CN112321781B - Preparation method of efficient low-cost acid color fixing agent - Google Patents
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- CN112321781B CN112321781B CN202011276043.4A CN202011276043A CN112321781B CN 112321781 B CN112321781 B CN 112321781B CN 202011276043 A CN202011276043 A CN 202011276043A CN 112321781 B CN112321781 B CN 112321781B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/04—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups
- C07C303/06—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups by reaction with sulfuric acid or sulfur trioxide
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- C07—ORGANIC CHEMISTRY
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- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/10—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenol
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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
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/02—After-treatment
- D06P5/04—After-treatment with organic compounds
- D06P5/08—After-treatment with organic compounds macromolecular
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Abstract
The invention provides a preparation method of an efficient low-cost acid color fixing agent, which takes phenol, concentrated sulfuric acid and formaldehyde as raw materials to synthesize an intermediate, takes 4,4' -dihydroxydiphenyl sulfone and 4-hydroxy benzene sulfonic acid as main mixtures, uses alkaline substances to adjust pH to 8-9, carries out condensation reaction by adding 37% formaldehyde solution to obtain the acid color fixing agent, and uses acetic acid to adjust acid when in use. The acid color fixing agent prepared by the method has the advantages of short synthetic route, no need of purification of the produced intermediate, low manufacturing cost, capability of meeting market demands in use performance, capability of saving cost for printing and dyeing enterprises, capability of greatly reducing the discharge of sewage, particularly the discharge of phenol-containing sewage, energy conservation and emission reduction. The color of the acid color fixing agent synthesized by the invention is reduced, the soaping fastness can reach 4-5 levels, particularly the alkali perspiration fastness can reach 4 levels or more, and the acid color fixing agent prepared by a condensation reaction method of high-purity 4,4' -dihydroxydiphenyl sulfone, 4-hydroxy benzenesulfonic acid and formaldehyde solution can be completely replaced.
Description
Technical Field
The invention relates to the technical field of acid color fixing agents, in particular to a preparation method of an efficient low-cost acid color fixing agent.
Background
The acidic color fixing agent is mainly used for improving the wet processing fastness of acidic dyes, acid mordant dyes for dyeing nylon and nylon/spandex fabrics, and generally comprises soaping-resistant color fastness, water-resistant color fastness, acid perspiration-resistant color fastness, alkali perspiration-resistant color fastness, chlorine-resistant color fastness, friction-resistant color fastness and seawater-resistant color fastness. The acid dye is dyed on nylon and nylon/spandex fabrics, mainly under the acid condition, the terminal amino groups of the nylon/spandex fibers absorb hydrogen ions to form cations, the acid dye is anionic and is absorbed on the nylon and the nylon/spandex fabrics through anions and cations, the acid dye absorbed on the fabrics through anion-cation bonds has poor wet treatment fastness, and the dye is easily eluted from the fabrics through soaping and other modes, so that the dyed nylon fabrics have poor color fastness. In particular to nylon/spandex woven elastic fabric, because spandex is difficult to color and has poor binding force, acid dye is only adhered to the surface of spandex fiber, and soaping is easier to fall off, the color fastness of the nylon/spandex woven elastic fabric dyed by the acid dye is poorer. In order to improve and improve the color fastness of the nylon/spandex dyed fabric, the dyeing mill usually adds an acid color fixing agent to perform color fixing treatment after dyeing is finished, so that the wet treatment fastness of the dyed fabric is improved.
The general acidic color fixing agent in the market at present is synthesized into a polymer product mainly formed by condensing 4,4' -dihydroxydiphenyl sulfone, 4-hydroxy benzene sulfonic acid and formaldehyde under alkaline conditions; or 4,4 '-dihydroxydiphenyl sulfone, acetic anhydride, concentrated sulfuric acid and formaldehyde are condensed under acidic conditions to obtain a polymer product, the two synthetic routes are used for taking 4,4' -dihydroxydiphenyl sulfone as raw materials, the purity is required to be high, the purity is required to be over 90-99%, a large amount of phenol-containing wastewater can be generated when the 4,4 '-dihydroxydiphenyl sulfone with high purity is produced, the treatment cost is high, the production cost of the raw materials is high, the price of the 4,4' -dihydroxydiphenyl sulfone is three times as high as the strict requirement of national environmental protection policy, and the color fixing agent manufacturer is hardly accepted. In addition, the color fixing agent in the current market has low comprehensive performance, poor alkali and perspiration fastness, is difficult to meet the requirements of a printing and dyeing mill, and has poor effect on the new water fastness.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of an efficient low-cost acid color fixing agent.
The technical scheme of the invention is as follows: the preparation method of the high-efficiency low-cost acid color fixing agent comprises the following steps of:
s1), 180-220g of phenol is put into a four-neck flask, the temperature is raised to 90-100 ℃, 195-210g of concentrated H is slowly added 2 SO 4 Controlling the dropping speed to ensure that the temperature is controlled to be 100+/-1, starting to keep warm and timing for 3 hours after the completion of dropping, and recording the temperature every 30 minutes;
s2), finishing sulfonation reaction to ensure that the acidity is 27-29;
s3), carrying out sulphone reaction, heating to 130 ℃, adding 85-110g of phenol, continuously heating to 165 ℃, starting heat preservation and timing, starting vacuumizing after 20min, lifting the vacuum degree to 0.005Mpa once every 20min, and maintaining for 2h when the vacuum degree reaches 0.03 Mpa;
s4), after the heat preservation is carried out for 2 hours at 165 ℃, 75-95g of phenol is added for continuous reaction, vacuum pumping is started after 20 minutes, the vacuum degree is increased once every 15 minutes to 0.006Mpa, the vacuum degree is maintained to 0.05Mpa after 90 minutes, and the pressure is maintained for continuous reaction;
s5), after the heat preservation is carried out for 4 hours, the acidity is measured once every 40 minutes, the acidity value is between 6.3 and 7, the reaction is ended, the obtained mixture is an intermediate product, and the next reaction is directly carried out without purification;
s6), firstly, slowly adding 30-40g of intermediate mixture and 30-40g of soft water into a four-mouth reaction bottle, slowly adding 6.0-9.0g of 46% caustic soda solution for neutralization, releasing heat, controlling the temperature to be not more than 70 ℃, adjusting the pH to be about 8.0, then cooling to 60 ℃, slowly adding 6.0-9.0g of 37% formaldehyde solution within 30 minutes, heating to 95-100 ℃, preserving the temperature for 4-5 hours, detecting the viscosity of a reaction system, if the viscosity reaches 5000cPs, stopping the reaction, cooling to 80 ℃, slowly adding 2-4g of diethylene glycol, cooling to 50 ℃, and adding water to adjust the solid content to be 40-50%.
Further, in step S1), the molar ratio of the concentrated sulfuric acid to phenol is 1:1.2-1.05.
Further, in the step S2), the molar ratio of the using amount of the phenol to the adding amount of the concentrated sulfuric acid in the sulphonylation reaction is 1:0.9-1.0, and the phenol is added in two portions.
Further, in the step S5), the intermediate product is 4,4' -dihydroxydiphenyl sulfone or 4-hydroxybenzenesulfone.
Further, in step S5), the intermediate product further comprises a small amount of 2,4' -dihydroxydiphenyl sulfone, triphenylsulfone monomer.
Further, the contents of the components of the intermediate product are as follows, and the following components are in percentage by mass:
further, the structures of the 4,4 '-dihydroxydiphenyl sulfone, the 2,4' -dihydroxydiphenyl sulfone, the triphenylsulfone and the 4-hydroxybenzenesulfonic acid are respectively as follows:
the beneficial effects of the invention are as follows:
1. the invention takes phenol, concentrated sulfuric acid, formaldehyde and sodium hydroxide as raw materials, and simultaneously utilizes a one-bath two-step method to synthesize the high-efficiency acid color fixing agent which has low cost, good color fixing effect and can meet the requirements of printing and dyeing factories;
2. compared with the production cost of the acid color fixing agent in the current market, the production cost of the acid color fixing agent is reduced by half, and the molecular weight ratio of the acid color fixing agent synthesized by the method is moderate;
3. the invention also contains a small amount of 2,4' -dihydroxydiphenyl sulfone and triphenylsulfone monomers, which is helpful for improving the bubble fastness of nylon and nylon/spandex dyed fabrics;
4. the acid color fixing agent obtained by the reaction avoids directly using high-purity 4,4 '-dihydroxydiphenyl sulfone, indirectly reduces the sewage discharge of 4,4' -dihydroxydiphenyl sulfone production, and is an ecological environment-friendly synthetic acid color fixing agent route;
5. the invention can accurately regulate and control the composition and proportion of the intermediate mixture through the novel process, thereby controlling the effect of the acid color fixing agent of the final product;
6. the color of the acid color fixing agent synthesized by the invention is reduced, the soaping fastness can reach 4-5 levels, particularly the alkali perspiration fastness can reach 4 levels or more, and the acid color fixing agent prepared by a condensation reaction method of high-purity 4,4' -dihydroxydiphenyl sulfone (more than 95%), 4-hydroxybenzenesulfonic acid and formaldehyde solution can be completely replaced;
7. according to the invention, the reaction conditions of phenol and concentrated sulfuric acid are controlled, so that the produced intermediate bisphenol S and phenol sulfonic acid reach the expected content, other byproducts are less, and the condensation reaction with formaldehyde is easy to carry out;
8. the acid color fixing agent prepared by the invention has the advantages of short synthetic route, no need of purification of the produced intermediate, low manufacturing cost, capability of meeting market demands in terms of service performance, cost saving for printing and dyeing enterprises, capability of greatly reducing the discharge of sewage, particularly phenol-containing sewage, and energy conservation and emission reduction, and is a green synthetic method of the acid color fixing agent.
Drawings
FIG. 1 is a synthetic scheme of example 1 of the present invention.
Detailed Description
The following is a further description of embodiments of the invention, taken in conjunction with the accompanying drawings:
example 1
The embodiment provides a preparation method of an efficient low-cost acid color fixing agent, which comprises the following steps:
step one, intermediate synthesis:
sulfonation reaction: phenol: 188g (2 mol); concentrated H 2 SO 4 ：200g(2.04mol)；
Sulphone reaction: phenol: 178.6g (1.9 mol);
the synthesis steps are as follows:
188g phenol is put into a four-mouth flask, the temperature is raised to 95 ℃, and 200g of concentrated H is slowly added 2 SO 4 Controlling the dropping speed to control the temperature to be 95-100 ℃, starting to keep the temperature and time for 3 hours after the completion of dropping, recording the temperature every 30 minutes, and observing the experimental phenomenon;
(II) after sulfonation, measuring acidity, and the correct value is 27;
heating to 130 ℃, adding 89.3g of phenol, continuously heating to 165 ℃, starting heat preservation and timing, starting vacuumizing after 20min, lifting the vacuum degree to 0.005Mpa every 20min, and maintaining the timing for 2h when reaching 0.03 Mpa;
fourthly, after the temperature is kept at 165 ℃ for 2 hours, 89.3g of phenol is added for continuous reaction, vacuum pumping is started after 20 minutes, the vacuum degree is lifted once every 15 minutes to be 0.006Mpa, the vacuum degree is kept at 0.05Mpa after 90 minutes, and the pressure is kept for continuous reaction;
and (V) after 4 hours of heat preservation, measuring the acidity, and measuring the acidity once every 40 minutes to ensure that the acidity value is about 6.3, ending the reaction, wherein the obtained mixture is an intermediate product, and directly carrying out the next reaction without purification.
And (3) synthesizing an acid color fixing agent in the second step:
the synthesis steps are as follows:
firstly, 40g of intermediate mixture and 40g of soft water are slowly added into a 1000ml four-port reaction bottle, 8.5g of 46% caustic soda solution is slowly added for neutralization, heat is released, the temperature is controlled to be not more than 70 ℃, the pH is regulated to be about 8.0, the temperature is reduced to 60 ℃,8.5g of 37% formaldehyde solution is slowly added within 30 minutes, the temperature is raised to 95-100 ℃ for 4.5 hours, the viscosity of a reaction system is detected, if the viscosity reaches 5000cPs, the reaction is stopped, the temperature is reduced to below 80 ℃, 3.0g of diglycol is slowly added, the temperature is reduced to 50 ℃, water is added, and the solid content is regulated to be about 50%.
Example 2
The embodiment provides a preparation method of an efficient low-cost acid color fixing agent, which comprises the following steps:
step one, intermediate synthesis:
sulfonation reaction: phenol: 200g; concentrated H 2 SO 4 ：210g；
Sulphone reaction: phenol: 188.6g;
the synthesis steps are as follows:
200g of phenol is put into a four-necked flask, the temperature is raised to 95 ℃, and 210g of concentrated H is slowly added 2 SO 4 Controlling the dropping speed to control the temperature to be 95-100 ℃, starting to keep the temperature and time for 3 hours after the completion of dropping, recording the temperature every 30 minutes, and observing the experimental phenomenon;
(II) after sulfonation, measuring acidity, and the correct value is 27;
heating to 130 ℃, adding 94.3g of phenol, continuously heating to 165 ℃, starting heat preservation and timing, starting vacuumizing after 20min, lifting the vacuum degree to 0.005Mpa every 20min, and maintaining the timing for 2h when the vacuum degree reaches 0.03 Mpa;
fourthly, after the temperature is kept at 165 ℃ for 2 hours, 94.3g of phenol is added for continuous reaction, vacuum pumping is started after 20 minutes, the vacuum degree is lifted once every 15 minutes to be 0.006Mpa, the vacuum degree is kept at 0.05Mpa after 90 minutes, and the pressure is kept for continuous reaction;
and (V) after 4 hours of heat preservation, measuring the acidity, and measuring the acidity once every 40 minutes to ensure that the acidity value is about 6.3, ending the reaction, wherein the obtained mixture is an intermediate product, and directly carrying out the next reaction without purification.
And (3) synthesizing an acid color fixing agent in the second step:
the synthesis steps are as follows:
firstly, 30g of intermediate mixture and 30g of soft water are slowly added into a 1000ml four-port reaction bottle, 6g of 46% caustic soda solution is slowly added for neutralization, heat is released, the temperature is controlled to be not more than 70 ℃, the pH is regulated to be about 8.0, the temperature is reduced to 60 ℃,6g of 37% formaldehyde solution is slowly added within 30 minutes, the temperature is raised to 95-100 ℃ for 4.5 hours, the viscosity of a reaction system is detected, if the viscosity reaches 5000cPs, the reaction is stopped, the temperature is reduced to be lower than 80 ℃, 2g of diethylene glycol is slowly added, the temperature is reduced to be lower than 50 ℃, and the solid content is regulated to be about 50 percent by adding water.
Example 3
The embodiment provides a preparation method of an efficient low-cost acid color fixing agent, which comprises the following steps:
step one, intermediate synthesis:
sulfonation reaction: phenol: 180g; concentrated H 2 SO 4 ：195g；
Sulphone reaction: phenol: 170g;
the synthesis steps are as follows:
180g of phenol is put into a four-necked flask, the temperature is raised to 95 ℃, 195g of concentrated H is slowly added 2 SO 4 Controlling the dropping speed to control the temperature to be 95-100 ℃, starting to keep the temperature and time for 3 hours after the completion of dropping, recording the temperature every 30 minutes, and observing the experimental phenomenon;
(II) after sulfonation, measuring acidity, and the correct value is 28;
heating to 130 ℃, adding 85g of phenol, continuously heating to 165 ℃, starting heat preservation and timing, starting vacuumizing after 20min, lifting the vacuum degree to 0.005Mpa once every 20min, and maintaining the timing for 2h when reaching 0.03 Mpa;
fourthly, after the temperature is kept at 165 ℃ for 2 hours, 85g of phenol is added for continuous reaction, vacuum pumping is started after 20 minutes, the vacuum degree is increased once every 15 minutes to 0.006mpa, the vacuum degree is kept at 0.05Mpa after 90 minutes, and the pressure is maintained for continuous reaction;
and (V) after 4 hours of heat preservation, measuring the acidity, and measuring the acidity once every 40 minutes to ensure that the acidity value is about 6.3, ending the reaction, wherein the obtained mixture is an intermediate product, and directly carrying out the next reaction without purification.
And (3) synthesizing an acid color fixing agent in the second step:
the synthesis steps are as follows:
firstly, adding 35g of intermediate mixture and 35g of soft water into a 1000ml four-port reaction bottle, slowly adding 9g of 46% caustic soda solution for neutralization, releasing heat, controlling the temperature to be not more than 70 ℃, adjusting the pH to be about 8.0, cooling to 60 ℃, slowly adding 9g of 37% formaldehyde solution in 30 minutes, heating to 95-100 ℃ for 4.5 hours, detecting the viscosity of a reaction system, if the viscosity reaches 5000cPs, stopping the reaction, cooling to below 80 ℃, slowly adding 4g of diethylene glycol, cooling to 50 ℃, adding water, and adjusting the solid content to be about 50%.
Example 4
Performance testing
A fabric: a pure nylon fabric; nylon/spandex fabric
The formula of the dye comprises the following components:
first, brilliant blue
Acid brilliant blue C-RL 2.0% (owf)
Glacial acetic acid 0.5g/L
The bath ratio is 1:10, 100 ℃ for 40 minutes
(II) scarlet
Acid scarlet FGS 2.0% (owf)
Glacial acetic acid 0.5g/L
The bath ratio is 1:10, 100 ℃ for 40 minutes
(III) Black
The color fixation process comprises the following steps:
example 1.0% (owf)
Glacial acetic acid 1.0g/L
The bath ratio is 1:15, the temperature is 75 ℃ for x25 minutes, the color fixation is finished, the cleaning is carried out by clean water, and the soap washing is avoided
Test results:
the soaping-resistant color fastness and the bubble fastness of the example 1 are shown in the table 1, the alkali-resistant perspiration color fastness is shown in the table 2, and the test effects of the table 1 and the table 2 show that the example 1 has good soaping fastness and bubble fastness to nylon and nylon/spandex fabrics, and the color fixing effect to pure nylon is better than that of the nylon/spandex fabrics. The alkali-resistant perspiration fastness of the nylon/spandex fabric is greatly improved in the embodiment 1, and the grade 4 or more can be achieved.
Table 1 example 1 evaluation of fastness to washing
Table 2 example 1 evaluation of alkali-fastness to perspiration
The foregoing embodiments and description have been provided merely to illustrate the principles and best modes of carrying out the invention, and various changes and modifications can be made therein without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (5)
1. The preparation method of the high-efficiency low-cost acid color fixing agent is characterized by comprising the following steps of:
s1), 180-220g of phenol is put into a four-neck flask, the temperature is raised to 90-100 ℃, 195-210g of concentrated H is slowly added 2 SO 4 Controlling the dropping speed to control the temperature to be 100 DEG C1, starting heat preservation and timing for 3 hours after dripping is completed, and recording the temperature every 30 minutes;
s2), finishing sulfonation reaction to ensure that the acidity is 27-29;
s3), carrying out sulphone reaction, heating to 130 ℃, adding 85-110g of phenol, continuously heating to 165 ℃, starting heat preservation and timing, starting vacuumizing after 20min, lifting the vacuum degree to 0.005Mpa once every 20min, and maintaining for 2h when the vacuum degree reaches 0.03 Mpa;
s4), after the heat preservation is carried out for 2 hours at 165 ℃, 75-95g of phenol is added for continuous reaction, vacuum pumping is started after 20 minutes, the vacuum degree is increased once every 15 minutes to 0.006Mpa, the vacuum degree is maintained to 0.05Mpa after 90 minutes, and the pressure is maintained for continuous reaction;
s5), after the heat preservation is carried out for 4 hours, the acidity is measured once every 40 minutes, the acidity value is between 6.3 and 7, the reaction is ended, the obtained mixture is an intermediate product, and the next reaction is directly carried out without purification;
s6), firstly, slowly adding 30-40g of intermediate mixture and 30-40g of soft water into a four-mouth reaction bottle, slowly adding 6.0-9.0g of 46% caustic soda solution for neutralization, releasing heat, controlling the temperature to be not more than 70 ℃, adjusting the pH to be about 8.0, then cooling to 60 ℃, slowly adding 6.0-9.0g of 37% formaldehyde solution within 30 minutes, heating to 95-100 ℃, preserving the temperature for 4-5 hours, detecting the viscosity of a reaction system, if the viscosity reaches 5000cPs, stopping the reaction, cooling to 80 ℃, slowly adding 2-4g of diethylene glycol, cooling to 50 ℃, and adding water to adjust the solid content to be 40-50%.
2. The method for preparing the efficient low-cost acidic color fixing agent according to claim 1, which is characterized in that: in the step S1), the molar ratio of the concentrated sulfuric acid to the phenol is 1:1.2-1.05.
3. The method for preparing the efficient low-cost acidic color fixing agent according to claim 1, which is characterized in that: in the step S5), the intermediate product is 4,4' -dihydroxydiphenyl sulfone and 4-hydroxy benzene sulfonic acid.
4. The method for preparing the efficient low-cost acidic color fixing agent according to claim 3, which is characterized in that: in step S5), the intermediate product further comprises a small amount of 2,4' -dihydroxydiphenyl sulfone, triphenylsulfone monomer.
5. The method for preparing the efficient low-cost acidic color fixing agent according to claim 3 or 4, which is characterized in that: the intermediate product comprises the following components in percentage by mass:
wherein, the structures of the 4,4 '-dihydroxydiphenyl sulfone, the 2,4' -dihydroxydiphenyl sulfone, the triphenylsulfone and the 4-hydroxy benzenesulfonic acid are respectively as follows:
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1901536A (en) * | 1930-11-11 | 1933-03-14 | Firm Of J R Geigy S A | Manufacture of tanning substances |
| FR1364988A (en) * | 1963-07-30 | 1964-06-26 | Geigy Ag J R | Finishing of dyes and prints on polyamide fibers |
| FR2398835A1 (en) * | 1977-07-28 | 1979-02-23 | Protex Manuf Prod Chimiq | Fixing agent for dyes on polyamide fibres - consists of phenolic novolak resin with low free phenol content |
| CN104513349A (en) * | 2013-09-26 | 2015-04-15 | 五邑大学 | Acidic dye-fixing agent and preparation method thereof |
| CN107841896A (en) * | 2017-11-24 | 2018-03-27 | 约克夏染料（中山）有限公司 | A kind of preparation method of acid dyes color fixing agent |
-
2020
- 2020-11-16 CN CN202011276043.4A patent/CN112321781B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1901536A (en) * | 1930-11-11 | 1933-03-14 | Firm Of J R Geigy S A | Manufacture of tanning substances |
| FR1364988A (en) * | 1963-07-30 | 1964-06-26 | Geigy Ag J R | Finishing of dyes and prints on polyamide fibers |
| FR2398835A1 (en) * | 1977-07-28 | 1979-02-23 | Protex Manuf Prod Chimiq | Fixing agent for dyes on polyamide fibres - consists of phenolic novolak resin with low free phenol content |
| CN104513349A (en) * | 2013-09-26 | 2015-04-15 | 五邑大学 | Acidic dye-fixing agent and preparation method thereof |
| CN107841896A (en) * | 2017-11-24 | 2018-03-27 | 约克夏染料（中山）有限公司 | A kind of preparation method of acid dyes color fixing agent |
Non-Patent Citations (1)
| Title |
|---|
| 酸性染料固色剂TF-506S的合成及性能研究;张红燕等;《印染助剂》;20100920(第09期);第189页 * |
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