CN103524385B - Preparation method for modified disperse dye dispersing agent and product - Google Patents
Preparation method for modified disperse dye dispersing agent and product Download PDFInfo
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Abstract
The invention discloses a preparation method for a modified disperse dye dispersing agent. The preparation method comprises the following steps of heating a naphthalene compound to 130-170 DEG C, adding sulfuric acid to perform sulfonation reaction, cooling to 100-130 DEG C after the sulfonation reaction is finished, adding water, cooling to 80-100 DEG C after the reaction is finished, adding an aldehyde compound to perform primary condensation reaction under a temperature condition until the reaction is finished, adding an isomer mixture of CLT (cross laminated timber) acid, heating to 80-100 DEG C, adding the aldehyde compound again to perform secondary condensation reaction, and obtaining the modified disperse dye dispersing agent after the reaction is finished. The invention also provides a dispersing agent product obtained by the method. Wastewater produced by the CLT acid produced in an organic pigment production process is used as a part of production raw materials for producing the modified disperse dye dispersing agent, so that the production cost of the modified disperse dye dispersing agent is reduced, and the pollution caused by the production of the wastewater through the CLT acid on the environment is alleviated; the modified disperse dye dispersing agent is suitable for industrial production.
Description
Technical field
The invention belongs to field of chemical technology, specifically relate to a kind of preparation method and product of modification dispersed dye diffusant.
Background technology
In the commercialization course of processing of dispersed dye, dispersed dye are ground into tiny particle, are conducive to its absorption in polyester fibre surface, are finally diffused in the inside of fiber and go, complete whole dyeing course.And adding of dispersion agent, be then be used to improve the dispersing property of such dyestuff in water, prevent in dyeing course, the phenomenons such as the crystal growth that tiny dye granule occurs in dye bath, gathering, aggegation, thus have influence on the quality of dyeing keratin-fiber.
Naphthalene system dispersed dye diffusant belongs to naphthalene sulfonic formaldehyde condensation compound, belong to use to obtain the most general type disperse dye diffusant in dispersed dye diffusant family, naphthalene system dispersed dye diffusant produce generally all with naphthalene or methylnaphthalene for raw material is prepared from through sulfonation, hydrolysis, condensation, neutralization, desalination etc., in order to reduce raw materials cost, very great dispersed dye diffusant production unit all replaces naphthalene or methylnaphthalene to produce with coal tar wash oil or oil washing oil at present.
The chloro-5-phenylmethylamine of CLT acid formal name used at school 2--4-sulfonic acid, it is a kind of important organic red pigment intermediate, mainly for the production of c.I. Pigment red 52 and c.I. Pigment red 53 on pigment industry, this pigment is widely used in paint, coating, colored ink, rubber and coloring plastic etc.CLT acid is that Year's consumption crosses one of organic intermediate of ten thousand tons in the world.In pigment dyestuff intermediate CLT acid production process, after the hydrogenation reduction stage completes, the various isomer mixture of CLT acid of nearly 1/4 can be produced, this component of mixture is more complicated, if be isolated not in time, the product purity that will affect the chloro-3-phenylmethylamine of certified products 6--4-sulfonic acid and the coloured light of pigment dyestuff be later synthesized.But how about the various isomer mixture of CLT acid of produce after separating nearly 1/4 is used, and makes it the raw material become in industrial production, it is a puzzlement researchist's difficult problem always.
The document of the domestic and international report section of having CLT acid factory effluent reuse is less.Publication number is that the Chinese patent literature of CN102731011A discloses high efficiency water reducing agent that a kind of CLT acid factory effluent is Material synthesis and production technique comprises CLT acid factory effluent, phenol compound and solvent mixture heating for dissolving, adjust pH; After adding aldehyde compound and auxiliary agent, insulation reaction; Reaction terminates rear cooling.Above-mentioned technique is using the waste water of the phenyl ring class isomer mixture of generation in CLT acid production as the raw materials for production of sulfamate high-effective water-reducing agent, on the one hand regeneration industrial waste, on the other hand, the raw materials cost of sulfamate high-effective water-reducing agent reduces about 30%, greatly improves the competitive power of product.
But the amount of the CLT acid factory effluent of annual domestic generation is very huge, only above-mentioned a kind of way of recycling is difficult to the technical problem thoroughly solving the recovery of CLT acid factory effluent.So for reducing environmental stress, reduce enterprise's input cost, the waste water recycling mode of exploitation diversification, has great strategic importance.
Summary of the invention
The invention provides a kind of preparation method of modification dispersed dye diffusant, the method adopts in naphthalene system dispersed dye diffusant production process, add the various isomer mixture of CLT acid, it is made to participate in the condensation reaction of aldehyde compound, thus produce the cheaper modification dispersed dye diffusant of price, both the production cost of modification dispersed dye diffusant had been reduced, additionally reduce the by product-CLT acid produced in pigment dyestuff intermediate CLT acid production process various isomer mixture possibility pollution on the environment, suitability for industrialized production is made to obtain comprehensively, the development of sustainability.
A preparation method for modification dispersed dye diffusant, comprising:
(1) naphthalene compound is heated to 130-170 DEG C, adds sulfuric acid and carry out sulfonation reaction, after sulfonation reaction terminates, be cooled to 100-130 DEG C, add water, under this temperature condition, reaction terminates;
(2) material that step (1) obtains is cooled to 80-100 DEG C, adds aldehyde cpd, under this temperature condition, carry out primary condensation reaction, to reacting end;
(3) in the reaction system liquid of step (2), add the isomer mixture of CLT acid, be warming up to 80-100 DEG C, add aldehyde cpd, carry out consecutive condensation, reaction terminates aftertreatment and obtains modification dispersed dye diffusant.
In step (1), described naphthalene compound comprises one or more in the compound such as naphthalene, methylnaphthalene, and other contain the industrial chemicals or waste liquid etc. of methylnaphthalene, naphthalene also to comprise coal tar wash oil, oil washing oil etc.In described coal tar wash oil, oil washing oil, the total weight percent content of methylnaphthalene and naphthalene is generally 50-90%, and the weight percent content of methylnaphthalene is generally 50-80%.Described sulfuric acid is generally the vitriol oil that purity is 98%.
The sulfonation reaction of naphthalene or methylnaphthalene is an electrophilic substitution reaction, and when temperature is lower, (35 ~ 60 DEG C) obtain product mainly α-naphthalenesulfonicacid or alpha-methyl-naphthalene sulfonic acid; Then mainly beta-naphthalenesulfonic-acid or beta-methylnaphthalene sulfonic acid is generated when temperature is higher.And the condensation reaction of naphthene sulfonic acid or methyl naphthalene sulfonic acid and formaldehyde is a cationoid reaction, when on naphthalene nucleus with the reactive behavior that can reduce naphthalene nucleus during the electron withdrawing groups such as sulfonic group, when α-naphthalenesulfonicacid or alpha-methyl-naphthalene sulfonic acid and formaldehyde condensation, steric hindrance is unfavorable for more greatly the carrying out of condensation reaction; Beta-naphthalenesulfonic-acid or beta-methylnaphthalene sulfonic acid then not presence bit inhibition effect, makes reaction carry out towards the direction generating beta-naphthalenesulfonic-acid or beta-methylnaphthalene sulfonic acid so should control reaction conditions in sulfonation reaction step; Experiment shows that vitriol oil concentration is more conducive to more greatly generating beta-naphthalenesulfonic-acid or beta-methylnaphthalene sulfonic acid, so the concentration of the preferred vitriol oil is more than or equal to 98%; The control of temperature of reaction is also conducive to beta-naphthalenesulfonic-acid in addition or beta-methylnaphthalene sulfonic acid generates, so temperature of reaction controls at 130-170 DEG C, is preferably 140-160 DEG C.Adding the object that water carries out reacting in this step is that the α-naphthalenesulfonicacid of generation or alpha-methyl-naphthalene sulfonic acid are converted into beta-naphthalenesulfonic-acid or beta-methylnaphthalene sulfonic acid, is beneficial to follow-up condensation reaction.
In step (1), the mol ratio of described sulfuric acid, water and naphthalene compound is 1-2:1-2:1.The time of described sulfonation reaction is about 1-6 hour, and after adding water, the time of reaction is about 0.5-4 hour.
In step (2), described aldehyde cpd comprises one or more in the compounds such as formaldehyde, trioxymethylene, acetaldehyde, propionic aldehyde, butyraldehyde, valeral, furfural, more preferably formaldehyde.Described aldehyde cpd and the mol ratio of naphthalene compound are 1.5-5:1.The reaction times of described condensation reaction is generally 3-7 hour.The aldehyde cpd added in this step is mainly used in carrying out condensation reaction with naphthalene compound.
In step (3), the isomer mixture of CLT acid can be arbitrary isomer of CLT acid or the mixture of isomer.As preferably, the isomer mixture of described CLT acid is at least two kinds in compound shown in formula (1)-(6):
As preferably, the isomer mixture of described CLT acid is the mixture of any ratio of the composition of compound shown in formula (1)-(6).In CLT acid factory effluent, mainly containing the compound shown in formula (1)-(6), during actual use, can directly add CLT acid factory effluent, the weight percent content of this compound shown in waste water Chinese style (1)-(6) is generally 20 ~ 40%.In the isomer mixture of described CLT acid, the isomer of CLT acid and the mol ratio of naphthalene compound are 0.1-1:1.The isomer that the aldehyde cpd added in this step is mainly used in realizing CLT acid participates in condensation reaction, in step (3), described aldehyde cpd comprises one or more in the compounds such as formaldehyde, trioxymethylene, acetaldehyde, propionic aldehyde, butyraldehyde, valeral, furfural, more preferably formaldehyde.The mol ratio 1-1.2:1 of described aldehyde cpd and the isomer of CLT acid.
The condensation reaction time of step (3) is generally 2-5 hour, the intermediates that a kind of solid content is 50-60% are obtained after having reacted, through neutralization, the last handling processes such as desalination, the modification dispersed dye diffusant liquid product that a kind of solid content is 30-40% can be obtained, also spray-driedly can obtain a kind of modification dispersed dye diffusant powder-like product.
Present invention also offers a kind of modification dispersed dye diffusant product prepared by aforesaid method, for formaldehyde as raw material, its structure is shown below:
In above formula, R1 is Cl, R2 is CH
3, R3 is H or CH
3, n=5-7, m=1-2.
This modification dispersed dye diffusant is both containing naphthene sulfonic acid quasi-molecule structure, again containing aniline sulfonic acid quasi-molecule structure, owing to introducing amino phenyl sulfonyl acid molecular structures, namely improve the avidity of dispersed dye diffusant and dispersed dye, the diffusive force of dispersed dye diffusant can be improved again.
Compared with prior art, beneficial effect of the present invention is embodied in:
(1) present method is a kind of commercial run, and its preparation process operation steps is simple, can complete in same reactor;
(2) the present invention make use of the various isomer mixture of byproduct-CLT acid that produces in the production process of the pigment dyestuff intermediate CLT acid a part of raw materials for production as production modification dispersed dye diffusant, by adding naphthalene compounds, sulfuric acid, aldehyde compound, under certain reaction conditions, carry out being obtained by reacting modification dispersed dye diffusant liquid product or modification dispersed dye diffusant powder-like product that solid content is 30-40%, both the production cost of modification dispersed dye diffusant had been reduced, additionally reduce the by product-CLT acid produced in pigment dyestuff intermediate CLT acid production process various isomer mixture possibility pollution on the environment, suitability for industrialized production is made to obtain comprehensively, the development of sustainability.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1
One, modification dispersed dye diffusant production formula (weight part):
Two, modification dispersed dye diffusant production technique:
In the reactor, add technical methylnaphthalene 20.0 parts (being selected from methylnaphthalene content >=60% of Zhejiang development of evil in febrile disease limited energy company), be warming up to 140 DEG C; Be added dropwise to 98% sulfuric acid amount 20.5 parts, temperature control to 160 DEG C; Dropwise, back flow reaction 5 hours; Be cooled to 110 DEG C; Add 5.4 parts, water; Back flow reaction 3 hours; Be cooled to 90 DEG C; Be added dropwise to 14.5 parts, 37% formaldehyde, temperature control to 90 DEG C; Back flow reaction 6 hours; Add the CLT acid waste water 16.5 parts (being selected from the CLT acid waste water that Zhejiang Qinyan Chemical Co., Ltd. produces) containing the various isomer of 23%CLT acid, be warming up to 90 DEG C; Be added dropwise to 1.5 parts, 37% formaldehyde, temperature control to 90 DEG C; Back flow reaction 4 hours; Obtain the intermediates that a kind of solid content is 55%.Neutralization residual sulfuric acid wherein, desalination, obtains the modification dispersed dye diffusant liquid product that a kind of solid content is 35%, also spray-driedly can obtain a kind of modification dispersed dye diffusant powder-like product.
Embodiment 2
One, modification dispersed dye diffusant production formula (weight part):
Two, modification dispersed dye diffusant production technique:
In the reactor, add coal tar wash oil 17.0 parts (adopt Hunan steel coal tar wash oil, the content of methylnaphthalene is about 50%), be warming up to 150 DEG C; Be added dropwise to 98% sulfuric acid amount 18.0 parts, temperature control to 160 DEG C; Dropwise, back flow reaction 5 hours; Be cooled to 110 DEG C; Add 3.9 parts, water; Back flow reaction 3 hours; Be cooled to 90 DEG C; Be added dropwise to 12.3 parts, 37% formaldehyde, temperature control to 90 DEG C; Back flow reaction 7 hours; Add the CLT acid waste water 27.9 parts containing the various isomer of 23%CLT acid, be warming up to 90 DEG C; Be added dropwise to 2.4 parts, 37% formaldehyde, temperature control to 90 DEG C; Back flow reaction 4 hours; Obtain the intermediates that a kind of solid content is 60%.Neutralization, desalination, obtains the modification dispersed dye diffusant liquid product that a kind of solid content is 40%, also spray-driedly can obtain a kind of modification dispersed dye diffusant powder-like product.
Modification dispersed dye diffusant embodiment 1 and embodiment 2 prepared carries out performance test, and test result is as shown in table 1:
Table 1
As shown in Table 1, the modification dispersed dye diffusant that the inventive method prepares meets the performance requriements of HG/T2499-2006 about dispersion agent completely.During the actual use of modification dispersed dye diffusant of the present invention, consumption is similar to the usage quantity of existing Dispersant MF, can adjust according to actual needs.
Claims (7)
1. a preparation method for modification dispersed dye diffusant, comprising:
(1) naphthalene compound is heated to 130-170 DEG C, adds sulfuric acid and carry out sulfonation reaction, after sulfonation reaction terminates, be cooled to 100-130 DEG C, add water, under this temperature condition, reaction terminates;
(2) material that step (1) obtains is cooled to 80-100 DEG C, adds aldehyde cpd, under this temperature condition, carry out primary condensation reaction, to reacting end;
(3) in the reaction system liquid of step (2), add the isomer mixture of CLT acid, be warming up to 80-100 DEG C, add aldehyde cpd, carry out consecutive condensation, reaction terminates aftertreatment and obtains modification dispersed dye diffusant;
The isomer mixture of described CLT acid is at least two kinds in compound shown in formula (1)-(6):
In step (2) and step (3), described aldehyde cpd is formaldehyde;
In step (2), described aldehyde cpd and the mol ratio of naphthalene compound are 1.5-5:1.
2. the preparation method of modification dispersed dye diffusant according to claim 1, is characterized in that, in step (1), described naphthalene compound is at least one in naphthalene, methylnaphthalene, coal tar wash oil, oil washing oil.
3. the preparation method of modification dispersed dye diffusant according to claim 1, is characterized in that, in step (1), the mol ratio of described sulfuric acid, water and naphthalene compound is 1-2:1-2:1.
4. the preparation method of modification dispersed dye diffusant according to claim 1, it is characterized in that, the isomer mixture of described CLT acid is CLT acid factory effluent, and the weight percent content of this compound shown in waste water Chinese style (1)-(6) is 20 ~ 40%.
5. the preparation method of modification dispersed dye diffusant according to claim 1, is characterized in that, in the isomer mixture of described CLT acid, the isomer of CLT acid and the mol ratio of naphthalene compound are 0.1-1:1.
6. the preparation method of modification dispersed dye diffusant according to claim 1, is characterized in that, in step (3), and the mol ratio 1-1.2:1 of described aldehyde cpd and the isomer of CLT acid.
7. a modification dispersed dye diffusant product, is characterized in that, described modification dispersed dye diffusant product is prepared by the preparation method described in the arbitrary claim of claim 1 ~ 6.
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| CN104892468A (en) * | 2015-05-21 | 2015-09-09 | 天津大学 | Preparation method of sodium 6-chloro-3-nitromethylbenzoyl-4-sulfonate |
| CN106590012B (en) * | 2016-11-30 | 2019-03-12 | 浙江秦燕科技股份有限公司 | The isomer mixture of CLT acid prepares the method and product of acid dyes original powder |
| CN106590013B (en) * | 2016-11-30 | 2019-03-05 | 浙江秦燕科技股份有限公司 | The isomer mixture of CLT acid prepares acid dyes original powder and product |
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Address after: Shangyu Weiyi Industrial Park 312369 Zhejiang city of Shaoxing province Shangyu city Hangzhou Bay No. 1 Patentee after: ZHEJIANG QINYAN TECHNOLOGY CO., LTD. Address before: Shangyu Weiyi Industrial Park 312369 Zhejiang city of Shaoxing province Shangyu city Hangzhou Bay No. 1 Patentee before: Zhejiang Qinyan Chemical Co., Ltd. |