An antibacterial and deodorant finishing agent for wool fabric and its preparation method and application

Abstract

The application discloses an antibacterial and deodorizing finishing agent for wool fabrics and a preparation method and application thereof, wherein the antibacterial and deodorizing finishing agent is a macromolecule polymerized by betaine monomers, allyl glycidyl ether-beta-cyclodextrin monomers and amide monomers. Compared with the prior art, the antibacterial and deodorizing finishing agent in the application introduces betaine monomers as bactericidal groups, and due to the long molecular chain, the antibacterial effect is better than that of betaine small molecules; meanwhile, the betaine monomers also introduce sulfonic acid groups, can be combined with wool fabrics in the form of ionic bonds, and can reduce the damage to the physical mechanical properties of the wool fabrics during finishing; the introduction of amide monomers can make the overall pH value of the macromolecule present in a neutral to weak acidic state, and can reduce the damage of the antibacterial agent to the fabric during finishing; the introduction of cyclodextrin molecules by using an epoxy group can adsorb and include odor molecules by virtue of the unique cavity structure, and can remove the peculiar smell generated by the wool fabrics during wearing.

Description

Technical Field

[0001] This invention belongs to the field of textile technology, specifically relating to an antibacterial and deodorizing finishing agent for wool fabrics, its preparation method, and its application. Background Technology

[0002] In the textile industry, wool fabrics are beloved for their unique elasticity, warmth, and the excellent comfort of natural fibers. However, because wool is a protein fiber with the highest moisture regain and strongest hygroscopicity among natural fibers, and its natural crimp makes it prone to trapping dirt and grime, wool fabrics easily absorb pollutants excreted through the skin, providing an ideal environment and material basis for the growth and reproduction of microorganisms. Contaminated textiles not only suffer from microbial decomposition, producing odors and deteriorating physical and mechanical properties or sensory quality, but also pose potential health risks such as skin allergies and cross-infection. Therefore, antibacterial and deodorizing finishing of wool fabrics is of great significance.

[0003] CN201410164116.9 describes a two-dip, two-nip finishing process using chitosan and titanium dioxide to impart antibacterial properties to wool fabrics. However, unmodified chitosan, as a natural macromolecular antibacterial agent, has poor adhesion to the fabric and is easily washed away. Studies have shown that titanium dioxide is a leaching antibacterial agent, slowly released over time, which can irritate human skin and potentially cause dermatitis. Furthermore, the released antibacterial agent can harm water bodies. CN201510545007.6 describes an antibacterial finishing process using curcumin as an antibacterial agent and waterborne polyurethane as a binder for wool fabrics. Its advantages include curcumin being a natural antibacterial agent with wide availability and water solubility, and a simple and easy-to-operate finishing process. However, because curcumin is extracted and separated from plant roots and stems, the process is complex and the yield is low, resulting in a high market price. Additionally, its inherent color causes a decrease in the whiteness of the finished fabric. CN201711204772.7 First, wool fabric is immersed in an aqueous sodium hydroxide solution to undergo an alkalization reaction, and then treated with polyhexamethylene biguanide to give it antibacterial and anti-felting effects. CN201711204842.9 Uses quaternary ammonium salts as antibacterial finishing agents, followed by coating with alkoxylated lanolin to give wool fabrics antibacterial and stain-resistant functions. The antibacterial properties of quaternary ammonium salts depend on the attraction between their positive charge and the negative charge on the bacterial cell wall, allowing them to penetrate the cell membrane and kill bacteria. However, the killed bacteria adhere to the surface of the quaternary ammonium salt molecules, inhibiting further release of their bactericidal activity.

[0004] Therefore, there is an urgent need to improve and develop antibacterial and deodorizing finishing agents for wool fabrics, enhance their antibacterial properties, and reduce the damage to fabrics caused by antibacterial agents. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of the prior art and provide an antibacterial and deodorizing finishing agent for wool fabrics, its preparation method and application, which has excellent bactericidal effect and can reduce the damage of antibacterial agents to wool fabrics when finishing them.

[0006] In a first aspect, the structure of the antibacterial and deodorizing finishing agent for wool fabrics in this invention is as follows:

[0007]

[0008] Where m = 1~1000, n = 1~1000, q = 1~800; p = 1~600, q = 1~600, l,o = 1~400;

[0009] R1 is -COO(CH2) a -or-(CH2) b -, a, b are positive integers between 1 and 10;

[0010] R2 and R4 are independently -H, -CH3, or -CH2CH3;

[0011] R3 is -(CH2)3- or -(CH2)4-;

[0012] R5 is -(CH2) c - where c is a positive integer between 0 and 10;

[0013] R6 is -(CH2) d - where d is a positive integer between 1 and 10;

[0014] R7 is -(CH2)e-, where e is a positive integer between 1 and 10;

[0015] A is -COO - or -SO3 - .

[0016] The structure of the antibacterial and deodorizing finishing agent for wool fabrics in some preferred embodiments of the present invention is as follows:

[0017]

[0018] Preferably, m = 20–600, n = 20–600, l = 1–300;

[0019] The structure of the antibacterial and deodorizing finishing agent for wool fabrics in some other preferred embodiments of the present invention is as follows:

[0020]

[0021] Preferably, p = 10–500, q = 10–500, o = 1–200;

[0022] Secondly, the present invention also aims to provide a method for preparing the aforementioned antibacterial and deodorizing finishing agent for wool fabrics, the synthetic route being as follows:

[0023]

[0024] Among them, compound D is propanesulfonate lactone or butanesulfonate lactone;

[0025] Monomer E is allyl β-cyclodextrin glycidyl ether, with the following structure:

[0026] Monomer H is

[0027] The definitions of m, n, l, p, q, o, R1~R7, and A are as described above;

[0028] The synthesis steps include:

[0029] (a) Preparation of betaine monomers F or G

[0030] Compound B, containing a tertiary amine group and a double bond, or compound C, containing a pyridine group and a double bond, reacts with compound D to yield betaine monomers F or G.

[0031] (b) Preparation of antibacterial and deodorizing finishing agent

[0032] Betaine monomers F or G, E, and H are mixed in water and polymerized by an initiator to obtain the target compound, an antibacterial and deodorizing finishing agent.

[0033] In step a of some preferred embodiments of the method described in this invention, the reaction conditions of compound B or C with compound D are: under inert gas protection, at 40-70°C in chloroform, diethyl ether, tetrahydrofuran, acetone, ethanol, methanol, or a mixture of the above solvents.

[0034] Preferably, in step a, the molar ratio of compound B or C to compound D is 1.0:0.6-1.0:1.4, and more preferably 1.0:0.8-1.0:1.2.

[0035] In some preferred embodiments of the method described in this invention, step a specifically involves: adding compound B or C and reactant D to a solvent, mechanically stirring under nitrogen atmosphere at a temperature of 40-70°C for 4-8 hours, cooling to room temperature, filtering, washing, and drying to obtain betaine monomer F.

[0036] In step b of some preferred embodiments of the method described in this invention, the polymerization reaction conditions for the three monomers are: under inert gas protection, polymerization is initiated by an initiator in water at 30-80°C.

[0037] In step b, the molar ratio of betaine monomer F or G to monomer H is 80:20-20:80, and the addition ratio of monomer E is 1%-10% of the total molar ratio of monomers F or G and H. Preferably, the molar ratio of betaine monomer F or G to monomer H is 60:20-20:60, and the addition ratio of monomer E is 1%-5%.

[0038] Step b of some preferred embodiments of the method described in this invention is as follows: three monomers F or G, E and H are simultaneously added to deionized water, and 0.01%-2% of an initiator is added. The amount of initiator varies depending on the type of initiator selected. Preferably, it is 0.05%-1%. The reaction is carried out in a nitrogen atmosphere at a temperature of 30-80°C for 4-8 hours. The mixture is then cooled to room temperature, purified, dried, and impurities are removed to obtain the final antibacterial and deodorizing finishing agent.

[0039] In some preferred embodiments of the method described in this invention, monomer E is prepared by reacting β-cyclodextrin (β-CD) with allyl glycidyl ether, as shown in the following reaction formula:

[0040]

[0041] The preparation process is as follows: β-cyclodextrin is dissolved in sodium hydroxide solution, and then allyl glycidyl ether is slowly added dropwise at 10-15℃. After the reaction is complete, allyl β-cyclodextrin glycidyl ether, i.e. monomer E, is obtained by separation.

[0042] Further, the specific preparation steps for monomer E are as follows: Cyclodextrin is added to a sodium hydroxide solution with a mass concentration of 0.5-2%, preferably 1%, and the solution is stirred until clear. Allyl glycidyl ether is slowly added dropwise, and the reaction is carried out at a temperature of 10-15℃ for 5-8 hours. After neutralization, the mixture is filtered, washed to remove unreacted raw materials, and dried to obtain monomer E. The feeding ratio of cyclodextrin to allyl glycidyl ether is 1:5-3.

[0043] Thirdly, the present invention also aims to disclose the application of the antibacterial and deodorizing finishing agent for wool fabrics in the finishing of wool fabrics.

[0044] In practical applications, the antibacterial and deodorizing finishing agent can be diluted with water to form a finishing solution with a concentration of 5-90g / L.

[0045] Fragrance finishing agents can be added to finishing solutions to slowly release fragrance, increase the fragrance retention time of fabrics, mask odors, and bring pleasure to people.

[0046] The finishing steps for wool fabrics are as follows: the wool fabric can be soaked in a finishing solution containing an antibacterial and deodorizing finishing agent with a concentration of 5-90g / L at a certain bath ratio of 1:10-1:60 for 30 minutes; take it out and place it in an 80℃ oven to dry; take it out, wash it thoroughly with deionized water, and put it in an oven at 80℃ again to dry, thus obtaining the antibacterial and deodorizing wool fabric.

[0047] The beneficial effects of this invention are as follows:

[0048] 1. Using polymer betaine as an antibacterial agent, when microorganisms approach the large molecules of the antibacterial agent, due to the long molecular chain, they can easily penetrate the bacterial cell membrane, thereby causing the cell contents to flow out and achieving a bactericidal effect. Its antibacterial effect is better than that of small molecule betaine antibacterial agents.

[0049] 2. Introducing amide monomers into the betaine polymer chain can make the overall pH value of the macromolecules neutral to weakly acidic, which can reduce the damage of antibacterial agents to wool fabrics when finishing them.

[0050] 3. The sulfonic acid groups in the antibacterial agent can combine with wool fabrics by ionic bonds, making the finishing process simpler and easier to operate, and the low-temperature finishing causes less damage to the physical and mechanical properties of wool fabrics.

[0051] 4. By introducing cyclodextrin molecules using epoxy groups in polymers, their unique cavity structure can adsorb and encapsulate some odor molecules, which can remove the odor generated by wool fabrics during human wear. At the same time, the tensile strength of the grafted fabric is also improved; or, aromatic finishing agents that can form an encapsulation effect with cyclodextrin can be added.

[0052] 5. The polymerization process of the antibacterial agent occurs in water, reducing the use of organic solvents, making it green, environmentally friendly, and energy-saving. Detailed Implementation

[0053] To address the problems associated with antibacterial agents used on wool fabrics, this solution proposes a treatment using a combination of β-cyclodextrin and polysulfobetaine. Polysulfobetaine imparts antibacterial properties to the fabric, while β-cyclodextrin deodorizes and can also encapsulate deodorants or fragrances to mask unpleasant odors. Its advantages include: combining antibacterial and deodorizing functions; broad-spectrum antibacterial activity, exhibiting strong bactericidal activity against both Gram-positive and Gram-negative bacteria; resistance to bacterial adhesion and protein adsorption, thus promptly removing killed bacterial cells and restoring bactericidal activity; good water solubility, and the transparent aqueous solution simplifies post-treatment operations, resulting in minimal color difference between the treated and untreated fabrics; non-cytotoxic, environmentally friendly, skin-friendly, and does not induce antibiotic resistance in bacteria, thus minimizing environmental impact.

[0054] The present invention will be further described below with reference to specific embodiments. It should be understood that the following embodiments are for illustrative purposes only and are not intended to limit the scope of the invention.

[0055] Example 1

[0056] Antibacterial and deodorizing finishing agent I and its preparation and application

[0057] The structural formula of antibacterial and deodorizing finishing agent I is as follows:

[0058]

[0059] In this specific implementation, m = 20~200, n = 20~100, l = 1~50;

[0060] Preparation of Antibacterial and Deodorizing Finishing Agent I

[0061] 1.1.1 Preparation of cyclodextrin derivatives

[0062] First, a 1% sodium hydroxide solution (100 mL) was prepared. Then, 30 g of β-cyclodextrin was added and stirred until the solution was clear. 3.017 g of allyl glycidyl ether was slowly added dropwise. The reaction was carried out at 10 °C for 5 h. The mixture was then neutralized, filtered, washed to remove unreacted raw materials, and dried to obtain the cyclodextrin derivative.

[0063] 1.1.2 Preparation of betaine monomer

[0064] Weigh 7.121 g of N-methylallylamine into a four-necked flask, purge with nitrogen, and adjust the temperature to 50 °C. After 20 min, weigh 12.2 g of butanesulfonate lactone, dissolve it in 100 mL of tetrahydrofuran, place it in a separatory funnel, and slowly add it dropwise into the four-necked flask. The addition is completed within 30 min. Continue stirring, and after 5 h of reaction, remove the product, filter it, and extract it with ethanol to obtain betaine monomer.

[0065] 1.1.3 Preparation of Polymer Antibacterial and Deodorizing Finishing Agent I

[0066] 9.660 g of betaine monomer, 3.559 g of acrylamide, and 3.123 g of cyclodextrin derivative were weighed into 160 mL of deionized water. 1% ammonium persulfate was used as an initiator. The mixture was stirred until the solution was clear and placed in a four-necked flask. The reaction was carried out at 70 °C under nitrogen atmosphere for 6 h. After cooling to room temperature, acetone was used to precipitate the solution. The solution was washed with anhydrous ethanol and dried under vacuum to obtain antibacterial and deodorizing finishing agent I.

[0067] 1.2 Finishing wool fabrics

[0068] Soak the wool fabric in a finishing solution containing the above-mentioned antibacterial and deodorizing finishing agent I for 30 minutes at a certain bath ratio; take it out and dry it in an oven at 80℃; take it out, wash it thoroughly with deionized water, and put it in the oven again at 80℃ to dry it, thus obtaining the antibacterial and deodorizing wool fabric.

[0069] In a specific embodiment, the antibacterial and deodorizing finishing agent can be diluted with water to form a finishing solution with a concentration of 40 g / L. Benzyl alcohol and other substances can also be added to the finishing solution. Benzyl alcohol has a molecular size that matches β-cyclodextrin and contains hydroxyl groups, allowing it to form hydrogen bonds with cyclodextrin, resulting in good inclusion effects. This achieves slow release of fragrance, increases the fragrance retention time of fabrics, masks odors, and creates a pleasant and comfortable experience.

[0070] Example 2

[0071] Antibacterial and deodorizing finishing agent II and its preparation and application

[0072] The structural formula of antibacterial and deodorizing finishing agent II is as follows:

[0073]

[0074] In this specific implementation, p = 20~100, q = 20~200, o = 1~20;

[0075] 2.1 Preparation of Antibacterial and Deodorizing Finishing Agent II

[0076] 2.1.1 Preparation of cyclodextrin derivatives

[0077] Prepare a 1% sodium hydroxide solution (100 mL), then add 34.000 g of β-cyclodextrin and stir until the solution is clear. Slowly add 3.419 g of allyl glycidyl ether and react at 10 °C for 5 h. Neutralize, filter, wash to remove unreacted raw materials, and dry to obtain the cyclodextrin derivative.

[0078] 2.1.2 Preparation of betaine monomer

[0079] Under light-protected conditions, 5.257 g of vinylpyridine was weighed into a four-necked flask, nitrogen gas was introduced, and the temperature was adjusted to 60 °C. After 20 min, 6.15 g of propanesulfonate lactone was weighed, dissolved in 100 mL of acetone, placed in a separatory funnel, and slowly added dropwise to the four-necked flask. The addition was completed within 30 min, and stirring was continued. After reacting for 5 h, the product was taken out, filtered, and extracted with ethanol to obtain betaine monomer.

[0080] 2.1.3 Preparation of Polymer Antibacterial and Deodorizing Finishing Agent II

[0081] 6.844 g of betaine monomer, 2.132 g of acrylamide, and 1.874 g of cyclodextrin derivative were weighed into 120 mL of deionized water. The initiator was 0.1% of a 1:4 mixture of potassium persulfate and sodium bisulfite. The mixture was stirred until the solution was clear and placed in a four-necked flask. The reaction was carried out at 30 °C under nitrogen for 6 h. After cooling to room temperature, the solution was precipitated with acetone, washed with anhydrous ethanol, and dried under vacuum to obtain antibacterial and deodorizing finishing agent II.

[0082] 2.2 Finishing wool fabrics

[0083] Soak the wool fabric in a finishing solution containing the above-mentioned antibacterial and deodorizing finishing agent II for 30 minutes at a certain bath ratio; take it out and dry it in an oven at 80℃; take it out, wash it thoroughly with deionized water, and put it in the oven again at 80℃ to dry it, thus obtaining the antibacterial and deodorizing wool fabric.

[0084] In a specific embodiment, the antibacterial and deodorizing finishing agent can be diluted with water to form a finishing solution with a concentration of 60 g / L. Without the addition of a fragrance finishing agent, cyclodextrin can encapsulate odor molecules in the air, such as ammonia, acetic acid, formaldehyde, and hydrogen sulfide, effectively reducing unpleasant odors.

[0085] The antibacterial and deodorizing finishing agents in Examples 1 and 2 have the following effects:

[0086] 1. Excellent antibacterial and deodorizing effects, with an inhibition rate of over 99% against Staphylococcus aureus and Escherichia coli, and a deodorizing efficiency of over 90% against ammonia, acetic acid, hydrogen sulfide, etc.

[0087] 2. While ensuring excellent antibacterial and deodorizing effects and washability, it also reduces the damage of antibacterial and deodorizing agents to fabrics, including mechanical properties and color.

[0088] 3. Aromatic finishing agents that can be added to form inclusion complexes with cyclodextrin.

[0089] Compare with Example 1

[0090] Antibacterial and deodorizing finishing agent III and its preparation and application

[0091] Referring to Example 1, without adding cyclodextrin derivatives in step 1.1.3, antibacterial and deodorizing finishing agent III was prepared. It was then used to treat wool fabrics according to step 1.2. The relevant parameters of the treated fabrics are shown in Table 1.

[0092] Compare with Example 2

[0093] Antibacterial and deodorizing finishing agent IV and its preparation and application

[0094] Referring to Example 2, without adding acrylamide in step 2.1.3, antibacterial and deodorizing finishing agent IV was prepared. This agent was then used to treat wool fabrics according to step 2.2. The relevant parameters of the treated fabrics are shown in Table 1.

[0095]

[0096] The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the embodiments. Those skilled in the art can make various equivalent modifications or substitutions without departing from the innovation of the present invention, and these equivalent modifications or substitutions are all included within the scope defined by the claims of this application.

Claims

1. An antibacterial and deodorant finishing agent for wool fabrics, characterized by, The antibacterial deodorizing finishing agent comprises a component with the following structural formula: or wherein m=1-1000, n=1-1000, q=1-800; p=1-600, l=1-50, o=1-400; R1is -COO (CH2) a - or -(CH2) b - a, b are each positive integers between 1 and 10; R2, R4 are independently -H, -CH3 or -CH2CH3; R3 is -(CH2)3- or -(CH2)4-; R5is -(CH2) c - and c is an integer from 0 to 10; R6is -(CH2) d - and d is a positive integer from 1 to 10. R7is -(CH2) e - and e is a positive integer from 1 to 10. A is -COO - or -SO3 - .

2. The antimicrobial and deodorant finishing agent for wool fabrics according to claim 1, characterized by, The antibacterial deodorizing finishing agent has the following structural formula: 。 3. The antimicrobial and deodorant finishing agent for wool fabrics according to claim 1, characterized by, The antibacterial deodorizing finishing agent has the following structural formula: 。 4. A process for preparing the antibacterial deodorizing finish according to claim 1, characterized by, The preparation method is as follows: or wherein: Compound D is propylsulfonic acid lactone or butylsulfonic acid lactone; Monomer E is allyl glycidyl ether-β-cyclodextrin, with the structure ; Monomer H is ; The specific synthesis steps include: (a) Preparation of betaine monomer F or G Compound B containing a tertiary amine group and a double bond or compound C containing a pyridine group and a double bond is reacted with compound D to obtain betaine monomer F or G; (b) Preparation of the antibacterial deodorizing finishing agent Betaine monomer F or G, monomer E and monomer H are mixed in water, and polymerization is initiated by an initiator to obtain the target compound antibacterial deodorizing finishing agent.

5. The method for preparing an antibacterial deodorizing finish according to claim 4, wherein the acid is sulfuric acid. In step (a), the reaction conditions of compound B or C and compound D are as follows: inert gas protection, reaction at 40-70°C in one or more mixed solvents of chloroform, diethyl ether, tetrahydrofuran, acetone, ethanol, methanol; The molar ratio of compound B or C to compound D is 1.0:0.6-1.0:1.

4.

6. The method for preparing an antibacterial deodorizing finish according to claim 4, wherein the acid is sulfuric acid. In step (b), the initiator is selected from one of peroxides, azo compounds and redox systems. The peroxides are selected from one of ammonium persulfate, potassium persulfate and hydrogen peroxide; The azo compound is azobisisobutyronitrile; The oxidizing agent in the redox system is selected from one of persulfate and hydrogen peroxide, and the reducing agent is selected from one of sulfite, hydroxylamine, mercapto compound and urea.

7. The method of preparing an anti-bacterial deodorizing finish according to claim 4, wherein the water-soluble or water-dispersible polymer is a water-soluble or water-dispersible polyurethane resin. In step (b), the polymerization reaction conditions of the three monomers are as follows: inert gas protection, polymerization initiated by an initiator at 20-90°C in water.

8. The method for preparing an antibacterial deodorizing finish according to claim 4, wherein the acid is sulfuric acid. In step (b), the molar ratio of betaine monomer F or G to monomer H is 80:20-20:80, and the addition ratio of monomer E is 1%-10% of the total moles of monomer F or G and monomer H.

9. The method for preparing the antibacterial and deodorizing finishing agent as described in claim 4, characterized in that, Monomer E is prepared by reacting β-cyclodextrin and allyl glycidyl ether, and the reaction formula is as follows: The specific preparation process is as follows: β-cyclodextrin is dissolved in sodium hydroxide solution, then allyl glycidyl ether is slowly added dropwise at 10-15°C, and after the reaction is completed, allyl β-cyclodextrin glycidyl ether, i.e. monomer E, is separated.

10. Use of the antibacterial deodorizing finishing agent according to claim 1 in the finishing of wool fabric.

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