Cationic modifier as well as preparation method and application process thereof

Abstract

The invention discloses a cationic modifier and a preparation method and an application process thereof, and the modifier has the following structural formula: # imgabs0 #. The cationic modifier has the beneficial effects that the dye-uptake rate of cellulose fibers modified by the cationic modifier is improved by about 30% compared with that of unmodified cellulose fibers, and residual water of dye liquor is almost colorless; anhydrous sodium sulphate for accelerating dyeing and sodium carbonate for fixing color are not needed in the dyeing process, so that a new salt-free dyeing process is really realized, and the residual water of the dyeing liquid can be recycled; compared with a conventional dyeing process, the novel salt-free dyeing process has the advantages that carbon emission is reduced by about 35% and sewage emission is reduced by 20 tons per ten thousand meters when the same dyeing depth is achieved through comparison data of a dyeing factory.

Description

Technical Field

[0001] The invention belongs to the technical field of chemical industry, and specifically 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, and 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 explorations in the realization of low-salt and salt-free dyeing technologies for cellulose fiber using 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, since 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, since this type of cationic reactive dye has a high affinity with cellulose fibers and is prone to color fringing, there are very few industrialized cationic reactive dyes on the market.

[0005] In order to save energy and reduce emissions and reduce the amount of salt used, printing and dyeing companies can use sodium polymaleate and sodium polyacrylate in the dyeing process of reactive dyes to weaken the charge repulsion between dyes and fibers, 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, but the dyed fabrics have problems such as poor hand feel, low color light stability, odor, and yellowing.

[0008] Currently, the best way to achieve salt-free dyeing is to perform cation 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 during the dyeing process through the combination of ionic bonds and reactive dyes.

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

[0010] ① Poor color fastness: Some cationic modifier groups will hinder the nucleophilic substitution reaction between the active groups of the dye and the anions of cellulose, reduce 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] ③ Poor level dyeing: Since the fiber surface is enriched with a large amount of positive charges after modification, it is easy to combine with negatively charged active 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 process, and there is little research on continuous pad dyeing process. Summary of the invention

[0015] The purpose of the present invention is to overcome the deficiencies of the prior art and provide a cationic modifier and a preparation method and application process thereof. The dyeing rate of cellulose fiber modified by the cationic modifier of the present invention is improved by about 30% compared with that of unmodified cellulose fiber, the bottom water of dye liquor is almost colorless, and no sodium sulfate is needed to promote dyeing and soda ash is needed to fix the color during the dyeing process, thus truly realizing a new salt-free dyeing process, so that the bottom water of dye liquor can be recycled; comparison data from dyeing factories show that when the same dyeing depth is achieved, the new salt-free dyeing process reduces carbon emissions by about 35% compared with a conventional dyeing process, and reduces sewage emissions by 20 tons / 10,000 meters.

[0016] To achieve the above objectives, the inventor of this case has proposed the technical solution of the present invention after long-term research and extensive practice. The technical solution and its implementation process will be further explained as follows.

[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 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 into a reactor in a certain proportion, adding a certain amount of butanone and sodium methoxide, gradually heating to 80 DEG C with stirring and keeping the temperature for 4 hours, then cooling to 50 DEG C, adding dimethyl sulfate and reacting for 1 hour, removing the solvent under vacuum, and then adding a proper 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 technical solution, the process for modifying cellulose fiber with a cationic modifier comprises the following steps:

[0023] Step S1, introducing the fiber or cotton fiber fabric for modification, dipping and rolling, with a liquid rate of 100%, and a vehicle 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] To further supplement the technical solution, the step S1 of dipping and rolling is as follows: the amount of the modifier is 5 to 30 g / L, and the amount of caustic soda is 2.5 to 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] To further supplement the technical solution, the dyeing process comprises 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 technical solution, the step S11 of padding the active dye liquor is double padding, the active dye is 5-80 g / L, and the padding rate is 45-55%.

[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, and the dye uptake rate of the modified cellulose fiber is improved 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; the dyeing process comparison data of the dyeing factory shows that when the same dyeing depth is achieved, the new salt-free dyeing process reduces carbon emissions by about 35% compared with the conventional dyeing process, and reduces sewage emissions by 20 tons / 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 commercially purchased and / or prepared by known means unless otherwise specified, and meet the requirements of standard chemical products unless otherwise specified.

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

[0042] In order to facilitate those skilled in the art to understand the 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 are added to the reactor in sequence, and then 28 parts of butanone are added, and 0.3 parts of sodium methoxide is added under stirring, and the temperature is gradually raised to 80°C and kept for reaction for 4 hours, and then the temperature is lowered to 50°C, and 38.8 parts of dimethyl sulfate are added to react for 1.5 hours, and the butanone solvent is removed under vacuum (for recycling), and then an appropriate amount of deionized water is 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 roll (modifier dosage 20g / L, caustic soda dosage 5g / L), liquid carrying rate 100%, vehicle speed 40m / min;

[0050] S2, stacking 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 fiber or modified cotton fabric obtained by 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, 100℃×90s steaming;

[0060] S44, 45℃ water washing;

[0061] S55, drying.

[0062] Performance Test:

[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 dyeing process.

[0065] (2) Conventional dyeing: using unmodified cotton fibers, padding with active 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 × 90s) → washing (40-50°C) → soap washing (2g / L DB-1W, 90-95°C) → hot water washing (70-80°C) → room temperature water washing → drying. (Among them: 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 Kelema (Shanghai) Technology Co., Ltd.

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

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

[0070] Black: The dye used is reactive super black SPG-EC, the brand is COLORSOL, and the manufacturer is Kelema (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 colorimeter Xrite 7800, 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 multiple people sniff it;

[0073] (6) AATCC 8 “Color fastness to rubbing (dry rubbing / wet rubbing)” method is used for the test.

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

[0075] (8) The light fastness test is carried out according to 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 processes all adopted the process of the invention of 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 using 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 in the dyeing process are calculated by using salt-free dyeing to achieve the same dyeing depth as conventional dyeing.

[0088] 1. Carbon emissions from dyeing 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 process:

[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. Some changes that may be made to certain parts thereof by technicians in this technical field all reflect the principles of the present invention and fall within the protection scope of the present invention.

Claims

1. A cationic modifier, characterized in that The cationic modifier has the following structural formula:

2. A cationic modifier according to claim 1, characterized in that, The main raw materials for preparing the cationic modifier include: isophorone diisocyanate (IPDI), dimethylethanolamine, methyldiethanolamine, butanone, sodium methoxide and dimethyl sulfate.

3. A method for preparing a cationic modifier according to any one of claims 1 to 2, characterized in that: The following steps are involved: Isophorone diisocyanate (IPDI), dimethylethanolamine and methyldiethanolamine are added to the reactor in a certain proportion, and then a certain amount of butanone and sodium methoxide are added. The temperature is gradually raised to 80°C with stirring and kept for 4 hours. Then the temperature is lowered to 50°C and dimethyl sulfate is added to react for 1 hour. The solvent is removed under vacuum, and then an appropriate amount of deionized water is added at room temperature to emulsify into a 30% emulsion.

4. A modification process in which the cationic modifier obtained by the preparation method according to claim 3 is applied to cellulose fibers.

5. The process for modifying cellulose fibers with a cationic modifier according to claim 4, characterized in that: The process for modifying cellulose fibers with a cationic modifier comprises the following steps: Step S1, introducing cellulose fiber or cotton fiber fabric for modification, dipping and rolling, with a liquid carrying rate of 100%, and a vehicle 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.

6. The process for modifying cellulose fibers with a cationic modifier according to claim 5, 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 the caustic soda is 2.5-15 g / L.

7. A dyeing process for the modified cellulose fiber obtained according to claim 5 or 6.

8. The dyeing process of modified cellulose fiber according to claim 7, characterized in that: The dyeing process comprises the following steps: Step S11, padding the reactive dye solution; Step S22, drying; Step S33, steaming (100-102° C.×90 s); Step S44, washing with water (40-50° C.); Step S55: drying.

9. The dyeing process of modified cellulose fiber according to claim 8, characterized in that: The step S11 of padding the active dye solution is double padding, the amount of active dye is 5-80 g / L, and the padding rate is 45-55%.

Images