Antibacterial finishing agent for bio-based fiber material and preparation method of antibacterial finishing agent

Abstract

The invention relates to the technical field of antibacterial finishing agents, and discloses an antibacterial finishing agent for a bio-based fiber material and a preparation method thereof.The antibacterial finishing agent is prepared from hydrogen-containing silicone oil, an alkenyl protocatechuate type photocatalyst antibacterial agent, an emulsifier, a co-emulsifier, a Karstedt catalyst and water, the preparation method of the antibacterial finishing agent comprises the following steps: adding the hydrogen-containing silicone oil, the emulsifier and the co-emulsifier into water, emulsifying by a homogenizing dispersion machine, introducing nitrogen, adding the alkenyl protocatechuate type photocatalyst antibacterial agent and the Karstedt catalyst, stirring and heating to 80-95 DEG C, carrying out heat preservation reaction for 4-6 hours, and cooling to room temperature to obtain the antibacterial finishing agent. The prepared antibacterial finishing agent is excellent in antibacterial performance, can still keep the antibacterial rate larger than or equal to 80% after being washed for 50 times at home, and has a long-acting antibacterial effect.

Description

Technical Field

[0001] This invention relates to the field of antibacterial finishing agents, and in particular to an antibacterial finishing agent for bio-based fiber materials and its preparation method. Background Technology

[0002] Bio-based fibers are fibers made from biological raw materials or polymers containing biomass monomers, including bio-based polyester, spandex, polylactic acid fiber, seaweed fiber, and chitosan fiber. They are important raw materials for textiles. Textiles, as materials we come into closest contact with in daily life, do not inherently inhibit microbial growth. However, due to their loose, porous structure, they readily absorb various impurities such as gases, liquids, and solids from the environment, providing favorable conditions for microbial growth and reproduction. Therefore, various fiber textiles have become excellent carriers for microbial survival and reproduction. To ensure human comfort and prevent bacteria and other microorganisms from harming human health, the development of antibacterial textiles is one of the main directions of textile development.

[0003] Current antibacterial textiles are mainly divided into three categories: (i) Using natural fibers with antibacterial effects as raw materials, antibacterial textiles are directly woven. (ii) Mixing antibacterial raw materials with spinning raw materials, then preparing antibacterial fibers through melt spinning, and then preparing textiles with antibacterial properties through weaving. This method is called spinning method. (iii) In the finishing process, antibacterial agents are used to finish textiles to obtain antibacterial textiles. This method is called finishing method. Since the antibacterial components of this method are mainly distributed on the surface of the fabric, the durability of the textiles is slightly worse than that of the spinning method.

[0004] Among them, the finishing method involves treating the antibacterial agent on the surface of the fabric by impregnation, padding or coating, and then using high-temperature baking or other means to fix the antibacterial agent on the surface of the fabric. The preparation of antibacterial textiles using this method is simple to operate, the process is relatively mature, the equipment requirements are relatively low, and the antibacterial effect is excellent. However, for bio-based fibers that lack reactive groups on the surface, such as bio-based polyester, the antibacterial durability is poor because the finishing agent does not have a strong bond with the fiber. Summary of the Invention

[0005] This invention proposes an antibacterial finishing agent for bio-based fiber materials, which has long-lasting and excellent antibacterial properties, thereby solving the problem of insufficient antibacterial properties in bio-based fiber materials.

[0006] To achieve the above objectives, the present invention adopts the following technical solution: An antibacterial finishing agent for bio-based fiber materials, comprising the following raw materials in parts by weight: 80-100 parts of hydrogen-containing silicone oil; 3-5 parts of alkenylated protocatechuic acid ester type photocatalytic antibacterial agent; 8-10 parts emulsifier; 30-40 parts of co-emulsifier; 0.001-0.002 parts of Karstedt catalyst; 200-300 parts water; Among them, the alkenylated protocatechuic acid ester type photocatalytic antibacterial agent is prepared by modifying nano zinc oxide with hydroxyl functional groups on its surface using a monoallyl diprotocatechuic acid ester silane coupling agent.

[0007] Furthermore, the preparation method of the monoallyl diprotocatechuate silane coupling agent is as follows: One molar equivalent of allyl pentaerythritol first undergoes a nucleophilic substitution reaction with one molar equivalent of 3-halopropyltrimethoxysilane in the presence of sodium hydroxide, and then undergoes an esterification reaction with two molar equivalents of protocatechuic acid in the presence of p-toluenesulfonic acid to obtain a monoallyl diprotocatechuic acid silane coupling agent.

[0008] Furthermore, the 3-halopropyltrimethoxysilane is 3-chloropropyltrimethoxysilane or 3-bromopropyltrimethoxysilane.

[0009] Furthermore, the emulsifier is emulsifier ER-20 or emulsifier AEO-7.

[0010] Furthermore, the co-emulsifier is glycerol or n-butanol.

[0011] A method for preparing an antibacterial finishing agent for bio-based fiber materials is as follows: Hydrogen-containing silicone oil, emulsifier, and co-emulsifier are added to water and emulsified in a homogenizer at a speed of 8000-12000 rpm for 20-40 minutes. Nitrogen gas is then introduced, followed by the addition of an alkenylated protocatechuic acid ester type photocatalytic antibacterial agent and Karstedt catalyst. The mixture is stirred and heated to 80-95℃, and the reaction is maintained at this temperature for 4-6 hours. After cooling to room temperature, the antibacterial finishing agent is obtained.

[0012] The beneficial effects of this invention are as follows: Using hydrogen-containing silicone oil, emulsifier, co-emulsifier, water, and an alkenylated protocatechuic ester-type photocatalytic antibacterial agent as raw materials, an antibacterial finishing agent is prepared based on the hydrosilylation reaction mechanism under the action of a Karstedt catalyst, where the alkenylated protocatechuic ester-type photocatalytic antibacterial agent reacts with the hydrogen-containing silicone oil. Utilizing the catechol groups with good adhesion properties, the antibacterial finishing agent forms a strong bond with the fabric carrier surface. After the equivalent of 50 household washes, it still maintains an antibacterial rate of ≥80%, exhibiting long-lasting and excellent antibacterial performance. Detailed Implementation

[0013] Experimental Example 1: I. Preparation of alkenylated protocatechuic acid ester type photocatalytic antibacterial agent, the specific method is as follows: One molar equivalent of allyl pentaerythritol first undergoes a nucleophilic substitution reaction with one molar equivalent of 3-chloropropyltrimethoxysilane in the presence of sodium hydroxide, and then undergoes an esterification reaction with two molar equivalents of protocatechuic acid in the presence of p-toluenesulfonic acid to obtain a monoallyl diprotocatechuic acid silane coupling agent. Alkenylated protocatechuate-based photocatalytic antibacterial agents were obtained by modifying nano-zinc oxide with hydroxyl functional groups on its surface using monoallyl diprotocatechuate silane coupling agent.

[0014] II. Preparation of alkenylated protocatechuic acid ester type photocatalytic antibacterial agent, specifically including the following steps: Step 1: Add 1.8 mL of allyl pentaerythritol and 0.5 g of sodium hydroxide to 50 mL of anhydrous dimethyl sulfoxide. After stirring and mixing evenly, purge with nitrogen for 15 min, then heat to 50 °C with stirring. Slowly add 1.8 mL of 3-chloropropyltrimethoxysilane and continue stirring. React at 65 °C for 8 h. Cool to room temperature, add 3.1 g of protocatechuic acid and 10 mL of toluene, mix evenly, then add 0.5 g of p-toluenesulfonic acid. Heat to 110 °C and react for 6 h. Cool to room temperature, filter, cool the filtrate, crystallize, filter under vacuum, and recrystallize with petroleum ether to obtain monoallyl diprotocatechuic acid silane coupling agent. The chemical structural formula of the monoallyl diprotocatechuate silane coupling agent is: ; The 1H NMR characterization results of the monoallyl diprotocatechuate silane coupling agent are as follows: 1 H NMR (400MHz, DMSO-D6, δ, ppm): 0.77-0.81 (t, 2H), 1.66-1.72 (m, 2H), 3.39-3.41 (t, 2H), 3.57-3.58 (d, 13H), 4.00-4.01 (d, 2H), 4.2 8-4.33(m, 4H), 5.16-5.26(m, 2H), 5.32(s, 2H), 5.71-5.79(m, 1H), 6.85-6.87(d, 2H), 7.40(s, 2H), 7.58-7.60(d, 2H), 8.32(s, 2H); Step 2: Add 0.2g of monoallyl diprotocatechuate silane coupling agent to 100mL of 80% ethanol aqueous solution, then add 2g of nano zinc oxide (particle size 50nm, purchased from Shanghai Hansi Chemical Co., Ltd.), ultrasonically disperse for 5min, stir and heat to 60℃, react for 4h, filter, wash the solid product with anhydrous ethanol, and dry in a vacuum drying oven at 60℃ for 8h to obtain alkenylated protocatechuate type photocatalytic antibacterial agent.

[0015] Example 1: An antibacterial finishing agent for bio-based fiber materials, comprising the following raw materials in parts by weight: 80g of hydrogen-containing silicone oil (hydrogen content 0.18-0.3%); 3g of alkenylated protocatechuic acid ester type photocatalytic antibacterial agent (prepared in Experimental Example 1); 8g of emulsifier ER-20; 32g of glycerol; 1 μL of Karstedt catalyst (Karstedt catalyst is a platinum(0)-1,3-diethylene-1,1,3,3-tetramethyldisiloxane complex solution, platinum content is 2%); 200mL of water; An antibacterial finishing agent for bio-based fiber materials, the preparation method of which is as follows: Hydrogen-containing silicone oil, emulsifier ER-20, and glycerol were added to water and emulsified in a homogenizer at 10,000 rpm for 30 minutes. Nitrogen gas was then introduced, followed by the addition of an alkenylated protocatechuic acid ester type photocatalytic antibacterial agent and Karstedt catalyst. The mixture was stirred and heated to 90°C, and the reaction was maintained at this temperature for 5 hours. After cooling to room temperature, the antibacterial finishing agent was obtained.

[0016] Example 2: An antibacterial finishing agent for bio-based fiber materials, comprising the following raw materials in parts by weight: 90g of hydrogen-containing silicone oil (hydrogen content 0.18-0.3%); 4g of alkenylated protocatechuic acid ester type photocatalytic antibacterial agent (prepared in Experimental Example 1); 9g of emulsifier ER-20; 36g of glycerol; 1.5 μL of Karstedt catalyst (Karstedt catalyst is a platinum(0)-1,3-diethylene-1,1,3,3-tetramethyldisiloxane complex solution with a platinum content of 2%); 250mL of water; An antibacterial finishing agent for bio-based fiber materials is prepared in the same way as in Example 1.

[0017] Example 3: An antibacterial finishing agent for bio-based fiber materials, comprising the following raw materials in parts by weight: 100g of hydrogen-containing silicone oil (hydrogen content 0.18-0.3%); 5g of alkenylated protocatechuic acid ester type photocatalytic antibacterial agent (prepared in Experimental Example 1); 10g of emulsifier ER-20; 40g of glycerol; 2 μL of Karstedt catalyst (Karstedt catalyst is a platinum(0)-1,3-diethylene-1,1,3,3-tetramethyldisiloxane complex solution, platinum content is 2%); 300mL of water; An antibacterial finishing agent for bio-based fiber materials is prepared in the same way as in Example 1.

[0018] Performance testing: 0.1 mL of 65% nitric acid solution and 0.4 g of dodecyltrimethylammonium chloride were added to 1 L of water, followed by 20 mL of 3-glycidoxypropyltrimethoxysilane and 40 mL of hexadecyltrimethoxysilane. The mixture was stirred until homogeneous and ultrasonically hydrolyzed at room temperature to form a homogeneous emulsion, which is the modified sol. Bio-based polyester fabric was immersed in the modified sol for 10 min, and after padding, the bio-based polyester fabric was placed under ammonia gas, dried at 80°C for 3 min, and cured at 160°C for 3 min to obtain the modified bio-based polyester fabric. The antibacterial finishing agent prepared in Examples 1-3 was configured as an antibacterial finishing solution of 40 g / L. The modified bio-based polyester fabric was impregnated with the finishing solution and subjected to two dips and two pads with a liquid retention rate of 90%. It was pre-dried at 80°C for 10 min and then baked at 150°C for 2 min. After cooling to room temperature, the bio-based polyester fabric to be tested was obtained.

[0019] I. Testing of antibacterial properties The washing method was performed according to the AIS method in standard GB / T 12490-2014 "Textiles - Tests for Color Fastness to Household and Commercial Washing". The bio-based polyester fabric to be tested was cut into 10cm × 10cm samples and placed in 150mL of a 5g / L soap solution at 40℃. Ten steel balls were added, and the samples were washed for 30 minutes. After washing, the samples were removed and rinsed twice more in 100mL water at 40℃, 1 minute each time. This procedure was repeated 10 times, equivalent to 5 household washes. Finally, the samples were dried, equivalent to 50 household washes. Following standard GB / T 20944.3-2008 "Evaluation of Antimicrobial Properties of Textiles - Part 3: Shaking Method", *Escherichia coli* (ATCC 11229) was selected as the test bacterium. The sterilized samples were irradiated with a 364nm, 250W UV lamp for 1 hour. Other steps were performed according to standard procedures. The antimicrobial rate was calculated and recorded. The test results are shown in Table 1. Table 1. Test results of antibacterial rate As shown in Table 1, the antibacterial finishing agent prepared in the embodiments of the present invention has excellent antibacterial properties, and after 50 washes equivalent to a household washing cycle, the antibacterial rate is ≥80.00%, indicating good antibacterial effect and long-lasting antibacterial properties.

[0020] II. Testing of Softness Circular samples with a diameter of 12 cm were cut from the bio-based polyester fabric to be tested and the bio-based polyester fabric (comparative example). The softness of the samples was evaluated using a smart style meter. The test results are shown in Table 2. Table 2 Test results of softness performance

Claims

1. An antibacterial finishing agent for bio-based fiber materials, characterized in that, Including the following parts by weight of raw materials: 80-100 parts of hydrogen-containing silicone oil; 3-5 parts of alkenylated protocatechuic acid ester type photocatalytic antibacterial agent; 8-10 parts emulsifier; 30-40 parts of co-emulsifier; 0.001-0.002 parts of Karstedt catalyst; 200-300 parts water; Among them, the alkenylated protocatechuic acid ester type photocatalytic antibacterial agent is prepared by modifying nano zinc oxide with hydroxyl functional groups on its surface using a monoallyl diprotocatechuic acid ester silane coupling agent.

2. The antibacterial finishing agent for bio-based fiber materials according to claim 1, characterized in that, The chemical structural formula of the monoallyl diprotocatechuate silane coupling agent is: 。 3. The antibacterial finishing agent for bio-based fiber materials according to claim 2, characterized in that, The preparation method of the monoallyl diprotocatechuate silane coupling agent is as follows: One molar equivalent of allyl pentaerythritol first undergoes a nucleophilic substitution reaction with one molar equivalent of 3-halopropyltrimethoxysilane in the presence of sodium hydroxide, and then undergoes an esterification reaction with two molar equivalents of protocatechuic acid in the presence of p-toluenesulfonic acid to obtain a monoallyl diprotocatechuic acid silane coupling agent.

4. The antibacterial finishing agent for bio-based fiber materials according to claim 3, characterized in that, The 3-halopropyltrimethoxysilane is 3-chloropropyltrimethoxysilane or 3-bromopropyltrimethoxysilane.

5. The antibacterial finishing agent for bio-based fiber materials according to claim 1, characterized in that, The emulsifier is either emulsifier ER-20 or emulsifier AEO-7.

6. The antibacterial finishing agent for bio-based fiber materials according to claim 1, characterized in that, The co-emulsifier is glycerol or n-butanol.

7. A method for preparing an antibacterial finishing agent for bio-based fiber materials as described in claim 1, characterized in that, The preparation method is as follows: Hydrogen-containing silicone oil, emulsifier, and co-emulsifier are added to water and emulsified in a homogenizer at a speed of 8000-12000 rpm for 20-40 minutes. Nitrogen gas is then introduced, followed by the addition of an alkenylated protocatechuic acid ester type photocatalytic antibacterial agent and Karstedt catalyst. The mixture is stirred and heated to 80-95℃, and the reaction is maintained at this temperature for 4-6 hours. After cooling to room temperature, the antibacterial finishing agent is obtained.

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