Antibacterial moisture absorbing softener and preparation method thereof

Abstract

The present application discloses an antibacterial hygroscopic softener and a preparation method thereof, wherein the preparation method comprises the following preparation steps: S1: reacting toluene diisocyanate and polyethylene glycol in a solvent to generate an intermediate I; S2: reacting the intermediate I with tetramethyldipropylenetriamine in an inert gas atmosphere to generate an intermediate II; S3: reacting hydrogen-containing silicone oil, allyl polyoxyethylene ether, and allyl epoxy-terminated polyoxyethylene ether in a solvent and a catalyst to generate a modified silicone oil; S4: reacting the modified silicone oil and a norfloxacin aqueous solution in a solvent, then adding the intermediate II to the reactant, reacting for a period of time and removing impurities to obtain the antibacterial hygroscopic softener.

Description

Technical Field

[0001] The present application relates to the field of polymer materials, and in particular to an antibacterial hygroscopic softener and a preparation method thereof. Background Art

[0002] With the improvement of living standards, people pay more and more attention to the quality of life, and the participation in outdoor sports is also increasing. However, the diversity and complexity of the outdoor sports environment also poses a problem for people's comfort and protection during exercise. It is necessary to ensure comfort at all times while doing a good job of self-protection to avoid mosquitoes or bacteria. At the same time, in recent years, the continuous high temperature weather in summer has seriously affected people's living comfort. If the clothing fabric can have excellent moisture absorption and breathability, it will greatly improve people's comfort in summer.

[0003] Although there are many products on the market that can achieve the effect of moisture absorption and quick drying, most of these products are polyether-modified silicone oils and polyamide compounds, which do not improve the softness and smoothness of clothing fabrics, and have almost no antibacterial and sterilization functions. In addition, the washing resistance of this type of additive is relatively poor. After several washes, its moisture absorption and quick drying performance decreases significantly.

[0004] If outdoor fabrics, home textile fabrics and summer clothing fabrics can be made to have excellent moisture absorption and breathability, soft and smooth effects, and excellent antibacterial and bactericidal effects, they will have broad market prospects. However, there is no post-finishing auxiliary agent on the market that is moisture absorption and breathability, antibacterial, soft and smooth. In order to give fabrics this special function, printing and dyeing factories generally use a variety of post-finishing auxiliary agents for compounding or use multiple processes to give fabrics these properties step by step. However, the compounding of auxiliary agents needs to consider the compatibility of various auxiliary agents, and multiple processes will greatly increase production costs and wastewater generation. Therefore, products that integrate moisture absorption and breathability, soft and smooth effects, and excellent antibacterial and bactericidal effects have good market prospects. Summary of the invention

[0005] The purpose of the present application is to endow fabrics such as towels with antibacterial, moisture-absorbing and breathable effects by modifying the softener.

[0006] In order to achieve the above objectives, the technical solution adopted in this application is: to provide an antibacterial hygroscopic softener, characterized in that its general structural formula is: Where M1 is M2 is

[0007] d, c, x, z, m, n are all integers, and 3≤a≤5; 2≤d≤3; 57≤c≤61; 4≤x≤9; 2≤z≤3; 13≤m≤17; 13≤n≤18.

[0008] The present application provides a method for preparing an antibacterial hygroscopic softener, which is characterized by comprising the following preparation steps: S1: reacting toluene diisocyanate and polyethylene glycol in a solvent to generate an intermediate I; S2: reacting the intermediate I with tetramethyldipropylenetriamine in an inert gas atmosphere to generate an intermediate II; S3: reacting hydrogen-containing silicone oil, allyl polyoxyethylene ether, and allyl epoxy-terminated polyoxyethylene ether in a solvent and a catalyst to generate a modified silicone oil; S4: reacting the modified silicone oil and a norfloxacin aqueous solution in a solvent, then adding the intermediate II to the reactant, reacting for a period of time and removing impurities to obtain the antibacterial hygroscopic softener; the general structural formula of the intermediate I is: Wherein n is an integer, and 13≤n≤18; the general structural formula of the intermediate II is: Wherein n is an integer, and 13≤n≤18; the general structural formula of the modified silicone oil is: Wherein c, x, y, z, and m are all integers, and 57≤c≤61; 5≤x≤9; 5≤y≤8; 2≤z≤3; 13≤m≤17; the general structural formula of the antibacterial hygroscopic softener is: Where M1 is M2 is

[0009] a, d, c, x, z, m, n are all integers, and 3≤a≤5; 2≤d≤3; 57≤c≤61; 4≤x≤9; 2≤z≤3; 13≤m≤17; 13≤n≤18.

[0010] As a preference, the number average molecular weight of the polyethylene glycol is 600-800.

[0011] Preferably, the hydrogen content of the hydrogen-containing silicone oil is 0.14% to 0.22%.

[0012] As a preference, the number average molecular weight of the allyl polyoxyethylene ether is 600-800.

[0013] As a preference, the number average molecular weight of the allyl epoxy-terminated polyoxyethylene ether is 300-500.

[0014] As a preferred embodiment, in parts by mass, the step S1 is specifically as follows: 500-600 parts of the toluene diisocyanate and 1200-1600 parts of the polyethylene glycol are added to a reaction kettle equipped with a stirrer, reflux condenser and a thermometer, and 0.2%-0.4% of triethylamine is added in a total mass fraction, the mixture is fully stirred, the temperature is raised to 60-80° C., and the mixture is kept warm for 4-6 hours to obtain the intermediate I.

[0015] As a preferred embodiment, the S2 step is specifically as follows: 1722 to 2122 parts of the intermediate I are added to a reactor equipped with a stirrer, a condenser reflux and a thermometer, and after the air in the reactor is discharged by an inert gas, 300 to 400 parts of the tetramethyldipropylenetriamine are slowly added dropwise to the reactor, and after maintaining the temperature at 50 to 60° C. for 4 to 6 hours, 2096 to 2496 parts of isopropanol are added and stirred thoroughly to obtain the intermediate II.

[0016] As another preferred embodiment, the S3 step is specifically as follows, measured by mass: 4500-6000 parts of the hydrogen-containing silicone oil, 1200-2400 parts of the allyl polyoxyethylene ether, and 1500-4000 parts of the allyl epoxy-terminated polyoxyethylene ether are added to a reaction kettle equipped with a stirrer, condensation reflux and a thermometer, and 3300-4885 parts of isopropanol and 2-5 parts of a 2% chloroplatinic acid-isopropanol solution are added at the same time, and under the protection of an inert gas, the temperature is raised to 70-80°C and kept warm for 6-8 hours to obtain the modified silicone oil.

[0017] Further preferably, in parts by mass, the S4 step is specifically as follows: 1100-1628 parts of the modified silicone oil and 192-319 parts of the norfloxacin aqueous solution with a mass ratio of 50% are added to a reactor equipped with a stirrer, condensation reflux and a thermometer, 1136-1756 parts of isopropanol are added as a solvent, the temperature is raised to 70-80°C, and the temperature is kept for 6-8 hours, and then 838-1498 parts of the intermediate II and 36-72 parts of acetic acid are added to the reactor, and after keeping the temperature for 8-10 hours, 1415-2252 parts of the isopropanol are separated under a vacuum negative pressure of -0.09 to -0.1 MPa to obtain the antibacterial hygroscopic softener.

[0018] Compared with the prior art, the beneficial effects of this application are:

[0019] (1) The antibacterial hygroscopic softener material of the present application introduces a norfloxacin quinolone structure into the structure, which, in synergy with the silicone segment and the tertiary amino group, can not only give the fabric excellent wearing comfort performance, but also give the fabric excellent antibacterial performance, and also avoid the generation of wastewater caused by considering the compatibility of various auxiliaries and multiple processes due to the need to give the fabric multiple functions;

[0020] (2) The coordinated effect of the polyurethane structure, polyamine branching structure and polyoxyethylene ether chain segment in the product structure can give the fabric excellent moisture absorption and breathability, thereby improving the wearing comfort of the fabric;

[0021] (3) The amino, silicone and urea structures in the product structure and their synergistic effects can give the finished fabric better wearing comfort. At the same time, the urea and urethane structures of polyurethane can enhance the adsorption and coating capabilities of the fabric, thereby improving the wash resistance of the fabric. DETAILED DESCRIPTION

[0022] Below, the present application is further described in conjunction with specific implementation methods. It should be noted that, under the premise of no conflict, the various embodiments or technical features described below can be arbitrarily combined to form new embodiments.

[0023] The terms "including" and "having" and any variations thereof in the specification and claims of this application are intended to cover non-exclusive inclusions. For example, a process, method, system, product or apparatus comprising a series of steps or units is not necessarily limited to those steps or units explicitly listed, but may include other steps or units not explicitly listed or inherent to these processes, methods, products or apparatuses.

[0024] The present application provides an antibacterial, moisture-absorbing, breathable softener material, the general structural formula of which is as follows:

[0025]

[0026] Where M1 is M2 is a, d, c, x, z, m, n are all integers, and 3≤a≤5; 2≤d≤3; 57≤c≤61; 4≤x≤9; 2≤z≤3; 13≤m≤17; 13≤n≤18.

[0027] The antibacterial moisture-absorbing softener of the present application has a norfloxacin quinolone structure, an organic silicon segment and a tertiary amine structure, which can not only give the fabric excellent wearing comfort performance, but also give the fabric excellent antibacterial performance, and also avoid the generation of wastewater caused by considering the compatibility of various auxiliaries and multiple processes due to the need to give the fabric multiple functions.

[0028] The present application provides a method for preparing an antibacterial hygroscopic softener, comprising the following steps, wherein the raw materials in the steps are calculated by weight:

[0029] S1: reacting toluene diisocyanate and polyethylene glycol in a solvent to generate intermediate Ⅰ;

[0030] S2: Intermediate Ⅰ reacts with tetramethyldipropylenetriamine in an inert gas atmosphere to generate intermediate Ⅱ;

[0031] S3: hydrogen-containing silicone oil, allyl polyoxyethylene ether, and allyl epoxy-terminated polyoxyethylene ether react in a solvent and a catalyst to generate modified silicone oil;

[0032] S4: reacting the modified silicone oil and the norfloxacin aqueous solution in a solvent, then adding the intermediate II to the reactant, reacting for a period of time and removing impurities to obtain the antibacterial hygroscopic softener of the present application.

[0033] In step S1, the reaction formula of toluene diisocyanate and polyethylene glycol is as follows:

[0034] Wherein n is an integer, and 13≤n≤18.

[0035] In step S2, the reaction formula of intermediate I and tetramethyldipropylenetriamine is as follows:

[0036] Wherein n is an integer, and 13≤n≤18.

[0037] In step S3, the hydrogen-containing silicone oil, allyl polyoxyethylene ether, and allyl epoxy-terminated polyoxyethylene ether are reacted in a solvent and a catalyst as follows:

[0038] Among them, b, c, x, y, z, m are all integers, and 7≤b≤11; 57≤c≤61; 5≤x≤9; 5≤y≤8; 2≤z≤3; 13≤m≤17.

[0039] In step S4, the modified silicone oil, norfloxacin and intermediate II react as follows:

[0040] Where M1 is

[0041] M2 is a, d, c, x, y, z, m, n are all integers, and 3≤a≤5; 2≤d≤3; 57≤c≤61; 4≤x≤9; 5≤y≤8; 2≤z≤3; 13≤m≤17; 13≤n≤18.

[0042] The present invention utilizes the reaction between isocyanate group and hydroxyl group to prepare intermediate I; then utilizes the reaction between isocyanate group and amino group to prepare intermediate II, and introduces tertiary amine group that can react with epoxy group into the structure of polyurethane. Allyl polyoxyethylene ether and allyl epoxy polyether are introduced into the structure of hydrogen-containing silicone oil by using hydrosilylation reaction. Then utilizes the reaction between epoxy group, norfloxacin and secondary amine and tertiary amine to introduce various functional groups into the product structure, and obtain the antibacterial hygroscopic softener of the present invention.

[0043] In some embodiments, the number average molecular weight of the polyethylene glycol in step S1 is 600-800.

[0044] In some embodiments, the hydrogen content of the hydrogen-containing silicone oil is 0.14% to 0.22%.

[0045] In some embodiments, the number average molecular weight of the allyl polyoxyethylene ether is 600-800.

[0046] In some embodiments, the number average molecular weight of the allyl epoxy-terminated polyoxyethylene ether is 300-500.

[0047] In some embodiments, step S1 is specifically as follows: 500-600 parts of toluene diisocyanate and 1200-1600 parts of polyethylene glycol are added to a reaction kettle equipped with a stirrer, reflux condenser and thermometer, and 0.2% to 0.4% of triethylamine is added in a total mass fraction, stirred thoroughly, heated to 60-80°C, and kept warm for 4-6 hours to obtain intermediate I.

[0048] In some embodiments, step S2 is specifically as follows: 1722 to 2122 parts of intermediate I are added to a reactor equipped with a stirrer, condenser reflux and a thermometer, and the air in the reactor is discharged by an inert gas, and then 300 to 400 parts of tetramethyldipropylenetriamine are slowly added dropwise to the reactor. After maintaining the temperature at 50 to 60°C for 4 to 6 hours, 2096 to 2496 parts of isopropanol are added, and the mixture is stirred thoroughly to obtain intermediate II.

[0049] In some embodiments, step S3 is specifically as follows: 4500 to 6000 parts of hydrogen-containing silicone oil, 1200 to 2400 parts of allyl polyoxyethylene ether, and 1500 to 4000 parts of allyl epoxy-terminated polyoxyethylene ether are added to a reactor equipped with an agitator, condensation reflux and a thermometer, and at the same time, 3300 to 4885 parts of isopropanol and 2 to 5 parts of a 2% chloroplatinic acid-isopropanol solution are added. All are under the protection of an inert gas, the temperature is raised to 70 to 80°C, and the temperature is kept for 6 to 8 hours to obtain modified silicone oil.

[0050] The antibacterial moisture-absorbing softener structure of the present application introduces a synergistic effect of a polyurethane structure, a polyamine branched structure and a polyoxyethylene ether chain segment, which can give the fabric excellent moisture absorption and breathability and improve the wearing comfort of the fabric.

[0051] In some embodiments, step S4 is specifically as follows: 1100 to 1628 parts of modified silicone oil and 192 to 319 parts of a 50% by weight aqueous solution of norfloxacin are added to a reactor equipped with a stirrer, condensation reflux and a thermometer, 1136 to 1756 parts of isopropanol are added as a solvent, the temperature is raised to 70 to 80°C, and the temperature is kept for 6 to 8 hours, and then 838 to 1498 parts of intermediate II and 36 to 72 parts of acetic acid are added to a reactor equipped with a stirrer, condensation reflux and a thermometer. After keeping the temperature for 8 to 10 hours, 1415 to 2252 parts of isopropanol are separated under a vacuum negative pressure of -0.09 to -0.1 MPa to obtain the antibacterial hygroscopic softener of the present application.

[0052] The introduction of the norfloxacin quinolone structure into the product structure, together with the synergistic effect of the silicone segment and the tertiary amino group, can not only give the fabric excellent wearing comfort, but also excellent antibacterial properties, while also avoiding the generation of wastewater caused by considering the compatibility of various auxiliaries and multiple processes due to the need to give the fabric multiple functions.

[0053] The amino, silicone and urea structures in the product structure enhance each other and can give the finished fabric better wearing comfort. At the same time, the urea and urethane structures of polyurethane can enhance the adsorption and coating ability of the fabric, thereby improving the wash resistance of the fabric.

[0054] Example 1

[0055] A method for preparing an antibacterial moisture-absorbing softener comprises the following steps, wherein the raw materials in the steps are calculated by weight:

[0056] S1: 522 parts of toluene diisocyanate and 1200 parts of polyethylene glycol with a number average molecular weight of 600 are added to a dry reaction kettle equipped with a stirrer, condensation reflux and a thermometer, and 0.3% of triethylamine is added, the mixture is stirred thoroughly, the temperature is raised to 70°C, and the temperature is kept for 5 hours to obtain intermediate I;

[0057] S2: 1722 parts of polyurethane intermediate I are added into a reaction kettle equipped with a stirrer, condenser reflux and thermometer, and the air in the reaction kettle is discharged by nitrogen, and then 374 parts of tetramethyldipropylenetriamine are slowly added dropwise into the reaction kettle, and the temperature is maintained at 50° C. for 6 hours, and then 2096 parts of isopropanol are added and stirred thoroughly to obtain intermediate II;

[0058] S3: 5000 parts of hydrogen-containing silicone oil with a hydrogen content of 0.14%, 1200 parts of allyl polyoxyethylene ether with a number average molecular weight of 600, and 1500 parts of allyl epoxy-terminated polyoxyethylene ether with a number average molecular weight of 300 are added to a reaction kettle equipped with a stirrer, condensation reflux and a thermometer, and 3300 parts of isopropanol and 5 parts of 2% chloroplatinic acid-isopropanol solution are added at the same time, all under the protection of nitrogen, the temperature is raised to 80°C, and the temperature is kept for 6 hours to obtain modified silicone oil;

[0059] S4: 1100 parts of modified silicone oil and 192 parts of 50% by mass norfloxacin aqueous solution are added to a reactor equipped with a stirrer, condensation reflux and a thermometer, 1136 parts of isopropanol are added as a solvent, the temperature is raised to 80°C, and the temperature is kept for 8 hours. Then, 838 parts of intermediate II and 36 parts of acetic acid are added to a reactor equipped with a stirrer, condensation reflux and a thermometer. After keeping the temperature for 8 hours, 1415 parts of isopropanol are separated under a vacuum negative pressure of -0.095 MPa to obtain the antibacterial hygroscopic softener of the present application.

[0060] Example 2

[0061] The polyethylene glycol in step S1 is adjusted to 1600 parts of polyethylene glycol having a number average molecular weight of 800;

[0062] The amount of intermediate I added in step S2 was adjusted to 2122 parts, and the amount of isopropanol added was adjusted to 2496 parts;

[0063] The amount of isopropanol added in step S4 was adjusted to 1176 parts, the amount of intermediate II added was adjusted to 998 parts, and finally 1500 parts of isopropanol were separated by impurity removal. The other preparation methods were consistent with the preparation method in Example 1.

[0064] Example 3

[0065] The amount of allyl polyoxyethylene ether added in step S3 was adjusted to 1600 parts, the number average molecular weight was adjusted to 800, and the amount of isopropanol added was adjusted to 3471 parts;

[0066] The amount of modified silicone oil added in step S4 was adjusted to 1157 parts by mass, the amount of isopropanol solvent added was 1180 parts, and finally 1459 parts of isopropanol were separated by impurities. The other preparation methods were consistent with the preparation method in Example 1.

[0067] Example 4

[0068] The amount of allyl epoxy-terminated polyoxyethylene ether added in step S3 was adjusted to 2500 parts, the number average molecular weight was adjusted to 500, and the amount of isopropanol added was adjusted to 3729 parts;

[0069] The amount of modified silicone oil added in step S4 was adjusted to 1243 parts by mass, the amount of isopropanol solvent added was 1244 parts, and finally 1523 parts of isopropanol were separated by impurities. The other preparation methods were consistent with the preparation method in Example 1.

[0070] Example 5

[0071] In step S3, the hydrogen content of the hydrogen-containing silicone oil is adjusted to 0.22%, the amount of allyl polyoxyethylene ether added is adjusted to 1800 parts, the amount of allyl epoxy-terminated polyoxyethylene ether added is adjusted to 2400 parts, and the amount of isopropanol added is adjusted to 3943 parts;

[0072] The amount of modified silicone oil added in step S4 was adjusted to 1314 parts, the amount of 50% norfloxacin aqueous solution added was adjusted to 319 parts, the amount of intermediate II added was adjusted to 1257 parts, and the amount of acetic acid added was adjusted to 54 parts. Finally, 1888 parts of isopropanol were separated by impurity removal. The other preparation methods were consistent with the preparation method in Example 1.

[0073] Example 6

[0074] In step S3, the amount of allyl polyoxyethylene ether added is adjusted to 2400 parts, the number average molecular weight is adjusted to 800, and the amount of isopropanol added is adjusted to 4200 parts;

[0075] The amount of modified silicone oil added in step S4 was adjusted to 1400 parts, the amount of isopropanol solvent added was adjusted to 1526 parts, and finally 1952 parts of isopropanol were separated by impurities. The other preparation methods were consistent with the preparation method in Example 5.

[0076] Example 7

[0077] In step S3, the amount of allyl epoxy-terminated polyoxyethylene ether added is adjusted to 4000 parts, the number average molecular weight is adjusted to 500, and the amount of isopropanol added is adjusted to 5629 parts;

[0078] The amount of modified silicone oil added in step S4 was adjusted to 1643 parts, the amount of isopropanol solvent added was adjusted to 1708 parts, and finally 2135 parts of isopropanol were separated by impurity removal. The other preparation methods were consistent with the preparation method in Example 5.

[0079] Example 8

[0080] The amount of 50% norfloxacin aqueous solution added in step S4 was adjusted to 255 parts, the amount of isopropanol solvent added was adjusted to 1580 parts, the amount of intermediate II added was adjusted to 1677 parts, and the amount of acetic acid added was adjusted to 72 parts. Finally, 2100 parts of isopropanol were separated by impurity removal. The other preparation methods were consistent with the preparation method in Example 5.

[0081] Example 9

[0082] The holding time after adding the isopropanol solvent in step S4 was adjusted to 10 hours, and the other preparation methods were consistent with the preparation method in Example 5.

[0083] Example 10

[0084] The time after adding intermediate II in step S4 was adjusted to 10 hours, and the other preparation methods were consistent with the preparation method in Example 5.

[0085] Comparative Example 1

[0086] In step S4, tetramethylhexanediamine is used instead of 50% norfloxacin aqueous solution, and other preparation methods are consistent with the preparation method in Example 5.

[0087] Comparative Example 2

[0088] Intermediate II is not prepared, and tetramethyldipropylenetriamine is used instead of intermediate II to carry out the reactions in steps S3 and S4. Other preparation methods are consistent with the preparation method in Example 5.

[0089] Comparative Example 3

[0090] The polyethylene glycol in step S1 was replaced by polypropylene glycol, and the other preparation methods were consistent with the preparation method in Example 5.

[0091] Comparative Example 4

[0092] The tetramethyldipropylenetriamine in step S2 was replaced by dimethylpropylenediamine, and the other preparation methods were consistent with the preparation method in Example 5.

[0093] Comparative Example 5

[0094] Purchase commercially available silicone oil for cotton1.

[0095] Comparative Example 6

[0096] Purchase commercially available silicone oil for cotton 2.

[0097] Performance Testing

[0098] Finishing process: 60 g / L of the softener prepared in each embodiment and each comparative example was used to pad the cotton knitted fabric with the working solution at a padding rate of 80%, followed by pre-baking at 170° C. for 45 to 60 seconds, allowing the fabric to regain moisture, and then conducting performance testing and evaluation.

[0099] 1. Softness test: According to GB / T18318 "Textiles·Determination of fabric bending length": Place a long strip sample on the platform, press a ruler on the sample, and the long axis of the sample is parallel to the length direction of the ruler. The ruler and the long axis of the sample move on the platform at the same time, so that the sample extends out of the platform and is suspended in the air, and bends under its own weight. When the downward bending head of the sample touches the inclined plane at a 41.5° angle to the horizontal, 1 / 2 of the extended length of the sample is the bending length. The bending stiffness of the sample is calculated by the bending length and the mass per unit area.

[0100] Sample: 6 pieces of 25mm*25mm warp and weft knitting, each sample is measured 4 times and the average value is taken;

[0101] Calculation of flexural stiffness:

[0102] G=mC 3 10 -2

[0103] Where: G——bending stiffness per unit width, mN·cm; m——mass per unit area of ​​the specimen, g / m 2 ; C——average bending length of the specimen, cm.

[0104] 2. Evaluation of moisture permeability: Determined in accordance with GB / T 12704.1-2009 "Test method for moisture permeability of textile fabrics Part 1: Moisture absorption method". The moisture permeability WVT value is used to represent the moisture permeability. The larger the value, the better the moisture permeability of the fabric.

[0105] 3. Air permeability evaluation: According to GB / T 5453-1997 "Determination of air permeability of textile fabrics", the average air flow rate is used for characterization. The larger the value, the better the air permeability of the fabric.

[0106] 4. Hydrophilicity evaluation: Use a standard dropper (25 drops / mL) to drop a drop of water from a height of 2 cm from the fabric surface. Test the time it takes for the fabric to absorb water under static conditions. Drop more than 3 times at different positions and take the average value.

[0107] 5. Washability evaluation: Wash according to GB / T 8629-2017 "Household Washing and Drying Procedure for Textile Testing", and test the hydrophilicity and feel of the fabric after washing.

[0108] 6. Hand feel evaluation: Use hand touch method to evaluate the overall hand feel, using a 1-5 point evaluation method, 1 point is the worst and 5 points is the best. 10 people evaluate at the same time and take the average value.

[0109] 7. Evaluation of antibacterial effect: Evaluation of antibacterial performance: Refer to the "Test Method for Antibacterial Performance of Fabrics (FZ / T 01021-1992)" for testing and evaluate with the percentage of bacteria reduction.

[0110] The test results of the above 1 to 6 performance evaluations are recorded in Table 1 below, and the antibacterial effect evaluations are recorded in Table 2 below.

[0111] Table 1 Performance test results of each embodiment and each comparative example

[0112]

[0113]

[0114] Analysis of the performance test results of Examples 1 to 10 shows that the antibacterial hygroscopic softener of the present application can improve the softness, air permeability and hygroscopicity of cotton knitted fabrics, effectively enhance the comfort of the fabric, and maintain good hydrophilic properties and feel after multiple washings.

[0115] By analyzing the performance test results of Examples 1 to 4, the number average molecular weights of polyethylene glycol, allyl polyoxyethylene ether and allyl epoxy-terminated polyoxyethylene ether were adjusted respectively during the preparation process, and the air permeability and moisture permeability of the fabric were finally increased, but the hand feel was reduced to a certain extent.

[0116] Comparing the performance test results of Example 1 and Example 5, Example 5 adjusts the hydrogen content of the hydrogen-containing silicone oil, which is helpful for the introduction of polyether segments and amino groups, and can significantly improve the softness, air permeability and moisture permeability of the fabric, and also improves the hand feel.

[0117] By analyzing Examples 5 to 7, the number average molecular weights of allyl polyoxyethylene ether and allyl epoxy-terminated polyoxyethylene ether were adjusted respectively. Although the hydrophilicity of the fabric was slightly improved, the softness of the fabric was reduced accordingly.

[0118] By analyzing Example 5 and Example 8 and adjusting the mass ratio of norfloxacin to intermediate II, a fabric with better softness was obtained, and the fabric also showed excellent air permeability, moisture permeability and hydrophilicity.

[0119] Analysis of Example 5 and Example 9-1 Example 10 shows that the change of reaction time has a certain influence on the product performance, but the influence is still within an acceptable range, and it is not meaningful to adjust the reaction conditions.

[0120] By analyzing the performance test results of Example 5 and Comparative Examples 3 to 4, it is found that the tetramethyldipropylenetriamine structure, polyurethane structure and polyoxyethylene structure are introduced into the antibacterial hygroscopic softener structure of the present application, which interact with each other and can give the product excellent wash resistance, air permeability and moisture permeability.

[0121] Table 2 Resistance performance of each embodiment and each comparative example

[0122]

[0123]

[0124] Analysis of the antibacterial results of the original cloth, Examples 1 to 10, and Comparative Examples 5 to 6 shows that the original cloth has no antibacterial rate, and long-term use will breed bacteria that is not good for human health. The two commercially available clothing treatment agents have certain antibacterial properties in the initial state, but after the clothes are washed 10 times, their antibacterial properties are reduced to 0.

[0125] The antibacterial moisture-absorbing softener of the present application can effectively inhibit the reproduction of Escherichia coli and Staphylococcus aureus, and still has a good antibacterial effect after multiple washings. It is suitable for application in clothing worn by humans, and inhibits the reproduction of bacteria while providing comfort.

[0126] In the comparison of the antibacterial effects of Examples 1 to 10, the clothes treated with Example 5 achieved the best bacterial inhibition rate, with an inhibition rate of 92.54% against Escherichia coli, and an inhibition rate of 86.54% against Escherichia coli after washing the clothes 10 times; the inhibition rate against Staphylococcus aureus reached 94.33%, and the inhibition rate of Escherichia coli was maintained at 84.31 after washing 10 times.

[0127] The antibacterial test results of Example 5 and Comparative Example 1 were analyzed. Although in the results presented in Table 1, there was little difference between the test results of Comparative Example 1 and Example 1 in terms of softness, breathability, hydrophilicity and feel, the antibacterial performance test results in Table 2 showed that other structures were used to replace the norfloxacin structure in Comparative Example 1, and the antibacterial performance of the treated clothing was poor.

[0128] Analysis of the antibacterial test results of Example 5 and Comparative Examples 2 to 4 shows that the synergistic effect of the quaternary ammonium salt group of norfloxacin and tetramethyldipropylenetriamine introduced into the product structure can give the fabric an excellent antibacterial effect. At the same time, the synergistic effect of the polyurethane, urea structure and amino group introduced into the structure can improve the washing durability of the product.

[0129] The antibacterial moisture-absorbing softener of the present application can improve the softness, air permeability, moisture permeability, hydrophilicity and feel of clothes after being used for clothing treatment, while giving the fabric excellent bacteria inhibition performance and wash durability, and does not generate a large amount of difficult-to-treat wastewater during the production process, and has certain economic adaptability.

[0130] The above describes the basic principles, main features and advantages of the present application. Those skilled in the art should understand that the present application is not limited by the above embodiments, and the above embodiments and the specification only describe the principles of the present application. The present application may have various changes and improvements without departing from the spirit and scope of the present application, and these changes and improvements fall within the scope of the present application for which protection is sought. The scope of protection claimed by the present application is defined by the attached claims and their equivalents.

Claims

1. An antibacterial hygroscopic softener, characterized in that: Its general structural formula is: Where M1 is M2 is d, c, x, z, m, n are all integers, and 3≤a≤5; 2≤d≤3; 57≤c≤61; 4≤x≤9; 2≤z≤3; 13≤m≤17; 13≤n≤18.

2. A method for preparing an antibacterial hygroscopic softener, characterized in that: The method comprises the following preparation steps: S1: reacting toluene diisocyanate and polyethylene glycol in a solvent to generate intermediate Ⅰ; S2: the intermediate I reacts with tetramethyldipropylenetriamine in an inert gas atmosphere to generate intermediate II; S3: hydrogen-containing silicone oil, allyl polyoxyethylene ether, and allyl epoxy-terminated polyoxyethylene ether react in a solvent and a catalyst to generate modified silicone oil; S4: reacting the modified silicone oil and the norfloxacin aqueous solution in a solvent, then adding the intermediate II to the reactant, reacting for a period of time and removing impurities to obtain the antibacterial hygroscopic softener; The general structural formula of the intermediate I is: Where n is an integer and 13≤n≤18; The general structural formula of the intermediate II is: Where n is an integer and 13≤n≤18; The general structural formula of the modified silicone oil is: Where c, x, y, z, m are all integers, and 57≤c≤61; 5≤x≤9; 5≤y≤8; 2≤z≤3; 13≤m≤17; The general structural formula of the antibacterial hygroscopic softener is: Where M1 is M2 is a, d, c, x, z, m, n are all integers, and 3≤a≤5; 2≤d≤3; 57≤c≤61; 4≤x≤9; 2≤z≤3; 13≤m≤17; 13≤n≤18.

3. The method for preparing the antibacterial hygroscopic softener according to claim 2, characterized in that: The number average molecular weight of the polyethylene glycol is 600-800.

4. The method for preparing the antibacterial hygroscopic softener according to claim 2, characterized in that: The hydrogen content of the hydrogen-containing silicone oil is 0.14% to 0.22%.

5. The method for preparing the antibacterial hygroscopic softener according to claim 2, characterized in that: The number average molecular weight of the allyl polyoxyethylene ether is 600-800.

6. The method for preparing the antibacterial hygroscopic softener according to claim 2, characterized in that: The number average molecular weight of the allyl epoxy-terminated polyoxyethylene ether is 300-500.

7. The method for preparing the antibacterial hygroscopic softener according to claim 2, characterized in that: In parts by mass, the step S1 is specifically as follows: 500-600 parts of the toluene diisocyanate and 1200-1600 parts of the polyethylene glycol are added to a reaction kettle equipped with a stirrer, condensation reflux and a thermometer, and 0.2%-0.4% of triethylamine is added in a total mass fraction, the mixture is fully stirred, the temperature is raised to 60-80° C., and the temperature is kept for 4-6 hours to obtain the intermediate I.

8. The method for preparing the antibacterial hygroscopic softener according to claim 2, characterized in that: In parts by mass, the S2 step is specifically as follows: 1722 to 2122 parts of the intermediate I are added to a reactor equipped with a stirrer, a condenser reflux and a thermometer, and after the air in the reactor is discharged by an inert gas, 300 to 400 parts of the tetramethyldipropylenetriamine are slowly added dropwise to the reactor, and after maintaining the temperature at 50 to 60° C. for 4 to 6 hours, 2096 to 2496 parts of isopropanol are added, and the mixture is fully stirred to obtain the intermediate II.

9. The method for preparing the antibacterial hygroscopic softener according to claim 2, characterized in that: In parts by mass, the S3 step is specifically as follows: 4500-6000 parts of the hydrogen-containing silicone oil, 1200-2400 parts of the allyl polyoxyethylene ether, and 1500-4000 parts of the allyl epoxy-terminated polyoxyethylene ether are added to a reaction kettle equipped with an agitator, condensation reflux and a thermometer, and at the same time, 3300-4885 parts of isopropanol and 2-5 parts of a 2% chloroplatinic acid-isopropanol solution are added, and under the protection of an inert gas, the temperature is raised to 70-80°C and kept warm for 6-8 hours to obtain the modified silicone oil.

10. The method for preparing the antibacterial hygroscopic softener according to claim 2, characterized in that: In parts by mass, the S4 step is specifically as follows: 1100 to 1628 parts of the modified silicone oil and 192 to 319 parts of the norfloxacin aqueous solution (50% by mass) are added to a reaction kettle equipped with a stirrer, condensation reflux and a thermometer, 1136 to 1756 parts of isopropanol are added as a solvent, the temperature is raised to 70 to 80°C, and the temperature is kept for 6 to 8 hours, and then 838 to 1498 parts of the intermediate II and 36 to 72 parts of acetic acid are added to the reaction kettle, and after keeping the temperature for 8 to 10 hours, 1415 to 2252 parts of the isopropanol are separated under a vacuum negative pressure of -0.09 to -0.1 MPa to obtain the antibacterial hygroscopic softener.

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