Bio-based antibacterial fiber fabric and preparation method thereof

Abstract

The present invention relates to the technical field of layered composite fabrics, and specifically to a bio-based antibacterial fiber fabric and a preparation method thereof. The preparation method comprises the following steps: reacting diisocyanate, polyether polyol, bio-based polyester polyol, and hexamidine dihydroxyethyl sulfonate in N,N-dimethylacetamide to obtain a polyurethane prepolymer solution; sequentially adding 2-(4-aminophenyl)-5-aminobenzimidazole and amino-modified nano zinc oxide to the polyurethane prepolymer solution for reaction, and dry-spinning the obtained polyurethane spinning solution to obtain polyurethane fiber, which is then spun into yarn and fabric in turn; melt-spinning bio-based nylon to obtain bio-based nylon fiber, which is then spun into yarn and fabric in turn; using polyurethane fabric as the inner layer fabric and bio-based nylon fabric as the outer layer fabric to obtain a bio-based antibacterial fiber fabric, which has good antibacterial and moisture absorption properties.

Description

Technical Field

[0001] The present invention relates to the technical field of layered composite fabrics, and in particular to a bio-based antibacterial fiber fabric and a preparation method thereof. Background Art

[0002] Synthetic fibers are primarily made from petroleum, a non-renewable resource. With the increasing depletion of petroleum resources, the development of bio-based fibers can effectively reduce the exploitation and utilization of non-renewable resources. Commonly used bio-based fibers are made from bio-based raw materials, such as bio-based nylon fibers made from bio-based 1,5-pentanediamine (produced from biomass materials through microbial processes), and bio-based polyurethane fibers made from bio-based 1,4-butanediol (produced through fermentation of biomass materials such as starch). Nylon fabrics made from nylon fibers offer excellent abrasion resistance and a long service life. Polyurethane fabrics (spandex fabrics) made from polyurethane fibers offer excellent elasticity, a soft and comfortable feel, and are suitable for direct skin contact. Combining these two fabrics can improve the overall performance of fabrics. However, polyurethane fabrics have poor moisture absorption, and the antibacterial properties of fabrics that come into direct contact with the skin require improvement.

[0003] Chinese patent CN114316790B discloses a method for preparing a thermally conductive polyurethane coating doped with hydrangea-shaped nano-zinc oxide. The method enhances the antibacterial properties of the polyurethane coating by dispersing the antibacterial nano-zinc oxide in an aqueous polyurethane emulsion. However, the antibacterial component is a single nano-zinc oxide, leaving room for improvement in antibacterial performance. Furthermore, the nano-zinc oxide is physically dispersed in the polyurethane emulsion, resulting in poor dispersion uniformity, which in turn affects the antibacterial performance. Summary of the Invention

[0004] In view of the shortcomings of the existing technology, the present invention provides a bio-based antibacterial fiber fabric and a preparation method thereof to solve the problem that the antibacterial and hygroscopic properties of polyurethane fabrics in the existing technology need to be improved.

[0005] In order to achieve the above object, the technical solution adopted by the present invention is as follows:

[0006] A method for preparing a bio-based antibacterial fiber fabric comprises the following steps:

[0007] Step 1: adding diisocyanate, polyether polyol, bio-based polyester polyol, and hexamidine dihydroxyethyl sulfonate to N,N-dimethylacetamide for reaction, and obtaining a polyurethane prepolymer solution after the reaction is completed;

[0008] Step 2: adding 2-(4-aminophenyl)-5-aminobenzimidazole to the polyurethane prepolymer solution and reacting. After the reaction is completed, adding amino-modified nano zinc oxide and continuing the reaction to obtain a polyurethane spinning solution;

[0009] Step 3, dry spinning the polyurethane spinning solution to obtain polyurethane fibers;

[0010] The polyurethane fiber is spun into polyurethane yarn, and the polyurethane yarn is spun into polyurethane fabric through a knitting process;

[0011] Step 4: melting the bio-based nylon, spinning the melt through a spinneret, cooling with side-blowing air, drawing, and winding to obtain bio-based nylon fiber;

[0012] Spinning bio-based nylon fibers into bio-based nylon yarns, and knitting the bio-based nylon yarns into fabrics to obtain bio-based nylon fabrics;

[0013] Polyurethane fabric is used as the inner fabric and bio-based nylon fabric is used as the outer fabric. The inner and outer fabrics are compounded to obtain bio-based antibacterial fiber fabric.

[0014] Preferably, in the step 1, the molar ratio of diisocyanate, polyether polyol, bio-based polyester polyol, and hexamidine diisothionate is (1.5-2): (0.45-0.5): (0.4-0.45): (0.15-0.2), the amount of N,N-dimethylacetamide added is 1-2 times the total mass of diisocyanate, polyether polyol, bio-based polyester polyol, and hexamidine diisothionate, and the reaction conditions are 70-80° C. for 2-4 hours;

[0015] The diisocyanate includes any one of hexamethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI);

[0016] The polyether polyol includes any one of polyoxypropylene glycol (PPG) and polytetramethylene ether glycol (PTMEG).

[0017] Preferably, the bio-based polyester polyol in step 1 is prepared by the following steps:

[0018] (1) Mix the bio-based diol and the dibasic acid, and heat-react at a pressure of 0.03-0.1 MPa and a temperature of 130-190°C. Sampling is performed every 30 minutes to determine the acid value of the reaction mixture until the acid value of the reaction mixture is ≤1 mgKOH / g;

[0019] During the reaction, a separation column is used to separate the water and bio-based glycol generated in the esterification reaction, and the separated and recovered bio-based glycol is refluxed into the reaction system;

[0020] (2) Add a catalyst and keep the reaction at a temperature of 190-210°C. Sampling is performed every 30 minutes to determine the acid value of the reaction mixture until the acid value of the reaction mixture is less than 0.3 mgKOH / g. After the reaction is completed, vacuum distillation is performed at a temperature of 120-140°C and a pressure of 0.07-0.09 MPa to remove water generated by the esterification reaction to obtain a bio-based polyester polyol.

[0021] Preferably, the molar ratio of the bio-based diol and the dibasic acid is (1.1-1.5):1; the amount of the catalyst added is 0.1%-0.3% of the total mass of the bio-based diol and the dibasic acid;

[0022] Bio-based diols include bio-based 1,4-butanediol;

[0023] Diacids include 1,6-adipic acid;

[0024] The catalyst includes stannous octoate.

[0025] Preferably, the number average molecular weight of the prepared bio-based polyester polyol is 400-800 g / mol.

[0026] Preferably, in the step 2, the mass ratio of the polyurethane prepolymer solution, 2-(4-aminophenyl)-5-aminobenzimidazole, and amino-modified nano-zinc oxide is 100:(1-1.5):(0.5-1), and the reaction conditions are 60-70°C for 6-8h, and the continued reaction conditions are 60-70°C for 2-4h.

[0027] Preferably, the amino-modified nano zinc oxide is prepared by the following method:

[0028] Add nano zinc oxide and 3-aminopropyltriethoxysilane (silane coupling agent KH550) to an ethanol aqueous solution and react at 50-70°C for 3-5 hours. After the reaction is completed, filter, wash, and dry to obtain amino-modified nano zinc oxide.

[0029] The mass ratio of nano zinc oxide, 3-aminopropyltriethoxysilane, and ethanol aqueous solution is 80:(10-20):(300-500);

[0030] The ethanol aqueous solution is a 90wt% ethanol aqueous solution.

[0031] Preferably, in step 3, the process parameters of dry spinning include: a spinneret with 3 holes and 36 heads, an upper nozzle temperature of 260° C., a lower nozzle temperature of 190° C., and a spinning speed of 800 m / min.

[0032] Preferably, in step 3, the yarn count of the polyurethane yarn is 30-50S (English count), and the weight of the polyurethane fabric is 120-150g / m 2 .

[0033] Preferably, in step four, the melting temperature is 270-280°C, the pressure of the spinneret is 15-18 MPa, the wind speed of the side blowing is 0.38 m / s, the temperature of the side blowing is 15-20°C, the oiling rate is 1.6%-1.8%, the drafting ratio is 1-1.2 times, and the winding speed is 4800-5000 m / min.

[0034] Preferably, in step 4, the yarn count of the bio-based nylon yarn is 30-50S, and the weight of the bio-based nylon fabric is 180-220g / m 2 .

[0035] Compared with the prior art, the present invention has the following beneficial effects:

[0036] The composite fabric of the present invention comprises a two-layer structure of an inner fabric and an outer fabric. Both the inner fabric and the outer fabric are prepared by a knitting process. The fabric has good air permeability. The outer fabric is a nylon fabric made of nylon resin as raw material, which has good moisture absorption and wear resistance and a long service life. The inner fabric is a polyurethane fabric with good elasticity, a soft and comfortable hand feel. Antibacterial components are introduced during the preparation process. The fabric has good antibacterial properties and can effectively inhibit the growth and reproduction of microorganisms when in direct contact with the skin. In addition, the raw materials for preparing the polyurethane include bio-based 1,4-butanediol, and the raw material nylon for preparing the nylon fabric is also bio-based nylon. The use of bio-based materials can effectively reduce the exploitation and utilization of non-renewable resources such as petroleum.

[0037] When preparing polyurethane fabrics, a polyurethane prepolymer is prepared using isocyanate and polyol as raw materials. The introduction of polyether segments in the polyether polyol can improve the hydrophilicity of the polyurethane, thereby improving the hygroscopic properties of the polyurethane fabric. The addition of the terminal hydroxyl compound hexamidine dihydroxyethyl sulfonate as a crosslinking agent, hexamidine dihydroxyethyl sulfonate as a cationic bactericide, has excellent bactericidal properties and can effectively improve the antibacterial properties of the polyurethane fabric. At the same time, the sulfonate is a hydrophilic group and can effectively improve the hygroscopic properties of the polyurethane fabric.

[0038] 2-(4-aminophenyl)-5-aminobenzimidazole with a diamine structure is used as a polyurethane chain extender. The introduction of the imidazole ring can also improve the antibacterial properties of polyurethane fabrics. The inorganic antibacterial material nano-zinc oxide is modified to obtain amino-modified nano-zinc oxide. The introduced amino group can perform a capping reaction on the polyurethane and connect the nano-zinc oxide to the polyurethane molecule with a stable chemical bond, which can further improve the antibacterial properties of the polyurethane fabric. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 This is a process flow chart for preparing the polyurethane fabric of the present invention;

[0040] Figure 2 This is a bar graph showing the antibacterial test results of the polyurethane fabrics prepared in Examples 2-5 of the present invention and Comparative Examples 1-2;

[0041] Figure 3 This is a bar graph showing the water absorption test results of the polyurethane fabrics prepared in Examples 2-5 of the present invention and Comparative Examples 1-2;

[0042] Figure 4 This is a bar chart showing the measurement results of the water diffusion time of the polyurethane fabrics prepared in Examples 2-5 of the present invention and Comparative Examples 1-2. DETAILED DESCRIPTION

[0043] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0044] Example 1

[0045] This embodiment discloses a method for preparing a bio-based polyester polyol, comprising the following steps:

[0046] (1) Bio-based 1,4-butanediol and 1,6-hexanediol were mixed at a molar ratio of 1.3:1, and the mixture was kept warm at 180°C under a pressure of 0.08 MPa, and the acid value of the reaction mixture was measured every 30 minutes until the acid value of the reaction mixture was ≤1 mgKOH / g (the acid value of the reaction mixture was specifically 0.9 mgKOH / g);

[0047] (2) adding bio-based 1,4-butanediol and 1,6-adipic acid by weight and 0.2% of stannous octoate, and reacting at a temperature of 200°C, sampling every 30 minutes to determine the acid value of the reaction mixture until the acid value of the reaction mixture is less than 0.3 mgKOH / g (the acid value of the reaction mixture is specifically 0.2 mgKOH / g). After the reaction is completed, performing reduced pressure distillation at a temperature of 130°C and a pressure of 0.08 MPa to remove water generated by the esterification reaction, thereby obtaining a bio-based polyester polyol;

[0048] The number average molecular weight of the polymer was measured by SEC-MALLS (size exclusion chromatography combined with multi-angle laser light scattering), and the number average molecular weight of the bio-based polyester polyol was 600 g / mol.

[0049] Example 2

[0050] This embodiment discloses a method for preparing a bio-based antibacterial fiber fabric, comprising the following steps:

[0051] Step 1: adding hexamethylene diisocyanate, polyoxypropylene glycol, bio-based polyester polyol, and hexamidine diisothionate to N,N-dimethylacetamide, reacting at 70° C. for 4 hours, and obtaining a polyurethane prepolymer solution after the reaction is completed;

[0052] The molar ratio of hexamethylene diisocyanate, polyoxypropylene glycol, bio-based polyester polyol, and hexamidine diisothionate is 1.5:0.45:0.4:0.15, and the amount of N,N-dimethylacetamide added is 1 times the total mass of hexamethylene diisocyanate, polyoxypropylene glycol, bio-based polyester polyol, and hexamidine diisothionate.

[0053] The bio-based polyester polyol is the bio-based polyester polyol prepared in Example 1;

[0054] Step 2: adding 2-(4-aminophenyl)-5-aminobenzimidazole to the polyurethane prepolymer solution, reacting at 60° C. for 8 hours, adding amino-modified nano zinc oxide, and continuing to react at 60° C. for 4 hours to obtain a polyurethane spinning solution;

[0055] The mass ratio of polyurethane prepolymer solution, 2-(4-aminophenyl)-5-aminobenzimidazole, and amino-modified nano zinc oxide is 100:1:0.5;

[0056] Amino-modified nano zinc oxide is prepared by the following method:

[0057] Nano-zinc oxide and 3-aminopropyltriethoxysilane were added to a 90 wt% ethanol aqueous solution in a mass ratio of 80:15:400. The mixture was reacted at 60°C for 4 hours. After the reaction, the mixture was filtered, washed with ethanol three times, and dried in a vacuum drying oven at 60°C to a constant weight to obtain amino-modified nano-zinc oxide.

[0058] Step 3, dry-spinning the polyurethane spinning solution to obtain polyurethane fibers, wherein the denier of the polyurethane fibers is 30D;

[0059] The process parameters of dry spinning include: spinneret with 3 holes and 36 heads, upper nozzle temperature of 260°C, lower nozzle temperature of 190°C, and spinning speed of 800m / min;

[0060] The polyurethane fiber is spun into polyurethane yarn, the yarn count of the polyurethane yarn is 40S, the polyurethane yarn is spun into polyurethane fabric through knitting technology, and the weight of the polyurethane fabric is 140g / m 2 ;

[0061] Step 4: melting the bio-based nylon, spinning the melt through a spinneret, cooling with side-blowing air, drawing, and winding to obtain bio-based nylon fiber;

[0062] Among them, the melting temperature is 275℃, the pressure of the spinneret is 16MPa, the wind speed of the side blowing is 0.38m / s, the temperature of the side blowing is 20℃, the oiling rate is 1.8%, the draft ratio is 1.2 times, and the winding speed is 5000m / min;

[0063] The bio-based nylon fiber is spun into bio-based nylon yarn with a yarn count of 40S. The bio-based nylon yarn is spun into fabric through a knitting process to obtain bio-based nylon fabric with a gram weight of 200g / m 2 ;

[0064] Polyurethane fabric is used as the inner fabric and bio-based nylon fabric is used as the outer fabric. The inner fabric and the outer fabric are sewn together with polyester thread to obtain bio-based antibacterial fiber fabric.

[0065] Example 3

[0066] This embodiment discloses a method for preparing a bio-based antibacterial fiber fabric, comprising the following steps:

[0067] Step 1: adding isophorone diisocyanate, polytetramethylene ether glycol, bio-based polyester polyol, and hexamidine diisothionate to N,N-dimethylacetamide, reacting at 80° C. for 2 hours, and obtaining a polyurethane prepolymer solution after the reaction is completed;

[0068] The molar ratio of isophorone diisocyanate, polytetramethylene ether glycol, bio-based polyester polyol, and hexamidine diisothionate is 2:0.5:0.45:0.2, and the amount of N,N-dimethylacetamide added is twice the total mass of isophorone diisocyanate, polytetramethylene ether glycol, bio-based polyester polyol, and hexamidine diisothionate.

[0069] The bio-based polyester polyol is the bio-based polyester polyol prepared in Example 1;

[0070] Step 2: adding 2-(4-aminophenyl)-5-aminobenzimidazole to the polyurethane prepolymer solution, reacting at 70° C. for 6 hours, and then adding amino-modified nano-zinc oxide, and continuing to react at 70° C. for 2 hours to obtain a polyurethane spinning solution;

[0071] The mass ratio of polyurethane prepolymer solution, 2-(4-aminophenyl)-5-aminobenzimidazole, and amino-modified nano zinc oxide is 100:1.5:1;

[0072] The preparation method of amino-modified nano zinc oxide is the same as that in Example 2;

[0073] Step 3, dry-spinning the polyurethane spinning solution to obtain polyurethane fibers, wherein the denier of the polyurethane fibers is 30D;

[0074] The process parameters of dry spinning are the same as those in Example 2;

[0075] The polyurethane fiber is spun into polyurethane yarn, the yarn count of the polyurethane yarn is 40S, the polyurethane yarn is spun into polyurethane fabric through knitting technology, and the weight of the polyurethane fabric is 140g / m 2 ;

[0076] Step 4: melting the bio-based nylon, spinning the melt through a spinneret, cooling with side-blowing air, drawing, and winding to obtain bio-based nylon fiber;

[0077] The specific preparation process of the bio-based nylon fiber is the same as that of Example 2;

[0078] The bio-based nylon fiber is spun into bio-based nylon yarn with a yarn count of 40S. The bio-based nylon yarn is spun into fabric through a knitting process to obtain bio-based nylon fabric with a gram weight of 200g / m 2 ;

[0079] Polyurethane fabric is used as the inner fabric and bio-based nylon fabric is used as the outer fabric. The inner fabric and the outer fabric are sewn together with polyester thread to obtain bio-based antibacterial fiber fabric.

[0080] Example 4

[0081] This embodiment discloses a method for preparing a bio-based antibacterial fiber fabric, comprising the following steps:

[0082] Step 1: adding hexamethylene diisocyanate, polytetramethylene ether glycol, bio-based polyester polyol, and hexamidine diisothionate to N,N-dimethylacetamide, reacting at 75° C. for 3 hours, and obtaining a polyurethane prepolymer solution after the reaction is completed;

[0083] The molar ratio of hexamethylene diisocyanate, polytetramethylene ether glycol, bio-based polyester polyol, and hexamidine diisothionate is 1.65:0.46:0.42:0.17, and the amount of N,N-dimethylacetamide added is 1.5 times the total mass of hexamethylene diisocyanate, polytetramethylene ether glycol, bio-based polyester polyol, and hexamidine diisothionate.

[0084] The bio-based polyester polyol is the bio-based polyester polyol prepared in Example 1;

[0085] Step 2: adding 2-(4-aminophenyl)-5-aminobenzimidazole to the polyurethane prepolymer solution, reacting at 65° C. for 7 hours, and then adding amino-modified nano-zinc oxide, and continuing to react at 65° C. for 3 hours to obtain a polyurethane spinning solution;

[0086] The mass ratio of polyurethane prepolymer solution, 2-(4-aminophenyl)-5-aminobenzimidazole, and amino-modified nano zinc oxide is 100:1.2:0.6;

[0087] The preparation method of amino-modified nano zinc oxide is the same as that in Example 2;

[0088] Step 3, dry-spinning the polyurethane spinning solution to obtain polyurethane fibers, wherein the denier of the polyurethane fibers is 30D;

[0089] The process parameters of dry spinning are the same as those in Example 2;

[0090] The polyurethane fiber is spun into polyurethane yarn, the yarn count of the polyurethane yarn is 40S, the polyurethane yarn is spun into polyurethane fabric through knitting technology, and the weight of the polyurethane fabric is 140g / m 2 ;

[0091] Step 4: melting the bio-based nylon, spinning the melt through a spinneret, cooling with side-blowing air, drawing, and winding to obtain bio-based nylon fiber;

[0092] The specific preparation process of the bio-based nylon fiber is the same as that of Example 2;

[0093] The bio-based nylon fiber is spun into bio-based nylon yarn with a yarn count of 40S. The bio-based nylon yarn is spun into fabric through a knitting process to obtain bio-based nylon fabric with a gram weight of 200g / m 2 ;

[0094] Polyurethane fabric is used as the inner fabric and bio-based nylon fabric is used as the outer fabric. The inner fabric and the outer fabric are sewn together with polyester thread to obtain bio-based antibacterial fiber fabric.

[0095] Example 5

[0096] This embodiment discloses a method for preparing a bio-based antibacterial fiber fabric, comprising the following steps:

[0097] Step 1: adding isophorone diisocyanate, polyoxypropylene glycol, bio-based polyester polyol, and hexamidine diisothionate to N,N-dimethylacetamide, and reacting at 75° C. for 3 hours to obtain a polyurethane prepolymer solution after the reaction is completed;

[0098] The molar ratio of isophorone diisocyanate, polyoxypropylene glycol, bio-based polyester polyol, and hexamidine diisothionate is 2:0.5:0.45:0.2, and the amount of N,N-dimethylacetamide added is 1.5 times the total mass of isophorone diisocyanate, polyoxypropylene glycol, bio-based polyester polyol, and hexamidine diisothionate.

[0099] The bio-based polyester polyol is the bio-based polyester polyol prepared in Example 1;

[0100] Step 2: adding 2-(4-aminophenyl)-5-aminobenzimidazole to the polyurethane prepolymer solution, reacting at 75° C. for 7 hours, and then adding amino-modified nano zinc oxide, and continuing to react at 75° C. for 3 hours to obtain a polyurethane spinning solution;

[0101] The mass ratio of polyurethane prepolymer solution, 2-(4-aminophenyl)-5-aminobenzimidazole, and amino-modified nano zinc oxide is 100:1.4:0.8;

[0102] The preparation method of amino-modified nano zinc oxide is the same as that in Example 2;

[0103] Step 3, dry-spinning the polyurethane spinning solution to obtain polyurethane fibers, wherein the denier of the polyurethane fibers is 30D;

[0104] The process parameters of dry spinning are the same as those in Example 2;

[0105] The polyurethane fiber is spun into polyurethane yarn, the yarn count of the polyurethane yarn is 40S, the polyurethane yarn is spun into polyurethane fabric through knitting technology, and the weight of the polyurethane fabric is 140g / m 2 ;

[0106] Step 4: melting the bio-based nylon, spinning the melt through a spinneret, cooling with side-blowing air, drawing, and winding to obtain bio-based nylon fiber;

[0107] The specific preparation process of the bio-based nylon fiber is the same as that of Example 2;

[0108] The bio-based nylon fiber is spun into bio-based nylon yarn with a yarn count of 40S. The bio-based nylon yarn is spun into fabric through a knitting process to obtain bio-based nylon fabric with a gram weight of 200g / m 2 ;

[0109] Polyurethane fabric is used as the inner fabric and bio-based nylon fabric is used as the outer fabric. The inner fabric and the outer fabric are sewn together with polyester thread to obtain bio-based antibacterial fiber fabric.

[0110] Comparative Example 1

[0111] This comparative example discloses a method for preparing a bio-based antibacterial fiber fabric, comprising the following steps:

[0112] Step 1: adding isophorone diisocyanate, polytetramethylene ether glycol, and bio-based polyester polyol to N,N-dimethylacetamide, reacting at 80° C. for 2 hours, and obtaining a polyurethane prepolymer solution after the reaction is completed;

[0113] The molar ratio of isophorone diisocyanate, polytetramethylene ether glycol, and bio-based polyester polyol is 2:0.6:0.95:0.2, and the amount of N,N-dimethylacetamide added is twice the total mass of isophorone diisocyanate, polytetramethylene ether glycol, and bio-based polyester polyol.

[0114] The bio-based polyester polyol is the bio-based polyester polyol prepared in Example 1;

[0115] Step 2: adding 2-(4-aminophenyl)-5-aminobenzimidazole to the polyurethane prepolymer solution, reacting at 70° C. for 6 hours, and then adding amino-modified nano-zinc oxide, and continuing to react at 70° C. for 2 hours to obtain a polyurethane spinning solution;

[0116] The mass ratio of polyurethane prepolymer solution, 2-(4-aminophenyl)-5-aminobenzimidazole, and amino-modified nano zinc oxide is 100:1.5:1;

[0117] The preparation method of amino-modified nano zinc oxide is the same as that in Example 2;

[0118] Step 3, dry-spinning the polyurethane spinning solution to obtain polyurethane fibers, wherein the denier of the polyurethane fibers is 30D;

[0119] The process parameters of dry spinning are the same as those in Example 2;

[0120] The polyurethane fiber is spun into polyurethane yarn, the yarn count of the polyurethane yarn is 40S, the polyurethane yarn is spun into polyurethane fabric through knitting technology, and the weight of the polyurethane fabric is 140g / m 2 ;

[0121] Step 4: melting the bio-based nylon, spinning the melt through a spinneret, cooling with side-blowing air, drawing, and winding to obtain bio-based nylon fiber;

[0122] The specific preparation process of the bio-based nylon fiber is the same as that of Example 2;

[0123] The bio-based nylon fiber is spun into bio-based nylon yarn with a yarn count of 40S. The bio-based nylon yarn is spun into fabric through a knitting process to obtain bio-based nylon fabric with a gram weight of 200g / m 2 ;

[0124] Polyurethane fabric is used as the inner fabric and bio-based nylon fabric is used as the outer fabric. The inner fabric and the outer fabric are sewn together with polyester thread to obtain bio-based antibacterial fiber fabric.

[0125] Comparative Example 2

[0126] This comparative example discloses a method for preparing a bio-based antibacterial fiber fabric, comprising the following steps:

[0127] Step 1: adding isophorone diisocyanate, polytetramethylene ether glycol, bio-based polyester polyol, and hexamidine diisothionate to N,N-dimethylacetamide, reacting at 80° C. for 2 hours, and obtaining a polyurethane prepolymer solution after the reaction is completed;

[0128] The molar ratio of isophorone diisocyanate, polytetramethylene ether glycol, bio-based polyester polyol, and hexamidine diisothionate is 2:0.5:0.45:0.2, and the amount of N,N-dimethylacetamide added is twice the total mass of isophorone diisocyanate, polytetramethylene ether glycol, bio-based polyester polyol, and hexamidine diisothionate.

[0129] The bio-based polyester polyol is the bio-based polyester polyol prepared in Example 1;

[0130] Step 2: adding 3,3'-dichloro-4,4'-diaminodiphenylmethane (chain extender MOCA) to the polyurethane prepolymer solution, reacting at 70°C for 6 hours, adding amino-modified nano zinc oxide after the reaction, and continuing to react at 70°C for 2 hours to obtain a polyurethane spinning solution;

[0131] The mass ratio of polyurethane prepolymer solution, 3,3'-dichloro-4,4'-diaminodiphenylmethane, and amino-modified nano zinc oxide is 100:1.5:1;

[0132] The preparation method of amino-modified nano zinc oxide is the same as that in Example 2;

[0133] Step 3, dry-spinning the polyurethane spinning solution to obtain polyurethane fibers, wherein the denier of the polyurethane fibers is 30D;

[0134] The process parameters of dry spinning are the same as those in Example 2;

[0135] The polyurethane fiber is spun into polyurethane yarn, the yarn count of the polyurethane yarn is 40S, the polyurethane yarn is spun into polyurethane fabric through knitting technology, and the weight of the polyurethane fabric is 140g / m 2 ;

[0136] Step 4: melting the bio-based nylon, spinning the melt through a spinneret, cooling with side-blowing air, drawing, and winding to obtain bio-based nylon fiber;

[0137] The specific preparation process of the bio-based nylon fiber is the same as that of Example 2;

[0138] The bio-based nylon fiber is spun into bio-based nylon yarn with a yarn count of 40S. The bio-based nylon yarn is spun into fabric through a knitting process to obtain bio-based nylon fabric with a gram weight of 200g / m 2 ;

[0139] Polyurethane fabric is used as the inner fabric and bio-based nylon fabric is used as the outer fabric. The inner fabric and the outer fabric are sewn together with polyester thread to obtain bio-based antibacterial fiber fabric.

[0140] In the above examples and comparative examples, bio-based 1,4-butanediol was purchased from Zhejiang Boju New Materials Co., Ltd., CAS No.: 110-63-4; stannous octoate was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd., CAS No.: 301-10-0; polyoxypropylene glycol was PPG-400, purchased from Guangzhou Jinwang Chemical Co., Ltd., molecular weight: 400; polytetramethylene ether glycol was PTMEG-650, purchased from Shandong Weishang Chemical Co., Ltd., average molar mass (g / mo l): 625-675; 2-(4-aminophenyl)-5-aminobenzimidazole was purchased from Wuhan Chengtian Fine Chemical Co., Ltd., CAS No.: 7621-86-5; nano zinc oxide was purchased from Darcynon Nanotechnology (Changzhou) Co., Ltd., model: DXN-HQ20, particle size range: 10-30 nm; bio-based nylon is bio-based nylon PA56, purchased from Shenzhen Wansuyuan Rubber and Plastic Co., Ltd.; polyester yarn was purchased from Huzhou Haotian Industry Co., Ltd., item number: 402 bleached yarn.

[0141] Test Case

[0142] The polyurethane fabrics prepared in the above examples and comparative examples were subjected to performance tests:

[0143] (1) Antibacterial performance: The antibacterial rates of the polyurethane fabrics prepared in Examples 2-5 and Comparative Examples 1-2 after washing 50 times were measured with reference to the standard FZ / T73023-2006 "Antibacterial Knitwear". The results are shown in Table 1:

[0144] Table 1

[0145]

[0146] As shown in Table 1, the polyurethane fabric prepared by the present invention has excellent antibacterial properties. Using the cationic bactericidal component hexamidine dihydroxyethyl sulfonate as a crosslinker for preparing the polyurethane prepolymer can effectively improve the antibacterial properties of the polyurethane fabric. Using 2-(4-aminophenyl)-5-aminobenzimidazole as a polyurethane chain extender and the introduction of imidazole rings can also improve the antibacterial properties of the polyurethane fabric. Using amino-modified nano zinc oxide as a capping agent can further enhance the antibacterial properties of the polyurethane fabric. Each antibacterial component is chemically bonded to the polyurethane molecule, and the antibacterial properties are stable and long-lasting. Compared with Example 3, in Comparative Example 1, the crosslinker hexamidine dihydroxyethyl sulfonate was not added, and the antibacterial properties of the polyurethane decreased. In Comparative Example 2, the chain extender was replaced by 3,3'-dichloro-4,4'-diaminodiphenylmethane instead of 2-(4-aminophenyl)-5-aminobenzimidazole, and the antibacterial properties also decreased.

[0147] (2) Hygroscopicity: The hygroscopicity of the polyurethane fabrics prepared in Examples 2-5 and Comparative Examples 1-2 was measured with reference to the standard GB / T21655.1-2008 “Evaluation of Moisture Absorption and Quick-Drying Properties of Textiles Part 1: Single Item Combined Test Method”. The specific test parameters were water absorption rate and water diffusion time. The test results are shown in Table 2:

[0148] Table 2

[0149]

[0150] Table 2 shows that the polyurethane fabric produced by the present invention exhibits excellent hygroscopic properties. Using the cationic bactericidal component hexamidine diisethionate as a crosslinker in the preparation of the polyurethane prepolymer, the sulfonate is a hydrophilic group that effectively improves the hygroscopic properties of the polyurethane fabric. Compared to Example 3, in Comparative Example 1, where the crosslinker hexamidine diisethionate was omitted, the hygroscopic properties of the polyurethane fabric were significantly reduced.

[0151] While embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions, and variations may be made to these embodiments without departing from the principles and spirit of the invention, and that the scope of the invention is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a bio-based antibacterial fiber fabric, characterized in that: The following steps are involved: Step 1: adding diisocyanate, polyether polyol, bio-based polyester polyol, and hexamidine dihydroxyethyl sulfonate to N,N-dimethylacetamide for reaction, and obtaining a polyurethane prepolymer solution after the reaction is completed; The molar ratio of diisocyanate, polyether polyol, bio-based polyester polyol and hexamidine diisothionate is (1.5-2):(0.45-0.5):(0.4-0.45):(0.15-0.2); Step 2: adding 2-(4-aminophenyl)-5-aminobenzimidazole to the polyurethane prepolymer solution and reacting. After the reaction is completed, adding amino-modified nano zinc oxide and continuing the reaction to obtain a polyurethane spinning solution; Wherein, the mass ratio of polyurethane prepolymer solution, 2-(4-aminophenyl)-5-aminobenzimidazole, and amino-modified nano zinc oxide is 100:(1-1.5):(0.5-1); Step 3, dry spinning the polyurethane spinning solution to obtain polyurethane fibers; The polyurethane fiber is spun into polyurethane yarn, and the polyurethane yarn is spun into polyurethane fabric through a knitting process; Step 4: melting the bio-based nylon, spinning the melt through a spinneret, cooling with side-blowing air, drawing, and winding to obtain bio-based nylon fiber; Spinning bio-based nylon fibers into bio-based nylon yarns, and knitting the bio-based nylon yarns into fabrics to obtain bio-based nylon fabrics; Polyurethane fabric is used as the inner fabric and bio-based nylon fabric is used as the outer fabric. The inner and outer fabrics are compounded to obtain bio-based antibacterial fiber fabric.

2. The method for preparing a bio-based antibacterial fiber fabric according to claim 1, characterized in that: In the step 1, the amount of N,N-dimethylacetamide added is 1-2 times the mass of the diisocyanate, polyether polyol, bio-based polyester polyol, and hexamidine diisothionate, and the reaction conditions are 70-80° C. for 2-4 hours; The diisocyanate includes any one of hexamethylene diisocyanate and isophorone diisocyanate; The polyether polyol includes any one of polyoxypropylene glycol and polytetramethylene ether glycol.

3. The method for preparing a bio-based antibacterial fiber fabric according to claim 1, characterized in that: The bio-based polyester polyol in step 1 is prepared by the following steps: (1) Mixing bio-based diol and dibasic acid, and reacting at a pressure of 0.03-0.1 MPa and a temperature of 130-190°C until the acid value of the reaction mixture is ≤1 mgKOH / g; (2) Add a catalyst and keep the reaction at a temperature of 190-210°C until the acid value of the reaction mixture is less than 0.3 mgKOH / g. After the reaction is completed, perform reduced pressure distillation at a temperature of 120-140°C and a pressure of 0.07-0.09 MPa to remove the water generated by the esterification reaction to obtain a bio-based polyester polyol.

4. The method for preparing a bio-based antibacterial fiber fabric according to claim 3, characterized in that: The molar ratio of the bio-based diol and the dibasic acid is (1.1-1.5):1; the amount of the catalyst added is 0.1%-0.3% of the total mass of the bio-based diol and the dibasic acid; Bio-based diols include bio-based 1,4-butanediol; Diacids include 1,6-adipic acid; The catalyst includes stannous octoate.

5. The method for preparing a bio-based antibacterial fiber fabric according to claim 1, characterized in that: In the step 2, the reaction conditions are: reaction at 60-70° C. for 6-8 hours, and the conditions for continued reaction are: reaction at 60-70° C. for 2-4 hours.

6. The method for preparing a bio-based antibacterial fiber fabric according to claim 1, characterized in that: In the step 3, the process parameters of dry spinning include: a spinneret with 3 holes and 36 heads, an upper nozzle temperature of 260° C., a lower nozzle temperature of 190° C., and a spinning speed of 800 m / min.

7. The method for preparing a bio-based antibacterial fiber fabric according to claim 1, characterized in that: In the step 3, the yarn count of the polyurethane yarn is 30-50S, and the weight of the polyurethane fabric is 120-150g / m 2 .

8. The method for preparing a bio-based antibacterial fiber fabric according to claim 1, characterized in that: In the step 4, the melting temperature is 270-280°C, the pressure of the spinneret is 15-18 MPa, the wind speed of the side blowing is 0.38 m / s, the temperature of the side blowing is 15-20°C, the oiling rate is 1.6%-1.8%, the drafting ratio is 1-1.2 times, and the winding speed is 4800-5000 m / min.

9. The method for preparing a bio-based antibacterial fiber fabric according to claim 1, characterized in that: In step 4, the yarn count of the bio-based nylon yarn is 30-50S, and the weight of the bio-based nylon fabric is 180-220g / m 2 .

10. A bio-based antibacterial fiber fabric prepared by the method for preparing a bio-based antibacterial fiber fabric according to any one of claims 1 to 9.

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