CN102093265A - Intermediate for electrochemical clean dyeing and preparation method thereof - Google Patents

Abstract

The invention relates to an intermediate for electrochemical clean dyeing and a preparation method thereof. The intermediate is alkyl anthraquinone sulfonate, has surface activity, can disperse and reduce dye, has electrochemical activity, can transmit electrons, and can serve as an intermediate and a dye dispersing agent for transmitting the electrons during the electrochemical clean dyeing. The preparation method comprises the following steps of: performing an acylation reaction on phthalic anhydride and alkylbenzene in the presence of anhydrous aluminium chloride to obtain 2-(4'-alkylbenzene formoxyl) benzoic acid; performing dehydration and ring closure on the 2-(4'-alkylbenzene formoxyl) benzoic acid to generate 2-alkyl anthraquinone; and performing sulfonation and neutralization to obtain alkyl anthraquinone sulfonate.

Description

Intermediates for electrochemical cleaning and dyeing and preparation methods thereof

technical field

The invention relates to a compound and a preparation method thereof, in particular to an intermediate used as redox electron transfer in electrochemical cleaning and dyeing and a preparation method thereof.

Background technique

As we all know, the dyeing of traditional vat dyes requires the use of reducing agents (sodium dithionate) to convert the dyes into soluble leucosomes before they can be dyed on fabrics. This process requires a large amount of reducing agents, and the dyeing process is complicated. A large amount of difficult-to-treat saline colored wastewater is produced. The above shortcomings can be overcome by using electrochemical reduction instead of traditional reducing agent reduction, and the complete recycling of dyeing wastewater. For soluble vat dyes, direct electrochemical dyeing can be carried out, but for insoluble vat dyes, it is difficult for the dye to directly contact with the electrode, and intermediates that can transfer electrons need to be added for indirect electrochemical dyeing. In the prior art, triethanolamine iron complexes are mainly used as electron transfer intermediates, but the main disadvantages of this process are poor levelness and generation of iron-containing wastewater.

Contents of the invention

The technical problem to be solved by the present invention is: to propose a more effective intermediate, which also has the dispersing effect of surfactants while transferring electrons, and can obtain fabrics with good level dyeing properties; Preparation.

The technical solution adopted in the present invention is: an intermediate used for electrochemical cleaning and dyeing, the intermediate is alkyl anthraquinone sulfonate, which is acylated by alkylbenzene and phthalic anhydride, It can be obtained by dehydration ring closure, sulfonation and neutralization. The alkyl group of the alkyl anthraquinone sulfonate is a mixture of one or more of straight chains or branched chains with a chain length of 6-16; the alkyl anthraquinone sulfonate is ammonium salt, sodium salt or one of the potassium salts.

The present invention not only has electrochemical activity, but also has surface active material, and its structure is as follows:

R=C _n H _2n+1 , n=6~16; M=NH ₄ ⁺ , Na ⁺ , K ⁺ .

In the above structure, the alkylanthraquinone group is lipophilic, and the sulfonate group is hydrophilic, so it has surface activity; and under electrochemical action, the molecular structure can undergo the following changes to be electrochemically active:

R=C _n H _2n+1 , n=6~16; M=NH ₄ ⁺ , Na ⁺ , K ⁺ .

The basic principle of its application in electrochemical cleaning and dyeing is: before electrification, most of the alkylanthraquinone sulfonates are firstly used as surfactants, adsorbed on the surface of insoluble vat dyes, and disperse the vat dyes; a small part of alkylanthraquinone sulfonates It is also adsorbed at the solid-liquid interface between the electrode and the solution. After electrification, the alkylanthraquinone sulfonate continuously obtains electrons at the cathode and transforms into a reduced state with better water solubility. The reduced state alkylanthraquinone sulfonate makes the vat dye Reduction, transforming into a water-soluble leucosome, while the alkylanthraquinone sulfonate is converted into an oxidized state, and the oxidized alkylanthraquinone sulfonate continues to obtain electrons at the cathode to become a reduced state, so The loop plays the role of transferring electrons.

The preparation method of the intermediate of the present invention is:

1) Add phthalic anhydride, anhydrous aluminum trichloride and chlorobenzene into the reaction flask, stir for 30min~1h, then add dropwise alkylbenzene and triethylamine, and react at 40~60°C after the dropwise addition After 4 to 6 hours, the product was washed with water until neutral, and the chlorobenzene was distilled off to obtain a white solid that was crude 2-(4'-alkylbenzoyl)benzoic acid;

2) Add the above crude 2-(4'-alkylbenzoyl)benzoic acid and polyphosphoric acid into the reaction kettle, react at 140-170°C for 2-4 hours, wash the product with ice water until neutral, and obtain a yellow to red solid It is crude 2-alkylanthraquinone; dissolve the crude 2-alkylanthraquinone with a mixed solution of hydrosulfite and NaOH, filter the filtrate through oxygen for 12-24 hours, filter, and the obtained precipitate is refined 2-alkylanthraquinone;

3) Dissolve the above-mentioned refined 2-alkylanthraquinone in chloroform, stir vigorously in an ice-water bath and add fuming sulfuric acid dropwise at the same time, after sulfonation for 2-4 hours, add a small amount of water, stir slowly, and let it stand for 24-48 hours , separate the upper organic layer, steam off the chloroform to obtain alkyl anthraquinone sulfonic acid;

4) The above-mentioned alkylanthraquinone sulfonic acid is neutralized to neutral by adding ammonia water, NaOH or KOH to obtain an alkylanthraquinone sulfonate solution, and the solution is crystallized and recrystallized to obtain pure alkylanthraquinone sulfonate.

Concrete synthetic route is as follows:

(1) Synthesis of 2-alkylanthraquinones

R＝C _n H _2n+1 , n＝6～16

(2) Purification of 2-alkylanthraquinones

R＝C _n H _2n+1 , n＝6～16

(3) Sulfonation of 2-alkylanthraquinones

R＝C _n H _2n+1 , n＝6～16

(4) Neutralization of alkyl anthraquinone sulfonic acid

R=C _n H _2n+1 , n=6~16; M=NH ₄ , Na, K.

The beneficial effects of the present invention are: the present invention is a more effective intermediate, which also has the dispersing effect of surfactant while transferring electrons, and can obtain fabrics with good level dyeing property.

Detailed ways

Example 1

1) Add 15.2g of anhydrous phthalic anhydride and 26.7g of anhydrous aluminum trichloride into 200mL of chlorobenzene and stir at room temperature. After 1 hour, add 19.0g of octylbenzene and 1.0g of triethylamine into the mixture from the dropping funnel reaction flask, and then reacted at 40°C for 4h. The reaction solution was poured into 500 mL of 10% hydrochloric acid solution and stirred, the organic layer was separated, and the organic layer was washed with hot water at about 80°C until the washed water was hardly acidic. After cooling, the chlorobenzene was distilled off, and the white solid obtained after drying was 2-(4'-octylbenzoyl)benzoic acid, with a yield of 85.4%.

2) Add 10g of crude 2-(4'-octylbenzoyl)benzoic acid and 50g of polyphosphoric acid into the reaction flask, react at 160°C for 2.5h, wash the product with ice water until neutral, and obtain crude 2-alkylanthraquinone , dissolve the crude 2-octyl anthraquinone with 50ml of newly prepared 10% hydrosulfite and 20% NaOH solution, filter and pass through oxygen for 24h, filter the precipitate, and the obtained yellow solid is refined 2-octyl anthraquinone, the yield 62.1%.

3) Dissolve the above 10g of refined 2-octylanthraquinone in 100mL of chloroform, stir vigorously in an ice-water bath while adding 17.2g of oleum dropwise, after sulfonation for 3 hours, add a small amount of distilled water, stir slowly, and let stand for 24 hours , The upper organic layer was separated, and the chloroform was distilled off to obtain dark brown viscous liquid octyl anthraquinone sulfonic acid with a yield of 71.8%.

4) The above-mentioned octyl anthraquinone was dissolved in water, NaOH solution was added dropwise until neutral, and the solution was recrystallized to obtain pure sodium octyl anthraquinone sulfonate with a yield of 66.7%.

Claims (4)

1. one kind is used for the painted intermediate of electrochemically cleaning, it is characterized in that: described this intermediate is an alkyl-anthraquinone sulfonate, is made through acylations, dehydration closed-loop, sulfonation, neutralization by alkylbenzene and Tetra hydro Phthalic anhydride.

2. the painted intermediate of electrochemically cleaning that is used for as claimed in claim 1 is characterized in that: one or more mixture in the straight or branched that described its alkyl of alkyl-anthraquinone sulfonate is a chain length 6～16.

3. the painted intermediate of electrochemically cleaning that is used for as claimed in claim 1 is characterized in that: described alkyl-anthraquinone sulfonate is the wherein a kind of of ammonium salt, sodium salt or sylvite.

4. painted intermediates preparation of electrochemically cleaning that is used for as claimed in claim 1 is characterized in that may further comprise the steps:

1) Tetra hydro Phthalic anhydride, aluminum trichloride (anhydrous) and chlorobenzene are added in the reaction flask, adding splashes into alkylbenzene and triethylamine after stirring 30min～1h, dropwise the back and react 4～6h down at 40～60 ℃, product water is washed till neutrality, steam chlorobenzene, the white solid that obtains is thick 2-(4 '-alkylbenzene formyl) phenylformic acid;

2) above-mentioned thick 2-(4 '-alkylbenzene formyl) phenylformic acid and polyphosphoric acid are added reactor, 140～170 ℃ of reaction 2～4h, product is washed till neutrality with frozen water, and the yellow that obtains to red solid is thick 2-alkyl-anthraquinone; Use the mixing solutions of vat powder and NaOH to dissolve thick 2-alkyl-anthraquinone, filter the logical oxygen 12～24h of rear filtrate, filter, the 2-alkyl-anthraquinone is made with extra care in being precipitated as of obtaining;

3) above-mentioned purified 2-alkyl-anthraquinone is dissolved in trichloromethane, vigorous stirring drips oleum simultaneously in the ice-water bath, behind sulfonation 2～4h, add less water, slowly stir evenly, leave standstill 24～48h, tell the upper strata organic layer, steam trichloromethane, obtain alkyl-anthraquinone sulfonic acid;

4) the abovementioned alkyl anthraquinone sulfonic acid is added ammoniacal liquor, NaOH or KOH and is neutralized to neutrality, obtain the alkyl-anthraquinone sulfonate solution, with solution carry out crystallization, recrystallization obtains pure alkyl-anthraquinone sulfonate.