Cationic modifier and its preparation method and application process

Abstract

The present invention discloses a cationic modifier, a preparation method and an application process thereof. The modifier has the following structural formula: The present invention has the beneficial effect that the dye uptake of cellulose fibers modified with the cationic modifier of the present invention is increased by about 30% compared with unmodified cellulose fibers, the bottom water of the dye liquor is almost colorless, and no sodium sulfate is required to promote dyeing and soda ash is required to fix the color during the dyeing process, thus truly realizing a new salt-free dyeing process and enabling the bottom water of the dye liquor to be recycled; comparative data from dyeing factories show that, when achieving the same dyeing depth, the new salt-free dyeing process reduces carbon emissions by about 35% compared with conventional dyeing processes and reduces wastewater emissions by 20 tons per 10,000 meters.

Description

Technical Field

[0001] The invention belongs to the technical field of chemical industry, and particularly relates to a cationic modifier and a preparation method and application process thereof. Background Art

[0002] Traditional reactive dyeing requires a large amount of sodium sulfate to promote dyeing and a large amount of soda ash to fix the color. The salt concentration of the wastewater discharged after dyeing is as high as 10g / L. China's current cotton cloth production is about 10 billion meters. The traditional dyeing process requires about 3 million tons of salt, all of which is discharged with the wastewater, causing serious salinization of the soil.

[0003] Scientists have conducted extensive research on low-salt and salt-free dyeing of cellulose fibers with reactive dyes, mainly in the development of cationic reactive dyes, the development and application of multifunctional salt substitutes, low-salt dyeing auxiliaries, and cellulose fiber modification.

[0004] The parent structure of cationic reactive dyes is mainly anthraquinone type, with a small amount of monoazo type structure, but the color spectrum is incomplete; at the same time, because the entire structure of the dye contains only one monochlorotriazine active group, the number of active groups is small and the reactivity is low, there is a problem of low fixation rate; furthermore, because this type of cationic reactive dye has a high affinity with cellulose fibers, it is prone to color fringing, so there are very few industrialized cationic reactive dyes on the market.

[0005] In order to save energy and reduce emissions and reduce salt usage, printing and dyeing companies can use sodium polymaleate and sodium polyacrylate in the dyeing process of reactive dyes to weaken the charge repulsion between the dye and the fiber, thereby reducing the amount of salt used. However, due to the large molecular weight of these two types of organic salts, their use causes the viscosity of the dyeing system to be too high, the fluidity of the dye bath to deteriorate, and the diffusion performance of the reactive dye to be limited, resulting in poor uniformity and permeability of the final dyed product.

[0006] Although trisodium nitrilotriacetic acid can improve the fixation rate of some reactive dyes and has good color fastness, the cost of this type of organic substitute salt is much higher than that of inorganic salts. The use of organic salts in dyeing is not economical, so organic salts cannot replace the use of inorganic salts.

[0007] In addition, salt-free dyeing is achieved by adding a variety of cross-linking agents such as active cross-linking agents or biomass additives during the dyeing process. However, the dyed fabrics have problems such as poor hand feel, low color stability, odor, and yellowing.

[0008] Currently, the best way to achieve salt-free dyeing is to perform cationic modification on cellulose fibers, that is, first modify the cellulose fibers with a cationic modifier so that the surface of the cellulose fibers carries a positive charge, and dyeing is achieved through the combination of ionic bonds and reactive dyes during the dyeing process.

[0009] The cationic modifiers currently on the market have the following problems:

[0010] ①Poor color fastness: The groups of some cationic modifiers will hinder the nucleophilic substitution reaction between the active groups of the dye and the anions of cellulose, reducing the diffusion rate of the dye into the fiber, resulting in a decrease in the effective fixation rate of the dye and poor color fastness;

[0011] ② Low utilization rate of modifier: It is easy to hydrolyze during the alkaline modification process, the utilization rate is not high, the dosage is too large and the cost is too high to be widely promoted and applied;

[0012] ③Poor level dyeing: Since the surface of the modified fiber is enriched with a large amount of positive charges, it is easy to combine with negatively charged reactive dyes, resulting in a fast dyeing process and poor level dyeing.

[0013] ④ Odor: The modifier has a fishy smell, which does not meet the requirements of GB / T18401-2010;

[0014] ⑤ Limitations of dyeing and finishing process research: Process research tends to focus on immersion dyeing, and there is little research on continuous pad dyeing. Summary of the Invention

[0015] The present invention aims to overcome the deficiencies of the prior art and provides a cationic modifier, a preparation method thereof, and an application process thereof. Cellulose fibers modified with the cationic modifier of the present invention have a dye uptake rate that is approximately 30% higher than that of unmodified cellulose fibers, the dye liquor residue is almost colorless, and no sodium sulfate is required to promote dyeing or soda ash is required to fix the color during the dyeing process, thereby truly realizing a new salt-free dyeing process and enabling the recycling of the dye liquor residue. Comparative data from dyeing factories show that, when achieving the same dyeing depth, the new salt-free dyeing process reduces carbon emissions by approximately 35% compared to conventional dyeing processes and reduces wastewater discharge by 20 tons per 10,000 square meters.

[0016] To achieve the above objectives, the inventors of this case, after long-term research and extensive practice, have come up with the technical solution of the present invention. The following will further explain this technical solution and its implementation process.

[0017] The first aspect of the present invention provides a cationic modifier having the following structural formula:

[0018]

[0019] As a further supplement to the present technical solution, the main raw materials for preparing the cationic modifier include: isophorone diisocyanate (IPDI), dimethylethanolamine, methyldiethanolamine, butanone, sodium methoxide, and dimethyl sulfate.

[0020] A preparation method of a cationic modifier comprises the following steps: adding isophorone diisocyanate (IPDI), dimethylethanolamine, and methyldiethanolamine in a certain proportion into a reactor, then adding a certain amount of butanone and sodium methoxide, gradually heating to 80°C with stirring and keeping the temperature for 4 hours, then cooling to 50°C, adding dimethyl sulfate, reacting for 1 hour, removing the solvent under vacuum, and then adding an appropriate amount of deionized water at room temperature to emulsify into a 30% emulsion to obtain the cationic modifier.

[0021] The second aspect of the present invention provides a modification process for cellulose fibers using the cationic modifier obtained according to the above preparation method.

[0022] As a further supplement to the present technical solution, the process for modifying cellulose fibers with a cationic modifier comprises the following steps:

[0023] Step S1, introducing the fiber or cotton fiber fabric for modification, dipping and padding, with a liquid carrying rate of 100%, and a speed of 40-60 m / min;

[0024] Step S2, stacking at 20-30°C for 16 hours;

[0025] Step S3, washing with hot water at 90-95°C;

[0026] Step S4, pickling with 3-5 g / L glacial acetic acid;

[0027] Step S5, washing with water at room temperature;

[0028] Step S6: drying.

[0029] As a further supplement to the technical solution, the step S1 of dipping and rolling is as follows: the amount of modifier used is 5-30 g / L, and the amount of caustic soda used is 2.5-15 g / L.

[0030] The third aspect of the present invention provides a dyeing process for modified cellulose fibers obtained according to the above cationic modifier process.

[0031] As a further supplement to this technical solution, the dyeing process includes the following steps:

[0032] Step S11, padding the reactive dye solution;

[0033] Step S22, drying;

[0034] Step S33, steaming (100-102° C.×90 s);

[0035] Step S44, washing with water (40-50° C.);

[0036] Step S55: drying.

[0037] As a further supplement to the present technical solution, the padding of the reactive dye liquor in step S11 is a double-dip and double-pad process, with 5 to 80 g / L of reactive dye and a padding rate of 45 to 55%.

[0038] Due to the application of the above technical solution, the present invention has the following advantages compared with the prior art:

[0039] The cationic modifier of the present invention adopts the cellulose fiber or cotton fiber fabric modification process technology of the present invention. The dye uptake of the modified cellulose fiber is increased by about 30% compared with the unmodified cellulose fiber, and the residual liquid after dyeing is almost colorless. The modified cellulose fiber of the present invention does not need to use sodium sulfate to promote dyeing and soda ash to fix color during dyeing, so that the bottom water of the dye solution can be recycled, and various fastnesses after dyeing are greatly improved. According to the comparison data of dyeing processes in dyeing factories, when achieving the same dyeing depth, the new salt-free dyeing process reduces carbon emissions by about 35% compared with conventional dyeing processes, and reduces sewage discharge by 20 tons per 10,000 meters. DETAILED DESCRIPTION

[0040] The experimental methods in the following examples are conventional methods unless otherwise specified. The experimental raw materials used can be purchased commercially and / or prepared by known means unless otherwise specified. Unless otherwise specified, they meet the requirements of standard chemical products.

[0041] In the experimental methods of the following examples, the parts of each substance are by weight.

[0042] In order to facilitate those skilled in the art to understand the present technical solution more clearly, the technical solution of the present invention will be described in detail below in conjunction with the comparative test of the application performance of salt-free dyeing and conventional dyeing in Table 1:

[0043] Example:

[0044] This embodiment provides a cationic modifier, which is prepared by the following method:

[0045] 45 parts of isophorone diisocyanate (IPDI), 18.7 parts of dimethylethanolamine, and 23.8 parts of methyldiethanolamine were added to the reactor in sequence, and then 28 parts of butanone were added. 0.3 parts of sodium methoxide was added under stirring, and the temperature was gradually raised to 80°C and kept for reaction for 4 hours. Then, the temperature was lowered to 50°C and 38.8 parts of dimethyl sulfate were added and reacted for 1.5 hours. The butanone solvent was removed under vacuum (for recycling), and then an appropriate amount of deionized water was added at room temperature to emulsify into a 30% emulsion to obtain a cationic modifier.

[0046] Application process:

[0047] (1) The present invention provides a process for modifying cellulose fiber or cotton fabric with a cationic modifier:

[0048] The modification process includes the following steps:

[0049] S1. Introduce cellulose fiber or cotton fabric, dip and pad (modifier dosage 20g / L, caustic soda dosage 5g / L), liquid carrying rate 100%, speed 40m / min;

[0050] S2, stack at 25℃ for 16h;

[0051] S3, 90℃ hot water washing;

[0052] S4, 3g / L glacial acetic acid pickling;

[0053] S5, wash with water at room temperature;

[0054] S6, drying, standby;

[0055] (2) The present invention provides a dyeing process for modified cellulose fibers or modified cotton fabrics obtained by using the above-mentioned cationic modifier:

[0056] The dyeing process includes the following steps:

[0057] S11, padding the modified fabric with reactive dye solution (two dips and two pads, reactive dye 80g / L)

[0058] S22, drying;

[0059] S33, steaming at 100℃ for 90s;

[0060] S44, 45℃ water washing;

[0061] S55, drying.

[0062] Performance testing:

[0063] 1. Comparative test of application performance between salt-free dyeing and conventional dyeing

[0064] (1) Salt-free dyeing: using cotton fibers modified by the process of the present invention and the dyeing process.

[0065] (2) Conventional dyeing: using unmodified cotton fibers, padding with reactive dye solution (two dips and two pads, dye 10-80 g / L, padding rate 45-55%) → drying → padding with fixative solution (200-220 g / L sodium sulfate, 60-90 g / L soda ash) → steaming (100-102°C × 90 s) → washing (40-50°C) → soaping (2 g / L DB-1W, 90-95°C) → hot water washing (70-80°C) → room temperature washing → drying. (Wherein: DB-1W is produced by Zhangjiagang Debao Chemical Co., Ltd.);

[0066] (3) Reactive dyes are commercially available products:

[0067] Dark yellow: The dye used is Reactive Orange SP-EC, the brand is COLORSOL, and the manufacturer is Kailema (Shanghai) Technology Co., Ltd.

[0068] Deep red: The dye used is reactive amber red SP-EC, brand COLORSOL, and the manufacturer is Kailema (Shanghai) Technology Co., Ltd.

[0069] Navy blue: The dye used is reactive dark blue SP-EC, brand name COLORSOL, and the manufacturer is Kailema (Shanghai) Technology Co., Ltd.

[0070] Black: The dye used is reactive super black SPG-EC, brand COLORSOL, and the manufacturer is Kailema (Shanghai) Technology Co., Ltd.

[0071] (4) K / S test method: stack 8 layers of dyed fabric samples, measure the K / S value 6 times at different locations using the Xrite 7800 colorimeter, and take the average value;

[0072] (5) Odor test method: Place the modified dyed fabric in a sealed bag and place it at 60°C for 1 hour before having multiple people sniff it;

[0073] (6) Friction resistance (dry rubbing / wet rubbing) adopts AATCC 8 "Color fastness to rubbing fastness tester method";

[0074] (7) Washing resistance (original change / staining) adopts AATCC 61-2A "Color fastness to washing rapid method";

[0075] (8) The light fastness test adopts AATCC 16.3 "Color fastness to light" method.

[0076] The specific test results are shown in Table 1.

[0077] Table 1 Comparative test results of application performance between salt-free dyeing and conventional dyeing

[0078]

[0079] Note: An increase of 1 in K / S is equivalent to a 10% increase in depth. The above data show that salt-free dyeing is about 30% darker than conventional dyeing.

[0080] 2. Performance test of the cationic modifier of the present invention and commercially available cationic modifiers:

[0081] The cationic modifier used in the embodiment of the present invention and the comparative cationic modifier K67 were from Shandong Tiancheng Chemical Co., Ltd. The application process all adopted the process of the invention in this case.

[0082] The specific test results are shown in Table 2.

[0083] Table 2 Dyeing performance comparison

[0084]

[0085] As can be seen from the data in Table 2, the best dyeing results can be obtained by adopting this patented technology.

[0086] Carbon emissions are calculated as follows:

[0087] At 40C S ×40C S 128×60 140g / m 2 Taking the production of 10,000 meters as an example, the carbon emissions during the dyeing process are calculated by using salt-free dyeing to achieve the same dyeing depth as conventional dyeing.

[0088] 1. Carbon emissions from dye and chemical auxiliaries

[0089] Table 3 Carbon emissions of dyeing and chemical auxiliaries

[0090]

[0091]

[0092] 2. Energy consumption of water, electricity and steam

[0093] Table 4 Energy consumption of water, electricity and steam

[0094]

[0095] 3. Carbon emission data of salt-free dyeing and conventional dyeing processes:

[0096] Table 5 CO2 (kgCO2-eq) emission data

[0097]

[0098] IV. Conclusion

[0099] At the same dyeing depth, salt-free dyeing can reduce carbon emissions by 35% compared to conventional dyeing.

[0100] The above technical solutions only reflect the preferred technical solutions of the technical solutions of the present invention. Any changes that may be made to certain parts thereof by those skilled in the art all reflect the principles of the present invention and fall within the scope of protection of the present invention.

Claims

1. A cationic modifier, characterized in that It is prepared by the following steps: adding isophorone diisocyanate (IPDI), dimethylethanolamine, and methyldiethanolamine in a certain proportion to a reactor, then adding a certain amount of butanone and sodium methoxide, stirring and gradually heating to 80°C and keeping the temperature for 4 hours, then cooling to 50°C and adding dimethyl sulfate, reacting for 1 hour, removing the solvent under vacuum, and then adding an appropriate amount of deionized water at room temperature to emulsify into a 30% emulsion.

2. Use of the cationic modifier prepared according to claim 1 in a cellulose fiber modification process.

3. The use according to claim 2, characterized in that The modification process of the cellulose fiber comprises the following steps: Step S1, introducing cellulose fibers for modification, dipping and rolling, with a liquid carrying rate of 100%, and a speed of 40-60 m / min; Step S2: stacking at 20-30°C for 16 hours; Step S3, washing with hot water at 90-95°C; Step S4, pickling with 3-5 g / L glacial acetic acid; Step S5, washing with water at room temperature once; Step S6: drying.

4. The use according to claim 3, characterized in that In the step S1, the dipping and rolling are as follows: the amount of the modifier is 5-30 g / L, and the amount of caustic soda is 2.5-15 g / L.

5. Use of the modified cellulose fiber obtained according to claim 4 in a dyeing process.

6. The use according to claim 5, characterized in that The dyeing process comprises the following steps: Step S11, padding the reactive dye solution; Step S22, drying; Step S33, steaming at 100-102° C. for 90 seconds; Step S44, washing with water at 40-50°C; Step S55: drying.

7. The use according to claim 6, characterized in that The padding of the reactive dye solution in step S11 is performed by two dipping and two padding, the amount of reactive dye used is 5-80 g / L, and the padding rate is 45-55%.

Images