Novel method for preparing long-acting antibacterial fiber product based on silane coupling agent in-situ quaternization

Abstract

The invention discloses a novel method for preparing a long-acting antibacterial fiber product based on silane coupling agent in-situ quaternization, which comprises the following steps: coupling and grafting amino silane to the surface of cellulose-based fiber or a product thereof, and further introducing halogenated long-chain alkane to realize quaternization of amino; therefore, a chemically bonded cationic molecular brush structure is formed on the surface of the fiber. The performance limitation of a single antibacterial mechanism is made up by constructing a quaternized cation and alkyl chain synergistic double-effect antibacterial mechanism, and the prepared grafted antibacterial cellulose-based fiber or a product thereof has the characteristics of efficient antibacterial property and long-acting stability. The method is simple in process, mild in condition, suitable for cellulose-based fibers such as cotton and hemp and products thereof, capable of achieving the long-acting antibacterial function and good in application prospect in the fields of medical spinning, daily protection and the like.

Description

Technical Field

[0001] This invention relates to a novel method for preparing long-lasting antibacterial fiber products based on in-situ quaternization of silane coupling agents, belonging to the field of antibacterial materials technology. Background Technology

[0002] With increasing environmental awareness and health consciousness, the demand for functional fiber products is growing. In daily use, most fabrics come into direct contact with the human body. Since ordinary fibers and fiber products lack the ability to clean microorganisms and their metabolic products, sweat, sebum, and other secretions from the skin, as well as oxygen, moisture, and heat emitted by the body, provide an ideal environment for bacteria and fungi, easily leading to microbial contamination of fiber products. Microbial contamination of fiber products not only damages their performance but also poses a significant threat to personal and public health. Therefore, improving the antibacterial properties of fiber products is receiving increasing attention and has become an important development direction for functional fiber products.

[0003] Common methods for antibacterial modification of fabrics include surface coating, physical blending, and grafting modification. Surface coating, however, has a limited storage capacity for antibacterial agents, leading to a risk of coating peeling and thus a time-limited antibacterial effect. Furthermore, common nano-antibacterial agents may pose cytotoxicity and other safety risks. Physical blending, on the other hand, results in poor compatibility and low dispersibility of the added antibacterial agents, making it difficult to distribute them evenly within the matrix. This leads to low surface antibacterial agent content and unstable antibacterial performance. Additionally, the antibacterial components may decompose and be destroyed during polymer processing.

[0004] Surface grafting modification is an effective strategy for imparting long-lasting antibacterial properties to fabrics. By chemically fixing antibacterial components onto the surface of the matrix material, it offers advantages such as improved antibacterial longevity and safety in cotton fabrics. Existing technologies often employ a route of first synthesizing the antibacterial agent and then performing surface grafting. For example, patent CN119842070A polymerizes polycationic guanidine salts with benzene ring-containing compounds to obtain polycationic... π-antibacterial agents are first synthesized and then applied to one side of the fabric surface. Patent CN113818249A synthesizes a reactive cationic antibacterial monomer using chitosan and methacryloyloxyethyltrimethylammonium chloride, and then applies it to the fabric using a pad-bake finishing method. Alternatively, patent CN119507213A prepares a novel polymer-based antibacterial agent using propylene oxide-modified polyhexamethylene guanidine hydrochloride, mixes it with an organic acid deodorizer, and then grafts it onto the fabric surface. However, these existing technologies, which first synthesize the antibacterial agent and then graft it onto the fabric surface, suffer from complex and time-consuming procedures.

[0005] To address the aforementioned problems, this invention employs an aminosilane grafting followed by in-situ quaternization to form a chemically bonded cationic molecular brush structure on the surface of cellulose-based fibers or their products. This modification process differs from the traditional, complex process of first synthesizing a specific antibacterial agent and then grafting it onto fabrics through multiple steps, significantly simplifying the modification process and improving efficiency. Furthermore, the modification conditions are mild, preserving the inherent properties of the cellulose-based fibers or their products. Moreover, the synergistic dual-effect antibacterial mechanism of the quaternized cations and alkyl chains effectively solves problems such as poor broad-spectrum antibacterial activity and poor antibacterial durability. Summary of the Invention

[0006] This invention addresses the problems of cumbersome processes, harsh reaction conditions, poor broad-spectrum antibacterial activity, and insufficient long-lasting effects in existing fabric antibacterial modification technologies. It proposes a novel method for preparing long-lasting antibacterial fiber products based on in-situ quaternization with silane coupling agents. This method forms a chemically bonded cationic molecular brush structure on the fiber surface, creating a dual-effect antibacterial mechanism through the synergistic effect of quaternized cations and alkyl chains. While maintaining a simple process and mild reaction, it achieves a significant improvement in broad-spectrum and long-lasting antibacterial performance.

[0007] To achieve the above objectives, the present invention provides a novel method for preparing long-lasting antibacterial fiber products based on in-situ quaternization of silane coupling agents, comprising the following steps: S1: Preprocessing The initial cellulose-based fibers or products are washed in deionized water for 10-30 minutes and then dried at 50-80℃ to obtain pretreated cellulose-based fibers or products. S2: Grafted aminosilane coupling agent S21: Dissolve the aminosilane coupling agent in an aqueous ethanol solution and stir to obtain a silane coupling solution; S22: The pretreated cellulose-based fibers or products obtained in step S1 are added to the above silane coupling solution for soaking, and then heated to react, to obtain the reacted fabric A; S23: After the above reaction, the fabric A is washed and dried to obtain cellulose-based fibers or products grafted with aminosilane coupling agent. S3: Quaternization treatment S31: Mix anhydrous ethanol and haloalkanes, stir, and obtain an alkane solution; S32: Add the cellulose-based fiber or product with grafted aminosilane coupling agent obtained in step S2 to the above alkane solution for soaking, and then heat to react to obtain the reaction fabric B. S33: After the above reaction, the fabric B is washed and dried to obtain grafted antibacterial cellulose-based fiber or product.

[0008] Using the above technical solution, this invention relates to a method for modifying fiber products with broad-spectrum antibacterial activity. This method is used to prepare antibacterial fiber products. First, the target fiber product is pretreated. Then, aminosilanes are coupled and grafted onto the fiber product. Further, long-chain alkanes are grafted onto the quaternary ammonium structure to form a cationic polymer brush structure. The resulting modified fabric surface structure possesses both cationic antibacterial sites and physical antibacterial and antifouling structures.

[0009] Preferably, the product is cotton fiber or a fiber product containing cellulose or hemicellulose chemical components.

[0010] Preferably, in step S21, the mass ratio of the aminosilane coupling agent to the aqueous ethanol solution is 1:7-10.

[0011] Preferably, the ethanol-water solution in step S21 is prepared by mixing anhydrous ethanol and deionized water at a volume ratio of 5-20:1.

[0012] Preferably, the aminosilane coupling agent in step S21 is one or both of N,N-dimethyl-3-aminopropyltrimethoxysilane and N,N-diethyl-3-aminopropyltrimethoxysilane.

[0013] Preferably, in step S22, the mass ratio of the pretreated cellulose-based fiber or product to the silane coupling solution is 1-10:90, the soaking time in step S22 is 30-120 min, and the heating reaction conditions are: 80-140℃ for 15-45 min.

[0014] Preferably, the mass ratio of anhydrous ethanol to haloalkanes in step S31 is 7-10:1.

[0015] Preferably, the haloalkane in step S31 is one or more of chlorobutane, chlorooctane, chlorododecane, and chlorohexadecane.

[0016] Preferably, the soaking time in step S32 is 1-3 hours, and the heating reaction conditions are: 80-140℃ for 15-60 minutes.

[0017] By adopting the above technical solution, the present invention can also use an air compressor to spray functional substances onto the surface of cotton fabrics, and its antibacterial effect is the same as that after soaking treatment, which is more conducive to large-scale production.

[0018] Preferably, the cleaning conditions in steps S23 and S33 are: alternating cleaning with anhydrous ethanol and deionized water 3-5 times, and drying temperature of 50-80℃.

[0019] Using the above technical solution, this invention introduces amino groups structurally through aminosilane coupling, and further achieves quaternization of the amino structure by grafting haloalkyl chains. The synergistic dual antibacterial effect of the quaternized cation and the alkyl chain compensates for the shortcomings of single antibacterial mechanisms. The alkyl chain structure and the silane molecule are linked by chemical bonds, effectively avoiding the problems of uneven distribution and loss of active components caused by physical recombination.

[0020] The beneficial effects of this invention are: (1) The fiber product modification method with long-lasting antibacterial activity proposed in this invention is simple to operate, short in time, mild in conditions, green and pollution-free in reaction process, which is conducive to large-scale production.

[0021] (2) The present invention can regulate the surface antibacterial structure and performance by adjusting the ratio of fiber products and grafting solution, solution reaction temperature and time.

[0022] (3) The fiber product modification method with broad-spectrum antibacterial activity proposed in this invention can effectively improve the antibacterial effect against Gram-positive bacteria such as Staphylococcus aureus compared with single quaternization grafting antibacterial.

[0023] (4) The fiber product modification method with broad-spectrum activity proposed in this invention can use an air compressor to spray functional substances onto the surface of cotton fabrics. The antibacterial effect remains basically the same as that of soaking, but it is more conducive to large-scale production. Attached Figure Description

[0024] Figure 1 The technical solution diagram of the present invention.

[0025] Figure 2 The process flow diagram of this invention.

[0026] Figure 3 Infrared spectra of embodiments 1-5 of the present invention.

[0027] Figure 4 Antibacterial effect diagrams of Examples 1-5 of the present invention.

[0028] Figure 5 The antibacterial effect diagram of Comparative Example 1 of the present invention.

[0029] Figure 6 The antibacterial effect diagram of Comparative Example 2 of the present invention. Detailed Implementation

[0030] To make the technical means, creative features, objectives and effects of this invention easier to understand, the invention will be further described below in conjunction with specific embodiments.

[0031] Example 1 A novel method for preparing long-lasting antibacterial fiber products based on in-situ quaternization of silane coupling agents includes the following steps: S1: Place the initial fabric sample in deionized water and sonicate for 10 minutes to remove surface contaminants. Dry the pretreated fabric at 70°C to obtain pretreated cellulose-based fibers.

[0032] S2: Dissolve 10g of N,N-dimethyl-3-aminopropyltrimethoxysilane in 80g of an aqueous ethanol solution and stir for 10min to obtain a silane coupling solution; add 4g of pretreated cellulose-based fibers to the above silane coupling solution, soak at room temperature for 30min, and then react at 120℃ for 30min. Wash the reacted fabric three times alternately with anhydrous ethanol and deionized water; dry at 70℃ for 1h to obtain cellulose-based fibers with N,N-dimethyl-3-aminopropyltrimethoxysilane coupling agent.

[0033] S3: Mix 80g of anhydrous ethanol and 10g of chlorobutane, and stir for 10min to obtain an alkane grafting solution. Add 4g of cellulose-based fibers grafted with N,N-dimethyl-3-aminopropyltrimethoxysilane coupling agent to the alkane grafting solution, soak at room temperature for 1h, and then react at 120℃ for 15min. Wash the reacted fabric three times alternately with anhydrous ethanol and deionized water, and dry at 70℃ for 30min to obtain grafted antibacterial cellulose-based fibers.

[0034] In this embodiment, the ethanol-water solution in step S2 is prepared by mixing anhydrous ethanol and deionized water at a volume ratio of 5:1.

[0035] Example 2 A novel method for preparing long-lasting antibacterial fiber products based on in-situ quaternization of silane coupling agents includes the following steps: S1: Place the initial fabric sample in deionized water and sonicate for 15 minutes to remove surface contaminants. Dry the pretreated fabric at 80°C to obtain pretreated cellulose-based fibers.

[0036] S2: Dissolve 10g of N,N-dimethyl-3-aminopropyltrimethoxysilane in 80g of aqueous ethanol solution and stir for 10min to obtain a silane coupling solution; add 5g of pretreated cellulose-based fibers to the above silane coupling solution, soak at room temperature for 60min, and then react at 140℃ for 15min; wash the reacted fabric alternately with anhydrous ethanol and deionized water 5 times, and dry at 70℃ for 1h to obtain cellulose-based fibers grafted with N,N-dimethyl-3-aminopropyltrimethoxysilane coupling agent.

[0037] S3: Mix 80g of anhydrous ethanol and 10g of chlorooctane and stir for 10min to obtain an alkane grafting solution; add 5g of cellulose-based fibers grafted with N,N-dimethyl-3-aminopropyltrimethoxysilane coupling agent to the alkane grafting solution, soak at room temperature for 2h, and then react at 140℃ for 45min; wash the reacted fabric alternately with anhydrous ethanol and deionized water 5 times, and dry at 70℃ for 30min to obtain grafted antibacterial cellulose-based fibers.

[0038] In this embodiment, the ethanol-water solution in step S2 is prepared by mixing anhydrous ethanol and deionized water at a volume ratio of 10:1.

[0039] Example 3 A novel method for preparing long-lasting antibacterial fiber products based on in-situ quaternization of silane coupling agents includes the following steps: S1: Place the initial fabric sample in deionized water and sonicate for 30 minutes to remove surface contaminants. Dry the pretreated fabric at 50°C to obtain pretreated cellulose-based fibers.

[0040] S2: Dissolve 10g of N,N-dimethyl-3-aminopropyltrimethoxysilane in 80g of aqueous ethanol solution and stir for 10min to obtain a silane coupling solution; add 7g of pretreated cellulose-based fibers to the above silane coupling solution, soak at room temperature for 30min, and then react at 105℃ for 45min; wash the reacted fabric three times alternately with anhydrous ethanol and deionized water, and dry at 70℃ for 1h to obtain cellulose-based fibers grafted with N,N-dimethyl-3-aminopropyltrimethoxysilane coupling agent.

[0041] S3: Mix 80g of anhydrous ethanol and 10g of chlorododecane and stir for 10min to obtain an alkane grafting solution; add 7g of cellulose-based fibers grafted with N,N-dimethyl-3-aminopropyltrimethoxysilane coupling agent to the alkane grafting solution, soak at room temperature for 1h, and then react at 105℃ for 60min; wash the reacted fabric three times alternately with anhydrous ethanol and deionized water, and dry at 70℃ for 30min to obtain grafted antibacterial cellulose-based fibers.

[0042] In this embodiment, the ethanol-water solution in step S2 is prepared by mixing anhydrous ethanol and deionized water at a volume ratio of 15:1.

[0043] Example 4 A novel method for preparing long-lasting antibacterial fiber products based on in-situ quaternization of silane coupling agents includes the following steps: S1: Place the initial fabric sample in deionized water and sonicate for 10 minutes to remove surface contaminants. Dry the pretreated fabric at 70°C to obtain pretreated cellulose-based fibers.

[0044] S2: Dissolve 10g of N,N-dimethyl-3-aminopropyltrimethoxysilane in 80g of aqueous ethanol solution and stir for 10min to obtain a silane coupling solution; add 3g of pretreated cellulose-based fibers to the above silane coupling solution, soak at room temperature for 100min, and then react at 120℃ for 40min; wash the reacted fabric three times alternately with anhydrous ethanol and deionized water, and dry at 70℃ for 1h to obtain cellulose-based fibers grafted with N,N-dimethyl-3-aminopropyltrimethoxysilane coupling agent.

[0045] S3: Mix 80g of anhydrous ethanol and 10g of hexadecyl chloride and stir for 10min to obtain an alkane grafting solution; add 3g of cellulose-based fibers grafted with N,N-dimethyl-3-aminopropyltrimethoxysilane coupling agent to the alkane grafting solution, soak at room temperature for 2h, and then react at 120℃ for 40min; wash the reacted fabric three times alternately with anhydrous ethanol and deionized water, and dry at 70℃ for 30min to obtain grafted antibacterial cellulose-based fibers.

[0046] In this embodiment, the ethanol-water solution in step S2 is prepared by mixing anhydrous ethanol and deionized water at a volume ratio of 20:1.

[0047] Example 5 A novel method for preparing long-lasting antibacterial fiber products based on in-situ quaternization of silane coupling agents includes the following steps: S1: Place the initial fabric sample in deionized water and sonicate for 20 minutes to remove surface contaminants. Dry the pretreated fabric at 70°C to obtain pretreated cellulose-based fibers.

[0048] S2: Dissolve 10g of N,N-diethyl-3-aminopropyltrimethoxysilane in 80g of aqueous ethanol solution and stir for 10min to obtain a silane coupling solution; add 5g of pretreated cellulose-based fibers to the above silane coupling solution, soak at room temperature for 80min, and then react at 130℃ for 45min; wash the reacted fabric three times alternately with anhydrous ethanol and deionized water, and dry at 70℃ for 1h to obtain cellulose-based fibers grafted with N,N-diethyl-3-aminopropyltrimethoxysilane coupling agent.

[0049] S3: Mix 80g of anhydrous ethanol and 10g of hexadecyl chloride and stir for 10min to obtain an alkane grafting solution; add 5g of cellulose-based fibers grafted with N,N-diethyl-3-aminopropyltrimethoxysilane coupling agent to the alkane grafting solution, soak at room temperature for 3h, and then react at 130℃ for 60min; wash the reacted fabric three times alternately with anhydrous ethanol and deionized water, and dry at 70℃ for 30min to obtain grafted antibacterial cellulose-based fibers.

[0050] Comparative Example 1 A control group was prepared by grafting only N,N-dimethyl-3-aminopropyltrimethoxysilane.

[0051] S1-S2: Same as Example 4.

[0052] Comparative Example 2 A control group was prepared by grafting only N,N-diethyl-3-aminopropyltrimethoxysilane.

[0053] S1-S2: Same as Example 5.

[0054] The summary table of the antibacterial properties of each group against Escherichia coli and Staphylococcus aureus is shown in Table 1.

[0055] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from its spirit or basic characteristics. Therefore, the embodiments should be considered exemplary and non-limiting in all respects, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, it is intended that all variations falling within the meaning and scope of equivalents of the claims be included within the present invention.

[0056] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A novel method for preparing long-lasting antibacterial fiber products based on in-situ quaternization of silane coupling agents, characterized in that, Includes the following steps: S1: Preprocessing The initial cellulose-based fibers or products are pretreated to obtain pretreated cellulose-based fibers or products. S2: Grafted aminosilane coupling agent S21: Dissolve the aminosilane coupling agent in an aqueous ethanol solution and stir to obtain a silane coupling solution; the aminosilane coupling agent is one or two of N,N-dimethyl-3-aminopropyltrimethoxysilane and N,N-diethyl-3-aminopropyltrimethoxysilane. S22: The pretreated cellulose-based fibers or products obtained in step S1 are added to the above silane coupling solution for soaking, and then heated to react, to obtain the reacted fabric A; S23: After the above reaction, the fabric A is washed and dried to obtain cellulose-based fibers or products grafted with aminosilane coupling agent. S3: Quaternization treatment S31: Mix anhydrous ethanol and haloalkanes, stir, and obtain an alkane solution; S32: Add the cellulose-based fiber or product with grafted aminosilane coupling agent obtained in step S2 to the above alkane solution for soaking, and then heat to react to obtain the reaction fabric B. S33: After the above reaction, the fabric B is washed and dried to obtain grafted antibacterial cellulose-based fiber or product.

2. The novel method for preparing long-lasting antibacterial fiber products based on in-situ quaternization of silane coupling agents as described in claim 1, characterized in that, In step S21, the mass ratio of aminosilane coupling agent to ethanol aqueous solution is 1:7-10.

3. A novel method for preparing long-lasting antibacterial fiber products based on in-situ quaternization of silane coupling agents as described in claim 2, characterized in that, The ethanol-water solution in step S21 is prepared by mixing anhydrous ethanol and deionized water at a volume ratio of 5-20:

1.

4. A novel method for preparing long-lasting antibacterial fiber products based on in-situ quaternization of silane coupling agents as described in claim 1, characterized in that, In step S22, the mass ratio of the pretreated cellulose-based fiber or product to the silane coupling solution is 1-10:90, the soaking time in step S22 is 30-120 min, and the heating reaction conditions are 80-140℃ for 15-45 min.

5. A novel method for preparing long-lasting antibacterial fiber products based on in-situ quaternization of silane coupling agents as described in claim 1, characterized in that, In step S31, the mass ratio of anhydrous ethanol to haloalkanes is 7-10:

1.

6. A novel method for preparing long-lasting antibacterial fiber products based on in-situ quaternization of silane coupling agents as described in claim 5, characterized in that, The haloalkane in step S31 is one or more of chlorobutane, chlorooctane, chlorododecane, and chlorohexadecane.

7. A novel method for preparing long-lasting antibacterial fiber products based on in-situ quaternization of silane coupling agents as described in claim 1, characterized in that, In step S32, the mass ratio of the cellulose-based fiber or product grafted with aminosilane coupling agent to the alkane solution is 1-10:90, the soaking time in step S32 is 1-3 hours, and the heating reaction conditions are 80-140℃ for 15-60 minutes.

8. A novel method for preparing long-lasting antibacterial fiber products based on in-situ quaternization of silane coupling agents as described in claim 1, characterized in that, The cleaning conditions in steps S23 and S33 are as follows: alternating cleaning with anhydrous ethanol and deionized water 3-5 times, and drying temperature of 50-80℃.

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