An antibacterial and heat-preserving composite yarn for knitting

Abstract

The present invention discloses an antibacterial and heat-preserving composite yarn for knitting. Using aluminum trichloride hexahydrate, tetraethyl orthosilicate, and aluminum isopropoxide as raw materials, porous mullite is prepared. After dissolving the modified polyester, mullite is added and mixed evenly, and then a polyester filament bundle is prepared by electrospinning. The polyester filament bundle is blended with wool to obtain a yarn. Then, chitosan is dissolved and citric acid is added, and the yarn is soaked therein to cause crosslinking between chitosan and the yarn. The modified polyester has a dendritic structure, and the mullite encapsulated inside can form a core-shell structure, so that the prepared composite yarn has good mechanical properties. A large number of Si-O-Si segments are contained in the branched chain segments, which cooperate with the porous mullite, so that the prepared composite yarn has good heat insulation performance. A large number of N-haloamine groups contained in the side chains can cooperate with chitosan to kill bacteria well, thereby achieving an antibacterial effect.

Description

Technical Field

[0001] The present invention relates to the technical field of composite yarn preparation, and particularly relates to an antibacterial and heat-preserving composite yarn for knitting. Background Art

[0002] Knitted fabrics are loved by consumers for their comfort, breathability, good elasticity, high extensibility and other characteristics. With the replacement of the clothing market and the improvement of consumers' taste level, the public's choice of clothing not only focuses on colors and styles, but also has higher and higher requirements for the style, matching, materials, etc. of clothing. More and more consumers choose knitted clothing with higher comfort, more application scenarios and more diversified matching. In terms of production, the production process of knitted products is shorter than that of woven products, with stronger raw material adaptability and more variety development, so it is favored by many enterprises. With the increasing improvement of people's living standards and the upgrading of domestic and foreign market consumption demands, while consumers pay attention to price and quality, they pay more attention to wearing experience. Therefore, people have higher and higher requirements for the wearing comfort of clothing, and knitted fabrics are widely favored by people due to their breathability and comfort. However, traditional clothing such as trousers needs to be thickened for warmth in autumn and winter. However, this method results in a heavier gram weight and cannot meet the requirements of modern people for the performance of fabrics. Summary of the Invention

[0003] The purpose of the present invention is to provide an antibacterial and heat-preserving composite yarn for knitting, so as to solve the problems of poor antibacterial effect and general heat-preserving effect of the yarn at the present stage.

[0004] The purpose of the present invention can be achieved by the following technical solutions:

[0005] An antibacterial and heat-preserving composite yarn for knitting is made by the following steps:

[0006] Step S1: Dissolve aluminum chloride hexahydrate in deionized water, add tetraethyl orthosilicate, stir for 30 - 40 s under the conditions of a rotation speed of 200 - 300 r / min and a temperature of 20 - 25 °C, add aluminum isopropoxide, stir for 15 - 20 s, then add anhydrous oxalic acid until the pH value is 3, stir for 7 - 9 h, and then calcine at a temperature of 1300 - 1350 °C for 1 - 3 h to obtain mullite;

[0007] Step S2: Dissolve the modified polyester in a mixed solvent of trifluoroacetic acid and dichloromethane, add mullite and mix evenly, and perform electrospinning under the conditions of a feeding rate of 15 - 20 m / min and a voltage of 24 - 26 kV to obtain a polyester fiber bundle;

[0008] Step S3: Blend the polyester fiber bundle and wool at a blending ratio of 5:1 to form a yarn. The specification of the yarn is 62.5 tex, the structure is single yarn, the twist direction is Z twist, and the twist density is 150 turns / m;

[0009] Step S4: Dissolve chitosan in acetic acid solution, add citric acid and mix evenly. Immerse the yarn in the solution. Under the conditions of a frequency of 20 - 30 kHz and a temperature of 90 - 95 °C, perform ultrasonic treatment for 10 - 15 min, then pre-dry at a temperature of 80 - 85 °C for 3 - 5 min, raise the temperature to 140 - 150 °C, and bake for 1 - 3 min to obtain an antibacterial and heat-preserving composite yarn for knitting.

[0010] Further, the mass ratio of aluminum chloride hexahydrate, deionized water, tetraethyl orthosilicate, and aluminum isopropoxide described in step S1 is 14.49:30:6.33:15.32.

[0011] Further, the volume ratio of trifluoroacetic acid to dichloromethane described in step S2 is 4:1, and the mass ratio of the modified polyester to mullite is 10 - 15:1.

[0012] Further, the dosage ratio of chitosan, acetic acid, and citric acid described in step S4 is 1 mmol:50 mL:2 g. The deacetylation degree of chitosan is 95%, and the viscosity is 100 mPa·s.

[0013] Further, the modified polyester is prepared by the following steps:

[0014] Step A1: Mix acrylic acid, diethanolamine, 1-hydroxybenzotriazole, and benzene, and react at a rotation speed of 150 - 200 r / min and a temperature of 25 - 30 °C for 2 - 3 h to obtain intermediate 1. Add 3-glycidoxypropylmethyldimethoxysilane and dimethyldichlorosilane to deionized water, stir at a rotation speed of 200 - 300 r / min and a temperature of 25 - 30 °C for 20 - 30 min, then add tetrahydrofuran and concentrated sulfuric acid, raise the temperature to 55 - 65 °C, keep warm for 5 - 10 min, add 1,1,3,3-tetramethyldisiloxane, and react for 3 - 5 h to obtain intermediate 2;

[0015] Step A2: Mix intermediate 1, intermediate 2, Kaster catalyst, and DMF evenly, and react at a rotation speed of 200 - 300 r / min and a temperature of 60 - 70 °C for 3 - 5 h to obtain intermediate 3. Mix intermediate 3, acrylamide, and ethanol evenly, and react at a rotation speed of 150 - 200 r / min, a temperature of 50 - 60 °C, and a basic pH for 6 - 8 h to obtain intermediate 4;

[0016] Step A3: Mix the intermediate 4, methylacryloyloxyethyltrimethylammonium chloride, methyl acrylate and benzene evenly, introduce nitrogen for protection, add potassium persulfate at a temperature of 80 - 90 °C, and react for 5 - 7 h to obtain a modified monomer. Mix the modified monomer, terephthalic acid, ethylene glycol and dibutyltin dilaurate, introduce nitrogen for protection, and react at a temperature of 225 - 235 °C and a pressure of 0.3 - 0.5 MPa for 2 - 2.5 h. Then raise the temperature to 260 - 265 °C and react for 2 - 2.5 h. Further raise the temperature to 270 - 275 °C and react for 1 - 1.5 h to obtain a modified polyester.

[0017] Furthermore, the molar ratio of acrylic acid, diethanolamine and 1 - hydroxybenzotriazole in Step A1 is 1:1:1.2, and the dosage ratio of 3 - glycidoxypropylmethyldimethoxysilane, dimethyldichlorosilane, deionized water and 1,1,3,3 - tetramethyldisiloxane is 1 mmol:5 mmol:10 mL:2 mmol. The dosage of concentrated sulfuric acid is 5 - 7% of the total mass of 3 - glycidoxypropylmethyldimethoxysilane, dimethyldichlorosilane and 1,1,3,3 - tetramethyldisiloxane.

[0018] Furthermore, the molar ratio of intermediate 1 and intermediate 2 in Step A2 is 2:1, the dosage of the Kaster catalyst is 0.03 - 0.05‰ of the total mass of intermediate 1 and intermediate 2, and the molar ratio of the epoxy group on intermediate 3 and acrylamide is 2:1.

[0019] Furthermore, the mass ratio of intermediate 4, methylacryloyloxyethyltrimethylammonium chloride and methyl acrylate in Step A3 is 5:10:2, the mass ratio of the modified monomer, terephthalic acid and ethylene glycol is 25:120:43, and the dosage of dibutyltin dilaurate is 0.35% of the total mass of the modified monomer, terephthalic acid and ethylene glycol.

[0020] Advantages of the present invention: A kind of antibacterial and heat-preserving composite yarn for knitting prepared by the present invention uses aluminum chloride hexahydrate, tetraethyl orthosilicate and aluminum isopropoxide as raw materials to prepare porous mullite. After dissolving the modified polyester, mullite is added and mixed evenly, and then electrospun to obtain a polyester filament bundle. The polyester filament bundle is blended with wool to obtain a yarn. Then, chitosan is dissolved and citric acid is added, and the yarn is soaked therein. The carboxyl group on citric acid can react with the hydroxyl group on chitosan and the active hydroxyl group on the surface of the yarn, so that chitosan crosslinks with the yarn, and then fills the gaps in the yarn. The modified polyester uses acrylic acid and diethanolamine as raw materials. Under the action of 1-hydroxybenzotriazole, the carboxyl group on acrylic acid dehydrates and condenses with the imine on diethanolamine to obtain intermediate 1. After hydrolyzing 3-glycidoxypropylmethyldimethoxysilane and dimethyldichlorosilane, they are polymerized with 1,1,3,3-tetramethyldisiloxane to form a terminal hydrogen bond polysiloxane to obtain intermediate 2. Under the action of a Kaster catalyst, the double bond on intermediate 1 reacts with the Si-H bond on intermediate 2 to obtain intermediate 3. Intermediate 3 and acrylamide react under alkaline conditions, so that the epoxy group on intermediate 3 reacts with the amide to obtain intermediate 4. Intermediate 4, methacryloyloxyethyltrimethylammonium chloride and methyl acrylate are polymerized to form a polyacrylate to obtain a modified monomer. The modified monomer, terephthalic acid and ethylene glycol are esterified and polymerized to obtain a modified polyester. The modified polyester has a dendritic structure, and the mullite encapsulated inside can form a core-shell structure, so that the prepared composite yarn has good mechanical properties. A large number of Si-O-Si chain segments are contained in the branched chain segments, which cooperate with the porous mullite, so that the prepared composite yarn has good heat insulation performance. At the same time, chitosan is used to crosslink and fill between the fibers, enhancing the connection between the fibers, thereby strengthening the mechanical properties and reducing the possibility of heat loss from the gaps between the fibers. The side chain contains a large number of N-haloamine groups, which can cooperate with chitosan to kill bacteria well, thereby achieving an antibacterial effect. Detailed implementation mode

[0021] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a 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 those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0022] Example 1: A kind of antibacterial and heat-preserving composite yarn for knitting is prepared by the following steps:

[0023] Step S1: Dissolve aluminum chloride hexahydrate in deionized water, add tetraethyl orthosilicate, stir for 30 s at a rotation speed of 200 r / min and a temperature of 20 °C, add aluminum isopropoxide, stir for 15 s, then add anhydrous oxalic acid until the pH value reaches 3, stir for 7 h, and then calcine at a temperature of 1300 °C for 1 h to obtain mullite;

[0024] Step S2: Dissolve the modified polyester in a mixed solvent of trifluoroacetic acid and dichloromethane, add mullite and mix evenly, and perform electrospinning at a pushing rate of 15 m / min and a voltage of 24 kV to obtain a polyester tow;

[0025] Step S3: Blend the polyester tow and wool at a blending ratio of 5:1 into a yarn. The specifications of the yarn are 62.5 tex, the structure is single yarn, the twist direction is Z twist, and the twist density is 150 turns / m;

[0026] Step S4: Dissolve chitosan in an acetic acid solution, add citric acid and mix evenly, soak the yarn in it, perform ultrasonic treatment for 10 min at a frequency of 20 kHz and a temperature of 90 °C, then pre-bake at a temperature of 80 °C for 3 min, raise the temperature to 140 °C, and bake for 1 min to obtain an antibacterial and heat-preserving composite yarn for knitting.

[0027] The mass ratio of aluminum chloride hexahydrate, deionized water, tetraethyl orthosilicate and aluminum isopropoxide described in Step S1 is 14.49:30:6.33:15.32, and the dosage of aluminum chloride hexahydrate is 200 g.

[0028] The volume ratio of trifluoroacetic acid to dichloromethane described in Step S2 is 4:1, the mass ratio of the modified polyester to mullite is 15:1, and the mass of the modified polyester is 1000 g.

[0029] The dosage ratio of chitosan, acetic acid and citric acid described in Step S4 is 1 mmol:50 mL:2 g. The deacetylation degree of chitosan is 95%, the viscosity is 100 mPa·s, and the dosage of acetic acid is 2 L.

[0030] The described modified polyester is prepared by the following steps:

[0031] Step A1: Mix acrylic acid, diethanolamine, 1-hydroxybenzotriazole and benzene, and react for 2 h at a rotation speed of 150 r / min and a temperature of 25 °C to obtain Intermediate 1. Add 3-glycidoxypropylmethyldimethoxysilane and dimethyldichlorosilane to deionized water, stir for 20 min at a rotation speed of 200 r / min and a temperature of 25 °C, then add tetrahydrofuran and concentrated sulfuric acid, raise the temperature to 55 °C, keep warm for 5 min, add 1,1,3,3-tetramethyldisiloxane, and react for 3 h to obtain Intermediate 2;

[0032] Step A2: Mix intermediate 1, intermediate 2, Kast catalyst, and DMF evenly. React for 3 h under the conditions of a rotation speed of 200 r / min and a temperature of 60 °C to obtain intermediate 3. Mix intermediate 3, acrylamide, and ethanol evenly. React for 6 h under the conditions of a rotation speed of 150 r / min, a temperature of 50 °C, and a basic pH to obtain intermediate 4;

[0033] Step A3: Mix intermediate 4, methacryloyloxyethyltrimethylammonium chloride, methyl acrylate, and benzene evenly. Introduce nitrogen for protection. Add potassium persulfate at a temperature of 80 °C and react for 5 h to obtain a modified monomer. Mix the modified monomer, terephthalic acid, ethylene glycol, and dibutyltin dilaurate, introduce nitrogen for protection, and react at a temperature of 225 °C and a pressure of 0.3 MPa for 2 h. Raise the temperature to 260 °C and react for 2 h. Raise the temperature to 270 °C and react for 1 h to obtain a modified polyester.

[0034] The molar ratio of acrylic acid, diethanolamine, and 1-hydroxybenzotriazole in Step A1 is 1:1:1.2. The dosage ratio of 3-glycidoxypropylmethyldimethoxysilane, dimethyldichlorosilane, deionized water, and 1,1,3,3-tetramethyldisiloxane is 1 mmol:5 mmol:10 mL:2 mmol. The dosage of concentrated sulfuric acid is 5% of the total mass of 3-glycidoxypropylmethyldimethoxysilane, dimethyldichlorosilane, and 1,1,3,3-tetramethyldisiloxane. The dosage of acrylic acid is 30 mol, and the dosage of 3-glycidoxypropylmethyldimethoxysilane is 20 mol.

[0035] The molar ratio of intermediate 1 and intermediate 2 in Step A2 is 2:1. The dosage of Kast catalyst is 0.03‰ of the total mass of intermediate 1 and intermediate 2. The molar ratio of the epoxy group on intermediate 3 and acrylamide is 2:1. The dosage of intermediate 1 is 15 mol.

[0036] The mass ratio of intermediate 4, methacryloyloxyethyltrimethylammonium chloride, and methyl acrylate in Step A3 is 5:10:2. The mass ratio of the modified monomer, terephthalic acid, and ethylene glycol is 25:120:43. The dosage of dibutyltin dilaurate is 0.35% of the total mass of the modified monomer, terephthalic acid, and ethylene glycol. The dosage of intermediate 4 is 1500 g, and the dosage of the modified monomer is 1000 g.

[0037] Example 2: An antibacterial and heat-preserving composite yarn for knitting is made by the following steps:

[0038] Step S1: Dissolve aluminum chloride hexahydrate in deionized water, add tetraethyl orthosilicate, stir for 35 s at a rotation speed of 200 r / min and a temperature of 23 °C, add aluminum isopropoxide, stir for 18 s, then add anhydrous oxalic acid until the pH value reaches 3, stir for 8 h, and then calcine at a temperature of 1330 °C for 2 h to obtain mullite;

[0039] Step S2: Dissolve the modified polyester in a mixed solvent of trifluoroacetic acid and dichloromethane, add mullite and mix evenly, and perform electrospinning at a pushing rate of 15 m / min and a voltage of 25 kV to obtain a polyester fiber bundle;

[0040] Step S3: Blend the polyester fiber bundle and wool at a blending ratio of 5:1 to form a yarn. The specifications of the yarn are 62.5 tex, the structure is single yarn, the twist direction is Z twist, and the twist density is 150 turns / m;

[0041] Step S4: Dissolve chitosan in an acetic acid solution, add citric acid and mix evenly, soak the yarn in it, perform ultrasonic treatment for 10 min at a frequency of 25 kHz and a temperature of 93 °C, then pre-bake at a temperature of 85 °C for 4 min, raise the temperature to 145 °C, and bake for 2 min to obtain an antibacterial and heat-preserving composite yarn for knitting.

[0042] The mass ratio of aluminum chloride hexahydrate, deionized water, tetraethyl orthosilicate and aluminum isopropoxide described in Step S1 is 14.49:30:6.33:15.32, and the dosage of aluminum chloride hexahydrate is 200 g.

[0043] The volume ratio of trifluoroacetic acid to dichloromethane described in Step S2 is 4:1, the mass ratio of the modified polyester to mullite is 18:1, and the mass of the modified polyester is 1000 g.

[0044] The dosage ratio of chitosan, acetic acid and citric acid described in Step S4 is 1 mmol:50 mL:2 g. The deacetylation degree of chitosan is 95%, the viscosity is 100 mPa·s, and the dosage of acetic acid is 2 L.

[0045] The modified polyester is prepared by the following steps:

[0046] Step A1: Mix acrylic acid, diethanolamine, 1-hydroxybenzotriazole and benzene, and react for 2.5 h at a rotation speed of 150 r / min and a temperature of 28 °C to obtain Intermediate 1. Add 3-glycidoxypropylmethyldimethoxysilane and dimethyldichlorosilane to deionized water, stir for 25 min at a rotation speed of 200 r / min and a temperature of 30 °C, then add tetrahydrofuran and concentrated sulfuric acid, raise the temperature to 60 °C, keep warm for 8 min, add 1,1,3,3-tetramethyldisiloxane, and react for 4 h to obtain Intermediate 2;

[0047] Step A2: Mix intermediate 1, intermediate 2, Kast catalyst and DMF evenly. React for 4 h under the conditions of a rotation speed of 200 r / min and a temperature of 65 °C to obtain intermediate 3. Mix intermediate 3, acrylamide and ethanol evenly. React for 7 h under the conditions of a rotation speed of 200 r / min, a temperature of 55 °C and a basic pH to obtain intermediate 4;

[0048] Step A3: Mix intermediate 4, methacryloyloxyethyltrimethylammonium chloride, methyl acrylate and benzene evenly. Pass in nitrogen for protection. Add potassium persulfate under the condition of a temperature of 85 °C and react for 6 h to obtain a modified monomer. Mix the modified monomer, terephthalic acid, ethylene glycol and dibutyltin dilaurate, pass in nitrogen for protection, and react for 2.5 h under the conditions of a temperature of 230 °C and a pressure of 0.4 MPa. Raise the temperature to 260 °C and react for 2.3 h. Raise the temperature to 273 °C and react for 1.5 h to obtain a modified polyester.

[0049] The molar ratio of acrylic acid, diethanolamine and 1-hydroxybenzotriazole described in Step A1 is 1:1:1.2. The dosage ratio of 3-glycidoxypropylmethyldimethoxysilane, dimethyldichlorosilane, deionized water and 1,1,3,3-tetramethyldisiloxane is 1 mmol:5 mmol:10 mL:2 mmol. The dosage of concentrated sulfuric acid is 6% of the total mass of 3-glycidoxypropylmethyldimethoxysilane, dimethyldichlorosilane and 1,1,3,3-tetramethyldisiloxane. The dosage of acrylic acid is 30 mol, and the dosage of 3-glycidoxypropylmethyldimethoxysilane is 20 mol.

[0050] The molar ratio of intermediate 1 and intermediate 2 described in Step A2 is 2:1. The dosage of Kast catalyst is 0.04‰ of the total mass of intermediate 1 and intermediate 2. The molar ratio of the epoxy group on intermediate 3 and acrylamide is 2:1. The dosage of intermediate 1 is 15 mol.

[0051] The mass ratio of intermediate 4, methacryloyloxyethyltrimethylammonium chloride and methyl acrylate described in Step A3 is 5:10:2. The mass ratio of the modified monomer, terephthalic acid and ethylene glycol is 25:120:43. The dosage of dibutyltin dilaurate is 0.35% of the total mass of the modified monomer, terephthalic acid and ethylene glycol. The dosage of intermediate 4 is 1500 g, and the dosage of the modified monomer is 1000 g.

[0052] Example 3: An antibacterial and heat-preserving composite yarn for knitting is prepared by the following steps:

[0053] Step S1: Dissolve aluminum chloride hexahydrate in deionized water, add tetraethyl orthosilicate, stir for 40 s under the conditions of a rotation speed of 300 r / min and a temperature of 25 °C, add aluminum isopropoxide, stir for 20 s, then add anhydrous oxalic acid until the pH value reaches 3, stir for 9 h, and then calcine at 1350 °C for 3 h to obtain mullite;

[0054] Step S2: Dissolve the modified polyester in a mixed solvent of trifluoroacetic acid and dichloromethane, add mullite and mix evenly, and perform electrospinning under the conditions of a pushing rate of 20 m / min and a voltage of 26 kV to obtain a polyester fiber bundle;

[0055] Step S3: Blend the polyester fiber bundle and wool at a blending ratio of 5:1 into a yarn. The specification of the yarn is 62.5 tex, the structure is single yarn, the twist direction is Z twist, and the twist density is 150 turns / m;

[0056] Step S4: Dissolve chitosan in an acetic acid solution, add citric acid and mix evenly, soak the yarn in it, perform ultrasonic treatment for 15 min under the conditions of a frequency of 30 kHz and a temperature of 95 °C, then pre-dry at 85 °C for 5 min, raise the temperature to 150 °C, and bake for 3 min to obtain an antibacterial and heat-preserving composite yarn for knitting.

[0057] The mass ratio of the aluminum chloride hexahydrate, deionized water, tetraethyl orthosilicate, and aluminum isopropoxide described in Step S1 is 14.49:30:6.33:15.32, and the amount of aluminum chloride hexahydrate used is 200 g.

[0058] The volume ratio of the trifluoroacetic acid and dichloromethane described in Step S2 is 4:1, the mass ratio of the modified polyester and mullite is 20:1, and the mass of the modified polyester is 1000 g.

[0059] The dosage ratio of the chitosan, acetic acid, and citric acid described in Step S4 is 1 mmol:50 mL:2 g. The degree of deacetylation of chitosan is 95%, the viscosity is 100 mPa·s, and the amount of acetic acid used is 2 L.

[0060] The modified polyester is prepared by the following steps:

[0061] Step A1: Mix acrylic acid, diethanolamine, 1-hydroxybenzotriazole and benzene, and react for 2 - 3 h under the conditions of a rotation speed of 150 - 200 r / min and a temperature of 25 - 30 °C to obtain Intermediate 1. Add 3-glycidoxypropylmethyldimethoxysilane and dimethyldichlorosilane to deionized water, stir for 20 - 30 min under the conditions of a rotation speed of 200 - 300 r / min and a temperature of 25 - 30 °C, then add tetrahydrofuran and concentrated sulfuric acid, raise the temperature to 55 - 65 °C, keep warm for 5 - 10 min, add 1,1,3,3-tetramethyldisiloxane, and react for 3 - 5 h to obtain Intermediate 2;

[0062] Step A2: Mix Intermediate 1, Intermediate 2, Kaster catalyst and DMF evenly, and react for 5 h under the conditions of a rotation speed of 300 r / min and a temperature of 70 °C to obtain Intermediate 3. Mix Intermediate 3, acrylamide and ethanol evenly, and react for 8 h under the conditions of a rotation speed of 200 r / min, a temperature of 60 °C and a basic pH to obtain Intermediate 4;

[0063] Step A3: Mix Intermediate 4, methacryloyloxyethyltrimethylammonium chloride, methyl acrylate and benzene evenly, introduce nitrogen protection, add potassium persulfate under the condition of a temperature of 90 °C, and react for 7 h to obtain a modified monomer. Mix the modified monomer, terephthalic acid, ethylene glycol and dibutyltin dilaurate, introduce nitrogen protection, and react for 2.5 h under the conditions of a temperature of 235 °C and a pressure of 0.5 MPa, raise the temperature to 265 °C and react for 2.5 h, then raise the temperature to 275 °C and react for 1.5 h to obtain a modified polyester.

[0064] The molar ratio of acrylic acid, diethanolamine and 1-hydroxybenzotriazole described in Step A1 is 1:1:1.2. The dosage ratio of 3-glycidoxypropylmethyldimethoxysilane, dimethyldichlorosilane, deionized water and 1,1,3,3-tetramethyldisiloxane is 1 mmol:5 mmol:10 mL:2 mmol. The dosage of concentrated sulfuric acid is 7% of the total mass of 3-glycidoxypropylmethyldimethoxysilane, dimethyldichlorosilane and 1,1,3,3-tetramethyldisiloxane. The dosage of acrylic acid is 30 mol, and the dosage of 3-glycidoxypropylmethyldimethoxysilane is 20 mol.

[0065] The molar ratio of Intermediate 1 and Intermediate 2 described in Step A2 is 2:1. The dosage of Kaster catalyst is 0.05‰ of the total mass of Intermediate 1 and Intermediate 2. The molar ratio of the epoxy group on Intermediate 3 and acrylamide is 2:1. The dosage of Intermediate 1 is 15 mol.

[0066] The mass ratio of intermediate 4, methacryloyloxyethyl trimethyl ammonium chloride, and methyl acrylate described in step A3 is 5:10:2, the mass ratio of the modified monomer, terephthalic acid, and ethylene glycol is 25:120:43, the dosage of dibutyltin dilaurate is 0.35% of the total mass of the modified monomer, terephthalic acid, and ethylene glycol, the dosage of intermediate 4 is 1500 g, and the dosage of the modified monomer is 1000 g.

[0067] Comparative example 1: This comparative example is the same as example 1 except that the operation of step S4 is not carried out.

[0068] Comparative example 2: This comparative example is the same as example 1 except that the modified monomer is not used. Instead, terephthalic acid, ethylene glycol, and dibutyltin dilaurate are directly mixed, nitrogen protection is introduced, and the reaction is carried out at a temperature of 225 °C and a pressure of 0.3 MPa for 2 h, then the temperature is raised to 260 °C and the reaction is carried out for 2 h, and then the temperature is raised to 270 °C and the reaction is carried out for 1 h. The obtained reaction product is used instead of the modified polyester. The mass ratio of terephthalic acid to ethylene glycol is 120:65, and the dosage of terephthalic acid is 1000 g.

[0069] According to the standard of GB / T20944.3-2008, the antibacterial rates of the composite yarns against Escherichia coli and Staphylococcus aureus are detected. The composite yarns prepared in examples 1 to 3 and comparative examples 1 to 2 are made into greige fabrics. The yarn length of the greige fabric is 16 cm / 50 needles, and the yarn length involved in the knitting of the needle cylinder needles and the needle dial needles is 9.5 cm / 50 needles. The greige fabric is placed on a hot stage at a certain temperature with the inner side of the greige fabric contacting the hot stage, and the temperature difference between the surface of the hot stage and the upper surface of the fabric is measured. The test results are shown in the following table.

[0070]

[0071]

[0072] As can be seen from the above table, the composite yarns prepared in examples 1 to 3 have good antibacterial properties and heat retention effects.

[0073] The above content is only an example and explanation of the concept of the present invention. Those skilled in the art of this technology can make various modifications or supplements to the specific embodiments described or use similar methods for substitution, as long as they do not deviate from the concept of the invention or exceed the scope defined by this claim book, they should fall within the protection scope of the present invention.

Claims

1. An antibacterial and heat-preserving composite yarn for knitting, characterized in that: It is made by the following steps: Step S1: Dissolve aluminum chloride hexahydrate in deionized water, add tetraethyl orthosilicate, stir, add aluminum isopropoxide, stir, add anhydrous oxalic acid, stir, and finally perform a calcination treatment to obtain mullite; Step S2: Dissolve the modified polyester in a mixed solvent of trifluoroacetic acid and dichloromethane, add mullite and mix evenly, and perform electrospinning to obtain a polyester tow; Step S3: Blend the polyester tow and wool into a yarn; Step S4: Dissolve chitosan in an acetic acid solution, add citric acid and mix evenly, soak the yarn therein, perform ultrasonic treatment, pre-bake, and finally raise the temperature for baking to obtain an antibacterial and heat-preserving composite yarn for knitting; The modified polyester is made by the following steps: Step A1: React acrylic acid, diethanolamine, 1-hydroxybenzotriazole and benzene to obtain Intermediate 1. Add 3-glycidoxypropylmethyldimethoxysilane and dimethyldichlorosilane to deionized water, stir, add tetrahydrofuran and concentrated sulfuric acid, raise the temperature and keep it warm, add 1,1,3,3-tetramethyldisiloxane, and react to obtain Intermediate 2; Step A2: React Intermediate 1, Intermediate 2, Kaster catalyst and DMF to obtain Intermediate 3. React Intermediate 3, acrylamide and ethanol to obtain Intermediate 4; Step A3: Mix Intermediate 4, methacryloyloxyethyltrimethylammonium chloride, methyl acrylate and benzene evenly, then add potassium persulfate and react to obtain a modified monomer. React the modified monomer, terephthalic acid, ethylene glycol and dibutyltin dilaurate, and then raise the temperature to continue the reaction to obtain the modified polyester.

2. The antibacterial and heat-locking composite yarn for knitting according to claim 1, wherein: The mass ratio of the aluminum chloride hexahydrate, deionized water, tetraethyl orthosilicate and aluminum isopropoxide in Step S1 is 14.49:30:6.33:15.

32.

3. The antibacterial and heat-preserving composite yarn for knitting according to claim 1, characterized in that: The volume ratio of the trifluoroacetic acid and dichloromethane in Step S2 is 4:1, and the mass ratio of the modified polyester and mullite is 10 - 15:

1.

4. The antibacterial and heat-preserving composite yarn for knitting according to claim 1, wherein: The dosage ratio of the chitosan, acetic acid and citric acid in Step S4 is 1 mmol:50 mL:2 g.

5. The antibacterial and heat-locking composite yarn for knitting according to claim 1, wherein: The molar ratio of the acrylic acid, diethanolamine and 1-hydroxybenzotriazole in Step A1 is 1:1:1.

2. The dosage ratio of 3-glycidoxypropylmethyldimethoxysilane, dimethyldichlorosilane, deionized water and 1,1,3,3-tetramethyldisiloxane is 1 mmol:5 mmol:10 mL:2 mmol, and the dosage of concentrated sulfuric acid is 5 - 7% of the sum of the masses of 3-glycidoxypropylmethyldimethoxysilane, dimethyldichlorosilane and 1,1,3,3-tetramethyldisiloxane.

6. The antibacterial and heat-preserving composite yarn for knitting according to claim 1, characterized in that: The molar ratio of Intermediate 1 and Intermediate 2 in Step A2 is 2:

1. The dosage of the Kaster catalyst is 0.03 - 0.05‰ of the sum of the masses of Intermediate 1 and Intermediate 2. The molar ratio of the epoxy group on Intermediate 3 and acrylamide is 2:

1.

7. The antibacterial and heat-preserving composite yarn for knitting according to claim 1, wherein: The mass ratio of intermediate 4, methacryloyloxyethyl trimethyl ammonium chloride and methyl acrylate described in step A3 is 5:10:2, the mass ratio of the modifying monomer, terephthalic acid and ethylene glycol is 25:120:43, and the dosage of dibutyltin dilaurate is 0.35% of the sum of the masses of the modifying monomer, terephthalic acid and ethylene glycol.

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