An antibacterial and heat-insulating fiber based on thermal insulation material and its preparation method

Abstract

This invention relates to the field of fiber technology and discloses an antibacterial and heat-insulating fiber based on thermal insulation materials and its preparation method. By surface-modifying inorganic antibacterial and heat-insulating hollow titanium dioxide microspheres with polythiophene and polybutadiene, an antibacterial and heat-insulating material with good antibacterial and heat-insulating properties is prepared. This material is then introduced into polypropylene chips along with a reactive quaternary ammonium salt antibacterial agent, methacryloyloxyethyltrimethylammonium chloride, and extruded via a melt reaction. The resulting fiber possesses both excellent heat insulation and long-lasting antibacterial properties, while also improving the fiber's comfort.

Description

Technical Field

[0001] This invention relates to the field of fiber technology, specifically to an antibacterial and heat-insulating fiber based on thermal insulation materials and its preparation method. Background Technology

[0002] With the improvement of people's living standards and the pursuit of health and comfort, the demand for textiles with both warmth and antibacterial functions is increasing. Polypropylene fiber, due to its advantages such as light weight and good warmth retention, is widely used in thermal underwear, outdoor clothing and other fields. However, ordinary polypropylene fiber itself does not have antibacterial properties and can easily become a carrier for bacterial growth. Moreover, its warmth retention performance mainly relies on the static air layer formed by fiber stacking, resulting in limited functionality and difficulty in meeting the needs of high-end applications.

[0003] Existing technologies typically employ blending with inorganic or organic antibacterial agents to enhance the antibacterial properties of fibers. However, inorganic antibacterial agents exhibit poor dispersibility and agglomeration within the polypropylene matrix, and also suffer from poor compatibility with the polypropylene matrix, leading to a decline in fiber mechanical properties and insufficient antibacterial durability. Organic antibacterial agents, on the other hand, suffer from poor heat resistance and are prone to migration and precipitation within the matrix.

[0004] In terms of improving the thermal insulation performance of fibers, the common method in the existing technology is to add inorganic thermal insulation fillers. However, ordinary fillers have weak interfacial bonding with the matrix, and excessive filler content will affect the spinning and processing performance of the fibers.

[0005] Therefore, it is necessary to prepare a polypropylene fiber with excellent processing performance and both antibacterial and heat insulation functions. Summary of the Invention

[0006] The purpose of this invention is to overcome the shortcomings of existing technologies and provide an antibacterial and heat-insulating fiber based on thermal insulation materials and its preparation method. By surface-modifying inorganic antibacterial and heat-insulating hollow titanium dioxide microspheres with polythiophene and polybutadiene, an antibacterial and heat-insulating material with good antibacterial and heat-insulating properties is prepared. This material is then introduced into polypropylene chips along with a reactive quaternary ammonium salt antibacterial agent, methacryloyloxyethyltrimethylammonium chloride, and extruded via a melt reaction. The resulting fiber possesses both excellent heat insulation and long-lasting antibacterial properties, while also improving the fiber's comfort.

[0007] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0008] A method for preparing antibacterial and heat-insulating fibers based on thermal insulation materials includes the following steps:

[0009] Step (1): Thiophene-3-acetic acid is mixed with tetrahydrofuran, and triethylamine and pentafluorophenyl trifluoroacetate are added in sequence. After the reaction is completed, the mixture is purified to obtain thiophene grafted onto pentafluorophenyl trifluoroacetate.

[0010] Thiophene, pentafluorophenyl trifluoroacetate grafted with thiophene, and chloroform were mixed evenly to obtain a thiophene solution; hollow titanium dioxide microspheres, ferric chloride, and chloroform were mixed, ultrasonically dispersed, and then the thiophene solution was added. After the reaction was completed, the mixture was purified to obtain polythiophene-modified hollow titanium dioxide microspheres.

[0011] Step (2): Mix polythiophene-modified hollow titanium dioxide microspheres and N,N-dimethylformamide, disperse by ultrasonication, add 1-amino-11-azido-3,6,9-trioxaundecan and triethylamine, react, filter, wash and dry after reaction to obtain azido-polythiophene-modified hollow titanium dioxide microspheres.

[0012] Step (3): Mix azide-modified hollow titanium dioxide microspheres, alkynylated polybutadiene, and N,N-dimethylformamide, disperse by ultrasonication, add copper sulfate pentahydrate aqueous solution and sodium ascorbate aqueous solution in sequence, react, filter to collect precipitate after reaction, wash, dry, and obtain antibacterial heat insulation material;

[0013] Step (4): Mix antibacterial heat insulation material, methacryloyloxyethyltrimethylammonium chloride, polypropylene chips, and benzoyl peroxide, melt and react. After the reaction is complete, extrude and granulate to obtain antibacterial heat insulation polypropylene chips.

[0014] Antibacterial and heat-insulating polypropylene chips and polypropylene chips are melt-mixed, melt-spun in a twin-screw spinning machine, cooled and stretched to obtain antibacterial and heat-insulating fibers based on heat-insulating materials.

[0015] Preferably, in step (1), when preparing pentafluorophenyl trifluoroacetate grafted with thiophene, the ratio of thiophene-3-acetic acid, triethylamine, pentafluorophenyl trifluoroacetate, and tetrahydrofuran is 5g:19-20mL:12-13mL:130-200mL; the reaction conditions are: stirring at room temperature for 1-2 hours.

[0016] Preferably, in step (1), when preparing trifluoroacetic acid pentafluorophenyl ester grafted thiophene, the purification operation includes: removing the solvent by rotary evaporation, dissolving in ethyl acetate, washing with saturated sodium bicarbonate aqueous solution, separating the organic phase, adding anhydrous magnesium sulfate to dry, filtering to obtain the filtrate, removing the solvent by rotary evaporation, and using a mixture of ethyl acetate and n-hexane in a volume ratio of 1:10 as an eluent for column chromatography purification.

[0017] Preferably, in step (1), when preparing polythiophene-modified hollow titanium dioxide microspheres: the ratio of thiophene, pentafluorophenyl trifluoroacetate grafted thiophene, and chloroform is 0.5g:0.5g:10mL; the ratio of hollow titanium dioxide microspheres, ferric chloride, chloroform, and thiophene solution is 1g:1.5-2g:20-50mL:8-12mL; the reaction conditions are: reaction at room temperature under a nitrogen atmosphere for 10-18h.

[0018] Preferably, in step (1), when preparing polythiophene-modified hollow titanium dioxide microspheres, the purification operation includes: adding methanol and letting it stand, filtering to obtain the precipitate, washing with methanol, and drying.

[0019] Preferably, in step (2), the ratio of polythiophene-modified hollow titanium dioxide microspheres, 1-amino-11-azido-3,6,9-trioxaundecan, triethylamine, and N,N-dimethylformamide is 5-8g:0.07-0.1g:2-2.5mL:200-300mL; the reaction conditions are: stirring at 50-60℃ for 20-30h.

[0020] Preferably, in step (3): the concentration of copper sulfate pentahydrate aqueous solution is 0.45wt%; the concentration of sodium ascorbate aqueous solution is 0.7wt%; the ratio of azide-modified hollow titanium dioxide microspheres, alkynylated polybutadiene, N,N-dimethylformamide, copper sulfate pentahydrate, and sodium ascorbate is 5-8g:10g:200-500mL:0.8-0.12g:0.1-0.15g; the reaction conditions are: stirring reaction for 10-15h in a nitrogen atmosphere at 50-60℃.

[0021] Preferably, in step (3), the alkynylated polybutadiene is prepared by the following steps:

[0022] A solution of hydroxyl-terminated polybutadiene was added to a potassium tert-butoxide solution and reacted. After the reaction was completed, the temperature was lowered, and a propyne bromine solution was added to continue the reaction. After the reaction was completed, the mixture was purified to obtain alkynylated polybutadiene.

[0023] Preferably, in step (3), when preparing alkynylated polybutadiene: the hydroxyl-terminated polybutadiene solution is prepared by mixing and dissolving hydroxyl-terminated polybutadiene and tetrahydrofuran in a ratio of 10-11g:50mL; the potassium tert-butoxide solution is prepared by mixing and dissolving potassium tert-butoxide and tetrahydrofuran in a ratio of 2-2.5g:50mL; and the propyne bromide solution is prepared by mixing and dissolving propyne bromide and tetrahydrofuran in a ratio of 1.5-2.5mL:100mL.

[0024] Preferably, in step (3), when preparing alkynylated polybutadiene, the ratio of terminal hydroxyl polybutadiene, potassium tert-butoxide, and propyne bromide is 10-11g:2-2.5g:1.5-2.5mL; the reaction conditions are: in a nitrogen atmosphere, the temperature is raised from 0℃ to room temperature for 1h; the reaction continues under the following conditions: in a nitrogen atmosphere, the reaction continues at 0℃ with stirring for 44h.

[0025] Preferably, in step (3), when preparing alkynylated polybutadiene, the purification operation includes: heating to room temperature to obtain the reaction product, extracting the reaction product with saturated sodium chloride aqueous solution, taking the organic phase, washing it with saturated sodium chloride aqueous solution, drying it with anhydrous magnesium sulfate, filtering it to obtain the filtrate, and removing the solvent by rotary evaporation.

[0026] Preferably, in step (3), the mass ratio of antibacterial heat insulation material, methacryloyloxyethyltrimethylammonium chloride, polypropylene chips, and benzoyl peroxide is 10-15:4-6:100:0.3-0.6; the reaction conditions are: melting reaction at 180-190℃ for 8-10 minutes.

[0027] Preferably, in step (3): the mass ratio of antibacterial and heat-insulating polypropylene chips to polypropylene chips is 30-50:50-70; the melt spinning conditions are: spinning temperature is 225-235℃ in zone 1, 240-250℃ in zone 2, and 245-250℃ in zone 3, spinning speed is 450-550m / min; drawing temperature is 120-135℃, and drawing ratio is 2-4 times.

[0028] Preferably, the antibacterial and warm fiber based on thermal insulation material is prepared by the preparation method of the antibacterial and warm fiber based on thermal insulation material as described above.

[0029] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0030] This invention modifies the surface of inorganic antibacterial and thermal insulation material hollow titanium dioxide microspheres with polythiophene and polybutadiene to produce an antibacterial and thermal insulation material with good antibacterial and thermal insulation properties. The material is then introduced into polypropylene chips along with the reactive quaternary ammonium salt antibacterial agent methacryloyloxyethyltrimethylammonium chloride. After melt reaction extrusion, the resulting fiber has both excellent thermal insulation and long-lasting antibacterial properties, while also improving the comfort of the fiber.

[0031] This invention utilizes hollow titanium dioxide microspheres as an inorganic thermal insulation material. Thiophene monomers are polymerized and modified on their surface. Then, 1-amino-11-azido-3,6,9-trioxaundecane is used to replace pentafluorophenyl ester with a protected group to prepare azido-functionalized polythiophene-modified hollow titanium dioxide microspheres. Finally, polybutadiene is further grafted onto them through an azido-acetylene click reaction to synthesize a composite material with both antibacterial and thermal insulation properties.

[0032] Among them, the hollow titanium dioxide microspheres can store air with low thermal conductivity in their cavity structure, and the presence of the cavity structure complicates the heat transfer path. At the same time, light can form multi-level reflections in the cavity structure. The combined effect of multiple mechanisms makes it suitable as a heat insulation material. In addition, since titanium dioxide has photocatalytic bactericidal properties, it can also be used as an inorganic antibacterial agent to improve the antibacterial performance of the material. Polythiophene, as a conjugated polymer, has excellent photothermal conversion efficiency and good photostability, and can synergistically fight bacteria with hollow titanium dioxide microspheres to jointly optimize the antibacterial performance of the material. The polybutadiene structure has good compatibility with the polypropylene matrix, and the presence of its unsaturated carbon-carbon double bonds can be used to graft polypropylene with the reactive quaternary ammonium salt antibacterial agent methacryloyloxyethyltrimethylammonium chloride, improving the compatibility of each component. Attached Figure Description

[0033] Figure 1 This is a bar chart showing the antibacterial rate of the antibacterial and heat-insulating fibers based on thermal insulation materials prepared in Examples 1-5 and Comparative Examples 1-2 of this invention during performance testing.

[0034] Figure 2 This is a bar chart showing the temperature difference of the antibacterial and heat-insulating fibers based on thermal insulation materials prepared in Examples 1-5 and Comparative Examples 1-2 of this invention during performance testing. Detailed Implementation

[0035] The present invention will be further illustrated below through specific embodiments. The following embodiments are specific implementations of the present invention, but the implementation of the present invention is not limited to the following embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and are included within the protection scope of the present invention.

[0036] Example 1

[0037] This embodiment discloses a method for preparing antibacterial and heat-insulating fibers based on thermal insulation materials, including the following steps:

[0038] Step (1): Thiophene-3-acetic acid and tetrahydrofuran were mixed, and triethylamine and pentafluorophenyl trifluoroacetate were added sequentially at 0℃. The mixture was stirred and reacted at room temperature for 1.5 h. After the reaction was completed, the solvent was removed by rotary evaporation, dissolved in ethyl acetate, washed with saturated sodium bicarbonate aqueous solution, and the organic phase was separated. Anhydrous magnesium sulfate was added and dried. The filtrate was filtered and the solvent was removed by rotary evaporation. The filtrate was purified by column chromatography using a mixture of ethyl acetate and n-hexane in a volume ratio of 1:10 to obtain thiophene grafted with pentafluorophenyl trifluoroacetate.

[0039] The ratio of thiophene-3-acetic acid, triethylamine, pentafluorophenyl trifluoroacetate, and tetrahydrofuran is 5g:19.6mL:12.1mL:150mL.

[0040] Thiophene, trifluoroacetic acid pentafluorophenyl ester grafted thiophene, and chloroform were mixed evenly in a ratio of 0.5g:0.5g:10mL to obtain a thiophene solution.

[0041] Hollow titanium dioxide microspheres, ferric chloride, and chloroform were mixed in a nitrogen atmosphere and ultrasonically dispersed for 1 hour. Thiophene solution was added and reacted at room temperature for 12 hours. After the reaction was completed, methanol was added and allowed to stand. The precipitate was filtered and washed with methanol and dried at 60°C for 12 hours to obtain polythiophene-modified hollow titanium dioxide microspheres.

[0042] The ratio of hollow titanium dioxide microspheres, ferric chloride, chloroform, and thiophene solution was 1g:1.94g:30mL:10mL.

[0043] Step (2): Mix polythiophene-modified hollow titanium dioxide microspheres and N,N-dimethylformamide, ultrasonically disperse for 1 h, add 1-amino-11-azido-3,6,9-trioxaundecane and triethylamine, stir and react at 50℃ for 24 h, after the reaction is completed, wash with water and dry at 60℃ for 24 h to obtain azido-polythiophene-modified hollow titanium dioxide microspheres;

[0044] The ratio of polythiophene-modified hollow titanium dioxide microspheres, 1-amino-11-azido-3,6,9-trioxaundecan, triethylamine, and N,N-dimethylformamide was 6 g:0.07 g:2.24 mL:300 mL.

[0045] Step (3): Mix azide-modified hollow titanium dioxide microspheres, alkynylated polybutadiene, and N,N-dimethylformamide, and ultrasonically disperse for 1 hour. Then, add 0.45wt% copper sulfate pentahydrate aqueous solution and 0.7wt% sodium ascorbate aqueous solution sequentially. Stir and react for 12 hours in a nitrogen atmosphere at 50°C. After the reaction is complete, filter to collect the precipitate, wash with water, and dry at 60°C for 24 hours to obtain antibacterial and heat-insulating material.

[0046] The ratio of azide-modified hollow titanium dioxide microspheres, alkynylated polybutadiene, N,N-dimethylformamide, copper sulfate pentahydrate, and sodium ascorbate was 8g:10g:300mL:0.1g:0.14g.

[0047] Alkynylated polybutadiene is prepared by the following steps:

[0048] Hydroxyl-terminated polybutadiene and tetrahydrofuran were mixed and dissolved in a ratio of 10.96 g: 50 mL to obtain a hydroxyl-terminated polybutadiene solution; potassium tert-butoxide and tetrahydrofuran were mixed and dissolved in a ratio of 2.07 g: 50 mL to obtain a potassium tert-butoxide solution; propyne bromide and tetrahydrofuran were mixed and dissolved in a ratio of 2 mL: 100 mL to obtain a propyne bromide solution.

[0049] In a nitrogen atmosphere at 0°C, a solution of hydroxyl-terminated polybutadiene was added to a potassium tert-butoxide solution and reacted at room temperature for 1 hour. After the reaction was completed, the temperature was lowered to 0°C, and a propyne bromine solution was added. The mixture was stirred and reacted in a nitrogen atmosphere at 0°C for 44 hours. After the reaction was completed, the temperature was raised to room temperature to obtain the reaction product. The reaction product was extracted with a saturated sodium chloride aqueous solution, and the organic phase was taken. After washing with a saturated sodium chloride aqueous solution, the phase was dried with anhydrous magnesium sulfate, filtered, and the filtrate was collected. The solvent was removed by rotary evaporation to obtain alkynylated polybutadiene.

[0050] The ratio of hydroxyl-terminated polybutadiene, potassium tert-butoxide, and propyne bromide is 10.96 g: 2.07 g: 2 mL.

[0051] Step (4): Mix antibacterial heat insulation material, methacryloyloxyethyltrimethylammonium chloride, polypropylene chips, and benzoyl peroxide in a mass ratio of 10:6:100:0.6, melt and react at 180°C for 10 minutes, and after the reaction is complete, extrude and granulate to obtain antibacterial heat insulation polypropylene chips.

[0052] Antibacterial and heat-insulating polypropylene chips and polypropylene chips were melt-mixed at a mass ratio of 30:70, melt-spun in a twin-screw spinning machine, cooled and stretched to obtain antibacterial and heat-insulating fibers based on heat-insulating materials.

[0053] The melt spinning conditions were as follows: spinning temperature was 230℃ in zone 1, 245℃ in zone 2, and 250℃ in zone 3; spinning speed was 450m / min; drawing temperature was 120℃; and drawing ratio was 4.

[0054] Example 2

[0055] This embodiment discloses a method for preparing antibacterial and heat-insulating fibers based on thermal insulation materials, including the following steps:

[0056] Step (1): Thiophene-3-acetic acid and tetrahydrofuran were mixed, and triethylamine and pentafluorophenyl trifluoroacetate were added sequentially at 0℃. The mixture was stirred and reacted at room temperature for 1.5 h. After the reaction was completed, the solvent was removed by rotary evaporation, dissolved in ethyl acetate, washed with saturated sodium bicarbonate aqueous solution, and the organic phase was separated. Anhydrous magnesium sulfate was added and dried. The filtrate was filtered and the solvent was removed by rotary evaporation. The filtrate was purified by column chromatography using a mixture of ethyl acetate and n-hexane in a volume ratio of 1:10 to obtain thiophene grafted with pentafluorophenyl trifluoroacetate.

[0057] The ratio of thiophene-3-acetic acid, triethylamine, pentafluorophenyl trifluoroacetate, and tetrahydrofuran is 5g:19.6mL:12.1mL:150mL.

[0058] Thiophene, trifluoroacetic acid pentafluorophenyl ester grafted thiophene, and chloroform were mixed evenly in a ratio of 0.5g:0.5g:10mL to obtain a thiophene solution.

[0059] Hollow titanium dioxide microspheres, ferric chloride, and chloroform were mixed in a nitrogen atmosphere and ultrasonically dispersed for 1 hour. Thiophene solution was added and reacted at room temperature for 12 hours. After the reaction was completed, methanol was added and allowed to stand. The precipitate was filtered and washed with methanol and dried at 60°C for 12 hours to obtain polythiophene-modified hollow titanium dioxide microspheres.

[0060] The ratio of hollow titanium dioxide microspheres, ferric chloride, chloroform, and thiophene solution was 1g:1.94g:30mL:10mL.

[0061] Step (2): Mix polythiophene-modified hollow titanium dioxide microspheres and N,N-dimethylformamide, ultrasonically disperse for 1 h, add 1-amino-11-azido-3,6,9-trioxaundecane and triethylamine, stir and react at 50℃ for 24 h, after the reaction is completed, wash with water and dry at 60℃ for 24 h to obtain azido-polythiophene-modified hollow titanium dioxide microspheres;

[0062] The ratio of polythiophene-modified hollow titanium dioxide microspheres, 1-amino-11-azido-3,6,9-trioxaundecan, triethylamine, and N,N-dimethylformamide was 6 g:0.07 g:2.24 mL:300 mL.

[0063] Step (3): Mix azide-modified hollow titanium dioxide microspheres, alkynylated polybutadiene, and N,N-dimethylformamide, and ultrasonically disperse for 1 hour. Then, add 0.45wt% copper sulfate pentahydrate aqueous solution and 0.7wt% sodium ascorbate aqueous solution sequentially. Stir and react for 12 hours in a nitrogen atmosphere at 50°C. After the reaction is complete, filter to collect the precipitate, wash with water, and dry at 60°C for 24 hours to obtain antibacterial and heat-insulating material.

[0064] The ratio of azide-modified hollow titanium dioxide microspheres, alkynylated polybutadiene, N,N-dimethylformamide, copper sulfate pentahydrate, and sodium ascorbate was 8g:10g:300mL:0.1g:0.14g; the preparation of alkynylated polybutadiene was the same as in Example 1.

[0065] Step (4): Mix antibacterial heat insulation material, methacryloyloxyethyltrimethylammonium chloride, polypropylene chips, and benzoyl peroxide in a mass ratio of 12:6:100:0.6, melt and react at 180°C for 10 minutes, and after the reaction is complete, extrude and granulate to obtain antibacterial heat insulation polypropylene chips.

[0066] Antibacterial and heat-insulating polypropylene chips and polypropylene chips were melt-mixed at a mass ratio of 35:65, melt-spun in a twin-screw spinning machine, cooled and stretched to obtain antibacterial and heat-insulating fibers based on heat-insulating materials.

[0067] The melt spinning conditions were as follows: spinning temperature was 230℃ in zone 1, 245℃ in zone 2, and 250℃ in zone 3; spinning speed was 450m / min; drawing temperature was 120℃; and drawing ratio was 4.

[0068] Example 3

[0069] This embodiment discloses a method for preparing antibacterial and heat-insulating fibers based on thermal insulation materials, including the following steps:

[0070] Step (1): Thiophene-3-acetic acid and tetrahydrofuran were mixed, and triethylamine and pentafluorophenyl trifluoroacetate were added sequentially at 0℃. The mixture was stirred and reacted at room temperature for 1.5 h. After the reaction was completed, the solvent was removed by rotary evaporation, dissolved in ethyl acetate, washed with saturated sodium bicarbonate aqueous solution, and the organic phase was separated. Anhydrous magnesium sulfate was added and dried. The filtrate was filtered and the solvent was removed by rotary evaporation. The filtrate was purified by column chromatography using a mixture of ethyl acetate and n-hexane in a volume ratio of 1:10 to obtain thiophene grafted with pentafluorophenyl trifluoroacetate.

[0071] The ratio of thiophene-3-acetic acid, triethylamine, pentafluorophenyl trifluoroacetate, and tetrahydrofuran is 5g:19.6mL:12.1mL:150mL.

[0072] Thiophene, trifluoroacetic acid pentafluorophenyl ester grafted thiophene, and chloroform were mixed evenly in a ratio of 0.5g:0.5g:10mL to obtain a thiophene solution.

[0073] Hollow titanium dioxide microspheres, ferric chloride, and chloroform were mixed in a nitrogen atmosphere and ultrasonically dispersed for 1 hour. Thiophene solution was added and reacted at room temperature for 12 hours. After the reaction was completed, methanol was added and allowed to stand. The precipitate was filtered and washed with methanol and dried at 60°C for 12 hours to obtain polythiophene-modified hollow titanium dioxide microspheres.

[0074] The ratio of hollow titanium dioxide microspheres, ferric chloride, chloroform, and thiophene solution was 1g:1.94g:30mL:10mL.

[0075] Step (2): Mix polythiophene-modified hollow titanium dioxide microspheres and N,N-dimethylformamide, ultrasonically disperse for 1 h, add 1-amino-11-azido-3,6,9-trioxaundecane and triethylamine, stir and react at 50℃ for 24 h, after the reaction is completed, wash with water and dry at 60℃ for 24 h to obtain azido-polythiophene-modified hollow titanium dioxide microspheres;

[0076] The ratio of polythiophene-modified hollow titanium dioxide microspheres, 1-amino-11-azido-3,6,9-trioxaundecan, triethylamine, and N,N-dimethylformamide was 6 g:0.07 g:2.24 mL:300 mL.

[0077] Step (3): Mix azide-modified hollow titanium dioxide microspheres, alkynylated polybutadiene, and N,N-dimethylformamide, and ultrasonically disperse for 1 hour. Then, add 0.45wt% copper sulfate pentahydrate aqueous solution and 0.7wt% sodium ascorbate aqueous solution sequentially. Stir and react for 12 hours in a nitrogen atmosphere at 50°C. After the reaction is complete, filter to collect the precipitate, wash with water, and dry at 60°C for 24 hours to obtain antibacterial and heat-insulating material.

[0078] The ratio of azide-modified hollow titanium dioxide microspheres, alkynylated polybutadiene, N,N-dimethylformamide, copper sulfate pentahydrate, and sodium ascorbate was 8g:10g:300mL:0.1g:0.14g; the preparation of alkynylated polybutadiene was the same as in Example 1.

[0079] Step (4): Mix antibacterial heat insulation material, methacryloyloxyethyltrimethylammonium chloride, polypropylene chips, and benzoyl peroxide in a mass ratio of 13:6:100:0.6, melt and react at 180°C for 10 minutes, and after the reaction is complete, extrude and granulate to obtain antibacterial heat insulation polypropylene chips.

[0080] Antibacterial and heat-insulating polypropylene chips and polypropylene chips were melt-mixed at a mass ratio of 40:60, melt-spun in a twin-screw spinning machine, cooled and stretched to obtain antibacterial and heat-insulating fibers based on heat-insulating materials.

[0081] The melt spinning conditions were as follows: spinning temperature was 230℃ in zone 1, 245℃ in zone 2, and 250℃ in zone 3; spinning speed was 450m / min; drawing temperature was 120℃; and drawing ratio was 4.

[0082] Example 4

[0083] This embodiment discloses a method for preparing antibacterial and heat-insulating fibers based on thermal insulation materials, including the following steps:

[0084] Step (1): Thiophene-3-acetic acid and tetrahydrofuran were mixed, and triethylamine and pentafluorophenyl trifluoroacetate were added sequentially at 0℃. The mixture was stirred and reacted at room temperature for 1.5 h. After the reaction was completed, the solvent was removed by rotary evaporation, dissolved in ethyl acetate, washed with saturated sodium bicarbonate aqueous solution, and the organic phase was separated. Anhydrous magnesium sulfate was added and dried. The filtrate was filtered and the solvent was removed by rotary evaporation. The filtrate was purified by column chromatography using a mixture of ethyl acetate and n-hexane in a volume ratio of 1:10 to obtain thiophene grafted with pentafluorophenyl trifluoroacetate.

[0085] The ratio of thiophene-3-acetic acid, triethylamine, pentafluorophenyl trifluoroacetate, and tetrahydrofuran is 5g:19.6mL:12.1mL:150mL.

[0086] Thiophene, trifluoroacetic acid pentafluorophenyl ester grafted thiophene, and chloroform were mixed evenly in a ratio of 0.5g:0.5g:10mL to obtain a thiophene solution.

[0087] Hollow titanium dioxide microspheres, ferric chloride, and chloroform were mixed in a nitrogen atmosphere and ultrasonically dispersed for 1 hour. Thiophene solution was added and reacted at room temperature for 12 hours. After the reaction was completed, methanol was added and allowed to stand. The precipitate was filtered and washed with methanol and dried at 60°C for 12 hours to obtain polythiophene-modified hollow titanium dioxide microspheres.

[0088] The ratio of hollow titanium dioxide microspheres, ferric chloride, chloroform, and thiophene solution was 1g:1.94g:30mL:10mL.

[0089] Step (2): Mix polythiophene-modified hollow titanium dioxide microspheres and N,N-dimethylformamide, ultrasonically disperse for 1 h, add 1-amino-11-azido-3,6,9-trioxaundecane and triethylamine, stir and react at 50℃ for 24 h, after the reaction is completed, wash with water and dry at 60℃ for 24 h to obtain azido-polythiophene-modified hollow titanium dioxide microspheres;

[0090] The ratio of polythiophene-modified hollow titanium dioxide microspheres, 1-amino-11-azido-3,6,9-trioxaundecan, triethylamine, and N,N-dimethylformamide was 6 g:0.07 g:2.24 mL:300 mL.

[0091] Step (3): Mix azide-modified hollow titanium dioxide microspheres, alkynylated polybutadiene, and N,N-dimethylformamide, and ultrasonically disperse for 1 hour. Then, add 0.45wt% copper sulfate pentahydrate aqueous solution and 0.7wt% sodium ascorbate aqueous solution sequentially. Stir and react for 12 hours in a nitrogen atmosphere at 50°C. After the reaction is complete, filter to collect the precipitate, wash with water, and dry at 60°C for 24 hours to obtain antibacterial and heat-insulating material.

[0092] The ratio of azide-modified hollow titanium dioxide microspheres, alkynylated polybutadiene, N,N-dimethylformamide, copper sulfate pentahydrate, and sodium ascorbate was 8g:10g:300mL:0.1g:0.14g; the preparation of alkynylated polybutadiene was the same as in Example 1.

[0093] Step (4): Mix antibacterial heat insulation material, methacryloyloxyethyltrimethylammonium chloride, polypropylene chips, and benzoyl peroxide in a mass ratio of 14:6:100:0.6, melt and react at 180°C for 10 minutes, and after the reaction is complete, extrude and granulate to obtain antibacterial heat insulation polypropylene chips.

[0094] Antibacterial and heat-insulating polypropylene chips and polypropylene chips were melt-mixed at a mass ratio of 45:55, melt-spun in a twin-screw spinning machine, cooled and stretched to obtain antibacterial and heat-insulating fibers based on heat-insulating materials.

[0095] The melt spinning conditions were as follows: spinning temperature was 230℃ in zone 1, 245℃ in zone 2, and 250℃ in zone 3; spinning speed was 450m / min; drawing temperature was 120℃; and drawing ratio was 4.

[0096] Example 5

[0097] This embodiment discloses a method for preparing antibacterial and heat-insulating fibers based on thermal insulation materials, including the following steps:

[0098] Step (1): Thiophene-3-acetic acid and tetrahydrofuran were mixed, and triethylamine and pentafluorophenyl trifluoroacetate were added sequentially at 0℃. The mixture was stirred and reacted at room temperature for 1.5 h. After the reaction was completed, the solvent was removed by rotary evaporation, dissolved in ethyl acetate, washed with saturated sodium bicarbonate aqueous solution, and the organic phase was separated. Anhydrous magnesium sulfate was added and dried. The filtrate was filtered and the solvent was removed by rotary evaporation. The filtrate was purified by column chromatography using a mixture of ethyl acetate and n-hexane in a volume ratio of 1:10 to obtain thiophene grafted with pentafluorophenyl trifluoroacetate.

[0099] The ratio of thiophene-3-acetic acid, triethylamine, pentafluorophenyl trifluoroacetate, and tetrahydrofuran is 5g:19.6mL:12.1mL:150mL.

[0100] Thiophene, trifluoroacetic acid pentafluorophenyl ester grafted thiophene, and chloroform were mixed evenly in a ratio of 0.5g:0.5g:10mL to obtain a thiophene solution.

[0101] Hollow titanium dioxide microspheres, ferric chloride, and chloroform were mixed in a nitrogen atmosphere and ultrasonically dispersed for 1 hour. Thiophene solution was added and reacted at room temperature for 12 hours. After the reaction was completed, methanol was added and allowed to stand. The precipitate was filtered and washed with methanol and dried at 60°C for 12 hours to obtain polythiophene-modified hollow titanium dioxide microspheres.

[0102] The ratio of hollow titanium dioxide microspheres, ferric chloride, chloroform, and thiophene solution was 1g:1.94g:30mL:10mL.

[0103] Step (2): Mix polythiophene-modified hollow titanium dioxide microspheres and N,N-dimethylformamide, ultrasonically disperse for 1 h, add 1-amino-11-azido-3,6,9-trioxaundecane and triethylamine, stir and react at 50℃ for 24 h, after the reaction is completed, wash with water and dry at 60℃ for 24 h to obtain azido-polythiophene-modified hollow titanium dioxide microspheres;

[0104] The ratio of polythiophene-modified hollow titanium dioxide microspheres, 1-amino-11-azido-3,6,9-trioxaundecan, triethylamine, and N,N-dimethylformamide was 6 g:0.07 g:2.24 mL:300 mL.

[0105] Step (3): Mix azide-modified hollow titanium dioxide microspheres, alkynylated polybutadiene, and N,N-dimethylformamide, and ultrasonically disperse for 1 hour. Then, add 0.45wt% copper sulfate pentahydrate aqueous solution and 0.7wt% sodium ascorbate aqueous solution sequentially. Stir and react for 12 hours in a nitrogen atmosphere at 50°C. After the reaction is complete, filter to collect the precipitate, wash with water, and dry at 60°C for 24 hours to obtain antibacterial and heat-insulating material.

[0106] The ratio of azide-modified hollow titanium dioxide microspheres, alkynylated polybutadiene, N,N-dimethylformamide, copper sulfate pentahydrate, and sodium ascorbate was 8g:10g:300mL:0.1g:0.14g; the preparation of alkynylated polybutadiene was the same as in Example 1.

[0107] Step (4): Mix antibacterial heat insulation material, methacryloyloxyethyltrimethylammonium chloride, polypropylene chips, and benzoyl peroxide in a mass ratio of 15:6:100:0.6, melt and react at 180°C for 10 minutes, and after the reaction is complete, extrude and granulate to obtain antibacterial heat insulation polypropylene chips.

[0108] Antibacterial and heat-insulating polypropylene chips and polypropylene chips were melt-mixed at a mass ratio of 50:50, melt-spun in a twin-screw spinning machine, cooled and stretched to obtain antibacterial and heat-insulating fibers based on heat-insulating materials.

[0109] The melt spinning conditions were as follows: spinning temperature was 230℃ in zone 1, 245℃ in zone 2, and 250℃ in zone 3; spinning speed was 450m / min; drawing temperature was 120℃; and drawing ratio was 4.

[0110] Comparative Example 1

[0111] This comparative example discloses a method for preparing antibacterial and heat-insulating fibers based on thermal insulation materials, including the following steps:

[0112] Step (1): Mix thiophene and chloroform at a ratio of 1g:10mL to obtain a thiophene solution;

[0113] Hollow titanium dioxide microspheres, ferric chloride, and chloroform were mixed in a nitrogen atmosphere and ultrasonically dispersed for 1 hour. Thiophene solution was added and reacted at room temperature for 12 hours. After the reaction was completed, methanol was added and allowed to stand. The precipitate was filtered and washed with methanol and dried at 60°C for 12 hours to obtain polythiophene-modified hollow titanium dioxide microspheres.

[0114] The ratio of hollow titanium dioxide microspheres, ferric chloride, chloroform, and thiophene solution was 1g:1.94g:30mL:10mL.

[0115] Step (2): Mix polythiophene-modified hollow titanium dioxide microspheres and polybutadiene at a mass ratio of 8:10 to obtain an antibacterial and heat-insulating material;

[0116] Step (3): Mix antibacterial heat insulation material, methacryloyloxyethyltrimethylammonium chloride, polypropylene chips and benzoyl peroxide in a mass ratio of 10:6:100:0.6, melt and react at 180°C for 10 min, and after the reaction is completed, extrude and granulate to obtain antibacterial heat insulation polypropylene chips.

[0117] Antibacterial and heat-insulating polypropylene chips and polypropylene chips were melt-mixed at a mass ratio of 30:70, melt-spun in a twin-screw spinning machine, cooled and stretched to obtain antibacterial and heat-insulating fibers based on heat-insulating materials.

[0118] The melt spinning conditions were as follows: spinning temperature was 230℃ in zone 1, 245℃ in zone 2, and 250℃ in zone 3; spinning speed was 450m / min; drawing temperature was 120℃; and drawing ratio was 4.

[0119] Comparative Example 2

[0120] This comparative example discloses a method for preparing antibacterial and heat-insulating fibers based on thermal insulation materials, including the following steps:

[0121] Step (1): Hollow titanium dioxide microspheres and polybutadiene are mixed at a mass ratio of 8:10 to obtain an antibacterial and heat-insulating material;

[0122] Step (2): Mix antibacterial heat insulation material, methacryloyloxyethyltrimethylammonium chloride, polypropylene chips, and benzoyl peroxide in a mass ratio of 10:6:100:0.6, melt and react at 180°C for 10 minutes, and after the reaction is complete, extrude and granulate to obtain antibacterial heat insulation polypropylene chips.

[0123] Antibacterial and heat-insulating polypropylene chips and polypropylene chips were melt-mixed at a mass ratio of 30:70, melt-spun in a twin-screw spinning machine, cooled and stretched to obtain antibacterial and heat-insulating fibers based on heat-insulating materials.

[0124] The melt spinning conditions were as follows: spinning temperature was 230℃ in zone 1, 245℃ in zone 2, and 250℃ in zone 3; spinning speed was 450m / min; drawing temperature was 120℃; and drawing ratio was 4.

[0125] In the above examples and comparative examples: the hollow titanium dioxide microspheres were commercially available and had a diameter of approximately 1 micrometer; the hydroxyl-terminated polybutadiene had a hydroxyl value of 0.84 mmol / g; and the polypropylene chips were fiber-grade polypropylene chips, with the product number Liaoyang Petrochemical 71735.

[0126] Test case

[0127] The performance of the antibacterial and thermally insulating fibers based on thermal insulation materials prepared in Examples 1-5 and Comparative Examples 1-2 was tested. Specific test results are shown in Table 1.

[0128] Table 1

[0129]

[0130] The tests for each indicator in Table 1 were conducted according to the following standards: the antibacterial rate was determined according to GB / T 20944.3 "Evaluation of Antibacterial Properties of Textiles"; the breaking elongation was determined according to GB / T14344 "Test Method for Tensile Properties of Chemical Fiber Filaments". The thermal insulation performance is expressed by temperature difference. The test method is as follows: the antibacterial and warm-insulating fibers based on thermal insulation materials prepared in Examples 1-5 and Comparative Examples 1-2 were woven into fabrics with a weight of 150 g / m2, which were recorded as samples 1-7. Samples 1-7 were placed on the heating platform of a thermocouple thermometer to raise the temperature of the fabric to 50°C, and the temperature difference between the front and back sides of the fabric was tested.

[0131] As can be seen from the test results in Table 1, the fiber prepared by this invention has excellent antibacterial and thermal insulation properties, and the mechanical properties of the fiber are not significantly affected. This is because hollow titanium dioxide microspheres serve as both thermal insulation material and inorganic antibacterial agent. Polythiophene can synergistically enhance the antibacterial properties of the material with the hollow titanium dioxide microspheres, thus optimizing the antibacterial performance. The polybutadiene structure has good compatibility with the polypropylene matrix, and the presence of its unsaturated carbon-carbon double bonds allows it to be grafted onto polypropylene with the reactive quaternary ammonium salt antibacterial agent methacryloyloxyethyltrimethylammonium chloride, thereby improving the compatibility of each component.

[0132] In Comparative Example 1, the polythiophene on the surface of the hollow titanium dioxide microspheres did not react with polybutadiene for grafting, resulting in reduced dispersibility of the inorganic thermal insulation material in the polypropylene matrix, which affected the mechanical properties of the fiber. In Comparative Example 2, no polythiophene was added to the surface of the hollow titanium dioxide microspheres, thus lacking the antibacterial properties-enhancing effect of polythiophene. At the same time, the dispersibility of the inorganic thermal insulation material in the polypropylene matrix was reduced, affecting the mechanical properties of the fiber.

[0133] It should be noted that the embodiments described above are only for explaining the present invention and do not constitute any limitation on the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory terms, not limiting terms. Modifications can be made to the present invention within the scope of the claims, and revisions can be made to the present invention without departing from the scope and spirit of the present invention. Although the present invention described herein relates to specific methods, materials, and embodiments, it does not mean that the present invention is limited to the specific examples disclosed herein; on the contrary, the present invention can be extended to all other methods and applications with the same function.

Claims

1. A method for producing an antibacterial thermal retaining fiber based on a thermal insulation material, characterized by, Includes the following steps: Step (1): Mix azide-modified hollow titanium dioxide microspheres, alkynylated polybutadiene, and N,N-dimethylformamide, disperse by ultrasonication, add copper sulfate pentahydrate aqueous solution and sodium ascorbate aqueous solution in sequence, react, filter to collect precipitate after reaction, wash, dry, and obtain antibacterial heat insulation material; In step (1), the azide-modified hollow titanium dioxide microspheres are prepared by the following steps: S1. Thiophene-3-acetic acid was mixed with tetrahydrofuran, and triethylamine and pentafluorophenyl trifluoroacetate were added sequentially. After the reaction was completed, the mixture was purified to obtain thiophene grafted onto pentafluorophenyl trifluoroacetate. S2. Thiophene, pentafluorophenyl trifluoroacetate grafted with thiophene, and chloroform are mixed evenly to obtain a thiophene solution; hollow titanium dioxide microspheres, ferric chloride, and chloroform are mixed, ultrasonically dispersed, and then the thiophene solution is added. After the reaction is completed, the mixture is purified to obtain polythiophene-modified hollow titanium dioxide microspheres. S3. Mix polythiophene-modified hollow titanium dioxide microspheres and N,N-dimethylformamide, disperse by ultrasonication, add 1-amino-11-azido-3,6,9-trioxaundecane and triethylamine, react, filter, wash and dry to obtain azido-polythiophene-modified hollow titanium dioxide microspheres. In step (1), the alkynylated polybutadiene is prepared by the following steps: A solution of hydroxyl-terminated polybutadiene was added to a potassium tert-butoxide solution and reacted. After the reaction was completed, the temperature was lowered, and a propyne bromide solution was added to continue the reaction. After the reaction was completed, the mixture was purified to obtain alkynylated polybutadiene. Step (2): Mix antibacterial heat insulation material, methacryloyloxyethyltrimethylammonium chloride, polypropylene chips, and benzoyl peroxide, melt and react. After the reaction is complete, extrude and granulate to obtain antibacterial heat insulation polypropylene chips. Antibacterial and heat-insulating polypropylene chips are melt-mixed, spun, cooled and stretched to obtain antibacterial and heat-insulating fibers based on heat-insulating materials.

2. The method for preparing an antibacterial and heat-insulating fiber based on thermal insulation material according to claim 1, characterized in that, In step (1), when preparing azide-modified hollow titanium dioxide microspheres, the ratio of thiophene-3-acetic acid, triethylamine, pentafluorophenyl trifluoroacetate, and tetrahydrofuran in S1 is 5g:19-20mL:12-13mL:130-200mL; the reaction conditions are: stirring at room temperature for 1-2 hours. In S2: the ratio of thiophene, pentafluorophenyl trifluoroacetate grafted thiophene, and chloroform is 0.5g:0.5g:10mL; the ratio of hollow titanium dioxide microspheres, ferric chloride, chloroform, and thiophene solution is 1g:1.5-2g:20-50mL:8-12mL; the reaction conditions are: reaction at room temperature under a nitrogen atmosphere for 10-18h. In S3, the ratio of polythiophene-modified hollow titanium dioxide microspheres, 1-amino-11-azido-3,6,9-trioxaundecan, triethylamine, and N,N-dimethylformamide is 5-8g:0.07-0.1g:2-2.5mL:200-300mL; the reaction conditions are: stirring at 50-60℃ for 20-30h.

3. The method for preparing an antibacterial and heat-insulating fiber based on thermal insulation material according to claim 1, characterized in that, In step (1), when preparing alkynylated polybutadiene: the hydroxyl-terminated polybutadiene solution is prepared by mixing and dissolving hydroxyl-terminated polybutadiene and tetrahydrofuran in a ratio of 10-11g:50mL; the potassium tert-butoxide solution is prepared by mixing and dissolving potassium tert-butoxide and tetrahydrofuran in a ratio of 2-2.5g:50mL; and the propyne bromide solution is prepared by mixing and dissolving propyne bromide and tetrahydrofuran in a ratio of 1.5-2.5mL:100mL.

4. The method for preparing an antibacterial and heat-insulating fiber based on thermal insulation material according to claim 1, characterized in that, In step (1), when preparing alkynylated polybutadiene, the ratio of terminal hydroxyl polybutadiene, potassium tert-butoxide, and propyne bromide is 10-11g:2-2.5g:1.5-2.5mL; the reaction conditions are: in a nitrogen atmosphere, the temperature is raised from 0℃ to room temperature for 1h; the reaction conditions for continued reaction are: in a nitrogen atmosphere, at 0℃, the reaction is continued with stirring for 40-50h.

5. The method for preparing an antibacterial and warm-insulating fiber based on thermal insulation material according to claim 1, characterized in that, In step (1): the concentration of copper sulfate pentahydrate aqueous solution is 0.45wt%; the concentration of sodium ascorbate aqueous solution is 0.7wt%; the ratio of azide-modified hollow titanium dioxide microspheres, alkynylated polybutadiene, N,N-dimethylformamide, copper sulfate pentahydrate, and sodium ascorbate is 5-8g:10g:200-500mL:0.8-0.12g:0.1-0.15g; the reaction conditions are: stirring reaction for 10-15h in a nitrogen atmosphere at 50-60℃.

6. The method for preparing an antibacterial and heat-insulating fiber based on thermal insulation material according to claim 1, characterized in that, In step (2), the mass ratio of antibacterial heat insulation material, methacryloyloxyethyltrimethylammonium chloride, polypropylene chips, and benzoyl peroxide is 10-15:4-6:100:0.3-0.6; the reaction conditions are: melting reaction at 180-190℃ for 8-10 minutes.

7. The method for preparing an antibacterial and heat-insulating fiber based on thermal insulation material according to claim 1, characterized in that, In step (2): the mass ratio of antibacterial and heat-insulating polypropylene chips to polypropylene chips is 30-50:50-70; the melt spinning conditions are: spinning temperature is 225-235℃ in zone 1, 240-250℃ in zone 2, and 245-250℃ in zone 3, spinning speed is 450-550m / min; drawing temperature is 120-135℃, and drawing ratio is 2-4 times.

8. An antibacterial and warm fiber based on thermal insulation material prepared by the preparation method of the antibacterial and warm fiber based on thermal insulation material as described in any one of claims 1-7.

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