阅读说明：本技术 一种用于纺织物的漂白稳定剂的制备方法 (Preparation method of bleaching stabilizer for textile ) 是由 白晋喜 于 2021-09-16 设计创作，主要内容包括：本发明公开了一种用于纺织物的漂白稳定剂的制备方法,包括将海藻酸钠加入去离子水中,加入聚乙烯亚胺和戊二醛,搅拌升温,加入碳酸钙,继续搅拌,得到海藻酸钠凝胶；加入十二烷基苯磺酸钠,滴加氯化钙后静置陈化,冷冻干燥后得到改性海藻酸钠；将N-(3,5-二乙基氨基苯甲酞)壳聚糖加入去离子水中,加入1,2,3,4-丁烷四羧酸和柠檬酸,搅拌,静置,冷冻干燥,研磨,得到改性N-(3,5-二乙基氨基苯甲酞)壳聚糖；将硅藻土加入去离子水中,搅拌,加入聚丙烯酸钠和阳离子聚丙烯酰胺,搅拌,冷冻干燥,洗涤,得到改性硅藻土；将改性海藻酸钠、改性N-(3,5-二乙基氨基苯甲酞)壳聚糖、改性硅藻土加入到钛酸四丁酯的水溶液中搅拌,滴加氢氧化钠调节pH值,得到所述氧漂稳定剂。(The invention discloses a preparation method of a bleaching stabilizer for textile fabrics, which comprises the steps of adding sodium alginate into deionized water, adding polyethyleneimine and glutaraldehyde, stirring and heating, adding calcium carbonate, and continuing stirring to obtain sodium alginate gel; adding sodium dodecyl benzene sulfonate, dropwise adding calcium chloride, standing for aging, and freeze-drying to obtain modified sodium alginate; adding N- (3, 5-diethyl aminobenzene phthalein) chitosan into deionized water, adding 1,2,3, 4-butanetetracarboxylic acid and citric acid, stirring, standing, freeze-drying, and grinding to obtain modified N- (3, 5-diethyl aminobenzene phthalein) chitosan; adding diatomite into deionized water, stirring, adding sodium polyacrylate and cationic polyacrylamide, stirring, freeze-drying, and washing to obtain modified diatomite; adding modified sodium alginate, modified N- (3, 5-diethyl aminobenzophthalein) chitosan and modified diatomite into an aqueous solution of tetrabutyl titanate, stirring, and dropwise adding sodium hydroxide to adjust the pH value to obtain the oxygen bleaching stabilizer.)

1. A preparation method of a bleaching stabilizer for textiles is characterized by comprising the following steps:

s1: adding sodium alginate into deionized water, stirring for 10-20 min to fully dissolve the sodium alginate, then adding polyethyleneimine and glutaraldehyde, continuing stirring, raising the temperature to 50-60 ℃, adding calcium carbonate after the temperature is reached, and continuing stirring for reaction for 10-15 h to obtain sodium alginate gel, wherein the mass-to-volume ratio of the sodium alginate to the polyethyleneimine to the glutaraldehyde to the calcium carbonate is (3-6) g, (4-5.5) g, (12-18) mL and (1.2-2.5) g;

s2: adding sodium dodecyl benzene sulfonate into the sodium alginate gel in the step S1, stirring at room temperature for 30-60 min, then dropwise adding calcium chloride, continuously stirring for 10-20 min, standing, aging for 10-20 h, and freeze-drying to obtain the modified sodium alginate, wherein the mass ratio of the sodium alginate gel to the sodium dodecyl benzene sulfonate in the step S1 is (1-3.5): (0.18 to 0.56);

s3: adding N- (3, 5-diethyl aminobenzene phthalein) chitosan into deionized water, then adding 1,2,3, 4-butanetetracarboxylic acid and citric acid, stirring for 0.5-2 h, standing for 4-6 h, freeze-drying, crushing and grinding to obtain modified N- (3, 5-diethyl aminobenzene phthalein) chitosan;

s4: adding diatomite into deionized water, stirring for 20-40 min, adding sodium polyacrylate and cationic polyacrylamide, heating to 40-50 ℃, continuing to stir for reaction for 3-5 h, freeze-drying, washing with distilled water for 4 times, and vacuum-drying to obtain modified diatomite;

s5: adding modified sodium alginate, modified N- (3, 5-diethyl aminobenzophthalein) chitosan and modified diatomite into an aqueous solution of tetrabutyl titanate, wherein the mass-to-volume ratio of the modified sodium alginate, the modified N- (3, 5-diethyl aminobenzophthalein) chitosan and the modified diatomite to the aqueous solution of tetrabutyl titanate is (3-8), (5.5-10), (3.8-7.8), (120-200) mL, mixing and stirring for 1-2 h, and dropwise adding sodium hydroxide to adjust the pH value to 7.2-8.6 to obtain the stabilizer.

2. The method for preparing the bleaching stabilizer for textiles according to claim 1, wherein the mass fraction of glutaraldehyde in step S1 is 4.5-12%.

3. The method for preparing the bleaching stabilizer for textiles according to claim 1, wherein the mass fraction of calcium chloride in step S2 is 3.5-5%.

4. The method as claimed in claim 1, wherein the mass ratio of the N- (3, 5-diethylaminobenzene phthalein) chitosan, 1,2,3, 4-butanetetracarboxylic acid and citric acid in step S3 is (2.3-4.6): (0.5-0.9): 0.8-1.5).

5. The method of claim 1, wherein the cationic polyacrylamide of step S4 has a molecular weight of 700 to 800 ten thousand.

6. The method for preparing the bleaching stabilizer for textile fabrics of claim 1, wherein the mass ratio of the diatomite, the sodium polyacrylate and the cationic polyacrylamide is (3.5-6): (1.2-2.5): (0.96-1.45).

7. The method for preparing the textile bleaching stabilizer according to claim 1, wherein the mass fraction of the tetrabutyl titanate aqueous solution is 12-20%.

Technical Field

The invention belongs to the technical field of preparation of textile auxiliaries, and particularly relates to a preparation method of a bleaching stabilizer for textiles.

Background

At present, the hydrogen peroxide is widely applied in the fabric bleaching process due to the characteristics of strong impurity removal capacity, low bleaching cost, high whiteness, difficult yellowing, good hand feeling and the like, the hydrogen peroxide is a classical chemical product, and the hydrogen peroxide bleaching agent is widely applied in the bleaching process of cellulose fibers and other fibers due to good stability, no corrosion to equipment and no pollution, is an excellent bleaching agent, has good whiteness stability and no pollution to the environment, and is a bleaching agent with a good development prospect. However, in the bleaching process, the decomposition of hydrogen peroxide is often uncontrolled, which results in the waste of hydrogen peroxide, poor whiteness, reduction of fiber strength, holes in the bleaching cloth and other problems. In order to uniformly and effectively decompose hydrogen peroxide in the bleaching process and avoid severe damage to fabrics, a certain amount of stabilizer, namely an oxygen bleaching stabilizer, must be added into the bleaching solution.

The oxygen bleaching stabilizer is also called hydrogen peroxide stabilizer, the main component of the oxygen bleaching stabilizer is silicon, the main component is sodium silicate, the effect of absorbing pigment is obvious, the bleaching effect is obvious, but silicon scale is easy to appear, and the silicon scale is deposited on the fabric, so that the fabric is rough and hard, and is difficult to rinse. Therefore, researchers are mainly developing towards non-silicon oxygen bleaching stabilizers, and although some non-silicon oxygen bleaching stabilizers appear on the market, the non-silicon oxygen bleaching stabilizers have poor pigment adsorption capacity and low whiteness of bleached products.

Disclosure of Invention

Aiming at the defects of poor pigment adsorption capacity, low whiteness of a bleached product and the like of an oxygen bleaching stabilizer in the prior art, the invention aims to provide a preparation method of a bleaching stabilizer for textiles, which comprises the following steps:

s1: adding sodium alginate into deionized water, stirring for 10-20 min to fully dissolve the sodium alginate, then adding polyethyleneimine and glutaraldehyde, continuing stirring, raising the temperature to 50-60 ℃, adding calcium carbonate after the temperature is reached, and continuing stirring for reaction for 10-15 h to obtain sodium alginate gel, wherein the mass-to-volume ratio of the sodium alginate to the polyethyleneimine to the glutaraldehyde to the calcium carbonate is (3-6) g, (4-5.5) g, (12-18) mL and (1.2-2.5) g.

S2: adding sodium dodecyl benzene sulfonate into the sodium alginate gel in the step S1, stirring at room temperature for 30-60 min, then dropwise adding calcium chloride, continuously stirring for 10-20 min, standing, aging for 10-20 h, and freeze-drying to obtain the modified sodium alginate, wherein the mass ratio of the sodium alginate gel to the sodium dodecyl benzene sulfonate in the step S1 is (1-3.5): (0.18-0.56).

S3: adding N- (3, 5-diethyl aminobenzene phthalein) chitosan into deionized water, then adding 1,2,3, 4-butanetetracarboxylic acid and citric acid, stirring for 0.5-2 h, standing for 4-6 h, freeze-drying, crushing and grinding to obtain the modified N- (3, 5-diethyl aminobenzene phthalein) chitosan.

S4: adding diatomite into deionized water, stirring for 20-40 min, adding sodium polyacrylate and cationic polyacrylamide, heating to 40-50 ℃, continuing to stir for reaction for 3-5 h, freeze-drying, washing with distilled water for 4 times, and vacuum-drying to obtain the modified diatomite.

S5: adding modified sodium alginate, modified N- (3, 5-diethyl aminobenzophthalein) chitosan and modified diatomite into an aqueous solution of tetrabutyl titanate, wherein the mass-to-volume ratio of the modified sodium alginate, the modified N- (3, 5-diethyl aminobenzophthalein) chitosan and the modified diatomite to the aqueous solution of tetrabutyl titanate is (3-8), (5.5-10), (3.8-7.8), (120-200) mL, mixing and stirring for 1-2 h, and dropwise adding sodium hydroxide to adjust the pH value to 7.2-8.6 to obtain the stabilizer.

Preferably, the mass fraction of glutaraldehyde in step S1 is 4.5 to 12%.

Preferably, the mass fraction of calcium chloride in step S2 is 3.5 to 5%.

Preferably, the mass ratio of the N- (3, 5-diethyl aminobenzophenophthalein) chitosan, the 1,2,3, 4-butanetetracarboxylic acid and the citric acid in the step S3 is (2.3-4.6): (0.5-0.9): 0.8-1.5).

Preferably, the molecular weight of the cationic polyacrylamide in the step S4 is 700-800 ten thousand.

Preferably, the mass ratio of the diatomite, the sodium polyacrylate and the cationic polyacrylamide is (3.5-6): (1.2-2.5): 0.96-1.45.

Preferably, the mass fraction of the tetrabutyl titanate aqueous solution is 12-20%.

Compared with the prior art, the invention has the following beneficial effects:

in the invention, the modified sodium alginate has high specific surface area, the surface contains rich groups which can adsorb metal ions and pigments, and the modified sodium alginate and the fibers on the fabric generate acting force and form a layer of film which can protect the fabric; the N- (3, 5-diethyl aminobenzene phthalein) chitosan has rich amino groups after being modified, and can form a similar net structure with metal ions, so the N- (3, 5-diethyl aminobenzene phthalein) chitosan has higher adsorption effect on the metal ions; the modified diatomite has high specific surface area and rich groups on the surface, and can generate interaction force with metal ions and pigments, thereby realizing high adsorption capacity.

Detailed Description

The following embodiments of the present invention are described in detail, and the embodiments are implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, it should be noted that, for those skilled in the art, a plurality of modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Example 1

A preparation method of a bleaching stabilizer for textiles specifically comprises the following steps:

s1: adding sodium alginate into deionized water, stirring for 10min to fully dissolve the sodium alginate, then adding polyethyleneimine and 4.5% glutaraldehyde by mass, continuing stirring, raising the temperature to 50 ℃, adding calcium carbonate after the temperature is reached, and continuing stirring for 10h to react to obtain sodium alginate gel, wherein the mass-volume ratio of the sodium alginate to the polyethyleneimine to the glutaraldehyde to the calcium carbonate is 3g:4g:12mL:1.2 g.

S2: adding sodium dodecyl benzene sulfonate into the sodium alginate gel in the step S1, stirring for 30min at room temperature, then adding 3.5% by mass of calcium chloride dropwise, continuing stirring for 10min, standing, aging for 10h, and freeze-drying to obtain the modified sodium alginate, wherein the mass ratio of the sodium alginate gel to the sodium dodecyl benzene sulfonate in the step S1 is 1: 0.18.

s3: adding N- (3, 5-diethyl aminobenzene phthalein) chitosan into deionized water, then adding 1,2,3, 4-butanetetracarboxylic acid and citric acid, stirring for 0.5h, standing for 4h, freeze-drying, crushing and grinding to obtain the modified N- (3, 5-diethyl aminobenzene phthalein) chitosan, wherein the mass ratio of the N- (3, 5-diethyl aminobenzene phthalein) chitosan to the 1,2,3, 4-butanetetracarboxylic acid to the citric acid is 2.3:0.5: 0.8.

S4: adding diatomite into deionized water, stirring for 20min, adding sodium polyacrylate and cationic polyacrylamide with the molecular weight of 700 ten thousand, heating to 40 ℃, continuing to stir for reaction for 3h, freeze-drying, washing with distilled water for 4 times, and vacuum-drying to obtain the modified diatomite, wherein the mass ratio of the diatomite to the sodium polyacrylate to the cationic polyacrylamide is 3.5:1.2: 0.96.

S5: adding modified sodium alginate, modified N- (3, 5-diethyl aminobenzophthalein) chitosan and modified diatomite into an aqueous solution of tetrabutyl titanate with the mass fraction of 12%, wherein the mass-volume ratio of the modified sodium alginate, the modified N- (3, 5-diethyl aminobenzophthalein) chitosan and the modified diatomite to the aqueous solution of tetrabutyl titanate is 3g to 5.5g to 3.8g to 120mL, mixing and stirring for 1h, and dropwise adding sodium hydroxide to adjust the pH value to 7.2 to obtain the stabilizer.

Example 2

A preparation method of a bleaching stabilizer for textiles specifically comprises the following steps:

s1: adding sodium alginate into deionized water, stirring for 20min to fully dissolve the sodium alginate, then adding polyethyleneimine and 12% glutaraldehyde by mass, continuing stirring, raising the temperature to 60 ℃, adding calcium carbonate after the temperature is reached, and continuing stirring and reacting for 15h to obtain sodium alginate gel, wherein the mass-volume ratio of the sodium alginate to the polyethyleneimine to the glutaraldehyde to the calcium carbonate is 6g:5.5g:18mL:2.5 g.

S2: adding sodium dodecyl benzene sulfonate into the sodium alginate gel in the step S1, stirring for 60min at room temperature, then adding 5% by mass of calcium chloride dropwise, continuing stirring for 20min, standing, aging for 20h, and freeze-drying to obtain the modified sodium alginate, wherein the mass ratio of the sodium alginate gel to the sodium dodecyl benzene sulfonate in the step S1 is 3.5: 0.56.

s3: adding N- (3, 5-diethyl aminobenzene phthalein) chitosan into deionized water, then adding 1,2,3, 4-butanetetracarboxylic acid and citric acid, stirring for 2h, standing for 6h, freeze-drying, crushing and grinding to obtain the modified N- (3, 5-diethyl aminobenzene phthalein) chitosan, wherein the mass ratio of the N- (3, 5-diethyl aminobenzene phthalein) chitosan to the 1,2,3, 4-butanetetracarboxylic acid to the citric acid is 4.6:0.9: 1.5.

S4: adding diatomite into deionized water, stirring for 40min, adding sodium polyacrylate and cationic polyacrylamide with the molecular weight of 800 ten thousand, heating to 50 ℃, continuing to stir for 5h, freeze-drying, washing with distilled water for 4 times, and vacuum-drying to obtain the modified diatomite, wherein the mass ratio of the diatomite to the sodium polyacrylate to the cationic polyacrylamide is 6:2.5: 1.45.

S5: adding modified sodium alginate, modified N- (3, 5-diethyl aminobenzophthalein) chitosan and modified diatomite into an aqueous solution of tetrabutyl titanate with the mass fraction of 20%, wherein the mass-volume ratio of the modified sodium alginate, the modified N- (3, 5-diethyl aminobenzophthalein) chitosan and the modified diatomite to the aqueous solution of tetrabutyl titanate is 8g to 10g to 7.8g to 200mL, mixing and stirring for 2h, and dropwise adding sodium hydroxide to adjust the pH value to 8.6 to obtain the stabilizer.

Example 3

A preparation method of a bleaching stabilizer for textiles specifically comprises the following steps:

s1: adding sodium alginate into deionized water, stirring for 15min to fully dissolve the sodium alginate, then adding polyethyleneimine and 6% glutaraldehyde by mass, continuing stirring, raising the temperature to 55 ℃, adding calcium carbonate after the temperature is reached, and continuing stirring and reacting for 12h to obtain sodium alginate gel, wherein the mass-volume ratio of the sodium alginate to the polyethyleneimine to the glutaraldehyde to the calcium carbonate is 4g:4.5g:14mL:1.9 g.

S2: adding sodium dodecyl benzene sulfonate into the sodium alginate gel in the step S1, stirring for 40min at room temperature, then adding 4% by mass of calcium chloride dropwise, continuing stirring for 15min, standing, aging for 13h, and freeze-drying to obtain the modified sodium alginate, wherein the mass ratio of the sodium alginate gel to the sodium dodecyl benzene sulfonate in the step S1 is 2.5: 0.27.

s3: adding N- (3, 5-diethyl aminobenzene phthalein) chitosan into deionized water, then adding 1,2,3, 4-butanetetracarboxylic acid and citric acid, stirring for 1h, standing for 5h, freeze-drying, crushing and grinding to obtain the modified N- (3, 5-diethyl aminobenzene phthalein) chitosan, wherein the mass ratio of the N- (3, 5-diethyl aminobenzene phthalein) chitosan to the 1,2,3, 4-butanetetracarboxylic acid to the citric acid is 3.4:0.7: 1.1.

S4: adding diatomite into deionized water, stirring for 30min, adding sodium polyacrylate and cationic polyacrylamide with the molecular weight of 750 ten thousand, heating to 45 ℃, continuing to stir for reaction for 4h, freeze-drying, washing with distilled water for 4 times, and vacuum-drying to obtain the modified diatomite, wherein the mass ratio of the diatomite to the sodium polyacrylate to the cationic polyacrylamide is 4.8:1.8: 1.15.

S5: adding modified sodium alginate, modified N- (3, 5-diethyl aminobenzophthalein) chitosan and modified diatomite into a water solution of tetrabutyl titanate with the mass fraction of 15%, wherein the mass-volume ratio of the modified sodium alginate, the modified N- (3, 5-diethyl aminobenzophthalein) chitosan and the modified diatomite to the water solution of tetrabutyl titanate is 5g to 7.4g to 5.9g to 150mL, mixing and stirring for 1.5h, and dropwise adding sodium hydroxide to adjust the pH value to 7.8 to obtain the stabilizer.

Example 4

A preparation method of a bleaching stabilizer for textiles specifically comprises the following steps:

s1: adding sodium alginate into deionized water, stirring for 18min to fully dissolve the sodium alginate, then adding polyethyleneimine and glutaraldehyde with the mass fraction of 11.2%, continuing stirring, raising the temperature to 55 ℃, adding calcium carbonate after the temperature is reached, and continuing stirring and reacting for 14h to obtain sodium alginate gel, wherein the mass-volume ratio of the sodium alginate to the polyethyleneimine to the glutaraldehyde to the calcium carbonate is 5g:5.2g:16mL:2.3 g.

S2: adding sodium dodecyl benzene sulfonate into the sodium alginate gel in the step S1, stirring for 50min at room temperature, then adding 4.8% by mass of calcium chloride dropwise, continuing stirring for 18min, standing, aging for 17h, and freeze-drying to obtain the modified sodium alginate, wherein the mass ratio of the sodium alginate gel to the sodium dodecyl benzene sulfonate in the step S1 is 3.4: 0.55.

s3: adding N- (3, 5-diethyl aminobenzene phthalein) chitosan into deionized water, then adding 1,2,3, 4-butanetetracarboxylic acid and citric acid, stirring for 1.5h, standing for 5h, freeze-drying, crushing and grinding to obtain the modified N- (3, 5-diethyl aminobenzene phthalein) chitosan, wherein the mass ratio of the N- (3, 5-diethyl aminobenzene phthalein) chitosan to the 1,2,3, 4-butanetetracarboxylic acid to the citric acid is 4.4:0.8: 1.4.

S4: adding diatomite into deionized water, stirring for 35min, adding sodium polyacrylate and cationic polyacrylamide with the molecular weight of 780 ten thousand, heating to 45 ℃, continuing to stir for reaction for 4h, freeze-drying, washing with distilled water for 4 times, and vacuum-drying to obtain the modified diatomite, wherein the mass ratio of the diatomite to the sodium polyacrylate to the cationic polyacrylamide is 5.7:2.3: 1.4.

S5: adding modified sodium alginate, modified N- (3, 5-diethyl aminobenzophthalein) chitosan and modified diatomite into an aqueous solution of tetrabutyl titanate with the mass fraction of 18%, wherein the mass-volume ratio of the modified sodium alginate, the modified N- (3, 5-diethyl aminobenzophthalein) chitosan and the modified diatomite to the aqueous solution of tetrabutyl titanate is 7g to 9g to 7.6g to 180mL, mixing and stirring for 2h, and dropwise adding sodium hydroxide to adjust the pH value to 8.3 to obtain the stabilizer.

Comparative example 1

A stabilizer prepared according to the method described in example 1 in patent document CN 102199873A.

Comparative example 2

An oxygen bleaching stabilizer produced by a company in the tin-free market is commercially purchased.

Examples of the experiments

And (3) performance testing: carrying out bleaching process on the oxygen bleaching stabilizers of the examples 1-4 and the comparative examples 1-2: carrying out secondary rolling, washing and drying, and carrying out detection, (1) detection standard: GB/T8424.2-2001 instrument evaluation method for relative whiteness of textile color fastness test, a WSB-3A intelligent digital whiteness meter is used for measuring the bleaching whiteness of the textile; (2) testing the viscosity of the oxygen bleaching stabilizer by using an NDJ-8S digital display rotational viscometer; (3) determining the capillary effect of the fabric according to FZ/T01071-2008 'textile capillary effect test method', and determining the rising height of the liquid delay sample within 30 min; (4) determining the breaking strength according to GB/T3923.1-2013 textile fabric tensile property; the results of the tests are shown in table 1,

table 1. test results:

as can be seen from Table 1, compared with the oxygen bleaching stabilizers in comparative examples 1 and 2, the stabilizers prepared in examples 1 to 4 of the invention have the advantages of strong stable adsorption capacity, higher breaking strength, high whiteness of bleached products and no rough and hard hand feeling of fabrics bleached by the bleaching.