Process for the preparation of a chelate builder and products and use thereof

Abstract

The application discloses a preparation method and product of a chelate builder and application thereof, and belongs to the field of chemical industry. The method comprises the following steps: uniformly mixing ethylenediaminetetraacetic acid (EDTA) and tris(2-aminoethyl)amine (TAEA), gradually increasing the temperature for reaction, and obtaining a viscous substance as an EDTA / TAEA reactant after the reaction is completed; dissolving the EDTA / TAEA reactant in a non-polar or weakly polar solvent, adding aspartic acid, adjusting the polarity of the solution by adding ethanol, which is beneficial to the dissolution of the reactant, gradually increasing the temperature under the stirring action, and removing the solvent by rotary evaporation after the reaction is completed, so as to obtain the chelate builder. The aspartic acid / ethylenediaminetetraacetic acid / tris(2-aminoethyl)amine gradually polymerized chelate provided by the application can be combined with a surfactant to significantly improve the oil agent and stain removal effect of a fabric product.

Description

Technical Field

[0001] This invention belongs to the field of finishing agents for textile fabrics, specifically relating to a method for preparing a chelate washing aid, a product thereof, and its application. Background Technology

[0002] Chelating dispersants come in a wide variety of types and properties, and are used in a broad range of fields. With increasingly stringent requirements for "environmental protection" and "phosphorus-free" standards, only highly efficient, multifunctional, phosphorus-free, and easily biodegradable chelating dispersants can meet market demands.

[0003] Currently, phosphorus-free chelating dispersants are mainly modified products and derivatives of polyacrylic acid. There are many studies both domestically and internationally on sodium polyacrylate (PAA-Na) and polycarboxylates ranging from ultra-low molecular weight to ultra-high molecular weight. There are even reports from abroad of PAA-Na with molecular weights less than 1000 and greater than 30 million.

[0004] However, phosphorus-free chelating dispersants with excellent chelating power and dispersibility are rare. Most of the chelating dispersants with large sales volume in the market, such as modified polyacrylic acid products and derivatives, contain phosphorus. To obtain phosphorus-free products with high chelating and dispersing power and biodegradability, there is still an urgent need for solutions in this field. Summary of the Invention

[0005] The purpose of this section is to outline some aspects of embodiments of the present invention and to briefly describe some preferred embodiments. Simplifications or omissions may be made in this section, as well as in the abstract and title of this application, to avoid obscuring the purpose of these documents; however, such simplifications or omissions should not be construed as limiting the scope of the invention.

[0006] In view of the problems existing in the above and / or prior art, the present invention is proposed.

[0007] Therefore, the purpose of this invention is to overcome the shortcomings of the prior art and provide a method for preparing a chelate detergent builder.

[0008] To solve the above-mentioned technical problems, the present invention provides the following technical solution: a method for preparing a chelate detergent builder, comprising,

[0009] Mix EDTA and tris(2-aminoethyl)amine (TAEA) thoroughly, gradually increase the temperature and react until the reaction is complete to obtain a viscous substance, which is the EDTA / TAEA reactant.

[0010] The EDTA / TAEA reactants are dissolved in a nonpolar or weakly polar solvent, aspartic acid is added, and the polarity of the solution is adjusted by adding ethanol, which is beneficial to the dissolution of the reactants. The temperature is gradually increased under stirring, and the solvent is removed by rotary evaporation after the reaction is completed. The remaining solid product is the chelate detergent aid.

[0011] In a preferred embodiment of the preparation method described in this invention, EDTA and tris(2-aminoethyl)amine (TAEA) are mixed evenly, wherein the molar ratio of EDTA to TAEA is 4:1 to 1:4.

[0012] In a preferred embodiment of the preparation method described in this invention, the mixing process includes a stirring speed of 200–600 r / min.

[0013] In a preferred embodiment of the preparation method described in this invention, the molar ratio of EDTA to TAEA is 1:1.

[0014] As a preferred embodiment of the preparation method described in this invention, the stepwise heating reaction includes starting at room temperature, heating at a rate of 1–4 °C / min, holding at 40–60 °C for 20–40 min, and continuing to heat at the same rate to 70–90 °C for 30–60 min.

[0015] In a preferred embodiment of the preparation method described in this invention, the aspartic acid is L-aspartic acid, and the molar ratio of aspartic acid to EDTA is 1:9 to 9:1.

[0016] In a preferred embodiment of the preparation method described in this invention, the non-polar or weakly polar solvent includes acetone, tetrahydrofuran, dichloromethane, and tetrachloromethane; and the ethanol accounts for no more than 5% of the total volume of the solvent.

[0017] As a preferred embodiment of the preparation method of the present invention, the step of gradually increasing the temperature under stirring is wherein the stirring speed is 100-500 r / min, the heating rate is 2-5℃ / min, the reaction is carried out when the temperature reaches 60-90℃, and the reaction time is 2-4 h.

[0018] Another objective of this invention is to overcome the shortcomings of the prior art and provide a method for preparing a chelate detergent builder to obtain the product.

[0019] Another objective of this invention is to overcome the shortcomings of the prior art and provide a method for preparing a chelate detergent builder, and to apply the product to the removal of stains from textile fabrics.

[0020] Beneficial effects of this invention:

[0021] (1) The aspartic acid / ethylenediaminetetraacetic acid / tris(2-aminoethyl)amine stepwise polymerization chelate provided by the present invention, when combined with a surfactant, can significantly improve the oil and stain removal effect of fabric products;

[0022] (2) This invention prepares an aspartic acid / ethylenediaminetetraacetic acid / tris(2-aminoethyl)amine stepwise polymerization chelate by stepwise polymerization. Aspartic acid can endow the chelate with biodegradable properties, while EDTA and TAEA have high-efficiency chelating properties. When added to textile dyeing and finishing processes in combination with surfactants, it can improve the stability of surfactants, bind with the hydrophilic groups of surfactants, enhance their agitation in water, enhance the removal performance of surfactants for stains such as oils, improve the cleaning efficiency, and this chelate does not have the pollution problem of commonly used phosphorus-containing detergents, is more environmentally friendly, achieves better results, and improves the stability of surfactants. Attached Figure Description

[0023] To more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort. Wherein:

[0024] Figure 1 The image shows the infrared spectrum of the chelate obtained in the embodiments of the present invention. Detailed Implementation

[0025] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, the specific embodiments of the present invention will be described in detail below with reference to the examples in the specification.

[0026] Many specific details are set forth in the following description in order to provide a full understanding of the invention. However, the invention may also be practiced in other ways different from those described herein, and those skilled in the art can make similar extensions without departing from the spirit of the invention. Therefore, the invention is not limited to the specific embodiments disclosed below.

[0027] Secondly, the term "one embodiment" or "embodiment" as used herein refers to a specific feature, structure, or characteristic that may be included in at least one implementation of the present invention. The phrase "in one embodiment" appearing in different places in this specification does not necessarily refer to the same embodiment, nor is it a single or selective embodiment that is mutually exclusive with other embodiments.

[0028] The method for determining the dispersing force in this embodiment of the invention is as follows: Kaolin is used as the simulated scale material. A turbid solution of 0.1% kaolin (≤300 mesh, 47% SiO2 + 38% Al2O3) is prepared, wherein the calcium hardness is 200 mg / L, the alkalinity is 100 mg / L (both calculated as CaCO3), and the pH is 8 ± 0.2. The solution is ultrasonically vibrated for 20 min. The dispersion is then placed into 250 mL graduated cylinders of the same specification. One cylinder is used as a blank solution (volume V0, mL) without reagents. The other cylinders are treated with reagents at 10 mg / L. The cylinders are then allowed to stand upright for 24 h. The volume of the supernatant in each graduated cylinder (V1, mL) is recorded. The dispersing force is calculated as (1 - V1 / V0) × 100%.

[0029] Fe 3+ Method for determining chelating capacity: Accurately weigh 48.21g of NH4Fe(SO4)2·12H2O (analytical grade) and dissolve it in 500mL of deionized water. Add 20mL of concentrated sulfuric acid, cool, transfer to a 1L volumetric flask, and dilute to the mark to prepare a 0.1mol / L ferric ammonium sulfate standard solution.

[0030] Weigh 0.5g of the sample to be tested into a 250mL beaker, add 120mL of deionized water, stir magnetically to dissolve and disperse the sample evenly, adjust the pH to 11-12 with 30% NaOH solution, and then titrate with 0.1mol / L ferric ammonium sulfate standard solution.

[0031] Note: (1) The pH will decrease during the titration process. When adjusting with NaOH solution, it should be added slowly and not too much or too fast at once.

[0032] (2) If the chelation value of the sample is too large or too small, the amount of the sample to be tested should be adjusted appropriately.

[0033] The endpoint is reached when a precipitate forms. Record the volume V, mL, of ferric ammonium sulfate standard solution consumed. Perform the test in triplicate and take the average value.

[0034] Fe 3+ Chelation value (in Fe) 3+ The formula is: (mg / g) = 5.584 × V / m. Where: m is the amount of sample to be tested, in g.

[0035] In this invention, intrinsic viscosity and number-average molecular weight are determined according to GB / T 22235—2008, the method for determining the viscosity of liquids.

[0036] Example 1

[0037] (1) Initial reaction of ethylenediaminetetraacetic acid (EDTA) with tris(2-aminoethyl)amine (TAEA):

[0038] Add EDTA and TAEA to the reaction vessel at a molar ratio of 4:1, mix them evenly by stirring at a speed of 400 r / min, gradually increase the temperature at a rate of 3℃ / min, hold at 50℃ for 30 min, continue to increase the temperature to 80℃ at the same rate, and react for 45 min. When the reaction is complete and a viscous substance is obtained, it is the reactant, which is the EDTA / TAEA reactant.

[0039] (2) Reaction of EDTA / TAEA reactants with aspartic acid:

[0040] The EDTA / TAEA reactant was dissolved in tetrahydrofuran solvent. Aspartic acid (with a tetrahydrofuran mass fraction of 85%) was added to the EDTA at a molar ratio of 1:9. The mixture was stirred until dissolved at 400 rpm, and the temperature was gradually increased at a rate of 3 °C / min until it reached 75 °C. The reaction was then carried out for 3 hours. The solvent was removed by rotary evaporation, and the remaining solid product was the chelate obtained by step-growth polymerization. The intrinsic viscosity of the chelate was 0.58 dL / g. -1 The number average molecular weight is 2300, the dispersibility is 65%, and the chelation value is 120 / (mg*g). -1 ).

[0041] Example 2

[0042] (1) Initial reaction of ethylenediaminetetraacetic acid (EDTA) with tris(2-aminoethyl)amine (TAEA):

[0043] Add EDTA and TAEA to the reaction vessel at a molar ratio of 2:1. Stir to mix them evenly at a stirring speed of 400 r / min. Gradually increase the temperature at a rate of 3℃ / min. Hold at 50℃ for 30 min. Continue to increase the temperature to 80℃ at the same rate and react for 45 min. Once the reaction is complete, a viscous substance is obtained, which is the reactant.

[0044] (2) Reaction of EDTA / TAEA reactants with aspartic acid:

[0045] The EDTA / TAEA reactant was dissolved in tetrahydrofuran solvent, and aspartic acid was added to EDTA at a molar ratio of 1:9. The mixture was stirred until dissolved, and the temperature was gradually increased at a rate of 3℃ / min until it reached 75℃. The reaction was then stopped and the solvent was removed by a rotary evaporator. The remaining solid product was the chelate obtained by stepwise polymerization.

[0046] Intrinsic viscosity and number-average molecular weight were determined according to GB / T 22235—2008, the method for determining the viscosity of liquids. The intrinsic viscosity was 0.63 / (dL*g-1), the number-average molecular weight was 2600, the dispersing power was 68%, and the chelation value was 140 / (mg*g-1).

[0047] Example 3

[0048] (1) Initial reaction of ethylenediaminetetraacetic acid (EDTA) with tris(2-aminoethyl)amine (TAEA):

[0049] Add EDTA and TAEA to the reaction vessel at a molar ratio of 1:1, stir to mix them evenly at a stirring speed of 400 r / min, gradually increase the temperature at a heating rate of 3℃ / min, hold at 50℃ for 30 min, continue to increase the temperature to 80℃ at the same heating rate, and react for 45 min. When the reaction is complete, a viscous substance is obtained, which is the reactant of the two.

[0050] (2) Reaction of EDTA / TAEA reactants with aspartic acid:

[0051] The EDTA / TAEA reactant was dissolved in tetrahydrofuran solvent, and aspartic acid was added to EDTA at a molar ratio of 1:9. The mixture was stirred until dissolved, and the temperature was gradually increased at a rate of 3℃ / min until it reached 75℃. The reaction was then stopped and the solvent was removed by a rotary evaporator. The remaining solid product was the chelate obtained by stepwise polymerization.

[0052] Intrinsic viscosity and number-average molecular weight were determined according to GB / T 22235—2008, the method for determination of liquid viscosity. The intrinsic viscosity was 0.68 / (dL*g-1), the number-average molecular weight was 2900, the dispersing power was 71%, and the chelation value was 210 / (mg*g-1).

[0053] Example 4

[0054] (1) Initial reaction of ethylenediaminetetraacetic acid (EDTA) with tris(2-aminoethyl)amine (TAEA):

[0055] Add EDTA and TAEA to the reaction vessel at a molar ratio of 1:2, stir to mix them evenly at a stirring speed of 400 r / min, gradually increase the temperature at a heating rate of 3℃ / min, hold at 50℃ for 30 min, continue to increase the temperature to 80℃ at the same heating rate, and react for 45 min. When the reaction is complete, a viscous substance is obtained, which is the reactant of the two.

[0056] (2) Reaction of EDTA / TAEA reactants with aspartic acid:

[0057] The EDTA / TAEA reactant was dissolved in tetrahydrofuran solvent, and aspartic acid was added to EDTA at a molar ratio of 1:9. The mixture was stirred until dissolved, and the temperature was gradually increased at a rate of 3℃ / min until it reached 75℃. The reaction was then stopped and the solvent was removed by a rotary evaporator. The remaining solid product was the chelate obtained by stepwise polymerization.

[0058] Intrinsic viscosity and number-average molecular weight: determined according to GB / T 22235—2008, method for determination of liquid viscosity. Intrinsic viscosity: 0.65 / (dL*g-1), number-average molecular weight: 2700, dispersing power: 69%, chelation value: 180 / (mg*g-1).

[0059] Increasing the proportion of TAEA at this point will decrease performance; therefore, the optimal ratio of EDTA to TAEA is 1:1.

[0060] Example 5

[0061] (1) Initial reaction of ethylenediaminetetraacetic acid (EDTA) with tris(2-aminoethyl)amine (TAEA):

[0062] Add EDTA and TAEA to the reaction vessel at a molar ratio of 1:1, stir to mix them evenly at a stirring speed of 400 r / min, gradually increase the temperature at a heating rate of 3℃ / min, hold at 50℃ for 30 min, continue to increase the temperature to 80℃ at the same heating rate, and react for 45 min. When the reaction is complete, a viscous substance is obtained, which is the reactant of the two.

[0063] (2) Reaction of EDTA / TAEA reactants with aspartic acid:

[0064] The EDTA / TAEA reactant was dissolved in tetrahydrofuran solvent, and aspartic acid was added to EDTA at a molar ratio of 1:4. The mixture was stirred until dissolved, and the temperature was gradually increased at a rate of 3℃ / min until it reached 75℃. The reaction was then stopped and the solvent was removed by a rotary evaporator. The remaining solid product was the chelate obtained by stepwise polymerization.

[0065] Intrinsic viscosity and number-average molecular weight: determined according to GB / T 22235—2008, method for determination of liquid viscosity. Intrinsic viscosity: 0.69 / (dL*g-1), number-average molecular weight: 3100, dispersing power: 81%, chelation value: 260 / (mg*g-1).

[0066] Example 6

[0067] (1) Initial reaction of ethylenediaminetetraacetic acid (EDTA) with tris(2-aminoethyl)amine (TAEA):

[0068] Add EDTA and TAEA to the reaction vessel at a molar ratio of 1:1, stir to mix them evenly at a stirring speed of 400 r / min, gradually increase the temperature at a heating rate of 3℃ / min, hold at 50℃ for 30 min, continue to increase the temperature to 80℃ at the same heating rate, and react for 45 min. When the reaction is complete, a viscous substance is obtained, which is the reactant of the two.

[0069] (2) Reaction of EDTA / TAEA reactants with aspartic acid:

[0070] The EDTA / TAEA reactant was dissolved in tetrahydrofuran solvent, and aspartic acid was added to EDTA at a molar ratio of 1:2. The mixture was stirred until dissolved, and the temperature was gradually increased at a rate of 3℃ / min until it reached 75℃. The reaction was then stopped and the solvent was removed by a rotary evaporator. The remaining solid product was the chelate obtained by stepwise polymerization.

[0071] Intrinsic viscosity and number-average molecular weight: determined according to GB / T 22235—2008, method for determination of liquid viscosity. Intrinsic viscosity: 0.71 / (dL*g-1), number-average molecular weight: 3300, dispersing power: 92%, chelation value: 485 / (mg*g-1).

[0072] The infrared spectrum of the chelate obtained in the embodiments of the present invention is shown in the figure. Figure 1 .

[0073] Example 7

[0074] (1) Initial reaction of ethylenediaminetetraacetic acid (EDTA) with tris(2-aminoethyl)amine (TAEA):

[0075] Add EDTA and TAEA to the reaction vessel at a molar ratio of 1:1, stir to mix them evenly at a stirring speed of 400 r / min, gradually increase the temperature at a heating rate of 3℃ / min, hold at 50℃ for 30 min, continue to increase the temperature to 80℃ at the same heating rate, and react for 45 min. When the reaction is complete, a viscous substance is obtained, which is the reactant of the two.

[0076] (2) Reaction of EDTA / TAEA reactants with aspartic acid:

[0077] The EDTA / TAEA reactant was dissolved in tetrahydrofuran solvent, and aspartic acid was added to EDTA at a molar ratio of 1:1. The mixture was stirred until dissolved, and the temperature was gradually increased at a rate of 3℃ / min until it reached 75℃. The reaction was then stopped and the solvent was removed by rotary evaporation. The remaining solid product was the chelate obtained by stepwise polymerization.

[0078] Intrinsic viscosity and number-average molecular weight: determined according to GB / T 22235—2008, method for determination of liquid viscosity. Intrinsic viscosity: 0.70 / (dL*g-1), number-average molecular weight: 3200, dispersing power: 87%, chelation value: 395 / (mg*g-1).

[0079] Increasing the amount of aspartic acid added further reduces performance; therefore, the optimal molar ratio of aspartic acid to EDTA is 1:2.

[0080] Example 8

[0081] (1) Initial reaction of ethylenediaminetetraacetic acid (EDTA) with tris(2-aminoethyl)amine (TAEA):

[0082] Add EDTA and TAEA to the reaction vessel at a molar ratio of 1:1, stir to mix them evenly at a stirring speed of 400 r / min, gradually increase the temperature at a heating rate of 3℃ / min, hold at 50℃ for 30 min, continue to increase the temperature to 80℃ at the same heating rate, and react for 45 min. When the reaction is complete, a viscous substance is obtained, which is the reactant of the two.

[0083] (2) Reaction of EDTA / TAEA reactants with aspartic acid:

[0084] The EDTA / TAEA reactant was dissolved in tetrahydrofuran solvent, and aspartic acid was added to EDTA at a molar ratio of 1:2. The mixture was stirred until dissolved, and the temperature was gradually increased at a rate of 3℃ / min until it reached 75℃. The reaction was then stopped and the solvent was removed by a rotary evaporator. The remaining solid product was the chelate obtained by stepwise polymerization.

[0085] (3) The dyeing bath degreasing process is adopted. The amount of chelating agent added is 1% of the surfactant (triethanolamine dodecylbenzenesulfonate surfactant). The temperature is raised to 130℃ at a rate of 2.0℃ / min, kept at 30min, and then cooled to 40℃ at a rate of 3.0℃ / min. The product is then washed and dried.

[0086] Among these processes, polyester knitted fabrics undergo an integrated dyeing and degreasing treatment.

[0087] The dyes used in the dyeing process consist of the following components and parts by weight: 0.04 parts by weight of Disperse Yellow, 0.0152 parts by weight of Disperse Red, 0.022 parts by weight of Disperse Blue, and 0.5 parts by weight of 98% glacial acetic acid; the amount of surfactant added is 2% of the dye bath concentration.

[0088] Referring to GB / T 251—2008 "Textiles - Tests for Color Fastness - Evaluation of Staining - Gray Scale", the degree of oil stain removal is judged by visual inspection, and the staining gray scale is used for comparison and rating. The oil removal effect is divided into 5 levels, with level 5 being the best and level 1 being the worst.

[0089] The result of this experiment was Level 2, which did not meet the standard requirements.

[0090] Example 9

[0091] (1) Initial reaction of ethylenediaminetetraacetic acid (EDTA) with tris(2-aminoethyl)amine (TAEA):

[0092] Add EDTA and TAEA to the reaction vessel at a molar ratio of 1:1, stir to mix them evenly at a stirring speed of 400 r / min, gradually increase the temperature at a heating rate of 3℃ / min, hold at 50℃ for 30 min, continue to increase the temperature to 80℃ at the same heating rate, and react for 45 min. When the reaction is complete, a viscous substance is obtained, which is the reactant of the two.

[0093] (2) Reaction of EDTA / TAEA reactants with aspartic acid:

[0094] The EDTA / TAEA reactant was dissolved in tetrahydrofuran solvent, and aspartic acid was added to EDTA at a molar ratio of 1:2. The mixture was stirred until dissolved, and the temperature was gradually increased at a rate of 3℃ / min until it reached 75℃. The reaction was then stopped and the solvent was removed by a rotary evaporator. The remaining solid product was the chelate obtained by stepwise polymerization.

[0095] (3) The dye bath degreasing process is adopted (same as Example 8). The amount of chelating agent added is 2% of the surfactant. The temperature is raised to 130°C at a rate of 2.0°C / min, kept at 30 min, and then cooled to 40°C at a rate of 3.0°C / min. The product is then washed and dried.

[0096] Referring to GB / T 251—2008 "Textiles - Tests for Color Fastness - Evaluation of Staining - Gray Scale", the degree of oil stain removal is judged by visual inspection, and the staining gray scale is used for comparison and rating. The oil removal effect is divided into 5 levels, with level 5 being the best and level 1 being the worst.

[0097] The result of this experiment was level 2.5, which did not meet the standard requirements.

[0098] Example 10

[0099] (1) Initial reaction of ethylenediaminetetraacetic acid (EDTA) with tris(2-aminoethyl)amine (TAEA):

[0100] Add EDTA and TAEA to the reaction vessel at a molar ratio of 1:1, stir to mix them evenly at a stirring speed of 400 r / min, gradually increase the temperature at a heating rate of 3℃ / min, hold at 50℃ for 30 min, continue to increase the temperature to 80℃ at the same heating rate, and react for 45 min. When the reaction is complete, a viscous substance is obtained, which is the reactant of the two.

[0101] (2) Reaction of EDTA / TAEA reactants with aspartic acid:

[0102] The EDTA / TAEA reactant was dissolved in tetrahydrofuran solvent, and aspartic acid was added to EDTA at a molar ratio of 1:2. The mixture was stirred until dissolved, and the temperature was gradually increased at a rate of 3℃ / min until it reached 75℃. The reaction was then stopped and the solvent was removed by a rotary evaporator. The remaining solid product was the chelate obtained by stepwise polymerization.

[0103] (3) The dye bath degreasing process is adopted (same as Example 8). The amount of chelating agent added is 4% of the surfactant. The temperature is raised to 130°C at a rate of 2.0°C / min, kept at 30 min, and then cooled to 40°C at a rate of 3.0°C / min. The product is then washed and dried.

[0104] Referring to GB / T 251—2008 "Textiles - Tests for Color Fastness - Evaluation of Staining - Gray Scale", the degree of oil stain removal is judged by visual inspection, and the staining gray scale is used for comparison and rating. The oil removal effect is divided into 5 levels, with level 5 being the best and level 1 being the worst.

[0105] The result of this experiment is level 3.5, which meets the standard requirements.

[0106] Example 11

[0107] (1) Initial reaction of ethylenediaminetetraacetic acid (EDTA) and tris(2-aminoethyl)amine (TAEA): EDTA and TAEA were added to the reaction vessel at a molar ratio of 1:1. The mixture was stirred until homogeneous. The stirring speed was 400 r / min. The temperature was gradually increased at a rate of 3 °C / min. The temperature was held at 50 °C for 30 min. The temperature was then increased to 80 °C at the same rate. The reaction was allowed to proceed for 45 min. The viscous substance obtained after the reaction was complete was the reactant.

[0108] (2) Reaction of EDTA / TAEA reactants with aspartic acid: Dissolve EDTA / TAEA reactants in tetrahydrofuran solvent, add aspartic acid to EDTA at a molar ratio of 1:2, and dissolve it under stirring at a speed of 400 r / min. Gradually increase the temperature at a rate of 3℃ / min until the temperature reaches 75℃ and react for 3 h. After the reaction is completed, remove the solvent by a rotary evaporator. The remaining solid product is the chelate obtained by stepwise polymerization.

[0109] (3) The dye bath degreasing process is adopted (same as Example 8). The amount of chelating agent added is 8% of the surfactant. The temperature is raised to 130°C at a rate of 2.0°C / min, kept at 30 min, and then cooled to 40°C at a rate of 3.0°C / min. The product is then washed and dried.

[0110] Referring to GB / T 251—2008 "Textiles - Tests for Color Fastness - Evaluation of Staining - Gray Scale", the degree of oil stain removal is judged by visual inspection, and the staining gray scale is used for comparison and rating. The oil removal effect is divided into 5 levels, with level 5 being the best and level 1 being the worst.

[0111] The result of this experiment is level 4, which meets the standard requirements.

[0112] Example 12

[0113] (1) Initial reaction of ethylenediaminetetraacetic acid (EDTA) and tris(2-aminoethyl)amine (TAEA): EDTA and TAEA were added to the reaction vessel at a molar ratio of 1:1. The mixture was stirred until homogeneous. The stirring speed was 400 r / min. The temperature was gradually increased at a rate of 3 °C / min. The temperature was held at 50 °C for 30 min. The temperature was then increased to 80 °C at the same rate. The reaction was allowed to proceed for 45 min. The viscous substance obtained after the reaction was complete was the reactant.

[0114] (2) Reaction of EDTA / TAEA reactants with aspartic acid: Dissolve EDTA / TAEA reactants in tetrahydrofuran solvent, add aspartic acid to EDTA at a molar ratio of 1:2, and dissolve it under stirring at a speed of 400 r / min. Gradually increase the temperature at a rate of 3℃ / min until the temperature reaches 75℃ and react for 3 h. After the reaction is completed, remove the solvent by a rotary evaporator. The remaining solid product is the chelate obtained by stepwise polymerization.

[0115] (3) The dye bath degreasing process is adopted (same as Example 8). The amount of chelating agent added is 16% of the surfactant. The temperature is raised to 130°C at a rate of 2.0°C / min, kept at 30 min, and then cooled to 40°C at a rate of 3.0°C / min. The product is then washed and dried.

[0116] Referring to GB / T 251—2008 "Textiles - Tests for Color Fastness - Evaluation of Staining - Gray Scale", the degree of oil stain removal is judged by visual inspection, and the staining gray scale is used for comparison and rating. The oil removal effect is divided into 5 levels, with level 5 being the best and level 1 being the worst.

[0117] The result of this experiment is level 4.5, which meets the standard requirements.

[0118] Example 13

[0119] (1) Initial reaction of ethylenediaminetetraacetic acid (EDTA) and tris(2-aminoethyl)amine (TAEA): EDTA and TAEA were added to the reaction vessel at a molar ratio of 1:1. The mixture was stirred until homogeneous. The stirring speed was 400 r / min. The temperature was gradually increased at a rate of 3 °C / min. The temperature was held at 50 °C for 30 min. The temperature was then increased to 80 °C at the same rate. The reaction was allowed to proceed for 45 min. The viscous substance obtained after the reaction was complete was the reactant.

[0120] (2) Reaction of EDTA / TAEA reactants with aspartic acid: Dissolve EDTA / TAEA reactants in tetrahydrofuran solvent, add aspartic acid to EDTA at a molar ratio of 1:2, and dissolve it under stirring at a speed of 400 r / min. Gradually increase the temperature at a rate of 3℃ / min until the temperature reaches 75℃ and react for 3 h. After the reaction is completed, remove the solvent by a rotary evaporator. The remaining solid product is the chelate obtained by stepwise polymerization.

[0121] (3) The dye bath degreasing process is adopted (same as Example 8). The amount of chelating agent added is 20% of the surfactant. The temperature is raised to 130°C at a rate of 2.0°C / min, kept at 30 min, and then cooled to 40°C at a rate of 3.0°C / min. The product is then washed and dried.

[0122] Referring to GB / T 251—2008 "Textiles - Tests for Color Fastness - Evaluation of Staining - Gray Scale", the degree of oil stain removal is judged by visual inspection, and the staining gray scale is used for comparison and rating. The oil removal effect is divided into 5 levels, with level 5 being the best and level 1 being the worst.

[0123] The result of this experiment is level 4.5, which meets the standard requirements.

[0124] It can be seen that further increasing the amount of chelating agent added at this point will not increase the detergency. Therefore, the optimal amount added for textile detergency applications is 16% of the surfactant.

[0125] Comparative Example 1

[0126] (1) Initial reaction of ethylenediaminetetraacetic acid (EDTA) and tris(2-aminoethyl)amine (TAEA): EDTA and TAEA were added to the reaction vessel at a molar ratio of 1:1. The mixture was stirred until homogeneous. The stirring speed was 400 r / min. The temperature was gradually increased at a rate of 3 °C / min. The temperature was held at 50 °C for 30 min. The temperature was then increased to 80 °C at the same rate. The reaction was allowed to proceed for 45 min. The viscous substance obtained after the reaction was complete was the reactant.

[0127] Intrinsic viscosity and number-average molecular weight: determined according to GB / T 22235—2008, method for determination of liquid viscosity. Intrinsic viscosity: 0.35 / (dL*g-1), number-average molecular weight: 900, dispersing power: 39%, chelation value: 118 / (mg*g-1).

[0128] Comparative Example 2

[0129] (1) Initial reaction of ethylenediaminetetraacetic acid (EDTA) and tris(2-aminoethyl)amine (TAEA): EDTA and TAEA were added to the reaction vessel at a molar ratio of 1:1. The mixture was stirred until homogeneous. The stirring speed was 400 r / min. The temperature was gradually increased at a rate of 3 °C / min. The temperature was held at 50 °C for 30 min. The temperature was then increased to 80 °C at the same rate. The reaction was allowed to proceed for 45 min. The viscous substance obtained after the reaction was complete was the reactant.

[0130] (2) Reaction of EDTA / TAEA reactants with lysine: Dissolve EDTA / TAEA reactants in tetrahydrofuran solvent, add lysine with EDTA at a molar ratio of 1:2, dissolve under stirring, rotate at 400 r / min, gradually increase the temperature at a rate of 3℃ / min, and react at 75℃ for 3h. After the reaction is completed, remove the solvent by rotary evaporation device. The remaining solid product is the chelate obtained by step polymerization.

[0131] Intrinsic viscosity and number-average molecular weight: determined according to GB / T 22235—2008, method for determination of liquid viscosity. Intrinsic viscosity: 0.63 / (dL*g-1), number-average molecular weight: 2800, dispersing power: 84%, chelation value: 379 / (mg*g-1).

[0132] Comparative Example 3

[0133] (1) Initial reaction of ethylenediaminetetraacetic acid (EDTA) and tris(2-aminoethyl)amine (TAEA): EDTA and TAEA were added to the reaction vessel at a molar ratio of 1:1. The mixture was stirred until homogeneous. The stirring speed was 400 r / min. The temperature was gradually increased at a rate of 3 °C / min. The temperature was held at 50 °C for 30 min. The temperature was then increased to 60 °C at the same rate. The reaction was allowed to proceed for 45 min. The viscous substance obtained after the reaction was complete was the reactant.

[0134] (2) Reaction of EDTA / TAEA reactants with aspartic acid: Dissolve EDTA / TAEA reactants in tetrahydrofuran solvent, add aspartic acid to EDTA at a molar ratio of 1:2, and dissolve it under stirring at a speed of 400 r / min. Gradually increase the temperature at a rate of 3℃ / min until the temperature reaches 55℃ and react for 3 h. After the reaction is completed, remove the solvent by a rotary evaporator. The remaining solid product is the chelate obtained by stepwise polymerization.

[0135] Intrinsic viscosity and number-average molecular weight: determined according to GB / T 22235—2008, method for determination of liquid viscosity. Intrinsic viscosity: 0.38 / (dL*g-1), number-average molecular weight: 600, dispersing power: 35%, chelation value: 85 / (mg*g-1).

[0136] Lowering the reaction temperature prevents the chemical reaction from occurring, resulting in a significant decrease in intrinsic viscosity and molecular weight, as well as a marked decrease in chelating force.

[0137] Comparative Example 4

[0138] (1) Reaction of ethylenediaminetetraacetic acid (EDTA) with aspartic acid: EDTA is dissolved in tetrahydrofuran solvent, and aspartic acid is added to EDTA at a molar ratio of 1:2. The mixture is stirred until dissolved, and the rotation speed is 400 r / min. The temperature is gradually increased at a rate of 3℃ / min until the temperature reaches 75℃ and the reaction is carried out for 3 h. The solvent is removed by rotary evaporation device, and the remaining solid product is the chelate obtained by step polymerization.

[0139] Intrinsic viscosity and number-average molecular weight: determined according to GB / T 22235—2008, method for determination of liquid viscosity. Intrinsic viscosity: 0.42 / (dL*g-1), number-average molecular weight: 1100, dispersing power: 48%, chelation value: 142 / (mg*g-1).

[0140] Comparative Example 5

[0141] (1) Under the conditions of Example 12, with the total amount of chelating agent and surfactant kept constant, a comparison was made without adding chelating agent:

[0142] Initial reaction of ethylenediaminetetraacetic acid (EDTA) and tris(2-aminoethyl)amine (TAEA): EDTA and TAEA are added to a reaction vessel at a molar ratio of 1:1. The mixture is stirred until homogeneous at a stirring speed of 400 r / min. The temperature is gradually increased at a rate of 3 °C / min. The temperature is held at 50 °C for 30 min, and then increased to 80 °C at the same rate. The reaction is allowed to proceed for 45 min until the reaction is complete and a viscous substance is obtained, which is the reactant.

[0143] Reaction of EDTA / TAEA reactants with aspartic acid: The EDTA / TAEA reactants were dissolved in tetrahydrofuran solvent, and aspartic acid was added to EDTA at a molar ratio of 1:2. The mixture was stirred until dissolved, and the temperature was gradually increased at a rate of 3℃ / min until it reached 75℃. The reaction was then stopped and the solvent was removed by a rotary evaporator. The remaining solid product was the chelate obtained by stepwise polymerization.

[0144] The process employs an integrated dyeing and bath degreasing technique, with surfactant added at 2% of the dyeing bath concentration. The temperature is increased to 130℃ at a rate of 2.0℃ / min, held for 30 minutes, and then decreased to 40℃ at a rate of 3.0℃ / min, followed by washing and drying.

[0145] Referring to GB / T 251—2008 "Textiles - Tests for Color Fastness - Evaluation of Staining - Gray Scale", the degree of oil stain removal is judged by visual inspection, and the staining gray scale is used for comparison and rating. The oil removal effect is divided into 5 levels, with level 5 being the best and level 1 being the worst.

[0146] The result of this experiment is level 3.5, which meets the standard requirements.

[0147] (2) Under the conditions of Example 12, with the total amount of chelating agent and surfactant kept constant, a comparison was made without adding surfactant:

[0148] Initial reaction of ethylenediaminetetraacetic acid (EDTA) and tris(2-aminoethyl)amine (TAEA): EDTA and TAEA are added to a reaction vessel at a molar ratio of 1:1. The mixture is stirred until homogeneous at a stirring speed of 400 r / min. The temperature is gradually increased at a rate of 3 °C / min. The temperature is held at 50 °C for 30 min, and then increased to 80 °C at the same rate. The reaction is allowed to proceed for 45 min until the reaction is complete and a viscous substance is obtained, which is the reactant.

[0149] Reaction of EDTA / TAEA reactants with aspartic acid: The EDTA / TAEA reactants were dissolved in tetrahydrofuran solvent, and aspartic acid was added to EDTA at a molar ratio of 1:2. The mixture was stirred until dissolved, and the temperature was gradually increased at a rate of 3℃ / min until it reached 75℃. The reaction was then stopped and the solvent was removed by a rotary evaporator. The remaining solid product was the chelate obtained by stepwise polymerization.

[0150] The process employs an integrated dyeing and bath degreasing technique, with the chelating agent added at 2% of the dyeing bath concentration. The temperature is increased to 130℃ at a rate of 2.0℃ / min, held for 30 minutes, and then decreased to 40℃ at a rate of 3.0℃ / min, followed by washing and drying.

[0151] Referring to GB / T 251—2008 "Textiles - Tests for Color Fastness - Evaluation of Staining - Gray Scale", the degree of oil stain removal is judged by visual inspection, and the staining gray scale is used for comparison and rating. The oil removal effect is divided into 5 levels, with level 5 being the best and level 1 being the worst.

[0152] The result of this experiment was level 2.5, which did not meet the standard requirements.

[0153] This invention addresses the aforementioned problems by developing a highly efficient chelating agent obtained through ternary stepwise polymerization, which enhances its detergency. Modification with aspartic acid increases its biodegradability. The product is phosphorus-free, and its EDTA and TAEA structures possess strong chelating power, enabling a synergistic effect with surfactants to improve the removal of oil stains and other dirt from textile fabrics.

[0154] It should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all such modifications or substitutions should be covered within the scope of the present invention.

Claims

1. A method for preparing a chelate detergent builder, characterized in that: include, Ethylenediaminetetraacetic acid (EDTA) and tris(2-aminoethyl)amine (TAEA) are mixed evenly and the temperature is gradually increased to react. When the reaction is complete, a viscous substance is obtained, which is the EDTA / TAEA reactant. The molar ratio of EDTA to TAEA is 1:

1. The gradual heating reaction includes starting at room temperature, heating at a rate of 1~4℃ / min, holding at 40~60℃ for 20~40min, and continuing to heat at the same rate to 70~90℃ for 30~60min. The EDTA / TAEA reactants were dissolved in tetrahydrofuran, and aspartic acid was added. The polarity of the solution was adjusted by adding ethanol, which is beneficial to the dissolution of the reactants. The temperature was gradually increased to 60-90℃ at a rate of 2-5℃ / min under stirring at 100-500 r / min for 2-4 h. After the reaction was completed, the solvent was removed by rotary evaporation. The remaining solid product was the chelate washing aid. The aspartic acid was L-aspartic acid, and the molar ratio of aspartic acid to EDTA was 1:

2.

2. The preparation method according to claim 1, characterized in that: The mixing process involves stirring at a speed of 200-600 r / min.

3. The chelate detergent additive prepared by the method described in claim 1 or 2.

4. The application of the chelate detergent builder according to claim 3 in stain removal from textile fabrics, characterized in that: include, The first step is to wash the woven or knitted fabric to remove oil stains; The second step involves adding a dodecylbenzenesulfonate triethanolamine salt surfactant and a chelating agent to the dye bath system, with the amount of chelating agent added being 1-20% of the surfactant. The third step involves heating the product to 120-135℃ at a rate of 1.0-3.0℃ / min, holding it at that temperature for 20-40 minutes, and then cooling it to 35-45℃ at a rate of 2.0-4.0℃ / min before washing and drying.

Images