A high temperature resistant oxidation fixing agent, preparation method and application thereof

Abstract

The present invention provides a high temperature resistant oxidation color fixing agent, a preparation method and its application. A dimethyldiallylammonium chloride derivative, a pH buffer and a solvent are mixed to obtain the high temperature resistant oxidation color fixing agent; wherein the dimethyldiallylammonium chloride derivative is a polymer polymer formed by copolymerizing dimethyldiallylammonium chloride and cyclohex-4-ene-1,2-dicarboxylic acid diene to form a main chain and grafted with p-phenylene diisocyanate. The high temperature resistant oxidation curing agent provided in the present application can enhance the binding ability of the fiber and the color fixing agent, and improve the high temperature resistance of the color fixing agent, improve the color fixing effect at high temperature, and effectively improve the yellowing problem of nitrogen-containing polymer materials during high temperature heat treatment and storage and transportation. At the same time, the high temperature resistant oxidation color fixing agent provided in the present application can be applied to polymer fiber materials at different stages such as polymerization and post-treatment, with flexible processing methods, wide application fields, no need for complicated processing steps, and broad application prospects.

Description

Technical Field

[0001] The invention relates to the technical field of textile dyeing and finishing, and in particular to a high temperature resistant oxidation fixing agent, a preparation method and application thereof. Background Art

[0002] Polyamide (also known as "nylon" and "chinlon"), polyurethane (also known as "spandex") and other polymers have -NH- groups in their molecular structures and have unique wearability. They have become an important member of textile fiber materials and have played an irreplaceable role in the fields of swimsuits, underwear, bras, sportswear, stockings, lace and other textile and clothing. However, the fiber molecular structure contains relatively unstable characteristic groups such as amide and amino groups. While these group structures give the fiber unique physical properties, they also have problems such as poor color fastness and easy yellowing, which puts higher requirements on printing and dyeing processing auxiliaries and processes.

[0003] Nylon fibers are mainly dyed with acid dyes. The dyeing principle is that under acidic conditions, the dyeing amino groups on the nylon fiber molecules are positively charged, which have charge attraction to the anionic sulfonic acid groups of the acid dye molecules, thereby achieving dyeing. However, this charge force is not strong. When the pH value is neutral or alkaline soap washing, the dye molecules are easily desorbed from the nylon fibers. Therefore, the color fastness of nylon fibers is poor, and acidic color fixing agents must be used for color fixing treatment to improve color fastness.

[0004] In addition, nylon fibers are prone to yellowing during high-temperature heat treatment and storage. During high-temperature heat processing, the amino and amide groups in the nylon molecular structure are easily oxidized by nitrogen oxides in the air and turn yellow or even brittle under the action of heat energy. Therefore, for nylon fabrics that require high-temperature hot pressing molds for underwear mold cups, they must be treated with high-temperature anti-yellowing agents in advance to protect the nylon fiber structure from high-temperature damage. During storage and transportation, when nylon fibers are in direct contact with packaging materials such as polyethylene films containing antioxidant BHT, due to the low solubility of BHT in polyethylene, it will be transferred to the fabric or clothing fabric during storage, and undergo complex chemical reactions with nitrogen oxides to form yellow substances, thereby causing storage yellowing of nylon textiles. In order to effectively prevent yellowing of textiles during storage and transportation, dyeing factories must use anti-phenol yellowing agents to treat nylon textiles with anti-phenol yellowing.

[0005] The above process is tedious and complicated. Therefore, synergistically solving the color fixation and high-temperature anti-yellowing properties of nylon fibers is of great significance for improving the quality of textiles containing nylon and spandex components. Summary of the invention

[0006] Purpose of the invention: The purpose of the present invention is to provide a high temperature resistant oxidation fixing agent, a preparation method and its application, so as to overcome the problem that the existing textiles are resistant to high temperature yellowing and the color fixing process is long and complicated, shorten the process flow, reduce the process cost, make the textiles effectively resistant to high temperature yellowing, and maintain the original color for a long time.

[0007] The technical solution of the present invention:

[0008] A high temperature resistant oxidation fixing agent, based on the total mass percentage of raw materials as 100%, comprises:

[0009] Dimethyldiallylammonium chloride derivative 30-35%;

[0010] pH buffer 7.3-7.9%;

[0011] The balance is solvent;

[0012] The dimethyldiallylammonium chloride derivative is a high molecular polymer obtained by copolymerizing dimethyldiallylammonium chloride and cyclohex-4-ene-1,2-dicarboxylic acid diene to form a main chain and grafting p-phenylene diisocyanate.

[0013] In some embodiments, the pH buffer comprises sodium acetate, sodium chloride and acetic acid; the mass ratio of sodium acetate, sodium chloride and acetic acid is 2.8-3:4.3-4.5:0.2-0.4.

[0014] In some embodiments, the solvent is deionized water.

[0015] In some embodiments, the method for preparing the dimethyldiallylammonium chloride derivative comprises:

[0016] Step 1: adding iodine and silver acetate to an aqueous solution of cyclohex-4-ene-1,2-dicarboxylic acid diallyl ester to carry out a reaction, filtering to remove solids after the reaction is completed, and retaining the reaction solution; the molar ratio of iodine, silver acetate and cyclohex-4-ene-1,2-dicarboxylic acid diallyl ester is 0.3-0.7:0.8-1.2:1;

[0017] Step 2: Add an aqueous solution of dimethyldiallylammonium chloride into a reactor, add the above reaction solution under stirring, then add an aqueous solution of an initiator, and stir to react under heating;

[0018] Step 3: Add p-phenylene diisocyanate to the reaction system of step 2, add a catalyst, heat and stir to catalyze the reaction, evaporate the solvent after the reaction, wash and dry to obtain a dimethyldiallylammonium chloride derivative.

[0019] In some embodiments, the molar ratio of the elemental iodine, silver acetate and diallyl cyclohex-4-ene-1,2-dicarboxylate is 0.5-0.7:1-1.2:1.

[0020] In some embodiments, the molar ratio of dimethyldiallylammonium chloride to cyclohex-4-ene-1,2-dicarboxylic acid diene is 3:1-1.5.

[0021] In some embodiments, the initiator is selected from one or a combination of ammonium persulfate, potassium persulfate, sodium persulfate, azobisisobutylamidine hydrochloride and azobisisopropylimidazoline; the added mass of the initiator is 1-3% of the total mass of dimethyldiallylammonium chloride and cyclohex-4-ene-1,2-dicarboxylic acid diene.

[0022] In some embodiments, the reaction temperature of the stirring reaction in step 2 is 55-75° C., and the reaction time is 5-6 h.

[0023] In some embodiments, the molar ratio of the added p-phenylene diisocyanate to the cyclohex-4-ene-1,2-dicarboxylic acid diene is 1.5-1.2:1.

[0024] In some embodiments, the catalyst is selected from one or more of quaternary ammonium salts, alkylamines, nitrogen-containing heterocyclic catalysts, imidazoles and their derivatives; preferably, the catalyst is selected from one or more combinations of triethylamine, trimethylamine, 2-phenylimidazole, 2-methylimidazole, morpholine, triethylamine chloride, tetraethylammonium acetate, etc.; the added amount of the catalyst is 5-8% of the mass of p-phenylene diisocyanate.

[0025] In some embodiments, the reaction temperature of the catalytic reaction in step 3 is 50-200° C., preferably 50-150° C.; the reaction time of the catalytic reaction is 0-72 h, preferably 2-24 h.

[0026] On the other hand, the present application also provides a method for preparing the above-mentioned high temperature resistant oxidation fixing agent, comprising:

[0027] According to the above formula, the dimethyldiallylammonium chloride derivative, the pH buffer and the solvent are evenly mixed to obtain the high temperature resistant oxidation fixing agent.

[0028] On the other hand, the present application also provides an application of the above-mentioned high temperature resistant oxidation fixing agent. Specifically, the high temperature resistant oxidation fixing agent is added to the polymerization stage or post-processing stage of the polymer fabric material, and can also be sprayed on the surface of the finished polymer fabric material.

[0029] Beneficial effects:

[0030] The present application provides a new structure of a high temperature oxidative color fixing agent. By modifying the main resin of the color fixing agent and introducing multiple isocyanate groups on its surface, a "bridge" can be built between the fiber and the color fixing agent, the binding ability of the fiber and the color fixing agent can be enhanced, and the high temperature resistance of the color fixing agent can be improved, the color fixing effect at high temperature can be improved, and the yellowing problem of nitrogen-containing polymer materials during high temperature heat treatment and storage and transportation can be effectively improved. At the same time, the high temperature oxidative color fixing agent provided by the present application can be applied to polymer fiber materials at different stages such as polymerization and post-processing. The processing method is flexible, the application field is wide, and no complicated processing steps are required, which has broad application prospects. DETAILED DESCRIPTION

[0031] The present invention will be described below in conjunction with specific embodiments. It should be noted that the following embodiments are examples of the present invention and are only used to illustrate the present invention, but not to limit the present invention. Other combinations and various modifications within the concept of the present invention may be performed without departing from the spirit or scope of the present invention.

[0032] Unless otherwise specified, the chemical reagents used in the present invention are all commercially available analytically pure. Dimethyldiallylammonium chloride used in the examples was purchased from Wuhu Aini Daily Chemicals; cyclohex-4-ene-1,2-dicarboxylic acid diene used was purchased from Fluorochem Ltd. In fact, it can also be prepared by itself through tetrahydrophthalic anhydride.

[0033] Preparation of dimethyldiallylammonium chloride derivative 1

[0034] Step 1: Add 2.6 g of elemental iodine and 6.7 g of silver acetate to 11.8 g of an aqueous solution of cyclohex-4-ene-1,2-dicarboxylic acid diene with a mass fraction of 86% to carry out a reaction. After the reaction is completed, filter to remove the solid and retain the reaction solution;

[0035] Step 2: Add 25 g of a 26% by mass aqueous solution of dimethyldiallylammonium chloride into a 100 ml four-necked reaction flask, add the above reaction solution under stirring, then add 3 mL of a 0.2 g / mL aqueous solution of ammonium persulfate initiator, and react at 55° C. with stirring for 6 h to obtain a mixture;

[0036] Step 3: Add 8.3 g of p-phenylene diisocyanate to the above mixture, add 0.28 g of triethylamine, heat and stir at 180°C to catalyze the reaction for 24 hours. After the reaction, evaporate the solvent, wash and dry to obtain dimethyldiallylammonium chloride derivative 1.

[0037] Preparation of dimethyldiallylammonium chloride derivative 2

[0038] Step 1: Add 2.6 g of elemental iodine and 6.7 g of silver acetate to 11.8 g of an aqueous solution of cyclohex-4-ene-1,2-dicarboxylic acid diene with a mass fraction of 86% to carry out a reaction. After the reaction is completed, filter to remove the solid and retain the reaction solution;

[0039] Step 2: Add 25 g of a 51% by mass aqueous solution of dimethyldiallylammonium chloride into a 100 ml four-necked reaction flask, add the above reaction solution under stirring, then add 3.4 mL of a 0.2 g / mL aqueous solution of ammonium persulfate initiator, and react at 55° C. with stirring for 6 h to obtain a mixture;

[0040] Step 3: Add 8.3 g of p-phenylene diisocyanate to the above mixture, add 0.28 g of triethylamine, heat and stir at 180°C to catalyze the reaction for 24 hours. After the reaction, evaporate the solvent, wash and dry to obtain dimethyldiallylammonium chloride derivative 2.

[0041] Preparation of dimethyldiallylammonium chloride derivative 3

[0042] Step 1: Add 2.6 g of elemental iodine and 6.7 g of silver acetate to 11.8 g of an aqueous solution of cyclohex-4-ene-1,2-dicarboxylic acid diene with a mass fraction of 86% to carry out a reaction. After the reaction is completed, filter to remove the solid and retain the reaction solution;

[0043] Step 2: Add 25 g of a 77% by mass aqueous solution of dimethyldiallylammonium chloride into a 100 ml four-necked reaction flask, add the above reaction solution under stirring, then add 4.4 mL of a 0.2 g / mL aqueous solution of ammonium persulfate initiator, and react at 55° C. with stirring for 6 h to obtain a mixture;

[0044] Step 3: Add 8.3 g of p-phenylene diisocyanate to the above mixture, add 0.28 g of triethylamine, heat and stir at 180°C to catalyze the reaction for 24 hours. After the reaction, evaporate the solvent, wash and dry to obtain dimethyldiallylammonium chloride derivative 3.

[0045] Preparation of dimethyldiallylammonium chloride derivative 4

[0046] Step 1: Add 2.6 g of elemental iodine and 6.7 g of silver acetate to 11.8 g of an aqueous solution of cyclohex-4-ene-1,2-dicarboxylic acid diene with a mass fraction of 86% to carry out a reaction. After the reaction is completed, filter to remove the solid and retain the reaction solution;

[0047] Step 2: Add 25 g of a 90% by mass aqueous solution of dimethyldiallylammonium chloride into a 100 ml four-necked reaction flask, add the above reaction solution under stirring, then add 4.9 mL of a 0.2 g / mL aqueous solution of ammonium persulfate initiator, and react at 55° C. with stirring for 6 h to obtain a mixture;

[0048] Step 3: Add 8.3 g of p-phenylene diisocyanate to the above mixture, add 0.28 g of triethylamine, heat and stir at 180°C to catalyze the reaction for 24 hours. After the reaction, evaporate the solvent, wash and dry to obtain dimethyldiallylammonium chloride derivative 4.

[0049] Preparation of dimethyldiallylammonium chloride derivative 5

[0050] Step 1: Add 2.6 g of elemental iodine and 6.7 g of silver acetate to 11.8 g of an aqueous solution of cyclohex-4-ene-1,2-dicarboxylic acid diene with a mass fraction of 86% to carry out a reaction. After the reaction is completed, filter to remove the solid and retain the reaction solution;

[0051] Step 2: Add 25 g of a 77% by mass aqueous solution of dimethyldiallylammonium chloride into a 100 ml four-necked reaction flask, add the above reaction solution under stirring, then add 4.4 mL of a 0.2 g / mL aqueous solution of ammonium persulfate initiator, and react at 55° C. with stirring for 6 h to obtain a mixture;

[0052] Step 3: Add 7.6 g of p-phenylene diisocyanate to the above mixture, add 0.28 g of triethylamine, heat and stir at 180°C to catalyze the reaction for 24 hours. After the reaction, evaporate the solvent, wash and dry to obtain dimethyldiallylammonium chloride derivative 5.

[0053] Preparation of dimethyldiallylammonium chloride derivative 6

[0054] Step 1: Add 2.6 g of elemental iodine and 6.7 g of silver acetate to 11.8 g of an aqueous solution of cyclohex-4-ene-1,2-dicarboxylic acid diene with a mass fraction of 86% to carry out a reaction. After the reaction is completed, filter to remove the solid and retain the reaction solution;

[0055] Step 2: Add 25 g of a 77% by mass aqueous solution of dimethyldiallylammonium chloride into a 100 ml four-necked reaction flask, add the above reaction solution under stirring, then add 4.4 mL of a 0.2 g / mL aqueous solution of ammonium persulfate initiator, and react at 55° C. with stirring for 6 h to obtain a mixture;

[0056] Step 3: Add 9.6 g of p-phenylene diisocyanate to the above mixture, add 0.28 g of triethylamine, heat and stir at 180°C to catalyze the reaction for 24 hours. After the reaction, evaporate the solvent, wash and dry to obtain dimethyldiallylammonium chloride derivative 6.

[0057] Preparation of derivative 1

[0058] Step 1: Add 25 g of a 77% aqueous solution of dimethyldiallylammonium chloride into a 100 ml four-necked reaction flask, add 11.8 g of an 86% aqueous solution of cyclohex-4-ene-1,2-dicarboxylic acid diene under stirring, then add 4.4 mL of a 0.2 g / mL aqueous solution of ammonium persulfate initiator, stir and react at 55° C. for 6 h, evaporate the solvent, wash and dry to obtain derivative 1.

[0059] Preparation of derivative 2

[0060] Step 1: Add 2.6 g of elemental iodine and 6.7 g of silver acetate to 11.8 g of an aqueous solution of cyclohex-4-ene-1,2-dicarboxylic acid diene with a mass fraction of 86% to carry out a reaction. After the reaction is completed, filter to remove the solid and retain the reaction solution;

[0061] Step 2: Add 25 g of a 77% aqueous solution of dimethyldiallylammonium chloride into a 100 ml four-necked reaction flask, add the above reaction solution under stirring, then add 4.4 mL of a 0.2 g / mL aqueous solution of ammonium persulfate initiator, and react at 55° C. with stirring for 6 h to obtain derivative 2;

[0062] Preparation of high temperature resistant oxidation fixing agent 1-6 and fixing agent 1-2

[0063] 30 g of the dimethyldiallylammonium chloride derivative 1-6 and the derivative 1-2 prepared above were respectively taken and mixed evenly with 2.8 g of sodium acetate, 4.3 g of sodium chloride, 0.2 g of acetic acid and 62.7 g of deionized water to obtain high temperature oxidation resistant color fixing agent 1-6 and color fixing agent 1-2.

[0064] The obtained high temperature resistant oxidation fixing agent 1-6 and fixing agent 1-2 were used to treat commercially available rose red nylon spandex fabrics, respectively. The treatment steps included: using the high temperature resistant oxidation fixing agent 1-6 and the fixing agent 1-2 to treat the fabrics at a bath ratio of 1:20 and a temperature of 70°C, respectively, dehydrating and drying after 30 minutes to obtain treated fabrics 1-8, respectively, and using untreated fabrics as blank controls.

[0065] The treated fabrics 1-8 and the untreated fabric were respectively subjected to the following tests, and the test data are shown in Table 1.

[0066] Test 1: The rubbing fastness test method is determined according to GB / T3920-2008 "Textiles - Color Fastness - Color Fastness to Rubbing".

[0067] Test 2: The soap fastness test method is determined according to GB / T3921-2008 "Textiles - Tests for Colour Fastness - Colour Fastness to Washing".

[0068] Test 3: The perspiration fastness test method is determined according to GB / T5713-2013 "Textiles - Tests for Colour Fastness - Water Fastness".

[0069] Test 4: High temperature color change test method: The fabric to be tested is heat-set on a setting machine (setting process: 190℃×200sec), and then the color change is rated using GB / T 250-2008 "Grey Sample Scale for Assessing Color Change in Textile Color Fastness Tests".

[0070] Table 1 Data of treated fabrics 1-8 and untreated fabrics tested 1-4

[0071]

[0072] It can be seen from Examples 1-4 that the content of cyclohex-4-ene-1,2-dicarboxylic acid diene and p-phenylene diisocyanate in the main resin has a certain influence on the high temperature stability of the color fixing agent. When the cyclohex-4-ene-1,2-dicarboxylic acid diene is too little, it directly affects the grafting of p-phenylene diisocyanate, and affects the high temperature oxidation resistance and the adhesion ability of the color fixing agent. When the content of cyclohex-4-ene-1,2-dicarboxylic acid diene is too much, the content of dimethyl diallyl ammonium chloride in the main resin is too little, and the color fixing effect of the color fixing agent is poor.

[0073] It can be seen from Example 3 and Comparative Examples 1-3 that the present application can build a "bridge" between the fiber and the color fixing agent by introducing multiple isocyanate groups on the surface of the main resin of the color fixing agent, thereby enhancing the bonding ability between the fiber and the color fixing agent, improving the high temperature resistance of the color fixing agent, improving the color fixing effect at high temperature, and effectively improving the yellowing problem of nitrogen-containing polymer materials during high temperature heat treatment and storage and transportation.

[0074] The present invention can also have many other embodiments. Without departing from the spirit and essence of the present invention, those skilled in the art can make various corresponding changes and modifications based on the present invention, but these corresponding changes and modifications should all fall within the scope of protection of the claims attached to the present invention.

Claims

1. A high temperature resistant oxidation fixing agent, characterized in that: The total mass percentage of raw materials is 100%, including: Dimethyldiallylammonium chloride derivative 30-35%; pH buffer 7.3-7.9%; The balance is solvent; The dimethyldiallylammonium chloride derivative is a high molecular polymer formed by copolymerizing dimethyldiallylammonium chloride and cyclohex-4-ene-1,2-dicarboxylic acid diene to form a main chain and grafting p-phenylene diisocyanate; The preparation method of the dimethyldiallylammonium chloride derivative comprises: Step 1: adding iodine and silver acetate to an aqueous solution of cyclohex-4-ene-1,2-dicarboxylic acid diallyl ester to carry out a reaction, filtering to remove solids after the reaction is completed, and retaining the reaction solution; the molar ratio of iodine, silver acetate and cyclohex-4-ene-1,2-dicarboxylic acid diallyl ester is 0.3-0.7:0.8-1.2:1; Step 2: Add an aqueous solution of dimethyldiallylammonium chloride into a reactor, add the above reaction solution under stirring, then add an aqueous solution of an initiator, and stir to react under heating; Step 3: adding p-phenylene diisocyanate to the reaction system of step 2, adding a catalyst, heating and stirring for catalytic reaction, evaporating the solvent after the reaction, washing and drying to obtain a dimethyldiallylammonium chloride derivative; The molar ratio of dimethyldiallylammonium chloride to cyclohex-4-ene-1,2-dicarboxylic acid diene is 3:1-1.5; The molar ratio of the added p-phenylene diisocyanate to cyclohex-4-ene-1,2-dicarboxylic acid diene is 1.5-1.2:

1.

2. The high temperature resistant oxidation fixing agent according to claim 1, characterized in that: The pH buffer comprises sodium acetate, sodium chloride and acetic acid; the mass ratio of the sodium acetate, sodium chloride and acetic acid is 2.8-3:4.3-4.5:0.2-0.

4.

3. The high temperature resistant oxidation fixing agent according to claim 1, characterized in that: The molar ratio of the iodine element, silver acetate and cyclohex-4-ene-1,2-dicarboxylic acid diallyl ester is 0.5-0.7:1-1.2:

1.

4. The high temperature resistant oxidation fixing agent according to claim 1, characterized in that: The initiator is selected from one or a combination of ammonium persulfate, potassium persulfate, sodium persulfate, azobisisobutylamidine hydrochloride and azobisisopropylimidazoline; the added mass of the initiator is 1-3% of the total mass of dimethyldiallylammonium chloride and cyclohex-4-ene-1,2-dicarboxylic acid diene.

5. The high temperature resistant oxidation fixing agent according to claim 1, characterized in that: In the step 2, the reaction temperature of the stirring reaction is 55-75°C, and the reaction time is 5-6 h; in the step 3, the reaction temperature of the catalytic reaction is 50-200°C, and the reaction time is 8-72 h.

6. The method for preparing the high temperature resistant oxidation fixing agent according to any one of claims 1 to 5, characterized in that: include: According to the above formula, the dimethyldiallylammonium chloride derivative, the pH buffer and the solvent are evenly mixed to obtain the high temperature resistant oxidation fixing agent.

7. The use of the high temperature resistant oxidation fixing agent according to any one of claims 1 to 5, characterized in that: include: The high temperature resistant oxidation fixing agent is added in the polymerization stage or post-processing stage of the polymer fabric material, and can also be sprayed on the surface of the finished polymer fabric material.

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