CN113373691A

CN113373691A - Preparation method and application of cationic modifier TCTAC

Info

Publication number: CN113373691A
Application number: CN202110716864.3A
Authority: CN
Inventors: 向中林; 钱晓红; 任学宏; 刘颖; 于小慧; 候跃威; 卢荣清; 王晓梅; 周嫦娥
Original assignee: JIANGSU LIANFA TEXTILE CO Ltd; Jiangnan University
Current assignee: JIANGSU LIANFA TEXTILE CO Ltd; Jiangnan University
Priority date: 2021-06-28
Filing date: 2021-06-28
Publication date: 2021-09-10
Anticipated expiration: 2041-06-28
Also published as: CN113373691B

Abstract

The invention discloses a preparation method and application of a cationic modifier TCTAC, and relates to the technical field of anti-wrinkle and antibacterial finishing of cotton fabrics. Dissolve 2,3-epoxy hydroxypropyl trimethyl ammonium chloride in deionized water and drip ammonia water, dissolve in deionized water after heating and stirring reaction to form 1-amino-3-hydroxypropyl trimethyl chloride Aqueous ammonium chloride solution; dissolving cyanuric chloride in acetone and adding 1-amino-3-hydroxypropyl trimethyl ammonium chloride aqueous solution dropwise, using sodium carbonate aqueous solution to adjust the pH value to 6-7, stirring the reaction until the end , cationic modifier TCTAC is obtained by salting out purification and drying. The invention has short synthesis period and high yield, and synthesizes a new type of cationic modifier, which can be used for anti-wrinkle/antibacterial dual-function treatment on cotton fabrics, can effectively inhibit the relative slip between fibers, thereby improving the wrinkle recovery ability. Cotton fabrics with excellent dry and wet wrinkle resistance properties can be obtained.

Description

Preparation method and application of cationic modifier TCTAC

Technical Field

The invention relates to the technical field of crease-resistant and antibacterial finishing of cotton fabrics.

Background

In the age of rapid social development, with the increasing perfection of textile goods, people are not limited to wearing comfort, and can pay attention to the improvement of functions of the textile goods, such as: uv-blocking fabrics, quick-drying fabrics, hydrophobic fabrics, flame-retardant fabrics, etc. On one hand, as the globalization progresses increasingly and the world interaction becomes more frequent, unnecessary troubles are brought to people while the material and the spiritual civilization rapidly develop, such as disease threat brought by the spread of bacteria to people, and the like. In daily life, people inevitably contact various bacteria, once the bacteria are under proper conditions, the bacteria can rapidly multiply and reproduce and spread everywhere along with the flow of people, and the life and the health of people are seriously threatened. And the textile provides a certain living environment for the propagation and breeding of bacteria, so that the development of an efficient antibacterial finishing agent is necessary to endow the textile with certain antibacterial performance. The cotton fabric belongs to natural fibers, has extremely excellent moisture absorption and moisture permeability, and cotton clothes are comfortable and soft to wear and are not easy to generate static electricity. The global consumption of cotton fabrics is arranged at the top of all textiles, but the cotton fabrics have some defects, such as poor crease resistance, easy crease in the normal wearing process and the trouble of needing ironing after cleaning, which greatly reduces the taking effect of the cotton fabrics. Therefore, the cotton fabric needs to be subjected to crease-resistant finishing.

In recent years, researches on compounding and finishing antibacterial and anti-wrinkle functions into cotton fabrics are actively carried out, which meets the requirements of the market on the wearability of textiles. The multifunctional finishing of cotton fabric is a technology for compounding two or more than two functions on textiles. The multifunctional finishing of the fabric enables the textile to develop towards high grade and deep level, which not only can overcome the defects of the textile, but also endows the textile with multiple functions.

At present, the common preparation method of the antibacterial/anti-wrinkle cotton fabric is to compound an antibacterial agent and an anti-wrinkle agent or blend polycarboxylic acid and chitosan for use, and prepare the fabric with the double functions of antibiosis and anti-wrinkle by a dipping or rolling baking method. For example, Wangjianggang and Gangying are endowed with better anti-wrinkle and antibacterial properties by the chitosan and polycarboxylic acid composite finishing cotton fabric. Heyuan et al finishes an antibacterial agent AGP and a polycarboxylic acid BTCA on a cotton fabric through a conventional rolling and baking process to obtain the antibacterial crease-resistant cotton fabric. Various antibacterial agents and BTCA are respectively finished on cotton fabrics by the people in the academy of China and the like, and the antibacterial rate of the fabrics is improved by adopting a finishing process of a two-bath two-step method. In recent years, the research of applying the ionic crosslinking technology to the crease-resistant finishing of cotton fabrics is endless. However, the application research of the connection of the cotton fabric ionic crosslinking technology and the antibacterial finishing is very deficient, and the research of preparing the antibacterial and anti-wrinkle cotton fabric by combining the halamine compound and the anti-wrinkle agent at home and abroad is not rare at present.

Disclosure of Invention

In order to overcome the defects of the prior art, the first object of the invention is to provide a preparation method of a cationic modifier TCTAC, which is used for providing a treatment for producing anti-wrinkle/antibacterial cotton fabrics.

The technical scheme of the invention comprises the following steps:

1) dissolving 2, 3-epoxy hydroxypropyl trimethyl ammonium chloride in deionized water, dropwise adding ammonia water, heating and stirring, and obtaining 1-amino-3-hydroxypropyl trimethyl ammonium chloride after the reaction is finished; dissolving 1-amino-3-hydroxypropyl trimethyl ammonium chloride in deionized water to form 1-amino-3-hydroxypropyl trimethyl ammonium chloride aqueous solution;

2) dissolving cyanuric chloride in acetone at 0 ℃, dropwise adding 1-amino-3-hydroxypropyl trimethyl ammonium chloride aqueous solution, adjusting the pH value to 6-7 by using sodium carbonate aqueous solution, stirring and reacting until the reaction is finished, and then obtaining the cationic modifier TCTAC through salting out, purification and drying.

The invention has short synthesis period and high yield, synthesizes a novel cationic modifier, and can be used for carrying out anti-wrinkle/antibacterial dual-function treatment on cotton fabrics.

The invention also aims to provide application of the cationic modifier TCTAC in crease-resistant antibacterial finishing of cotton fabrics.

According to the invention, grey cloth is finished, cation modification and halamine are combined, the cross-linking agent BPTCD is used for crease-resistant finishing of cotton fabrics, and as the molecules of the cross-linking agent BPTCD contain a plurality of active groups capable of chemically forming bonds with fibers, a three-dimensional network structure can be generated in the fabrics, relative slippage between fibers is effectively inhibited, so that crease recovery capability is improved, and the cotton fabrics with good dry and wet crease resistance can be obtained.

The specific arrangement comprises the following steps:

1) dissolving a cation modifier TCTAC and sodium hydroxide in deionized water to prepare a first impregnation solution, treating Cotton gray cloth by adopting a two-impregnation two-rolling process, and then pre-drying, first-drying, washing and drying to obtain I/Cotton;

2) dissolving 3, 3, 4, 4-benzophenone tetracarboxylic dianhydride and sodium hypophosphite in deionized water at the temperature of 80 ℃ to prepare second impregnation liquid, adopting a two-impregnation and two-rolling process to treat I/Cotton, and then pre-drying, second baking, washing and drying to obtain ICL/Cotton;

3) and (3) adjusting the pH value of the sodium hypochlorite aqueous solution to be neutral by using acid, soaking the ICL/Cotton in the acid, taking out the solution, washing and drying the solution to obtain the Cl-ICL/Cotton.

The invention has the beneficial effects that:

the triazine cationic modifier TCTAC prepared by the invention is used for carrying out cationic modification on cotton fabrics, so that positive charges are attached to the surfaces of the cotton fabrics. The polybasic carboxylic acid type crease-

resistant finishing agent

3, 3, 4, 4-benzophenone tetracarboxylic dianhydride (BPTCD) is finished on the surface of the fabric through a rolling and baking process, so that a large amount of carboxyl anions are carried on the surface of the fabric and form ionic crosslinking with cations, and the antibacterial/crease-resistant composite function of the cotton fabric is obtained after chlorination by sodium hypochlorite. The process conditions were optimized and the mechanical properties, stability and antibacterial properties of the finished fabrics were tested. Improves the ultraviolet resistance and the wrinkle recovery performance in a wet state.

Further, as the amount of the cationic modifier TCTAC increases, the dry crease recovery angle and the warp direction breaking strength retention rate increase continuously. With the increase of the dosage of the cationic modifier TCTAC, carboxyl on the BPTCD and the cationic modifier TCTAC generate more ionic crosslinking, the crosslinking degree between fibers is enhanced, and the crease recovery angle is improved. The positive charge of the cotton fabric is increased to facilitate the attraction of negatively charged ions, which facilitates the esterification of BPTCD with cellulose fibers, and thus the wrinkle recovery angle is increased. However, the amount of the cationic modifier TCTAC is too high, the amount of caustic soda is increased, the strength loss of the fabric is increased continuously, and the whiteness is reduced gradually, so that the selection of the cationic modifier TCTAC is considered comprehensively to be 50 g/L.

Further, as the dosage of BPTCD is increased, the recovery angle of dry wrinkles is continuously increased, and the retention rate of warp breaking strength is gradually reduced. But when the dosage of BPTCD is 50g/L, the retention rate of the warp breaking strength is 75%, the crease recovery angle is improved by 85 degrees, and the excellent crease resistance is achieved. With the increase of the dosage of BPTCD, the dosage of SHP is also increased, and the SHP is expensive in manufacturing cost, brings about a large amount of phosphorus pollution and is not environment-friendly. Thus the choice of BPTCD was 50 g/L.

Further, the length of the curing time directly affects the degree of crosslinking reaction between the finish and the cellulose fibers. The longer the baking time, the higher the wrinkle recovery angle of the fabric, the easier and more complete the esterification reaction. But has the defects of hard hand feeling, poor whiteness, strength reduction and the like of the fabric, and the serviceability of the fabric is influenced. Therefore, the baking time was selected to be 150 s.

Further, as the baking temperature increases, the wrinkle recovery angle correspondingly increases. This is because the higher the temperature, the higher the degree of esterification of the cotton fibers with BPTCD over a certain temperature range. However, too high a baking temperature may cause dehydration of glucosyl groups on the cotton fibers, increase of carboxyl groups, decrease of polymerization degree, and increase of strength loss, i.e., gradual decrease of strength retention rate at warp break. The baking temperature was therefore chosen to be 160 ℃.

Drawings

FIG. 1 is an SEM image of Cotton.

FIG. 2 is an infrared spectrum of the cationic modifier TCTAC.

FIG. 3 is a nuclear magnetic hydrogen spectrum of the cationic modifier TCTAC.

FIG. 4 is an SEM image of I/Cotton.

FIG. 5 is an infrared spectrum of Cotton, Cotton/IC and Cl-Cotton/ICL.

FIG. 6 is an SEM image of ICL/Cotton.

FIG. 7 is an XRD analysis of ICL/Cotton, I/Cotton and Cotton.

FIG. 8 is an SEM image of Cl-ICL/Cotton.

FIG. 9 is a TG thermal stability analysis chart of Cotton, Cl-ICL/Cotton, I/Cotton and ICL/Cotton.

FIG. 10 Cl-ICL/Cotton UV resistance.

FIG. 11 water wash stability of Cl-ICL/Cotton dry and wet crease recovery angle.

FIG. 12 water wash stability of Cl-ICL/Cotton chlorine content.

Detailed Description

Firstly, preparing a sample:

example 1:

1) preparation of cationic modifier TCTAC:

1. 0.01mol of 2, 3-epoxyhydroxypropyltrimethylammonium chloride (EPTAC) and 20 mL of deionized water were weighed out and dissolved in a round-bottomed flask and stirred for 20 min, and then 0.01mol of an aqueous ammonia solution was slowly dropped into the round-bottomed flask with a constant-pressure funnel and stirred at 80 ℃ for 12 h. After the reaction, the reaction mixture was filtered under suction to obtain 1-amino-3-hydroxypropyltrimethylammonium chloride (ACTAC).

2. Weighing 0.01mol of cyanuric chloride and 40 mL of acetone, dissolving in a three-neck flask and stirring for 20 min, dissolving 0.01mol of 1-amino-3-hydroxypropyl trimethyl ammonium chloride in 20 mL of deionized water, slowly dropping into the three-neck flask through a constant pressure funnel, maintaining the temperature of the system at 0 ℃, adjusting the pH value of the whole reaction system to 6-7 by using a sodium carbonate solution with the concentration of 0.1 g/L, and continuously stirring for 3 h. After the reaction is finished, a solid product is obtained by salting out and purification, the solid product is placed in a vacuum drying oven at the temperature of 45 ℃ for 24 hours to obtain a cation modifier TCTAC, and the yield is calculated to be 90% after weighing.

3433 cm, as seen in FIG. 2^-1The absorption peak is the absorption peak caused by N-H vibration; 2983 cm^-1And 3126 cm^-1The vibration of the upper 1-amino-3-hydroxypropyl trimethyl ammonium chloride at-CH 3 and-CH 2 caused the absorption peak of stretching vibration, 1488 cm^-1Is treated as the stretching vibration peak of quaternary ammonium salt, 1366 cm^-1And 1674 cm ^-11074 cm near the overlapped absorption peak of vibration of triazine ring skeleton^-1The nearby part is a C-H stretching vibration peak, 777 cm^-1Is also one of the absorption peaks of the triazine ring.

As seen from FIG. 3, 2.97 to 3.12 ppm are the chemical shift values of the hydrogen atom on-CH 3 on ammonium chloride, 3.38 to 3.47 ppm are the chemical shift values of the hydrogen atom on-CH 2 attached to the amino group, 3.56 to 3.83 ppm are the chemical shift values of the hydrogen atom on-CH attached to the hydroxyl group, 3.84 to 4.00 ppm are the chemical shift values of the hydrogen atom on-CH 2 attached to ammonium chloride, 5.57 to 5.70 ppm are the chemical shift values of the hydrogen atom on-OH, and 5.96 to 6.08 ppm are the chemical shift values of the hydrogen atom on-NH.

2) Modification treatment of cotton fabric:

1.5 g of cationic modifier TCTAC and 3.2 g of sodium hydroxide are dissolved in 100 mL of deionized water, and Cotton grey cloth (i.e. Cotton) is immersed in the deionized water at a bath ratio of 1: 30, the soaking time is 15 min, the second soaking and the second rolling are carried out, and the rolling residual rate is 100 percent. Pre-drying the Cotton fabric at 80 ℃ for 3min, then baking the Cotton fabric at 100 ℃ for 120 s, taking out the Cotton fabric, washing the Cotton fabric with water, pickling the Cotton fabric, removing unreacted reagents (removing acid in pickling) by washing the Cotton fabric with water, and finally drying the Cotton fabric with a constant-temperature drying oven at 45 ℃ to obtain the I/Cotton with positive charges on the surface.

As can be seen in fig. 1, the raw cotton has a relatively smooth surface and is substantially free of impurities. As can be seen from FIG. 4, I/Cotton is grafted with a cationic modifier and covered with a film-like material.

2. 5.0 g of 3, 3, 4, 4-benzophenonetetracarboxylic dianhydride (BPTCD) and 2.9g of Sodium Hypophosphite (SHP) were dissolved in 100 mL of hot water at 80 ℃ and then the I/Cotton obtained by cationization was immersed therein at a bath ratio of 1: 30, the soaking time is 15 min, the second soaking and the second rolling are carried out, and the rolling residual rate is 100 percent. Pre-drying the Cotton fabric at 80 ℃ for 3min, then baking at 160 ℃ for 120 s, taking out the Cotton fabric, washing with water, soaping to remove unreacted reagents, and finally drying in a constant-temperature drying oven at 45 ℃ to obtain ICL/Cotton.

As shown in FIG. 5, ICL/Cotton (b) was at 1711 cm for the ionically crosslinked cotton fabric compared to the virgin cotton (a)^-1Where the BPTCD and carbonyl bending of TCTAC overlapped the vibration absorption peak. Indicating that the BPTCD and TCTAC are successfully grafted on the cotton fabric.

As can be seen from FIG. 6, ICL/Cotton had a rough surface and a slightly wavy morphology due to the ionic and esterified crosslinks. Indicating that the sample was successfully prepared and that the cotton fiber structure was not damaged.

As can be seen from fig. 7, the crystallinity of the cotton fabric after ionic crosslinking becomes smaller and the amorphous regions begin to increase. In the finishing system of polycarboxylic acid, the finishing agent enters the surface of fiber crystals to reduce the size of the crystals, thereby reducing crystallinity. The cross-linking of the cotton fabric is laterally verified, and the BPTCD has low relative molecular mass and can penetrate through the molecular gaps of cellulose to destroy the hydrogen bonds among molecular chains, so that the crystallinity of the cotton fiber is reduced. But in any event, the crystal structure of the cotton fibers is not substantially changed.

3. Weighing 2 g of sodium hypochlorite aqueous solution with the concentration of 6wt% and dissolving the sodium hypochlorite aqueous solution in 18 g of deionized water, adjusting the pH value to be neutral by using dilute sulfuric acid with the concentration of 20wt%, putting the dried ICL/Cotton into the solution to be soaked for 1 hour, taking out the solution, washing the solution by using a large amount of deionized water, and drying the solution in a vacuum drying oven at 45 ℃ to obtain Cl-ICL/Cotton.

As can be seen from FIG. 5, compared with the ICL/Cotton, the carbonyl absorption characteristic peak of the finished Cotton fabric is 1711 cm from that of Cl-ICL/Cotton^-1The position is moved to 1717 cm^-1Passing through sodium hypochloriteAfter chlorination, the N-H bond on the cotton fabric is changed into an N-Cl bond, and the characteristic peak is moved to a high wave due to the electron-withdrawing effect of chloride ions. The above results all demonstrate the success of grafting the sample.

As can be seen from FIG. 8, Cl-ICL/Cotton caused ionic crosslinking and esterification crosslinking, and the fabric surface became rough and slightly fluctuated in shape. Indicating that the sample was successfully prepared and that the cotton fiber structure was not damaged.

The samples were evaluated for thermal stability by TG and the curves are shown in figure 9. The raw cotton fabric curve shows a major weight loss region, with a weight loss of 80.3% over a temperature range of 380-500 ℃, an initial decomposition temperature of 283 ℃, and a carbon residue of 3.9% due to partial decomposition of the main chain and combustion of the carbonaceous skeleton. The I/Cotton weight loss was 80.4%, the carbon residue was 6.3%, and the initial decomposition temperature was 249^oC. Weight loss of ICL/Cotton was 66.4%, carbon residue was 6.3%, and initial decomposition temperature was 252^oC. The weight loss of Cl-ICL/Cotton was 67.5%, the carbon residue was 6.1%, and the initial decomposition temperature was 251 ℃. The thermal stability of the finished fabric is improved compared to that of raw cotton fabric due to the covalent cross-linking of BPTCD with cotton fabric and the ionic cross-linking of BPTCD with TCTAC.

Comparative example 1:

dissolving a certain mass of 3, 3, 4, 4-benzophenone tetracarboxylic dianhydride (BPTCD) and Sodium Hypophosphite (SHP) in 100 mL of hot water at 80 ℃, and immersing raw Cotton (Cotton) which is not subjected to cationization treatment in the hot water, wherein the bath ratio is 1: 30, the soaking time is 15 min, the second soaking and the second rolling are carried out, and the rolling residual rate is 100 percent. Pre-baking the Cotton fabric at 80 ℃ for 3min, baking the Cotton fabric at 160 ℃ for 120 s, taking out the Cotton fabric, washing the Cotton fabric with water, soaping the Cotton fabric to remove unreacted reagents, and finally drying the Cotton fabric in a constant-temperature drying oven at 45 ℃ to obtain the NICL/Cotton.

Comparative example 2:

the Cotton fabric was finished with BTCA under the same reaction conditions to give BTCA/Cotton.

60 g/L BTCA and 60 g/L Sodium Hypophosphite (SHP) were dissolved in 100 mL deionized water, and then the untreated Cotton greige cloth (i.e., Cotton) was immersed therein at a bath ratio of 1: 30, soaking time is 15 min, two soaking and two rollingAnd the rolling residual rate is 100 percent. Cotton fabric is 80^oC, pre-baking for 3min, baking for 180 s at 170 ℃, taking out, washing with water, soaping to remove unreacted reagents, and finally drying in a constant-temperature drying oven at 45 ℃ to obtain BTCA/Cotton.

Secondly, performance test:

1. the various performances of the test piece are tested, and the test results are shown in the table.

Comparing Cl-NICL/Cotton with Cl-ICL/Cotton, it can be shown that the crease resistance of the ionically crosslinked Cotton fabric is improved compared with that of the non-ionically crosslinked Cotton fabric, the dry state crease recovery angle is improved by 24 degrees, and the wet state crease recovery angle is improved by 37 degrees, because the ionically crosslinked between the wet state cellulose molecular chains, the binding force between the fiber molecular chains is enhanced, and the crystalline state is improved. The chlorine content, UPF and stiffness are slightly increased, and the whiteness is reduced. The crease resistance of the fabric after the ionic crosslinking finishing can be comparable to that of BTCA. According to the crease recovery angle (WRA) of the durable press textile, the WRA is generally 250-300 degrees, the DP grade is more than or equal to 3.5, and the tensile strength loss is less than or equal to 40 percent, so that the Cl-ICL/Cotton can be found to basically meet the basic requirements of the durable press textile, and the strength loss is small.

2. Antibacterial test analysis:

under the optimal process conditions, the antibacterial performance of the un-chlorinated and chlorinated post-treated cotton fabrics is measured. Wherein, the chlorine content of the chlorinated fabric is 0.27%.

Note:^athe concentration of Staphylococcus aureus is 8.40 × 10⁵CFU/sample；^bEscherichia coli O157: h7 concentration of 1.00X 10⁶ CFU/sample

Theoretically, the higher the chlorine content is, the higher the contact probability of active chlorine and bacteria is, and the antibacterial effect of the base material can be more effectively improved.

Using goldThe antimicrobial activity of Staphylococcus aureus and Escherichia coli was tested, wherein each group of samples was inoculated with Staphylococcus aureus at a concentration of 8.40X 10⁵CFU/sample; escherichia coli O157: the concentration of H7 was 1.00X 10⁶CFU/sample. The un-chlorinated samples gave a small reduction in the number of staphylococcus aureus and escherichia coli in 30min because the bacteria adhered to the test sample surface rather than killing the bacteria. The chlorinated sample can kill 100% of Staphylococcus aureus in 5 min and 100% of Escherichia coli in 10 min. This is because the oxidation of the N-Cl bonds on the finished fabric deactivates the microorganisms. The conclusion shows that the composite finished cotton fabric has excellent antibacterial performance and high sterilization speed.

3. And (3) testing ultraviolet stability:

the chlorine content can be regenerated again by re-chlorination, but cannot be regenerated due to the somewhat unrecoverable chlorine content. BPTCD is a benzophenone derivative^[63]The energy capable of absorbing ultraviolet light is converted into other energy. It can be seen from fig. 10 that the addition of BPTCD can significantly improve the uv stability of the halamine antibacterial agent, the chlorine content can still reach 0.08% after 24 h irradiation, and the chlorine content can recover 79% after re-chlorination. The crease resistance of the cotton fabric is slightly reduced under the ultraviolet irradiation, partial chemical bonds formed between the cotton fibers and the BPTCD are aged and broken by the energy of the ultraviolet, and the formed ionic bonds are broken. And comparing the obtained dry-wet state crease recovery angle of Cl-ICL/Cotton of 223 degrees with the dry-wet state crease recovery angle of Cl-NICL/Cotton of 225 degrees after 24 hours, and obtaining that the BPTCD is benzophenone derivatives which absorb partial ultraviolet energy, and chemical bonds and ionic bonds formed by crosslinking are protected and can not cause a large amount of breakage.

4. And (3) testing the water washing resistance:

the cotton fabric has an antibacterial/anti-wrinkle composite function after being subjected to ionic crosslinking and chlorination, the chlorine content is an important index of the antibacterial property of the halamine compound finished cotton fabric, and the dry-wet crease recovery angle is an important index of the non-ironing property of the crosslinking agent finished cotton fabric. The chlorine content of the cotton fabric modified by the halamine compound is reduced along with the hydrolysis of an N-Cl bond during washing, and the wrinkle recovery angle of the cotton fabric crosslinked by the polybasic carboxylic acid type anti-wrinkling agent is reduced along with the hydrolysis of an ether bond during washing.

As can be seen from FIG. 11, after 1, 5 and 10 water washes, the dry-wet crease recovery angle of Cl-ICL/Cotton is slightly reduced, wherein the dry-wet crease recovery angles of Cl-NICL/Cotton are 225.8 degrees and 191.5 degrees, and the comparison shows that the ionic bond formed by ionic crosslinking still partially exists after water washes. As can be seen from FIG. 12, after 10 times of washing, the loss of chlorine content was 33.3%, and the recovery of chlorine content was 74%. This is due, on the one hand, to the hydrolysis of the N-Cl bond, which can be recovered by re-chlorination. On the other hand, the ester bond formed by BPTCD and cotton fiber is hydrolyzed, and the hydrolysis of the ester bond causes permanent loss of chlorine content and cannot be recovered. After 25 times of water washing, the reduction of the dry and wet crease recovery angle of Cl-ICL/Cotton is slightly obvious, which is caused by that ionic bonds formed by ionic crosslinking are destroyed after multiple times of water washing, and ether bonds formed by BPTCD and Cotton fibers are partially hydrolyzed. The chlorine content loss rate is 63 percent, the chlorine content recovery rate is 66 percent, the chlorine content of the re-chlorinated cotton fabric can still reach 0.20 percent, and the cotton fabric still has good bactericidal performance.

Claims

1. a preparation method of cationic modifier TCTAC, is characterized in comprising the following steps:

1) Dissolve 2,3-epoxyhydroxypropyltrimethylammonium chloride in deionized water, add ammonia water dropwise, heat and stir, after the reaction is completed, obtain 1-amino-3-hydroxypropyltrimethylammonium chloride Ammonium; dissolve 1-amino-3-hydroxypropyltrimethylammonium chloride in deionized water to form an aqueous solution of 1-amino-3-hydroxypropyltrimethylammonium chloride;

2) Dissolve cyanuric chloride in acetone at 0°C, add 1-amino-3-hydroxypropyltrimethylammonium chloride aqueous solution dropwise, use sodium carbonate aqueous solution to adjust the pH value to 6-7, and stir to react until After the end, the cationic modifier TCTAC is obtained by salting out purification and drying.

2. the application of the cationic modifier TCTAC obtained by the preparation method as claimed in claim 1 in the anti-wrinkle and antibacterial finishing of cotton fabrics.

3. application according to claim 2, is characterized in that, comprises the following steps:

1) Dissolve the cationic modifier TCTAC and sodium hydroxide in deionized water to form the first dipping solution, and use the second dipping and second rolling process to treat the cotton cloth, and then pre-bake, first bake, wash and dry. , get I/Cotton;

2) Dissolve 3,3,4,4-benzophenone tetracarboxylic dianhydride and sodium hypophosphite in deionized water at 80°C to prepare the second dipping solution, and use the process of two dipping and two rolling to make I/Cotton After the treatment, pre-baking, second baking, washing and drying are performed to obtain ICL/Cotton;

3) Adjust the pH of the sodium hypochlorite aqueous solution to neutrality with acid, soak the ICL/Cotton in it and take it out, then wash and dry to obtain Cl-ICL/Cotton.

4. The application according to claim 3, wherein the concentration of the cationic modifier TCTAC in the first immersion solution is 50 g/L.

5 . The application according to claim 3 , wherein the concentration of the 3,3,4,4-benzophenone tetracarboxylic dianhydride in the second dipping solution is 50 g/L. 6 .

6 . The application according to claim 3 , wherein the temperature of the second baking is 160° C., and the time of the second baking is 150 s. 7 .