Near-infrared shielding fabric and preparation method thereof
By introducing functionalized polyamide and modified vanadium dioxide into near-infrared shielding fabrics and conducting specific chemical reactions, a fabric with excellent near-infrared protection, antibacterial and flame retardant properties was produced, solving the performance problems of existing fabrics. Insufficient problem.
Patent Information
- Application Number
- CN202411855732.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-17
- Publication Date
- 2025-01-14
AI Technical Summary
The existing near-infrared shielding fabrics have shortcomings in their anti-near infrared functions and lack antibacterial and flame retardant properties, which limits their application range.
Functionalized by the condensation polymerization of dimethyl pent-2-enedioate, quaternized diethyl malonate and 1,2-bis(4-aminophenyl)ethane-1,2-dione Polyamide is mixed with modified vanadium dioxide to form a spinning solution. Polyamide fiber is produced by electrostatic spinning. After being spun into fabric, it is reacted with phosphorus pentasulfide and nickel dichloride hexahydrate in sequence to produce a near-infrared shielding fabric.
The fabric not only has excellent near-infrared protection properties, but also has good antibacterial and flame retardant properties, making it suitable for diverse use environments.
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Abstract
Description
Technical Field
[0001] The invention relates to the technical field of textile fabrics, in particular to a near-infrared shielding fabric and a preparation method thereof. Background Art
[0002] Infrared is a type of electromagnetic wave. Its wavelength is longer than visible light in the spectrum. It is a type of radiation with strong thermal effect. Due to different wavelengths, infrared can be divided into near infrared, mid-infrared, and far infrared. For example, infrared emitted by heaters, torches, electric stoves, etc. are mostly near infrared. Due to their short wavelengths, they can produce a large amount of thermal effect. However, if the human body is exposed to them for a long time, it will cause skin burns and eye lens degeneration. Fabrics with anti-near infrared radiation function can effectively prevent the human body from radiating infrared waves, isolating the spread of heat and anti-infrared detection, and play an important role in life, industry and military fields.
[0003] Near-infrared shielding fabrics are a special type of fabric mainly used in the military industry. They have the function of preventing near-infrared rays from penetrating and reflecting, so as to achieve concealment and protection effects. In addition to the military industry, the application of near-infrared shielding fabrics has gradually expanded to the civilian field. For example, some outdoor equipment and cold-proof clothing have also begun to use this fabric to improve its warmth retention and concealment. With the development of science and technology, the technology of near-infrared shielding fabrics is also constantly improving. In order to adapt to more complex and severe diversified use environments, it is necessary to develop a near-infrared shielding fabric that not only has excellent near-infrared protection function, but also has antibacterial and flame retardant properties. This makes the application range of near-infrared shielding fabrics wider and can meet the needs of different fields. Summary of the invention
[0004] The object of the present invention is to provide a near-infrared shielding fabric and a preparation method thereof, so as to solve the problems existing in the prior art.
[0005] In order to solve the above technical problems, the present invention provides the following technical solutions: A near-infrared shielding fabric, wherein the near-infrared shielding fabric is prepared by polycondensing dimethyl pentane-2-enedioate, quaternized diethyl malonate and 1,2-bis(4-aminophenyl)ethane-1,2-dione to obtain a functionalized polyamide; polymerizing bis(2-chloroethyl)phosphite and 1,3-bis(3-aminopropyl)tetramethyldisiloxane on pre-modified vanadium dioxide to obtain modified vanadium dioxide; preparing a spinning solution from the functionalized polyamide and the modified vanadium dioxide, and electrospinning to obtain polyamide fibers; and sequentially reacting the polyamide fibers with phosphorus pentasulfide and nickel dichloride hexahydrate after spinning the polyamide fibers into polyamide fabrics; The quaternized diethyl malonate is prepared by reacting 2-(dimethylamino) diethyl malonate and 1-chlorohexane; The pre-modified vanadium dioxide is prepared by reacting vanadium dioxide and 3-aminopropyltriethoxysilane.
[0006] A method for preparing a near-infrared shielding fabric, the method for preparing the near-infrared shielding fabric comprising the following preparation steps: (1) 2-(dimethylamino) diethyl malonate and anhydrous acetone were mixed in a mass ratio of 1:(6-8) to prepare a 2-(dimethylamino) diethyl malonate solution; 1-chlorohexane and anhydrous acetone in an equal molar amount of 2-(dimethylamino) diethyl malonate were mixed in a mass ratio of 1:(3-4) to prepare a 1-chlorohexane solution; under a nitrogen atmosphere, at 50-60°C and stirring at 300-500 r / min, the 1-chlorohexane solution was uniformly added dropwise to the 2-(dimethylamino) diethyl malonate solution over a period of 15 minutes; the reaction was continued by stirring for 6-8 hours; and the quaternary ammonium salt diethyl malonate was prepared by drying at 50-60°C for 8-10 hours under vacuum conditions; (2) Add dimethyl pentyl-2-enedioate and quaternary ammonium salt diethyl malonate in a molar ratio of 1:(0.5-0.7) to N,N-dimethylformamide (6-8 times the mass of dimethyl pentyl-2-enedioate) and mix well to prepare a diester monomer solution; under a nitrogen atmosphere, at 30-40°C and stirring at 300-500 r / min, add the diamine monomer solution dropwise to the diester monomer solution within 20 minutes, raise the temperature to 150-160°C, continue stirring and reacting for 50-60 minutes, filter, wash with ether 3-5 times, and dry at 50-60°C under vacuum conditions for 8-10 hours to obtain a functionalized polyamide; (3) Pre-modified vanadium dioxide, bis(2-chloroethyl) phosphite, triethylamine, and N,N-dimethylformamide were mixed uniformly in a mass ratio of 1:(3-4):(0.01-0.03):(30-40), and 1,3-bis(3-aminopropyl)tetramethyldisiloxane in an equal molar amount of bis(2-chloroethyl) phosphite was added, and the mixture was stirred at 70-80°C and 300-500 r / min for 6-8 hours, filtered, washed with anhydrous ethanol and deionized water for 3-5 times each, and dried at 50-60°C under vacuum conditions for 8-10 hours to obtain modified vanadium dioxide; (4) Functionalized polyamide, modified vanadium dioxide, azobisisobutyronitrile, and N,N-dimethylformamide are mixed uniformly in a mass ratio of 1:(0.04-0.06):(0.001-0.002):(6-7), and stirred at 10-30°C and 300-500 r / min for 10-20 min to prepare a spinning solution; the spinning solution is loaded into a micro pump, and an aluminum foil is covered on an ice plate as a receiving device, and electrospinning is performed in an electrospinning device. Silk is used to obtain polyamide fiber; the polyamide fiber is spun into polyamide fabric by a textile machine; the polyamide fabric is immersed in the finishing liquid, stirred and refluxed at 102-104°C and 300-500r / min for 1-2h, 0.5-0.6 times the mass of the finishing liquid of nickel dichloride hexahydrate solution is added, stirring and refluxed for 2-3h, taken out, washed with deionized water for 3-5 times, and dried at 50-60°C under vacuum conditions for 8-10h to obtain near-infrared shielding fabric.
[0007] As an optimization, the preparation method of the diamine monomer solution in step (2) is: dimethyl pentane-2-enedioate, 1 times the total molar amount of quaternary ammonium diethyl malonate, 1,2-bis(4-aminophenyl)ethane-1,2-dione, and N,N-dimethylformamide are uniformly mixed in a mass ratio of 1:(6~8) to prepare the solution.
[0008] As an optimization, the preparation method of the pre-modified vanadium dioxide in step (3) is as follows: vanadium dioxide and anhydrous ethanol are uniformly mixed in a mass ratio of 1:(20-30), silane hydrolyzate is added in an amount of 8-10 times the mass of vanadium dioxide, the mixture is stirred at 50-60°C and 300-500 r / min for 2-3 h, filtered, washed with anhydrous ethanol for 3-5 times, and dried at 70-80°C under vacuum conditions for 8-10 h to obtain pre-modified vanadium dioxide.
[0009] As an optimization, the preparation method of the silane hydrolyzate is: 3-aminopropyltriethoxysilane and anhydrous ethanol are mixed uniformly in a mass ratio of 1:(40~50), the pH is adjusted to 4~6 with a 1 mol / L oxalic acid aqueous solution, and the mixture is stirred at 10~30°C and 300~500r / min for 50~60min to prepare a silane hydrolyzate.
[0010] As an optimization, the particle size of the vanadium dioxide is 300~400nm.
[0011] As an optimization, the process parameters of the electrospinning in step (4) are as follows: the receiving distance is adjusted to 16-18 cm, the voltage during spinning is 23-25 kV, the propulsion rate is 0.6-0.7 mL / h, the ambient temperature is 20-30 °C, and the spinning humidity is 50%-60%.
[0012] As an optimization, the preparation method of the finishing liquid in step (4) is: phosphorus pentasulfide, pyridine, and 1,4-dioxane are uniformly mixed in a mass ratio of 1: (0.3~0.4): (50~60) to prepare a finishing liquid.
[0013] As an optimization, the preparation method of the nickel dichloride hexahydrate solution in step (4) is: nickel dichloride hexahydrate, ethanol and methanol are uniformly mixed in a mass ratio of 1:(5~6):(5~6) to prepare a nickel dichloride hexahydrate solution.
[0014] Compared with the prior art, the beneficial effects achieved by the present invention are: When preparing near-infrared shielding fabric, the present invention comprises the following steps: reacting 2-(dimethylamino) diethyl malonate and 1-chlorohexane to obtain quaternized diethyl malonate; polycondensing pent-2-enedioic acid dimethyl ester, quaternized diethyl malonate and 1,2-bis(4-aminophenyl)ethane-1,2-dione to obtain functionalized polyamide; reacting vanadium dioxide and 3-aminopropyltriethoxysilane to obtain pre-modified vanadium dioxide; polymerizing and growing bis(2-chloroethyl) phosphite and 1,3-bis(3-aminopropyl)tetramethyldisiloxane on pre-modified vanadium dioxide to obtain modified vanadium dioxide; preparing a spinning solution from the functionalized polyamide and the modified vanadium dioxide by electrostatic spinning to obtain polyamide fiber; and weaving the polyamide fiber into a polyamide fabric and then reacting the polyamide fiber with phosphorus pentasulfide and nickel dichloride hexahydrate in sequence to obtain the near-infrared shielding fabric.
[0015] Firstly, 2-(dimethylamino) diethyl malonate and 1-chlorohexane are reacted to obtain quaternary ammonium diethyl malonate; dimethyl pentane-2-enedioate, quaternary ammonium diethyl malonate and 1,2-bis(4-aminophenyl)ethane-1,2-dione are polycondensed to obtain functionalized polyamide, and a quaternary ammonium salt structure is introduced into the side chain of the functionalized polyamide molecule, and a carbon-carbon double bond and a 1,2-diketone structure are introduced into the main chain of the functionalized polyamide molecule; the introduction of the quaternary ammonium salt structure can improve the antibacterial properties of near-infrared shielding fabrics; the introduction of the carbon-carbon double bond can react with the PH bond on the modified vanadium dioxide to undergo a phosphohydrogen addition reaction, A cross-linked network is formed to improve the mechanical properties of near-infrared shielding fabrics. The 1,2-diketone structure introduced on the main chain reacts with phosphorus pentasulfide and nickel dichloride hexahydrate in sequence during post-treatment to generate a thiodiene nickel complex. This thiodiene nickel complex has strong absorption in the near-infrared region, giving the near-infrared shielding fabric excellent infrared protection. At the same time, the thiodiene nickel complex formed by the 1,2-diketone structure between the functionalized polyamide molecular chains is also a cross-linking site, which allows cross-linking between the functionalized polyamide molecular chains, inhibits the relative slip between the molecular chains, and further improves the mechanical properties of the near-infrared shielding fabric.
[0016] Secondly, vanadium dioxide and 3-aminopropyltriethoxysilane are reacted to obtain pre-modified vanadium dioxide, and amino groups are introduced into the pre-modified vanadium dioxide; bis(2-chloroethyl) phosphite and 1,3-bis(3-aminopropyl)tetramethyldisiloxane are polymerized and grown on the pre-modified vanadium dioxide to obtain modified vanadium dioxide, and phosphorus, Si-O bonds and PH bonds are introduced into the modified vanadium dioxide; the introduction of phosphorus and Si-O bonds can improve the flame retardant properties of near-infrared shielding fabrics, and the introduction of PH bonds can react with carbon-carbon double bonds introduced on the main chain of functionalized polyamide molecules for phosphorus-hydrogen addition to form a cross-linked network, thereby further improving the mechanical properties of near-infrared shielding fabrics; functionalized polyamide and modified vanadium dioxide are prepared into a spinning solution, and polyamide fibers are obtained by electrospinning; after the polyamide fibers are spun into polyamide fabrics, they are sequentially reacted with phosphorus pentasulfide and nickel dichloride hexahydrate to obtain near-infrared shielding fabrics; the 1,2-diketone structure introduced on the main chain of the functionalized polyamide molecule is sequentially reacted with pentasulfide and nickel dichloride hexahydrate to obtain near-infrared shielding fabrics. Phosphorus sulfide and nickel dichloride hexahydrate react to form a thiodiene nickel complex, which has strong absorption in the near-infrared region, giving the near-infrared shielding fabric excellent infrared protection performance. At the same time, the thiodiene nickel complex formed by the 1,2-diketone structure between the functionalized polyamide molecular chains is also a cross-linking site, which makes the functionalized polyamide molecular chains cross-linked, inhibits the relative slip between the molecular chains, and further improves the mechanical properties of the near-infrared shielding fabric. In addition, vanadium dioxide also has a certain ability to protect against near-infrared rays. This is because the optical properties of vanadium dioxide will change significantly before and after the phase transition. Below the phase transition temperature (about 68°C), vanadium dioxide is in a monoclinic phase, showing semiconductor properties and high transmittance to infrared light; when the temperature is higher than the phase transition temperature, vanadium dioxide transforms into a rutile phase, showing metallic properties and high reflectivity to infrared light. Surface modification of vanadium dioxide helps vanadium dioxide to be evenly dispersed in the matrix resin. DETAILED DESCRIPTION
[0017] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention. Example 1
[0018] A method for preparing a near-infrared shielding fabric, the method for preparing the near-infrared shielding fabric comprising the following preparation steps: (1) 2-(dimethylamino) diethyl malonate and anhydrous acetone were mixed in a mass ratio of 1:6 to prepare a 2-(dimethylamino) diethyl malonate solution. 1-Chlorohexane and anhydrous acetone in an equal molar amount of 2-(dimethylamino) diethyl malonate were mixed in a mass ratio of 1:3 to prepare a 1-chlorohexane solution. Under a nitrogen atmosphere, at 50°C and 300 r / min stirring conditions, the 1-chlorohexane solution was uniformly added dropwise to the 2-(dimethylamino) diethyl malonate solution over a period of 15 minutes. The reaction was continued by stirring for 8 hours. The mixture was dried at 50°C for 10 hours under vacuum conditions to obtain quaternary ammonium salt diethyl malonate. (2) Add dimethyl pentyl-2-enedioate and quaternary ammonium diethyl malonate in a molar ratio of 1:0.5 to N,N-dimethylformamide (6 times the mass of dimethyl pentyl-2-enedioate) and mix them evenly to prepare a diester monomer solution; dimethyl pentyl-2-enedioate, 1,2-bis(4-aminophenyl)ethane-1,2-dione (1 times the total molar amount of quaternary ammonium diethyl malonate) and N,N-dimethylformamide in a mass ratio of 1:6 and mix them evenly to prepare a diamine monomer solution; under a nitrogen atmosphere, at 30°C and 300 r / min stirring conditions, the diamine monomer solution was uniformly added dropwise to the diester monomer solution within 20 minutes, the temperature was raised to 150°C, the stirring reaction was continued for 60 minutes, the filter was suction filtered, the solution was washed with ether 3 times, and the solution was dried at 50°C for 10 hours under vacuum conditions to prepare a functionalized polyamide; (3) 3-aminopropyltriethoxysilane and anhydrous ethanol were mixed at a mass ratio of 1:40, the pH was adjusted to 4 with a 1 mol / L oxalic acid aqueous solution, and the mixture was stirred at 10°C and 300 r / min for 60 min to prepare a silane hydrolyzate; vanadium dioxide and anhydrous ethanol were mixed at a mass ratio of 1:20, silane hydrolyzate with a mass of 8 times that of vanadium dioxide was added, the mixture was stirred at 50°C and 300 r / min for 3 h, filtered, washed with anhydrous ethanol for 3 times, and dried at 70°C under vacuum for 10 min. h, to obtain pre-modified vanadium dioxide; pre-modified vanadium dioxide, bis(2-chloroethyl) phosphite, triethylamine, and N,N-dimethylformamide were uniformly mixed in a mass ratio of 1:3:0.01:30, 1,3-bis(3-aminopropyl)tetramethyldisiloxane in an equal molar amount of bis(2-chloroethyl) phosphite was added, and the mixture was stirred at 70°C and 300 r / min for 8 h, filtered, washed with anhydrous ethanol and deionized water for 3 times each, and dried at 50°C for 10 h under vacuum conditions to obtain modified vanadium dioxide; (4) Functionalized polyamide, modified vanadium dioxide, azobisisobutyronitrile, and N,N-dimethylformamide were mixed uniformly in a mass ratio of 1:0.04:0.001:6, and stirred at 10°C and 300 r / min for 20 min to prepare a spinning solution; the spinning solution was loaded into a micro pump, and an ice plate covered with aluminum foil was used as a receiving device. The receiving distance was adjusted to 16 cm. During the spinning process, the voltage was 23 kV, the propulsion rate was 0.6 mL / h, the ambient temperature was 20°C, and the spinning humidity was 50%. Electrospinning was performed in an electrospinning device to obtain polyamide fiber; polyamide was used to spin the polyamide fiber using a textile machine. The fiber is spun into a polyamide fabric; phosphorus pentasulfide, pyridine and 1,4-dioxane are mixed evenly at a mass ratio of 1:0.3:50 to prepare a finishing liquid; nickel dichloride hexahydrate, ethanol and methanol are mixed evenly at a mass ratio of 1:5:5 to prepare a nickel dichloride hexahydrate solution; the polyamide fabric is immersed in the finishing liquid, stirred and refluxed at 102°C and 300r / min for 2h, 0.5 times the mass of nickel dichloride hexahydrate solution of the finishing liquid is added, and stirring and refluxing are continued for 3h, the fabric is taken out, washed with deionized water 3 times, and dried at 50°C for 10h under vacuum conditions to obtain a near-infrared shielding fabric. Example 2
[0019] A method for preparing a near-infrared shielding fabric, the method for preparing the near-infrared shielding fabric comprising the following preparation steps: (1) 2-(dimethylamino) diethyl malonate and anhydrous acetone were mixed at a mass ratio of 1:7 to prepare a 2-(dimethylamino) diethyl malonate solution. 1-Chlorohexane and anhydrous acetone in an equal molar amount of 2-(dimethylamino) diethyl malonate were mixed at a mass ratio of 1:3.5 to prepare a 1-chlorohexane solution. Under a nitrogen atmosphere, at 55°C and 400 r / min stirring conditions, the 1-chlorohexane solution was uniformly added dropwise to the 2-(dimethylamino) diethyl malonate solution over a period of 15 minutes. The reaction was continued by stirring for 7 hours. The mixture was dried at 55°C under vacuum conditions for 9 hours to obtain quaternary ammonium salt diethyl malonate. (2) Add dimethyl pentyl-2-enedioate and quaternary ammonium diethyl malonate in a molar ratio of 1:0.6 to N,N-dimethylformamide (7 times the mass of dimethyl pentyl-2-enedioate) and mix them evenly to prepare a diester monomer solution; dimethyl pentyl-2-enedioate, 1,2-bis(4-aminophenyl)ethane-1,2-dione (1 times the total molar amount of quaternary ammonium diethyl malonate) and N,N-dimethylformamide in a mass ratio of 1:7 and mix them evenly to prepare a diamine monomer solution; under a nitrogen atmosphere, at 35°C and 400 r / min stirring conditions, the diamine monomer solution was uniformly added dropwise to the diester monomer solution within 20 minutes, the temperature was raised to 155°C, the stirring reaction was continued for 55 minutes, the filter was suction filtered, the solution was washed with ether 4 times, and the solution was dried at 55°C under vacuum conditions for 9 hours to obtain a functionalized polyamide; (3) 3-aminopropyltriethoxysilane and anhydrous ethanol were mixed at a mass ratio of 1:45, the pH was adjusted to 5 with a 1 mol / L oxalic acid aqueous solution, and the mixture was stirred at 20°C and 400 r / min for 55 min to prepare a silane hydrolyzate; vanadium dioxide and anhydrous ethanol were mixed at a mass ratio of 1:25, silane hydrolyzate with a mass of 9 times that of vanadium dioxide was added, the mixture was stirred at 55°C and 400 r / min for 2.5 h, filtered, washed with anhydrous ethanol 4 times, and dried at 75°C under vacuum for 9 min. h, to obtain pre-modified vanadium dioxide; pre-modified vanadium dioxide, bis(2-chloroethyl) phosphite, triethylamine, and N,N-dimethylformamide were uniformly mixed in a mass ratio of 1:3.5:0.02:35, 1,3-bis(3-aminopropyl)tetramethyldisiloxane in an equal molar amount of bis(2-chloroethyl) phosphite was added, and the mixture was stirred at 75°C and 400r / min for 7h, filtered, washed with anhydrous ethanol and deionized water 4 times each, and dried at 55°C under vacuum conditions for 9h to obtain modified vanadium dioxide; (4) Functionalized polyamide, modified vanadium dioxide, azobisisobutyronitrile, and N,N-dimethylformamide were mixed uniformly in a mass ratio of 1:0.05:0.0015:6.5, and stirred at 20°C and 400 r / min for 15 min to prepare a spinning solution; the spinning solution was loaded into a micro pump, and an aluminum foil covered on an ice plate was used as a receiving device. The receiving distance was adjusted to 17 cm. During the spinning process, the voltage was 24 kV, the propulsion rate was 0.65 mL / h, the ambient temperature was 25°C, and the spinning humidity was 55%. Electrospinning was performed in an electrospinning device to obtain polyamide fiber; the polyamide fiber was formed by a textile machine. Weaving into polyamide fabric; mixing phosphorus pentasulfide, pyridine and 1,4-dioxane at a mass ratio of 1:0.35:55 to prepare a finishing liquid; mixing nickel dichloride hexahydrate, ethanol and methanol at a mass ratio of 1:5.5:5.5 to prepare a nickel dichloride hexahydrate solution; immersing the polyamide fabric in the finishing liquid, stirring and refluxing at 103°C and 400r / min for 1.5h, adding 0.55 times the mass of nickel dichloride hexahydrate solution of the finishing liquid, continuing to stir and reflux for 2.5h, taking out, washing with deionized water 4 times, and drying at 55°C under vacuum conditions for 9h to obtain near-infrared shielding fabric. Example 3
[0020] A method for preparing a near-infrared shielding fabric, the method for preparing the near-infrared shielding fabric comprising the following preparation steps: (1) 2-(dimethylamino) diethyl malonate and anhydrous acetone were mixed in a mass ratio of 1:8 to prepare a 2-(dimethylamino) diethyl malonate solution; 1-chlorohexane and anhydrous acetone in an equal molar amount of 2-(dimethylamino) diethyl malonate were mixed in a mass ratio of 1:4 to prepare a 1-chlorohexane solution; under a nitrogen atmosphere, at 60°C and 500 r / min stirring conditions, the 1-chlorohexane solution was uniformly added dropwise to the 2-(dimethylamino) diethyl malonate solution over a period of 15 minutes; the reaction was continued by stirring for 6 hours; and the mixture was dried at 60°C under vacuum conditions for 8 hours to obtain quaternary ammonium salt diethyl malonate; (2) Add dimethyl pentyl-2-enedioate and quaternary ammonium diethyl malonate in a molar ratio of 1:0.7 to N,N-dimethylformamide (8 times the mass of dimethyl pentyl-2-enedioate) and mix them evenly to prepare a diester monomer solution; dimethyl pentyl-2-enedioate, 1,2-bis(4-aminophenyl)ethane-1,2-dione (1 times the total molar amount of quaternary ammonium diethyl malonate) and N,N-dimethylformamide in a mass ratio of 1:8 and mix them evenly to prepare a diamine monomer solution; under a nitrogen atmosphere, at 40°C and 500 r / min stirring conditions, the diamine monomer solution is uniformly added dropwise to the diester monomer solution within 20 minutes, the temperature is raised to 160°C, the stirring reaction is continued for 50 minutes, the filter is suctioned, the solution is washed with ether 5 times, and the solution is dried at 60°C under vacuum conditions for 8 hours to obtain a functionalized polyamide; (3) 3-aminopropyltriethoxysilane and anhydrous ethanol were mixed at a mass ratio of 1:50, the pH was adjusted to 6 with a 1 mol / L oxalic acid aqueous solution, and the mixture was stirred at 30°C and 500 r / min for 50 min to prepare a silane hydrolyzate; vanadium dioxide and anhydrous ethanol were mixed at a mass ratio of 1:20, 10 times the mass of vanadium dioxide was added to the silane hydrolyzate, and the mixture was stirred at 60°C and 500 r / min for 2 h, filtered, washed with anhydrous ethanol 5 times, and dried at 80°C under vacuum conditions. 8h to obtain pre-modified vanadium dioxide; pre-modified vanadium dioxide, bis(2-chloroethyl) phosphite, triethylamine, and N,N-dimethylformamide were mixed uniformly at a mass ratio of 1:3:0.01:30, 1,3-bis(3-aminopropyl)tetramethyldisiloxane in an equal molar amount of bis(2-chloroethyl) phosphite was added, stirred at 80°C and 500r / min for 6h, filtered, washed with anhydrous ethanol and deionized water 5 times each, and dried at 60°C under vacuum conditions for 8h to obtain modified vanadium dioxide; (4) Functionalized polyamide, modified vanadium dioxide, azobisisobutyronitrile, and N,N-dimethylformamide were mixed uniformly in a mass ratio of 1:0.06:0.002:7, and stirred at 30°C and 500 r / min for 10 min to prepare a spinning solution; the spinning solution was loaded into a micro pump, and an ice plate covered with aluminum foil was used as a receiving device. The receiving distance was adjusted to 18 cm. During the spinning process, the voltage was 25 kV, the propulsion rate was 0.7 mL / h, the ambient temperature was 30°C, and the spinning humidity was 60%. Electrospinning was performed in an electrospinning device to obtain polyamide fiber; polyamide was used to spin the polyamide fiber using a textile machine. The fiber is spun into a polyamide fabric; phosphorus pentasulfide, pyridine and 1,4-dioxane are mixed evenly at a mass ratio of 1:0.4:60 to prepare a finishing liquid; nickel dichloride hexahydrate, ethanol and methanol are mixed evenly at a mass ratio of 1:6:6 to prepare a nickel dichloride hexahydrate solution; the polyamide fabric is immersed in the finishing liquid, stirred and refluxed at 104°C and 500r / min for 1h, 0.6 times the mass of nickel dichloride hexahydrate solution of the finishing liquid is added, stirring and refluxing is continued for 2h, the fabric is taken out, washed with deionized water for 5 times, and dried at 50°C for 10h under vacuum conditions to obtain a near-infrared shielding fabric.
[0021] Comparative Example 1: The preparation method of the near-infrared shielding fabric of Comparative Example 1 is different from that of Example 2 in that step (1) is not performed, and step (2) is modified as follows: dimethyl pentyl-2-enedioate and diethyl malonate are added in a molar ratio of 1:0.6 to N,N-dimethylformamide (7 times the mass of dimethyl pentyl-2-enedioate) and mixed evenly to prepare a diester monomer solution; dimethyl pentyl-2-enedioate and diethyl malonate (1 times the total molar amount of 1,2-bis(4-amino)propene) are added to a 1:1 mixture of 1,2-bis(4-amino)propene and 1,2-bis(4-amino)propene. phenyl)ethane-1,2-dione and N,N-dimethylformamide were mixed uniformly at a mass ratio of 1:7 to prepare a diamine monomer solution; under a nitrogen atmosphere, at 35°C and 400r / min stirring conditions, the diamine monomer solution was uniformly added dropwise to the diester monomer solution within 20 minutes, the temperature was raised to 155°C, the stirring reaction was continued for 55 minutes, suction filtered, washed with ether 4 times, and dried at 55°C for 9 hours under vacuum conditions to obtain a functionalized polyamide. The remaining steps are the same as in Example 2.
[0022] Comparative Example 2: The preparation method of the near-infrared shielding fabric of Comparative Example 2 is different from that of Example 2 in that step (2) is different. Step (2) is modified as follows: dimethyl glutarate and quaternized diethyl malonate are added in a molar ratio of 1:0.6 to N,N-dimethylformamide (7 times the mass of dimethyl glutarate) and mixed evenly to prepare a diester monomer solution; dimethyl glutarate, 1,2-bis(4-aminophenyl)ethane-1,2-dione (1 times the total molar amount of quaternized diethyl malonate) and N,N-dimethylformamide are mixed evenly in a mass ratio of 1:7 to prepare a diamine monomer solution; under a nitrogen atmosphere, at 35°C and 400r / min stirring conditions, the diamine monomer solution is uniformly added dropwise to the diester monomer solution within 20 minutes, the temperature is raised to 155°C, the stirring reaction is continued for 55 minutes, the filter is suctioned, washed with ether 4 times, and dried at 55°C under vacuum conditions for 9 hours to obtain a functionalized polyamide. The remaining steps are the same as in Example 2.
[0023] Comparative Example 3: The preparation method of the near-infrared shielding fabric of Comparative Example 3 is different from that of Example 2 only in step (2). Step (2) is modified as follows: dimethyl pentane-2-enedioate and quaternized diethyl malonate are added in a molar ratio of 1:0.6 to N,N-dimethylformamide (7 times the mass of dimethyl pentane-2-enedioate) and mixed evenly to prepare a diester monomer solution; dimethyl pentane-2-enedioate, 1,6-hexanediamine (1 times the total molar amount of quaternized diethyl malonate), and N,N-dimethylformamide are mixed evenly in a mass ratio of 1:7 to prepare a diamine monomer solution; under a nitrogen atmosphere, at 35°C and 400 r / min stirring conditions, the diamine monomer solution is uniformly added dropwise to the diester monomer solution within 20 minutes, the temperature is raised to 155°C, the stirring reaction is continued for 55 minutes, the filter is suctioned, the solution is washed with ether 4 times, and the solution is dried at 55°C under vacuum conditions for 9 hours to obtain a functionalized polyamide. The remaining steps are the same as in Example 2.
[0024] Comparative Example 4: The preparation method of the near-infrared shielding fabric of Comparative Example 4 is different from that of Example 2 in that step (3) is not performed, and step (4) is modified as follows: functionalized polyamide, vanadium dioxide, azobisisobutyronitrile, and N,N-dimethylformamide are mixed uniformly in a mass ratio of 1:0.05:0.0015:6.5, stirred at 20°C and 400r / min for 15min, and prepared into a spinning solution; the spinning solution is loaded into a micro pump, an ice plate covered with aluminum foil is used as a receiving device, the receiving distance is adjusted to 17cm, the voltage during the spinning process is 24kV, the propulsion rate is 0.65mL / h, the ambient temperature is 25°C, the spinning humidity is 55%, and electrospinning is performed in an electrospinning device Silk, to obtain polyamide fiber; use a textile machine to weave the polyamide fiber into polyamide fabric; phosphorus pentasulfide, pyridine, and 1,4-dioxane are mixed evenly at a mass ratio of 1:0.35:55 to prepare a finishing liquid; nickel dichloride hexahydrate, ethanol, and methanol are mixed evenly at a mass ratio of 1:5.5:5.5 to prepare a nickel dichloride hexahydrate solution; the polyamide fabric is immersed in the finishing liquid, stirred and refluxed at 103°C and 400r / min for 1.5h, 0.55 times the mass of nickel dichloride hexahydrate solution is added, stirring and refluxed for 2.5h, taken out, washed with deionized water 4 times, and dried at 55°C under vacuum conditions for 9h to obtain a near-infrared shielding fabric. The remaining steps are the same as those in Example 2.
[0025] Comparative Example 5: The preparation method of the near-infrared shielding fabric of Comparative Example 5 is different from that of Example 2 in that step (4) is different. Step (4) is modified as follows: functionalized polyamide, modified vanadium dioxide, azobisisobutyronitrile, and N,N-dimethylformamide are mixed uniformly in a mass ratio of 1:0.05:0.0015:6.5, and stirred at 20°C and 400 r / min for 15 min to prepare a spinning solution; the spinning solution is loaded into a micro pump, an ice plate covered with aluminum foil is used as a receiving device, the receiving distance is adjusted to 17 cm, the voltage during the spinning process is 24 kV, the propulsion rate is 0.65 mL / h, the ambient temperature is 25°C, the spinning humidity is 55%, and electrospinning is performed in an electrospinning device to obtain polyamide fiber; and the polyamide fiber is spun into a near-infrared shielding fabric using a textile machine.
[0026] Test Example 1 Infrared protection performance test Test method: Lambda 950 UV-visible spectrophotometer was used to test the transmittance of the prepared embodiments and comparative examples in the wavelength range of 760-1250 nm, and the transmittance of the embodiments and comparative examples at a wavelength of 950 nm was calculated. The wavelength scanning interval was 2 nm, 3 samples were selected for each group of samples, and 3 measurements were performed, and then the average of the 3 results was taken. The results are shown in Table 1.
[0027] Table 1
[0028] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 5 in Table 1, it can be found that the near-infrared shielding fabric prepared by the present invention has good infrared protection performance.
[0029] By comparison, the transmittances of Examples 1 to 3 at a wavelength of 950 nm are lower than those of Comparative Examples 3 and 5 at a wavelength of 950 nm, indicating that the functionalized polyamide is prepared by polycondensation of dimethyl pentane-2-enedioate, quaternized diethyl malonate and 1,2-bis(4-aminophenyl)ethane-1,2-dione, and the 1,2-diketone structure is introduced into the main chain of the functionalized polyamide molecule; the functionalized polyamide and modified vanadium dioxide are prepared into a spinning solution, and polyamide fibers are obtained by electrospinning; the polyamide fibers are spun into polyamide fabrics, and then reacted with phosphorus pentasulfide and nickel dichloride hexahydrate in sequence to obtain near-infrared shielding fabrics; the 1,2-diketone structure introduced into the main chain of the functionalized polyamide molecule reacts with phosphorus pentasulfide and nickel dichloride hexahydrate in sequence to generate a thiodiene-type nickel complex, which has strong absorption in the near-infrared region, giving the near-infrared shielding fabrics excellent infrared protection properties.
[0030] Test Example 2 Flame retardant performance test Test method: According to GB / T5454 "Textile Combustion Performance Test Oxygen Index Method", the limiting oxygen index of the examples and comparative examples was tested using an oxygen index instrument. The results are shown in Table 2.
[0031] Table 2
[0032] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 5 in Table 2, it can be found that the near-infrared shielding fabric prepared by the present invention has good flame retardant properties.
[0033] By comparison, the limiting oxygen index of Examples 1 to 3 is greater than that of Comparative Example 4, indicating that vanadium dioxide and 3-aminopropyltriethoxysilane are reacted to obtain pre-modified vanadium dioxide, and amino groups are introduced into the pre-modified vanadium dioxide; bis(2-chloroethyl) phosphite and 1,3-bis(3-aminopropyl)tetramethyldisiloxane are polymerized and grown on the pre-modified vanadium dioxide to obtain modified vanadium dioxide, and phosphorus element and Si-O bond are introduced into the modified vanadium dioxide; the introduction of phosphorus element and Si-O bond can improve the flame retardant properties of near-infrared shielding fabrics.
[0034] Test Example 3 Antimicrobial performance testing Test method: The antibacterial performance of the embodiment and the comparative example was analyzed by comparing the number of E. coli colonies cultured in agar medium for 16 hours using the oscillation method GB / T20944.3. The results are shown in Table 3.
[0035] Table 3
[0036] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 5 in Table 3, it can be found that the near-infrared shielding fabric prepared by the present invention has good antibacterial properties.
[0037] By comparison, the antibacterial rates of Examples 1 to 3 are greater than that of Comparative Example 1, indicating that quaternary ammonium diethyl malonate is prepared by reacting 2-(dimethylamino) diethyl malonate and 1-chlorohexane; functionalized polyamide is prepared by condensing dimethyl pent-2-enedioate, quaternary ammonium diethyl malonate and 1,2-bis(4-aminophenyl)ethane-1,2-dione, and a quaternary ammonium salt structure is introduced into the side chain of the functionalized polyamide molecule. The introduction of the quaternary ammonium salt structure can improve the antibacterial properties of near-infrared shielding fabrics.
[0038] Test Example 4 Mechanical properties testing Test method: The examples and comparative examples were prepared into standard specimens according to GB / T 3923.1, and the breaking strength of the standard specimens was tested. The results are shown in Table 4.
[0039] Table 4
[0040] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 5 in Table 4, it can be found that the near-infrared shielding fabric prepared by the present invention has good mechanical properties.
[0041] By comparison, the breaking strength of Examples 1 to 3 is greater than that of Comparative Examples 2 and 4, indicating that the functionalized polyamide is prepared by condensation of dimethyl pentane-2-enedioate, quaternized diethyl malonate and 1,2-bis(4-aminophenyl)ethane-1,2-dione, and a carbon-carbon double bond is introduced into the main chain of the functionalized polyamide molecule; vanadium dioxide and 3-aminopropyltriethoxysilane are reacted to prepare pre-modified vanadium dioxide, and an amino group is introduced into the pre-modified vanadium dioxide; bis(2-chloroethyl) phosphite and 1,3-bis(3-aminopropyl)tetramethyldisiloxane are polymerized and grown on the pre-modified vanadium dioxide to prepare modified vanadium dioxide, and a PH bond is introduced into the modified vanadium dioxide; the introduction of the PH bond can undergo phosphine-hydrogen addition with the carbon-carbon double bond introduced into the main chain of the functionalized polyamide molecule to form a cross-linked network, thereby further improving the mechanical properties of the near-infrared shielding fabric.
[0042] By comparison, the breaking strength of Examples 1 to 3 is greater than that of Comparative Examples 3 and 5, indicating that the functionalized polyamide is prepared by polycondensation of dimethyl pentane-2-enedioate, quaternized diethyl malonate and 1,2-bis(4-aminophenyl)ethane-1,2-dione, and a 1,2-diketone structure is formed on the main chain of the functionalized polyamide molecule; the functionalized polyamide and modified vanadium dioxide are prepared into a spinning solution, and the polyamide fiber is prepared by electrospinning; the polyamide fiber is spun into a polyamide fabric in sequence The near-infrared shielding fabric is prepared by reacting with phosphorus pentasulfide and nickel dichloride hexahydrate; the 1,2-diketone structure introduced on the main chain of the functionalized polyamide molecule reacts with phosphorus pentasulfide and nickel dichloride hexahydrate in sequence to generate a thiodiene-type nickel complex, and the thiodiene-type nickel complex formed by the 1,2-diketone structure between the functionalized polyamide molecular chains serves as a cross-linking site, thereby cross-linking the functionalized polyamide molecular chains, inhibiting the relative slip between the molecular chains, and further improving the mechanical properties of the near-infrared shielding fabric.
[0043] The specific implementation methods described above further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above description is only a specific implementation method of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.
Claims
1. A near-infrared shielding fabric, characterized in that: The near-infrared shielding fabric is prepared by polycondensing dimethyl pentane-2-enedioate, quaternized diethyl malonate and 1,2-bis(4-aminophenyl)ethane-1,2-dione to obtain functionalized polyamide; polymerizing bis(2-chloroethyl)phosphite and 1,3-bis(3-aminopropyl)tetramethyldisiloxane on pre-modified vanadium dioxide to obtain modified vanadium dioxide; preparing a spinning solution from the functionalized polyamide and the modified vanadium dioxide, and electrospinning to obtain polyamide fibers; and weaving the polyamide fibers into polyamide fabrics, and then reacting the polyamide fibers with phosphorus pentasulfide and nickel dichloride hexahydrate in sequence to obtain the near-infrared shielding fabric. The quaternized diethyl malonate is prepared by reacting 2-(dimethylamino) diethyl malonate and 1-chlorohexane; The pre-modified vanadium dioxide is prepared by reacting vanadium dioxide and 3-aminopropyltriethoxysilane.
2. A method for preparing a near-infrared shielding fabric, characterized in that: The preparation method of the near-infrared shielding fabric comprises the following preparation steps: (1) 2-(dimethylamino) diethyl malonate and anhydrous acetone were mixed in a mass ratio of 1:(6-8) to prepare a 2-(dimethylamino) diethyl malonate solution; 1-chlorohexane and anhydrous acetone in an equal molar amount of 2-(dimethylamino) diethyl malonate were mixed in a mass ratio of 1:(3-4) to prepare a 1-chlorohexane solution; under a nitrogen atmosphere, at 50-60°C and stirring at 300-500 r / min, the 1-chlorohexane solution was uniformly added dropwise to the 2-(dimethylamino) diethyl malonate solution over a period of 15 minutes; the reaction was continued by stirring for 6-8 hours; and the quaternary ammonium salt diethyl malonate was prepared by drying at 50-60°C for 8-10 hours under vacuum conditions; (2) Add dimethyl pentyl-2-enedioate and quaternary ammonium salt diethyl malonate in a molar ratio of 1:(0.5-0.7) to N,N-dimethylformamide (6-8 times the mass of dimethyl pentyl-2-enedioate) and mix well to prepare a diester monomer solution; under a nitrogen atmosphere, at 30-40°C and stirring at 300-500 r / min, add the diamine monomer solution dropwise to the diester monomer solution within 20 minutes, raise the temperature to 150-160°C, continue stirring and reacting for 50-60 minutes, filter, wash with ether 3-5 times, and dry at 50-60°C under vacuum conditions for 8-10 hours to obtain a functionalized polyamide; (3) Pre-modified vanadium dioxide, bis(2-chloroethyl) phosphite, triethylamine, and N,N-dimethylformamide were mixed uniformly in a mass ratio of 1:(3-4):(0.01-0.03):(30-40), and 1,3-bis(3-aminopropyl)tetramethyldisiloxane in an equal molar amount of bis(2-chloroethyl) phosphite was added, and the mixture was stirred at 70-80°C and 300-500 r / min for 6-8 hours, filtered, washed with anhydrous ethanol and deionized water for 3-5 times each, and dried at 50-60°C under vacuum conditions for 8-10 hours to obtain modified vanadium dioxide; (4) Functionalized polyamide, modified vanadium dioxide, azobisisobutyronitrile, and N,N-dimethylformamide are mixed uniformly in a mass ratio of 1:(0.04-0.06):(0.001-0.002):(6-7), and stirred at 10-30°C and 300-500 r / min for 10-20 min to prepare a spinning solution; the spinning solution is loaded into a micro pump, and an aluminum foil is covered on an ice plate as a receiving device, and electrospinning is performed in an electrospinning device. Silk is used to obtain polyamide fiber; the polyamide fiber is spun into polyamide fabric by a textile machine; the polyamide fabric is immersed in the finishing liquid, stirred and refluxed at 102-104°C and 300-500r / min for 1-2h, 0.5-0.6 times the mass of the finishing liquid of nickel dichloride hexahydrate solution is added, stirring and refluxed for 2-3h, taken out, washed with deionized water for 3-5 times, and dried at 50-60°C under vacuum conditions for 8-10h to obtain near-infrared shielding fabric.
3. The method for preparing a near-infrared shielding fabric according to claim 2, characterized in that: The preparation method of the diamine monomer solution in step (2) is as follows: dimethyl pentane-2-enedioate, 1 times the total molar amount of quaternary ammonium salt diethyl malonate, and N,N-dimethylformamide are uniformly mixed in a mass ratio of 1:(6-8) to prepare the solution.
4. The method for preparing a near-infrared shielding fabric according to claim 2, characterized in that: The preparation method of the pre-modified vanadium dioxide in step (3) is as follows: vanadium dioxide and anhydrous ethanol are uniformly mixed in a mass ratio of 1:(20-30), silane hydrolyzate is added in an amount of 8-10 times the mass of vanadium dioxide, the mixture is stirred at 50-60°C and 300-500 r / min for 2-3 hours, filtered, washed with anhydrous ethanol for 3-5 times, and dried at 70-80°C under vacuum conditions for 8-10 hours to obtain pre-modified vanadium dioxide.
5. The method for preparing a near-infrared shielding fabric according to claim 4, characterized in that: The preparation method of the silane hydrolyzate is as follows: 3-aminopropyltriethoxysilane and anhydrous ethanol are uniformly mixed in a mass ratio of 1:(40-50), the pH value is adjusted to 4-6 with a 1 mol / L oxalic acid aqueous solution, and the silane hydrolyzate is prepared by stirring at 10-30° C. and 300-500 r / min for 50-60 min.
6. The method for preparing a near-infrared shielding fabric according to claim 4, characterized in that: The particle size of the vanadium dioxide is 300-400 nm.
7. The method for preparing a near-infrared shielding fabric according to claim 2, characterized in that: The process parameters of the electrospinning in step (4) are as follows: the receiving distance is adjusted to 16-18 cm, the voltage during the spinning process is 23-25 kV, the propulsion rate is 0.6-0.7 mL / h, the ambient temperature is 20-30 ° C, and the spinning humidity is 50%-60%.
8. The method for preparing a near-infrared shielding fabric according to claim 2, characterized in that: The preparation method of the finishing liquid in step (4) is: phosphorus pentasulfide, pyridine, and 1,4-dioxane are uniformly mixed in a mass ratio of 1: (0.3-0.4): (50-60) to prepare a finishing liquid.
9. The method for preparing a near-infrared shielding fabric according to claim 2, characterized in that: The preparation method of the nickel dichloride hexahydrate solution in step (4) is: nickel dichloride hexahydrate, ethanol and methanol are uniformly mixed in a mass ratio of 1:(5-6):(5-6) to prepare a nickel dichloride hexahydrate solution.