Highly abrasion-resistant antibacterial fabric, method for producing the same, and clothing

Abstract

This application belongs to the field of textile materials and functional finishing technology, and specifically relates to a polysiloxane with carboxyl and amino groups in its side chains, a high-abrasion-resistant and antibacterial fabric, the same preparation method, and clothing using the high-abrasion-resistant and antibacterial fabric. The method involves designing and synthesizing a polysiloxane with carboxyl and amino groups in its side chains, including primary amino, secondary amino, carboxyl, and Si-O-Si structures. Cellulose is oxidized with an oxyacid salt to form aldehyde groups, and then the polysiloxane with carboxyl and amino groups in its side chains is fixed onto the cellulose surface. Subsequently, nano-zinc oxide is synthesized in situ using ultrasound-assisted synthesis. This is achieved by bonding ZnO to the ZnO surface using N,N-bident ligands, N,O-isobidentent ligands, and O,O-bident ligands. 2+ Chelation forms a stable chelate ring bonded to nano-ZnO. The polysiloxane structure also has a self-lubricating function, satisfying the wear resistance of the cellulose fabric itself, as well as the requirements of washability, wear resistance, and long-term fixation of nano-zinc oxide on the surface of the cellulose fabric, thereby improving the stability of the antibacterial effect of the cellulose fabric.

Description

Technical Field

[0001] This application belongs to the field of textile materials and functional finishing technology of textiles, and specifically relates to a polysiloxane with carboxyl and amino groups in the side chain, a high abrasion-resistant antibacterial fabric and its preparation method, as well as clothing using the high abrasion-resistant antibacterial fabric. Background Technology

[0002] Textiles, as the body's covering layer, are crucial for protecting against environmental damage. Cellulose fabrics, commonly used in summer clothing, urgently need upgrades in advanced functions such as antibacterial properties, thermal regulation, washability, and abrasion resistance. Current methods for improving the antibacterial properties of cellulose fabrics mainly involve loading nano-silver particles or nano-zinc oxide particles onto the fiber surface, thereby modifying the fabric and imparting antibacterial effects. However, the interaction between cellulose and inorganic materials is weak, and these particles are easily detached during friction or washing, leading to a significant decrease in antibacterial performance.

[0003] To enhance the interaction between cellulose and inorganic nanoparticles, polymers such as water-based acrylates, water-based polyurethanes, polysaccharides, and polycarboxylic acids are used as bridges. These polymers are coated onto the surface of cellulose fabrics using methods such as pad-dry-baking and spraying. While firmly binding cellulose, they can also adsorb inorganic nanoparticles. However, these polymers are difficult to completely encapsulate inorganic nanoparticles, and the polymers contain a large number of hydrophilic groups such as carboxyl groups, which are easily detached during washing and friction of cellulose fabrics, leading to a decrease in antibacterial properties. Summary of the Invention

[0004] To address the shortcomings of existing technologies, this application designs and synthesizes polysiloxanes with primary amine, secondary amine, carboxyl, and Si-O-Si side chains containing carboxyl and amino groups. Cellulose is first oxidized and then fixed onto the cellulose surface. Subsequently, nano-zinc oxide is synthesized in situ using ultrasound-assisted synthesis. This is achieved by bonding ZnO to the ZnO surface via N,N-bident ligands, N,O-isobidentent ligands, and O,O-bidentent ligands. 2+ Chelation forms a stable chelate ring, satisfying the requirements of washability, abrasion resistance, and long-term fixation of nano zinc oxide on the surface of cellulose fabrics, thereby improving the stability of the antibacterial effect of cellulose fabrics.

[0005] To achieve the above technical objectives, the technical solution adopted in this application is as follows:

[0006] In the first aspect, a polysiloxane containing carboxyl and amino groups in its side chain is obtained by condensation reaction of an alkyl silane oligomer with a silane coupling agent containing a primary amino group and a silane coupling agent containing a carboxyl and a secondary amino group.

[0007] The alkylsilane oligomer is obtained by hydrolysis and condensation of an alkylsilane coupling agent under acidic conditions.

[0008] The alkyl group is selected from hydrocarbon groups having 1-12 carbon atoms;

[0009] Polysiloxanes with carboxyl and amino groups in their side chains contain a Si-O-Si backbone, at least one primary amino group, a secondary amino group, and a carboxyl group.

[0010] Polysiloxanes with side chains containing carboxyl and amino groups have secondary amino groups linked to carboxyl groups by alkyl groups of 2 to 3 carbon atoms.

[0011] Preferably, the secondary amino groups of the polysiloxane containing carboxyl and amino groups in the side chain are linked by -CH2CH2-.

[0012] Preferably, the carboxyl groups of the polysiloxane containing carboxyl and amino groups in the side chain are linked by -CH2CH2-.

[0013] Preferably, the alkyl group is selected from hydrocarbon groups having 1-6 carbon atoms;

[0014] Preferably, the alkyl group is selected from methyl;

[0015] Preferably, the acidic condition is an aqueous solution environment with a pH of 4-5;

[0016] Preferably, the silane coupling agent containing a primary amino group is selected from any one of γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane, N-β-aminoethyl-γ-aminopropyltriethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldiethoxysilane, 3-diethylenetriaminepropyltrimethoxysilane, 3-diethylenetriaminepropylmethyldimethoxysilane, 3-diethylenetriaminepropyltriethoxysilane, and 3-diethylenetriaminepropylmethyldiethoxysilane.

[0017] The silane coupling agent containing carboxyl and secondary amino groups is obtained by Michael addition reaction of a silane coupling agent containing primary amino groups with an unsaturated carboxylic acid.

[0018] Preferably, the unsaturated carboxylic acid is selected from one or more of acrylic acid, methacrylic acid, itaconic acid, maleic acid, methylmaleic acid, fumaric acid, and methylfumaric acid;

[0019] Preferably, the silane coupling agent containing carboxyl and secondary amino groups comprises , or The structure.

[0020] Secondly, the use of the aforementioned polysiloxanes with carboxyl and amino groups in the abrasion-resistant and antibacterial finishing of cellulose fabrics.

[0021] Thirdly, a highly abrasion-resistant and antibacterial fabric is composed of a base fabric oxidized with oxyacid salts, a surface-modified layer, and inorganic oxides.

[0022] Among them, the surface-modified layer is covalently bonded to the base fabric; the surface-modified layer is chelated with the inorganic oxide through coordination bonds.

[0023] Preferably, the covalent bond is a Schiff base -C=N- structure;

[0024] Preferably, the surface-modified layer is chelated with the inorganic oxide through coordination bonds to form N,N-bident ligands, N,O-isobident ligands, or O,O-bident ligands that chelate with inorganic ions in the inorganic oxide through coordination bonds.

[0025] The base fabric is selected from cotton fiber or regenerated cellulose fiber;

[0026] Preferably, the base fabric is selected from regenerated cellulose fibers;

[0027] Preferably, the regenerated cellulose fiber is selected from one or more of viscose fiber, modal, lyocell and bamboo pulp regenerated cellulose fiber;

[0028] The oxyacid salt is selected from periodate or persulfate;

[0029] Preferably, the periodate is selected from one or more of sodium periodate, ammonium metaperiodate, sodium secondary periodate, and potassium periodate;

[0030] Preferably, the persulfate is selected from one or more of ammonium persulfate, sodium persulfate, and potassium persulfate.

[0031] The surface modification layer is a polysiloxane with carboxyl and amino groups in its side chain, as described above.

[0032] The inorganic oxide is selected from zinc oxide.

[0033] Fourthly, the preparation method of the above-mentioned fabric includes: adding an oxyacid salt to the base fabric to oxidize it to obtain an oxidized fabric, then adding the above-mentioned polysiloxane containing carboxyl and amino groups in the side chain to modify the oxidized fabric to obtain a modified fabric, and finally using zinc chloride to precipitate in situ on the surface of the modified fabric to synthesize nano zinc oxide to obtain a highly wear-resistant and antibacterial fabric.

[0034] Preferably, the base fabric is first washed with a nonionic detergent and then oxidized with an oxyacid salt.

[0035] Furthermore, the method for preparing the fabric described above specifically includes the following steps:

[0036] S1. Wash the fabric with a non-ionic detergent solution, then rinse with deionized water and dry at room temperature to obtain the pre-treated fabric.

[0037] S2. The pretreated fabric prepared in S1 is immersed in a phosphate buffer solution with pH=7.0-8.0, oxyacid salts are added, and after ultrasonic treatment, it is rinsed with deionized water and dried to obtain the oxidized fabric.

[0038] S3. The oxidized fabric prepared in S2 is immersed in an acetate-sodium acetate buffer solution with pH=5.5-7.0, and the polysiloxane with carboxyl and amino groups in the side chain is added. After ultrasonic treatment, it is rinsed with deionized water and dried to obtain the modified fabric.

[0039] S4. The modified fabric prepared in S3 is immersed in zinc chloride solution and ultrasonically treated. The pH of the system is adjusted to 9-10. After zinc hydroxide precipitate is generated, it is heated and ultrasonically treated at 50-80℃, then rinsed with deionized water and baked and dried at 100-150℃ to finally obtain a highly wear-resistant and antibacterial fabric.

[0040] Preferably, the concentration of the nonionic detergent aqueous solution in step S1 is 0.5-2 g / L;

[0041] Preferably, in step S1, the fabric is washed with a nonionic detergent aqueous solution at 40-60°C;

[0042] Preferably, in step S2, the reaction vessel is wrapped to protect it from light after the addition of the oxyacid salt;

[0043] Preferably, the concentration of the oxyacid salt added in step S2 is 1-10 g / L;

[0044] Preferably, in step S3, the concentration of polysiloxane containing carboxyl and amino groups in the side chain is 5-15 g / L.

[0045] Preferably, the concentration of zinc chloride solution added in step S4 is 0.5-2 mol / L.

[0046] Fifthly, a garment whose raw materials include the fabrics described above.

[0047] The beneficial effects of the technical solutions proposed above in this application are as follows: Polysiloxanes with side chains containing carboxyl and amino groups, including primary amino, secondary amino, carboxyl, and Si-O-Si structures, are designed and synthesized. Cellulose is oxidized with oxyacid salts to form aldehyde groups, and then the polysiloxanes with side chains containing carboxyl and amino groups are fixed onto the cellulose surface. Subsequently, nano-zinc oxide is synthesized in situ using ultrasound-assisted synthesis. This is achieved through the interaction of N,N-bident ligands, N,O-isobidentent ligands, and O,O-bidentent ligands with the ZnO surface. 2+Chelation forms a stable chelate ring bonded to nano-ZnO. The polysiloxane structure also has a self-lubricating function, satisfying the wear resistance of the cellulose fabric itself, as well as the requirements of the nano-zinc oxide on the surface of the cellulose fabric for washability, wear resistance, and long-term fixation, thereby improving the stability of the antibacterial effect of the cellulose fabric. Attached Figure Description

[0048] To more clearly illustrate the technical solutions in the embodiments of this application and to more completely understand this application and its beneficial effects, the drawings used in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0049] Figure 1 The infrared spectrum of the polysiloxane with carboxyl and amino groups in the side chain prepared in Example 8. Detailed Implementation

[0050] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Furthermore, it should be understood that after reading the teachings of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the appended claims.

[0051] It should be noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of exemplary embodiments according to the invention. As used herein, the singular form is intended to include the plural form as well, unless the context clearly indicates otherwise. Furthermore, it should be understood that when the terms "comprising" and / or "including" are used in this specification, they indicate the presence of features, steps, operations, devices, components, and / or combinations thereof.

[0052] Unless otherwise specified, the experimental conditions used in the examples are generally in accordance with conventional conditions in the art or the conditions recommended by the reagent company. Unless otherwise specified, the materials and reagents used in the examples can be purchased commercially.

[0053] Example 1

[0054] Synthesis of carboxyl-grafted silane coupling agent: 46.8 g (0.65 mol) of acrylic acid and 0.25 g of p-hydroxyanisole were added to a reaction vessel, followed by 98 g (0.6 mol) of γ-aminopropylmethyldimethoxysilane and 80 mL of ethanol. Mechanical stirring was started and nitrogen gas was continuously introduced into the flask for protection. The temperature was raised to 60 °C and stirred continuously at this temperature for 12 hours. After the reaction was completed, the temperature was lowered to 50 °C and the solvent and unreacted monomers were removed by vacuum distillation, thereby obtaining the carboxyl-grafted silane coupling agent.

[0055] 1 H-NMR (CDCl3): δ 0.18 (3H, s), 0.80 (2H, t, J = 2.67 Hz), 1.67 (2H,tt, J = 4.36, 2.67 Hz), 2.13(1H, s), 2.47 (2H, t, J = 6.74 Hz), 2.57 (2H, t,J = 4.36 Hz), 2.77-3.00 (8H,m), 12.11(1H, br).

[0056] 13 C-NMR (CDCl3): δ -0.2, 15.7, 29.1, 34.2, 44.5, 49.6, 50.3(2C),176.5.

[0057] Example 2

[0058] Synthesis of carboxyl-grafted silane coupling agent: Based on Example 1, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane was used to replace γ-aminopropylmethyldimethoxysilane, and the amount used was 123.8 g (0.6 mol). The amounts of acrylic acid and p-hydroxyanisole were the same as in Example 1, and the remaining operations were the same as in Example 1.

[0059] 1 H-NMR (CDCl3): δ 0.15 (3H, s), 0.83 (2H, t, J = 2.67 Hz), 1.69 (2H,tt, J = 4.41, 2.67 Hz), 2.09(2H, s), 2.46 (2H, t, J = 6.74 Hz), 2.55 (t, J =4.41 Hz), 2.68-3.00 (12H, m), 12.03(1H, br).

[0060] 13C-NMR (CDCl3): δ -0.4, 15.9, 29.4, 34.3, 44.2, 49.5(2C), 49.9, 50.6(2C), 176.1.

[0061] Example 3

[0062] Synthesis of carboxyl-grafted silane coupling agent: 65 g (0.5 mol) itaconic acid and 0.3 g p-hydroxyanisole were added to a reaction vessel, followed by 73.5 g (0.45 mol) γ-aminopropylmethyldimethoxysilane. Mechanical stirring was started and nitrogen gas was continuously introduced into the flask for protection. The temperature was raised to 80 °C and stirred continuously at this temperature for 12 hours. After the reaction was completed, the solvent and unreacted monomers were removed by vacuum distillation at 80 °C, thereby obtaining the carboxyl-grafted silane coupling agent.

[0063] 1 H-NMR (CDCl3): δ 0.18 (3H, s), 0.81 (2H, dd, J = 2.67, 2.67 Hz), 1.72 (2H, dddd, J = 4.34, 4.34, 2.67, 2.67 Hz), 2.11 (1H, s), 2.54 (2H, dd, J =4.34, 4.34 Hz), 2.69-3.00 (11H, m), 12.10 (2H, br).

[0064] 13 C-NMR (CDCl3): δ -0.2, 15.7, 29.2, 35.6, 46.4, 49.3(2C), 50.0, 50.5,180.9, 181.0.

[0065] Example 4

[0066] Synthesis of carboxyl-grafted silane coupling agent: Based on Example 3, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane was used to replace γ-aminopropylmethyldimethoxysilane, and the amount used was 93g (0.45mol). The amounts of itaconic acid and p-hydroxyanisole were the same as in Example 1, and the remaining operations were the same as in Example 3.

[0067] 1H-NMR (CDCl3): δ 0.16 (3H, s), 0.78 (2H, dd, J = 2.67, 2.67 Hz), 1.69(2H, dddd, J = 4.40, 4.40, 2.67, 2.67 Hz), 2.08(2H, s), 2.46(2H, dd, J =4.40, 4.40 Hz), 2.71-3.00 (15H, m), 12.06(2H, br).

[0068] 13 C-NMR (CDCl3): δ -0.4, 15.7, 29.3, 35.4, 46.5, 49.5(2C), 49.8, 50.5(2C), 50.9, 180.4, 181.2.

[0069] Example 5

[0070] 54 g of deionized water, 162 g of anhydrous ethanol, 53.5 g (0.3 mol) of methyltriethoxysilane, and 29.7 g (0.2 mol) of dimethyldiethoxysilane were mixed and stirred. Formic acid was added to adjust the pH of the reaction mixture to 4-5. The mixture was heated to 65 °C with stirring and reacted for 8 hours. After cooling to room temperature and standing for 24 hours, the supernatant was removed. The lower product was dissolved in acetone. 100 mL of deionized water was added to the acetone solution three times to wash the mixture. The filter cake was collected by vacuum filtration and transferred to a vacuum drying oven at 80 °C to dry for 12 hours to obtain methylsilane oligomers.

[0071] The obtained methylsilane oligomer was mixed with 23.5 g (0.1 mol) of carboxyl-grafted silane coupling agent prepared in Example 1, 16.3 g (0.1 mol) of γ-aminopropylmethyldimethoxysilane and 60 mL of isopropanol in a reaction vessel. The mixture was heated to 85-90 °C and reacted for 2 hours. After the reaction was completed, the temperature was lowered to 70 °C and the solvent and the product generated by the reaction were removed by vacuum distillation. The temperature was further lowered to room temperature and allowed to stand for 24 hours. Finally, the mixture was vacuum dried at 80 °C for 12 hours to obtain a polysiloxane containing carboxyl and amino groups in the side chain.

[0072] Example 6

[0073] The preparation method of the methylsilane oligomer is the same as in Example 5. The obtained methylsilane oligomer is added to a reaction vessel along with 27.8 g (0.1 mol) of carboxyl grafted silane coupling agent and 16.3 g (0.1 mol) of γ-aminopropylmethyldimethoxysilane prepared in Example 2. The subsequent operations are the same as in Example 5.

[0074] Example 7

[0075] The preparation method of the methylsilane oligomer is the same as in Example 5. The obtained methylsilane oligomer is added to a reaction vessel along with 29.3 g (0.1 mol) of carboxyl grafted silane coupling agent and 16.3 g (0.1 mol) of γ-aminopropylmethyldimethoxysilane prepared in Example 3 and mixed. The subsequent operations are the same as in Example 5.

[0076] Example 8

[0077] The preparation method of the methylsilane oligomer is the same as in Example 5. The obtained methylsilane oligomer is added to a reaction vessel along with 33.6 g (0.1 mol) of carboxyl grafted silane coupling agent and 16.3 g (0.1 mol) of γ-aminopropylmethyldimethoxysilane prepared in Example 4 and mixed. The subsequent operations are the same as in Example 5.

[0078] The infrared spectrum of the polysiloxane with carboxyl and amino groups in the side chain prepared in Example 8 is shown below. Figure 1 As shown, position a is 3200-3500cm. -1 The broad peaks indicate the presence of NH and COOH groups in polysiloxanes with carboxyl and amino groups in their side chains; the b position is 1710-1730 cm⁻¹. -1 The strong absorption peak indicates the stretching vibration of the carbonyl C=O group in polysiloxanes containing carboxyl and amino groups in the side chain; the c position is 1550-1570 cm⁻¹. -1 The intermediate absorption peak indicates the bending vibration of NH in polysiloxanes containing carboxyl and amino groups in the side chains; the d position is 1230-1250 cm⁻¹. -1 The intermediate absorption peak is a characteristic absorption peak of silanyl methyl groups, located at 2930-2960 cm⁻¹. -1 Strong absorption peak (CH stretching vibration) at 1400 cm⁻¹ -1 The presence of a moderate absorption peak (CH bending vibration) indicates the presence of Si-CH3 in polysiloxanes with carboxyl and amino groups in the side chain; the e-position is 1030-1050 cm⁻¹. -1 The strong absorption peak indicates the Si-O-Si skeletal vibration, suggesting the presence of a polysiloxane skeleton in polysiloxanes with carboxyl and amino groups in the side chains.

[0079] Example 9

[0080] Regenerated cellulose fibers (modal fibers) were washed with a 1 g / L nonionic detergent aqueous solution at 50°C for 30 min at a liquor ratio of 1:50 (the liquor ratio is the ratio of the fabric weight in kilograms to the washing solution in liters), followed by thorough rinsing with deionized water and drying at room temperature for 12 hours.

[0081] The regenerated cellulose fibers were immersed in phosphate buffer (PB) at pH 7.5 with a bath ratio of 1:40. The reaction vessel was wrapped with aluminum foil to prevent photolysis of periodate. 5 g / L of sodium periodate was added to the phosphate buffer, and the mixture was treated with ultrasonic vibration (20 kHz, 750 W) for 30 minutes. The mixture was then rinsed with deionized water and dried at room temperature for 12 hours to obtain oxidized regenerated cellulose fibers.

[0082] The oxidized regenerated cellulose fibers were immersed in an acetate-sodium acetate buffer solution at pH 6.0 with a bath ratio of 1:40. 8 g / L of the polysiloxane with carboxyl and amino side chains prepared in Example 5 was added. The mixture was then ultrasonically vibrated (20 kHz, 750 W) for 90 minutes, rinsed with deionized water, and dried at room temperature for 12 hours to obtain the modified regenerated cellulose fibers.

[0083] Modified regenerated cellulose fibers were immersed in a 1 mol / L zinc chloride solution at a bath ratio of 1:40 and treated with ultrasonic vibration (20 kHz, 750 W) for 30 minutes. Subsequently, the pH was adjusted to 9.5-10.5 using a 0.1 mol / L sodium hydroxide solution, forming a white Zn(OH)2 precipitate. At this point, the precipitate was placed in a water bath and heated to 60-70℃ while continuing ultrasonic vibration (20 kHz, 750 W) for 30 minutes. After rinsing with deionized water, the precipitate was baked in a 120℃ oven for 2 hours to obtain highly wear-resistant and antibacterial regenerated cellulose fibers.

[0084] Example 10

[0085] The preparation steps are the same as in Example 9, except that 12 g / L of the polysiloxane prepared in Example 5 with carboxyl and amino groups in the side chain is added.

[0086] Example 11

[0087] The preparation steps are the same as in Example 9, except that 8 g / L of the polysiloxane prepared in Example 6 with carboxyl and amino groups in the side chain is added.

[0088] Example 12

[0089] The preparation steps are the same as in Example 9, except that 12 g / L of the polysiloxane prepared in Example 6 with carboxyl and amino groups in the side chain is added.

[0090] Example 13

[0091] The preparation steps are the same as in Example 9, except that 8 g / L of the polysiloxane prepared in Example 7 with carboxyl and amino groups in the side chain is added.

[0092] Example 14

[0093] The preparation steps are the same as in Example 9, except that 12 g / L of the polysiloxane prepared in Example 7 with carboxyl and amino groups in the side chain is added.

[0094] Example 15

[0095] The preparation steps are the same as in Example 9, except that 8 g / L of the polysiloxane prepared in Example 8 with carboxyl and amino groups in the side chain is added.

[0096] Example 16

[0097] The preparation steps are the same as in Example 9, except that 12 g / L of the polysiloxane prepared in Example 8 with carboxyl and amino groups in the side chain is added.

[0098] Comparative Example 1

[0099] The preparation steps are the same as in Example 9, except that 8 g / L of the carboxyl grafted silane coupling agent prepared in Example 1 and 8 g / L of 3-aminopropylmethyldimethoxysilane are added.

[0100] Test section

[0101] The abrasion resistance test was conducted according to Part 2 of GB / T 4802.2-2008: Modified Martindale Method. The fabric sample was placed on a Martindale abrasion tester and subjected to 100 abrasion cycles. After completion, the sample was illuminated by an incandescent fluorescent lamp, and visually compared with the unrubbed original sample to assess the pilling and fuzzing grade. The grade range was 1-5, with grade 5 being the best and grade 1 the worst.

[0102] The antibacterial activity test was conducted according to the AATCC 100-2004 standard for testing the antibacterial properties of textiles. Gram-negative Escherichia coli and Gram-positive Staphylococcus aureus were used as test strains. A blank control group was set up, and the inhibition rate of the tested fabric samples against Escherichia coli and Staphylococcus aureus was calculated respectively.

[0103] For the antibacterial activity test after washing, the fabric sample was filled with 50 stainless steel beads with a diameter of 6 mm according to method 2A in AATCC 61-2006, washed at (49±1)℃ for 45 minutes, and the process was repeated for 5 cycles before the above antibacterial activity test was performed.

[0104] The antibacterial activity test after friction was conducted by placing the fabric sample on a Martindale abrasion tester and performing 100 abrasion cycles.

[0105] The test results of the high abrasion-resistant and antibacterial regenerated cellulose fibers obtained in Examples 9-16 and Comparative Example 1, according to the above test methods, are listed in Table 1.

[0106] Table 1

[0107]

[0108] Analysis of the data in Table 1 shows that the friction performance of the fabric samples in Examples 9-16 is level 4. The polysiloxane segments have the characteristics of self-lubrication, wear resistance and strong film-forming properties. The in-situ synthesis of ZnO makes the surface of the regenerated cellulose fiber smoother and less prone to pilling. Comparative Example 1 uses a small molecule silane coupling agent, and the film integrity is not as good as that of Examples 9-16, and the corresponding friction performance is slightly reduced.

[0109] The C2-C3 bond on the glucose ring of cellulose is broken by periodate oxidation, and the hydroxyl groups at the C2 and C3 positions are oxidized into two aldehyde groups, thereby obtaining regenerated cellulose fibers containing aldehyde groups. The polysiloxanes with carboxyl and amino groups in the side chains prepared in Examples 5-8 contain primary amino groups. In a weakly acidic solution, these primary amino groups react with the aldehyde groups generated by periodate oxidation in a Schiff base reaction to form a stable covalent bond -CH=N-. The polysiloxanes with carboxyl and amino groups in the side chains are then grafted onto the regenerated cellulose fibers. Subsequently, the carboxyl and secondary amino groups in the polysiloxanes with carboxyl and amino groups coordinate with Zn to achieve Zn... 2+ The in-situ loading of this coordination crosslinking network anchors ZnO to the fiber surface, thus maintaining an antibacterial rate of over 93% even after washing and rubbing.

[0110] Finally, it should be noted that the above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of them. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention. Although the specific embodiments of the present invention have been described above, they are not intended to limit the protection scope of the present invention. Those skilled in the art should understand that various modifications or variations that can be made by those skilled in the art without creative effort based on the technical solutions of the present invention are still within the protection scope of the present invention.

Claims

1. A polysiloxane with carboxyl and amino groups in its side chain, characterized in that, It is obtained by condensation reaction of alkyl silane oligomers with silane coupling agents containing primary amino groups and silane coupling agents containing carboxyl and secondary amino groups; The alkylsilane oligomer is obtained by hydrolysis and condensation of an alkylsilane coupling agent under acidic conditions. The alkyl group is selected from hydrocarbon groups having 1-12 carbon atoms; Polysiloxanes with carboxyl and amino groups in their side chains contain a Si-O-Si backbone, at least one primary amino group, a secondary amino group, and a carboxyl group. Polysiloxanes with side chains containing carboxyl and amino groups have secondary amino groups linked to carboxyl groups by alkyl groups of 2 to 3 carbon atoms. The silane coupling agent containing carboxyl and secondary amino groups is obtained by Michael addition reaction of a silane coupling agent containing primary amino groups with an unsaturated carboxylic acid.

2. The polysiloxane containing carboxyl and amino groups in its side chain according to claim 1, characterized in that, The secondary amino groups of the polysiloxane containing carboxyl and amino groups in the side chain are linked by -CH2CH2-. And / or, the carboxyl groups of the polysiloxane containing carboxyl and amino groups in the side chain are linked by -CH2CH2-; And / or, the alkyl group is selected from hydrocarbon groups having 1-6 carbon atoms; And / or, the acidic conditions are an aqueous solution environment with a pH of 4-5; And / or, the silane coupling agent containing a primary amino group is selected from any one of γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane, N-β-aminoethyl-γ-aminopropyltriethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldiethoxysilane, 3-diethylenetriaminepropyltrimethoxysilane, 3-diethylenetriaminepropylmethyldimethoxysilane, 3-diethylenetriaminepropyltriethoxysilane and 3-diethylenetriaminepropylmethyldiethoxysilane.

3. The polysiloxane containing carboxyl and amino groups in its side chain according to claim 1, characterized in that, The unsaturated carboxylic acid is selected from one or more of the following: acrylic acid, methacrylic acid, itaconic acid, maleic acid, methylmaleic acid, fumaric acid, and methylfumaric acid; And / or, the silane coupling agent containing carboxyl and secondary amino groups comprises , or The structure.

4. The use of polysiloxanes with carboxyl and amino groups in the side chains as described in any one of claims 1-3 in the abrasion-resistant and antibacterial finishing of cellulose fabrics.

5. A highly abrasion-resistant and antibacterial fabric, comprising a base fabric oxidized with oxyacid salts, a surface-modified layer, and inorganic oxides; in, The surface-modified layer is covalently bonded to the base fabric; the surface-modified layer is chelated with inorganic oxides through coordination bonds. The base fabric is selected from cotton fiber or regenerated cellulose fiber; The oxyacid salt is selected from periodate or persulfate; The surface modification layer is a polysiloxane with carboxyl and amino groups in its side chain as described in any one of claims 1-3; The inorganic oxide is selected from zinc oxide.

6. The fabric according to claim 5, characterized in that, The covalent bond is a Schiff base -C=N- structure; And / or, the base fabric is selected from regenerated cellulose fibers; And / or, the regenerated cellulose fiber is selected from one or more of viscose fiber, modal, lyocell and bamboo pulp regenerated cellulose fiber; And / or, the periodate is selected from one or more of sodium periodate, ammonium metaperiodate, sodium secondary periodate and potassium periodate; And / or, the persulfate is selected from one or more of ammonium persulfate, sodium persulfate, and potassium persulfate.

7. A method for preparing the fabric as described in any one of claims 5-6, characterized in that, Oxidized fabric is obtained by adding oxyacid salts to the base fabric and then modifying the oxidized fabric by adding polysiloxanes with carboxyl and amino groups in the side chain as described above. Finally, nano zinc oxide is synthesized by in-situ precipitation of zinc chloride on the surface of the modified fabric to obtain a highly wear-resistant and antibacterial fabric.

8. The method for preparing the fabric according to claim 7, characterized in that, The preparation method specifically includes the following steps: S1. Wash the fabric with a non-ionic detergent solution, then rinse with deionized water and dry at room temperature to obtain the pre-treated fabric. S2. The pretreated fabric prepared in S1 is immersed in a phosphate buffer solution with pH=7.0-8.0, oxyacid salts are added, and after ultrasonic treatment, it is rinsed with deionized water and dried to obtain the oxidized fabric. S3. The oxidized fabric prepared in S2 is immersed in an acetate-sodium acetate buffer solution with pH=5.5-7.0, and the polysiloxane with carboxyl and amino groups in the side chain is added. After ultrasonic treatment, it is rinsed with deionized water and dried to obtain the modified fabric. S4. The modified fabric prepared in S3 is immersed in zinc chloride solution and ultrasonically treated. The pH of the system is adjusted to 9-10. After zinc hydroxide precipitate is generated, it is heated and ultrasonically treated at 50-80℃, then rinsed with deionized water and baked and dried at 100-150℃ to finally obtain a highly wear-resistant and antibacterial fabric.

9. The method for preparing the fabric according to claim 8, characterized in that, The concentration of the nonionic detergent aqueous solution in step S1 is 0.5-2 g / L; And / or, in step S1, the fabric is washed with a nonionic detergent aqueous solution at 40-60°C; And / or, in step S2, the reaction vessel is wrapped to protect it from light after the addition of the oxyacid salt; And / or, the concentration of oxyacid salt added in step S2 is 1-10 g / L; And / or, in step S3, the concentration of polysiloxane containing carboxyl and amino groups in the side chain is 5-15 g / L; And / or, the concentration of zinc chloride solution added in step S4 is 0.5-2 mol / L.

10. A garment made of fabric as described in any one of claims 5-6.

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