the solution to 4 with sodium hydroxide solution or potassium hydroxide solution, stirring for 20-30min, and filtering under reduced pressure to obtain filter cake containing 4, 4' -diamino disulfonated diphenyl sulfone.
By adopting the technical scheme, the 4,4 '-diamino disulfonated diphenyl sulfone is prepared by taking concentrated sulfuric acid, fuming sulfuric acid and 4, 4' -diamino diphenyl sulfone as raw materials and is separated out by ice water, so that the reaction temperature can be controlled, and the occurrence of side reactions is reduced; the yield of the 4,4 '-diamino disulfonated diphenyl sulfone can reach 64 to 70 percent by controlling the dosage of fuming sulfuric acid, the reaction temperature, the reaction time and the dripping speed of the 4, 4' -diamino diphenyl sulfone.
Further, adding water into the filter cake, stirring for 30-40min, filtering under reduced pressure, and removing insoluble substances; adding sodium chloride solid accounting for 10-20% of the volume of the filtrate into the filtrate for salting out, and filtering under reduced pressure to obtain the 4, 4' -diamino disulfonated diphenyl sulfone.
By adopting the technical scheme, excessive raw materials and monosulfonated byproducts can be removed after water is added into a filter cake and pressure reduction filtration is carried out; the tri-sulfonated and tetra-sulfonated byproducts can be removed by salting out the sodium chloride solid, so that the purity of the target product can reach 95%.
Further, the mass fraction of concentrated sulfuric acid in S1 was 98%, and the mass fraction of fuming sulfuric acid was 65%.
Further, 4' -diaminodiphenyl sulfone in S2 was added within 30-60 min.
By adopting the technical scheme, the feeding time of the 4, 4' -diamino diphenyl sulfone is controlled to be 30-60min, the reaction speed can be controlled, the occurrence of side reactions is reduced, and the yield of the target product is improved.
Further, the alkaline agent in S2 is one of a sodium hydroxide solution or a potassium hydroxide solution.
The invention also aims to provide the application of the 4, 4' -diamino disulfonated diphenyl sulfone in the reactive dye.
In summary, compared with the prior art, the invention has the following beneficial effects:
1. the 4, 4' -diamino disulfonic diphenyl sulfone is used as an intermediate for preparing the reactive dye, the reactive dye with a plurality of reactive groups can be prepared, the fixation rate of the reactive dye reaches more than 85 percent, and the problem of low fixation rate of the traditional reactive dye is solved;
2. concentrated sulfuric acid, fuming sulfuric acid and 4,4 ' -diamino diphenyl sulfone are used as raw materials to prepare 4,4 ' -diamino disulfonic diphenyl sulfone, and the 4,4 ' -diamino disulfonic diphenyl sulfone is separated out through ice water, so that the reaction temperature can be controlled, and the occurrence of side reactions is reduced; the yield of the 4,4 '-diamino disulfonated diphenyl sulfone can reach 64-70 percent by controlling the dosage of fuming sulfuric acid, the reaction temperature, the reaction time and the dripping speed of the 4, 4' -diamino diphenyl sulfone;
3. adding water into the filter cake, and filtering under reduced pressure to remove excessive raw materials and monosulfonated byproducts; the tri-sulfonated and tetra-sulfonated byproducts can be removed by salting out the sodium chloride solid, so that the purity of the target product can reach 95%.
Drawings
FIG. 1 is a mass spectrum of 4,4 '-diamino-3, 3' -disulfonic acid diphenyl sulfone of example 1;
FIG. 2 is an infrared spectrum of a red reactive dye compound (I-1) in application example 1;
FIG. 3 is a UV spectrum of a red reactive dye compound (I-1) of application example 1;
FIG. 4 is an infrared spectrum of an orange-red reactive dye compound (I-2) in application example 2;
FIG. 5 is a UV spectrum of orange-red reactive dye compound (I-2) in application example 2;
FIG. 6 is an infrared spectrum of an orange reactive dye compound (I-3) in application example 3;
FIG. 7 is a UV spectrum of orange reactive dye compound (I-3) in application example 3.
Detailed Description
The present invention will be described in further detail below.
First, an embodiment
Example 1: the 4,4 '-diamino-3, 3' -disulfonic acid diphenyl sulfone is prepared by the following method:
s1: uniformly stirring 40g of concentrated sulfuric acid with the mass fraction of 98% and 40g of fuming sulfuric acid with the mass fraction of 65% to obtain a sulfonating agent;
s2: 24.83g of 4, 4' -diamino diphenyl sulfone is uniformly added into the sulfonating agent within 30min at room temperature; then heating to 80 ℃ at the speed of 2 ℃/min, and reacting for 5 hours to obtain reaction liquid;
s3: after the reaction solution was cooled to room temperature, it was added to 200g of ice water while stirring; adjusting the pH value of the solution to 4 by using a sodium hydroxide solution, stirring for 20min, and filtering under reduced pressure to obtain a filter cake with the yield of the 4,4 '-diamino-3, 3' -disulfonic acid diphenyl sulfone being 65.8%;
s4: adding 200g of water into the filter cake, stirring for 30min, filtering under reduced pressure, and removing insoluble substances; adding sodium chloride solid accounting for 10% of the volume of the filtrate into the filtrate for salting out, and filtering under reduced pressure to obtain the 4,4 '-3, 3' -diamino disulfonic acid diphenyl sulfone with the purity of 95%.
Examples 2 to 15
According to the production method described in example 1, except that some of the raw materials, the amounts used, and the reaction conditions were set to the values shown in Table 1 or Table 2.
TABLE 1
Figure BDA0002040576620000041
As can be seen from the data in Table 1, the yield of 4,4 '-diamino-3, 3' -disulfonic acid diphenylsulfone prepared by the process of the present invention is 60-70%; after purification, the purity of the target product 4,4 '-diamino-3, 3' -disulfonic acid diphenyl sulfone can reach 95%. As can be seen from examples 1-5, as the amount of oleum increases, the yield of the desired product decreases; when the dosage of the concentrated sulfuric acid is more than 1, the yield of the target product is increased; as can be seen from example 1, example 6 and example 7, as the reaction temperature increases, the yield of the target product decreases; as can be seen from example 1, example 8 and example 9, the yield of the objective product increases as the reaction time is prolonged; as can be seen from example 1, example 10 and example 11, when the dropping time of 4, 4' -diaminodiphenyl sulfone was prolonged, the yield of the objective product was increased. From the above, it can be seen from example 12 that when the amount of concentrated sulfuric acid used is greater than 1, the reaction temperature is lowered, the reaction time is prolonged, and the dropping time of 4,4 ' -diaminodiphenyl sulfone is prolonged, the yield of 4,4 ' -diamino-3, 3 ' -disulfonic acid diphenyl sulfone is improved.
TABLE 2
Figure BDA0002040576620000042
Figure BDA0002040576620000051
According to the data in Table 1 and the data in Table 2, it can be seen from the results of examples 1, 13, 14 and 15 that the yield of 4,4 '-diamino-3, 3' -disulfonic acid diphenylsulfone can reach about 65% when the amount of ice water is 200-300g, the alkali agent is sodium hydroxide solution or potassium hydroxide solution, the stirring time is 30-40min, and the amount of sodium chloride solid is 15-25% of the volume of the filtrate.
Second, comparative example
Comparative examples 1 to 6
This comparative example used the preparation method of example 1 to prepare 4,4 '-diamino-3, 3' -disulfonic acid diphenylsulfone, except that some of the raw materials, amounts and reaction conditions were as shown in Table 3.
TABLE 3
Figure BDA0002040576620000052
As can be seen from the data in tables 1 and 3, according to example 1, comparative example 1 and comparative example 2, when the amount of oleum is too large or too small, the yield of the target product is reduced; according to example 1, comparative example 3 and comparative example 4, it can be seen that when the reaction temperature is too high or too low, the yield of the target product is reduced; as can be seen from example 1, comparative example 5 and comparative example 6, when the reaction time is too short or too long, the yield of the target product is reduced; as can be seen from example 1 and comparative example 7, when the dropping time is too short, the yield of the objective product is lowered; as can be seen from examples 1 and 9 and comparative example 8, the addition time is too long, and the effect on the increase of the yield of the target product is small. In conclusion, the yield of the prepared 4,4 '-diamino-3, 3' -disulfonic acid diphenyl sulfone can reach 60-70% by adopting the method and the parameter conditions.
Third, application example
The dispersant used in the following application examples was EW-719 wet dispersant manufactured by Daohui chemical technology (Shanghai) Ltd.
Application example 1: the preparation method of the red reactive dye by using the 4,4 '-diamino-3, 3' -disulfonic acid diphenyl sulfone prepared in the example 1 as an intermediate comprises the following steps:
s1: primary condensation reaction: adding 0.101mol of cyanuric chloride into 100mL of ice water, adding a dispersant EW, pulping, slowly adding 0.1mol of H acid, and reacting at 0 ℃ for 2h to obtain a polycondensate;
s2: secondary condensation reaction: adding 0.1mol of para-ester into water to prepare 100mL of solution, regulating the pH value to be 6.0-7.0, slowly adding the solution into the first condensation product, heating the system to 5 ℃, regulating the pH value to be 5.0-5.5 by using 10 wt% of sodium carbonate solution, and reacting for 5 hours to obtain a second condensation product;
s3: diazotization reaction: 0.05mol of 3,3 '-diamino-4, 3' -disulfonic acid diphenyl sulfone is added into 100ml of water, the temperature is reduced to 0 ℃, 0.25mol of hydrochloric acid is added, and the mixture is stirred for 30 min. Preparing 20 wt% aqueous solution from 0.102mol sodium nitrite, slowly adding the aqueous solution into 4,4 '-diamino-3, 3' -disulfonic acid diphenyl sulfone solution, reacting for 1h at 0 ℃, and removing redundant nitrous acid by sulfamic acid to obtain diazo solution;
s4: coupling reaction: the diazo solution was slowly added to the polycondensate at 5 ℃, and the pH was adjusted to 6.0 to 7.0 with 10 wt% sodium carbonate solution, and reacted for 2h to obtain the red reactive dye compound (i-1), as shown below:
Figure BDA0002040576620000061
application example 2: the 4,4 '-diamino-3, 3' -disulfonic acid diphenyl sulfone prepared in the example 1 is used as an intermediate to synthesize the orange red reactive dye, and the preparation method comprises the following steps:
s1: primary condensation reaction: adding 0.101mol of cyanuric chloride into 100mL of ice water, adding a dispersant EW for pulping, slowly adding a 20% aqueous solution of 0.1mol of gamma acid, and reacting at 0 ℃ for 2h to obtain a condensate;
s2: secondary condensation reaction: adding 0.1mol of para-ester into water to prepare 100mL of solution, regulating the pH value to be 6.0-7.0, slowly adding the solution into the first condensation product, heating the system to 5 ℃, regulating the pH value to be 5.0-5.5 by using 10 wt% of sodium carbonate solution, and reacting for 5 hours to obtain a second condensation product;
s3: diazotization reaction: 0.05mol of 3,3 '-diamino-4, 3' -disulfonic acid diphenyl sulfone is added into 100ml of water, the temperature is reduced to 0 ℃, 0.25mol of hydrochloric acid is added, and the mixture is stirred for 30 min. Preparing 20 wt% aqueous solution from 0.102mol sodium nitrite, slowly adding the aqueous solution into 4,4 '-diamino-3, 3' -disulfonic acid diphenyl sulfone solution, reacting for 1h at 0 ℃, and removing redundant nitrous acid by sulfamic acid to obtain diazo solution;
s4: coupling reaction: slowly adding the diazo solution into the polycondensate at the temperature of 5 ℃, adjusting the pH value to be 6.0-7.0 by using a 10 wt% sodium carbonate solution, and reacting for 2 hours to obtain the orange-red reactive dye compound (I-2), wherein the formula is as follows:
Figure BDA0002040576620000071
application example 3: an orange reactive dye was synthesized using 4,4 '-diamino-3, 3' -disulfonic acid diphenyl sulfone prepared in example 1 as an intermediate, the preparation method comprising the following steps:
s1: primary condensation reaction: adding 0.101mol of cyanuric chloride into 100mL of ice water, adding a dispersant EW for pulping, then slowly adding 0.1mol of a 20% aqueous solution of J acid, and reacting at 0 ℃ for 2h to obtain a condensate;
s2: secondary condensation reaction: adding 0.1mol of para-ester into water to prepare 100mL of solution, regulating the pH value to be 6.0-7.0, slowly adding the solution into the first condensation product, heating the system to 5 ℃, regulating the pH value to be 5.0-5.5 by using 10 wt% of sodium carbonate solution, and reacting for 5 hours to obtain a second condensation product;
s3: diazotization reaction: 0.05mol of 3,3 '-diamino-4, 3' -disulfonic acid diphenyl sulfone is added into 100ml of water, the temperature is reduced to 0 ℃, 0.25mol of hydrochloric acid is added, and the mixture is stirred for 30 min. Preparing 20 wt% aqueous solution from 0.102mol sodium nitrite, slowly adding the aqueous solution into 4,4 '-diamino-3, 3' -disulfonic acid diphenyl sulfone solution, reacting for 1h at 0 ℃, and removing redundant nitrous acid by sulfamic acid to obtain diazo solution;
s4: coupling reaction: the diazo solution was slowly added to the polycondensate at 5 c, and the pH was adjusted to 6.0-7.0 with 10 wt% sodium carbonate solution, and reacted for 2h to obtain orange reactive dye compound (i-3), as shown below:
Figure BDA0002040576620000081
fourth, reference example
Reference example 1: c.i. reactive red 194:
Figure BDA0002040576620000082
reference example 2: reactive orange 16:
Figure BDA0002040576620000083
reference example 3: reactive orange K-GN:
Figure BDA0002040576620000084
fifth, performance test
Taking the reactive dye compounds in application examples 1-3 and reference examples 1-3, dyeing the fabric according to a reactive dye constant temperature process at 60 ℃, wherein the dyeing conditions are alkaline and medium temperature environments with pH of 10-11 and temperature of 60 ℃, the dyeing concentration is 2% o.w.f. (dye to fabric weight), the bath ratio is 20:1, after dyeing, the fabric is subjected to constant temperature and humidity treatment, and the performance of the fabric is tested according to the following standards, and the test results are shown in table 4.
1. And (3) fixation rate: the test is carried out according to GB/T2391-2014 determination of the fixation rate of the reactive dye.
2. Solubility: the test was carried out according to GB/T218379-2015 "filter paper method for determination of solubility of water-soluble dyes".
3. Color fastness to washing: the test is carried out according to GB/T3921-2008 soaping color fastness resistance of textile color fastness test.
4. Color fastness to rubbing: the test is carried out according to GB/T3920-2008 ' color fastness to rubbing ' of textile color fastness test '.
5. Color fastness to perspiration: the test is carried out according to GB/T3922-2013 color fastness to perspiration of textile color fastness test.
6. Color fastness to light: according to GB/T8427-2008 color fastness test for textiles, artificial light color fastness resistance: xenon arc "for testing.
TABLE 4
Figure BDA0002040576620000091
According to the data in table 4, when application example 1 is compared with reference example 1, application example 2 is compared with reference example 2, and application example 3 is compared with reference example 3, it can be seen that the reactive dyes in application examples 1-3 have the color fixing rate of more than 80% compared with the existing reactive dyes, and have good solubility, washing fastness, rubbing fastness, perspiration fastness and light fastness, which indicates that the reactive dye prepared by using 4,4 '-diamino-3, 3' -disulfonic acid diphenyl sulfone as an intermediate in the preparation method has excellent comprehensive performance, and solves the problem of low color fixing rate of the traditional reactive dye.
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.

Claims (4)

1. A preparation method of 4, 4' -diamino disulfonic diphenyl sulfone is characterized in that: the method comprises the following steps: the weight portion is:
s1: taking 40-60 parts of concentrated sulfuric acid and 30-50 parts of fuming sulfuric acid, and uniformly stirring to obtain a sulfonating agent;
s2: 24.83 parts of 4, 4' -diamino diphenyl sulfone is uniformly added into the sulfonating agent at room temperature; then heating to 80-90 ℃ and reacting for 5-7h to obtain reaction liquid;
s3: after the reaction solution is cooled to room temperature, adding the reaction solution into 300 parts of ice water by 200 parts while stirring; adjusting pH to 4 with alkaline agent, stirring for 20-30min, and filtering under reduced pressure to obtain filter cake containing 4, 4' -diamino disulfonated diphenyl sulfone;
4, 4' -diamino disulfonated diphenyl sulfone having the following molecular structure:
Figure FDA0002780105830000011
wherein M is H;
the 4, 4' -diaminodiphenyl sulfone in S2 was added within 30-60 min.
2. The process according to claim 1, wherein the reaction mixture comprises the following components: adding water into the filter cake, stirring for 30-40min, filtering under reduced pressure, and removing insoluble substances; adding sodium chloride solid accounting for 10-20% of the volume of the filtrate into the filtrate for salting out, and filtering under reduced pressure to obtain the 4, 4' -diamino disulfonated diphenyl sulfone.
3. The process according to claim 1, wherein the reaction mixture comprises the following components: in S1, the mass fraction of concentrated sulfuric acid is 98%, and the mass fraction of oleum is 65%.
4. The process according to claim 1, wherein the reaction mixture comprises the following components: the alkaline agent in S2 is one of sodium hydroxide solution or potassium hydroxide solution.
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Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1439801A (en) * 1973-05-10 1976-06-16 Ici Ltd Reactive azo dyestuffs
CH649092A5 (en) * 1979-09-24 1985-04-30 Ciba Geigy Ag Disazo compounds
US5276182A (en) * 1990-07-09 1994-01-04 The Dow Chemical Company Process for preparing polyurea oligomers
CN101440071B (en) * 2008-12-13 2011-06-22 山西大同大学 4,4'-bis[5,6-dichloro-2-benzothiazoleazoamino]biphenyl-3,3'-disulfonic acid and its preparation method and application
PT2418256E (en) * 2010-07-29 2013-05-24 Clariant Finance Bv Ltd Acid dyes
CN106189282B (en) * 2016-08-19 2020-05-26 深圳市志海实业股份有限公司 Calcium-zinc composite stabilizer based on sulfonated polyimide and preparation method thereof

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