阅读说明：本技术 TiO2核壳纳米粒子复合红外吸收纤维的制备方法 (TiO2Preparation method of core-shell nanoparticle composite infrared absorption fiber ) 是由 陈苏 郭敏 于 2021-06-25 设计创作，主要内容包括：本发明涉及一种TiO-(2)核壳纳米粒子复合红外吸收纤维的制备。该方法包括以下步骤：采用溶胶-凝胶法制备了尺寸均匀的TiO-(2)纳米粒子；以TiO-(2)纳米粒子为核,采用改进的法制备了TiO-(2)@SiO-(2)核壳纳米粒子；利用气喷纺丝技术制备了具有独特的纤维-粒子-纤维点线结构的复合纤维膜。该方法设备简单,可操作性强,得到的核壳纳米粒子和复合纤维膜具有良好的红外吸收性能。(The invention relates to a TiO compound 2 Preparing the core-shell nano particle composite infrared absorption fiber. The method comprises the following steps: adopts a sol-gel method to prepare TiO with uniform size 2 Nanoparticles; with TiO 2 With nanoparticles as cores, modified Method for preparing TiO 2 @SiO 2 Core-shell nanoparticles; the composite fiber membrane with a unique fiber-particle-fiber dotted line structure is prepared by using an air jet spinning technology. The method has simple equipment and strong operability, and the obtained core-shell nano particles and the composite particlesThe fibrous film has good infrared absorption properties.)

1. TiO2₂The preparation method of the core-shell nanoparticle composite infrared absorption fiber comprises the following specific steps:

(1) preparing TiO by adopting a sol-gel method and using tetrabutyl titanate, thioglycollic acid, deionized water and a solvent₂The nano particle dispersion liquid is centrifuged, washed and dried to obtain TiO₂Nanoparticles;

(2) by means of improvementsMethod with TiO₂Preparing TiO from nano particles, ammonia water, ethanol solution of tetraethyl orthosilicate, ethanol solution of ammonia water and deionized water and solvent₂@SiO₂Centrifuging, washing and drying the core-shell nano particle dispersion liquid to obtain TiO₂@SiO₂Core-shell nanoparticles;

(3) dissolving a spinning polymer in a solvent to obtain a polymer spinning solution;

(4) adding TiO into the mixture₂@SiO₂Adding the core-shell nano particles into a polymer spinning solution, and performing ultrasonic mixing to obtain a mixed spinning solution;

(5) placing the injector filled with the mixed spinning solution on a multi-stage micro-flow injection pump, setting parameters of air jet spinning, and preparing to obtain TiO₂The core-shell nano particle is compounded with the infrared absorption fiber.

2. The method of claim 1, wherein: the solvent in the step (1) is one or two of ethanol or methanol; the mass concentration of tetrabutyl titanate is 0.5-2%; the mass concentration of the thioglycolic acid is 0.04-0.2%; the mass concentration of the deionized water is 2-10%; the reaction time is 2-3 h.

3. The method of claim 1, wherein: the solvent in the step (2) is one or two of ethanol or methanol; TiO2₂The mass concentration of the nano particles is 0.2-1%; the mass concentration of the ammonia water is 2-11%; the mass concentration of the tetraethyl orthosilicate ethanol solution is 5-15%; the mass concentration of the ethanol solution of ammonia water and deionized water is 5-10%; the reaction temperature is 20-30 ℃, and the reaction time is 24-36 h.

4. The method of claim 1, wherein: in the step (2), the mass concentration of ethanol in the ethanol solution of tetraethyl orthosilicate is 50-75%, and the mass concentration of tetraethyl orthosilicate is 25-50%; the mass concentration of ethanol in the ethanol solution of ammonia water and deionized water is 40-70%, the mass concentration of ammonia water is 20-40%, and the mass concentration of deionized water is 10-20%.

5. The method of claim 1, wherein: in the step (3), the polymer is one or more of polyurethane, polyacrylonitrile, polyvinylpyrrolidone or polyvinyl alcohol; the solvent is one or more of ethanol, N-dimethylformamide or N, N-dimethylacetamide.

6. The method of claim 1, wherein: TiO in the mixed spinning solution in the step (4)₂@SiO₂The mass concentration of the core-shell nano particles is 0.2-1%, and the mass concentration of the polymer is 10-20%; TiO2₂@SiO₂The average particle diameter of the core-shell nanoparticles is 100-200 nm.

7. The method of claim 1, wherein: the air jet spinning parameters in the step (5) are as follows: the liquid outlet rate of the spinning solution is 3-15 mL/h; the air pressure is set to be 0.1-0.2 MPa; the distance from the spinning nozzle to the receiver is 30-50 cm; the environmental temperature is 20-35 ℃; the environmental humidity is 55-65%; the spinning time is 3-6 h.

Technical Field

The invention relates to a TiO compound₂A method for preparing core-shell nano particle composite infrared absorption fiber, in particular to a TiO nano particle composite infrared absorption fiber₂@SiO₂A method for preparing core-shell nano particle composite infrared absorption fiber.

Background

The nano infrared absorption fiber has important application prospect. Developed countries have begun to make "invisible clothing" from fibers with infrared absorption, which have a good shielding effect on the human body. This is mainly due to the size of the nanomaterials being much smaller than the infrared wavelength. Therefore, the wave transmittance is much stronger than that of the conventional material, the specific surface area of the nano material is 3-4 orders of magnitude larger than that of the conventional coarse particles, and the infrared absorption rate is much larger than that of the conventional material, so that the infrared wave reflectivity is greatly reduced, and the reflected signal received by the infrared detector becomes weak.

The nano material can be easily filled into the fiber, and some nano particles have strong property of absorbing mid-infrared frequency band, such as nano TiO₂Nano SiO₂Etc. have such a function. Nano TiO2₂Nano SiO₂After the composite powder is combined with the polymer fiber, the composite powder has strong absorption performance for mid-infrared bands, has good shielding effect for infrared detectors of the bands, and has strong absorption effect for human infrared rays by adding the nanofiber, so that the shielding effect and the warming effect can be achieved.

Disclosure of Invention

The invention aims to improve the defects of the prior art and provides TiO₂A method for preparing core-shell nano particle composite infrared absorption fiber. The method has excellent performance and controllable diameter and can be used for preparing the infrared absorption fiber in a large scale.

The technical scheme of the invention is as follows: TiO2₂The preparation method of the core-shell nanoparticle composite infrared absorption fiber comprises the following specific steps:

(1) preparing TiO with uniform size by adopting a sol-gel method and using tetrabutyl titanate, thioglycollic acid, deionized water and a solvent₂The nano particle dispersion liquid is centrifuged, washed and dried to obtain TiO₂Nanoparticles;

(2) by means of improvementsMethod with TiO₂Preparing TiO from nano particles, ammonia water, ethanol solution of tetraethyl orthosilicate (solution A), ethanol solution of ammonia water and deionized water (solution B) and solvent₂@SiO₂Centrifuging, washing and drying the core-shell nano particle dispersion liquid to obtain TiO₂@SiO₂Core-shell nanoparticles;

(3) dissolving a spinning polymer in a solvent to obtain a polymer spinning solution;

(4) adding TiO into the mixture₂@SiO₂Adding the core-shell nano particles into a polymer spinning solution, and performing ultrasonic mixing to obtain a mixed spinning solution;

(5) placing the injector filled with the mixed spinning solution on a multi-stage micro-flow injection pump, setting parameters of air jet spinning, and preparing to obtain TiO₂The core-shell nano particle is compounded with the infrared absorption fiber.

Preferably, the solvent in the step (1) is one or two of ethanol or methanol; the mass concentration of tetrabutyl titanate is 0.5-2%; the mass concentration of the thioglycolic acid is 0.04-0.2%; the mass concentration of the deionized water is 2-10%; the reaction time is 2-3 h.

Preferably, the solvent in the step (2) is one or two of ethanol or methanol; TiO2₂The mass concentration of the nano particles is 0.2-1%; the mass concentration of the ammonia water is 2-11%; the mass concentration of the ethanol solution (solution A) of tetraethyl orthosilicate is 5-15%; the mass concentration of the ethanol solution (solution B) of ammonia water and deionized water is 5-10%; the reaction temperature is 20-30 ℃, and the reaction time is 24-36 h.

Preferably, the ethanol solution of tetraethyl orthosilicate (solution A) in the step (2) has the mass concentration of 50-75% and the mass concentration of tetraethyl orthosilicate is 25-50%; the mass concentration of ethanol in the ethanol solution (solution B) of ammonia water and deionized water is 40-70%, the mass concentration of ammonia water is 20-40%, and the mass concentration of deionized water is 10-20%.

Preferably, in the step (3), the polymer is one or more of polyurethane, polyacrylonitrile, polyvinylpyrrolidone or polyvinyl alcohol; the solvent is one or more of ethanol, N-dimethylformamide or N, N-dimethylacetamide.

Preferably TiO in the mixed spinning solution in the step (4)₂@SiO₂The mass concentration of the core-shell nano particles is 0.2-1%, and the mass concentration of the polymer is 10-20%; TiO2₂@SiO₂The average particle diameter of the core-shell nanoparticles is 100-200 nm.

Preferably, the air-jet spinning parameters in the step (5) are as follows: the liquid outlet rate of the spinning solution is 3-15 mL/h; the air pressure is set to be 0.1-0.2 MPa; the distance from the spinning nozzle to the receiver is 30-50 cm; the environmental temperature is 20-35 ℃; the environmental humidity is 55-65%; the spinning time is 3-6 h.

Has the advantages that:

(1) TiO prepared by the method of the invention₂The core-shell nano particles have uniform size, have strong absorption performance in mid-infrared bands and have good absorption effect on human infrared rays;

(2) the invention can realize infrared absorption of TiO by utilizing the micro-fluidic air-jet spinning technology₂The core-shell nano particles are compounded with the common fiber membrane, the large-scale preparation of the infrared absorption fiber can be realized, and the diameter of the fiber can be accurately controlled by adjusting spinning parameters;

(3) the infrared absorption fiber prepared by the method has strong absorption performance in the mid-infrared band and has good absorption effect on human infrared.

Detailed Description

Example 1.

0.8g of tetrabutyltitanate and 0.08g of thioglycolic acid were added to 120g of ethanol and stirred magnetically at room temperature for 30 min. 4g of deionized water were then quickly poured into the solution. The mixed solution was stirred at room temperature for 2 h. The precipitate was collected by centrifugation and washed 2 times with ethanol to remove excess thioglycolic acid to give TiO₂Nanoparticles. 0.6g of TiO₂The nanoparticles were dispersed in 200g of ethanol and poured into a 500mL four-necked flask, and 28g of ammonia water was added and stirred uniformly. 11.5g of ethanol and 6g of tetraethyl orthosilicate were mixed well to obtain solution A. Solution B was obtained by mixing 9g of ethanol, 6.5g of ammonia and 1.8g of deionized water. Solution a and solution B were added dropwise to the flask simultaneously, while continuing mechanical stirring at 30 ℃. Reacting for 24h to obtain the product of TiO₂As a core, SiO₂TiO as shell₂@SiO₂A core-shell nanoparticle dispersion. The precipitate was collected by centrifugation and washed several times with ethanol to give TiO₂@SiO₂Core-shell nanoparticles having an average particle size of 130 nm.

6.5g of polyurethane was dissolved in 50g N, N-dimethylformamide to give a spinning solution, and 0.28g of TiO was added₂@SiO₂And adding the core-shell nano particles into the polymer spinning solution, and performing ultrasonic mixing to obtain a mixed spinning solution. Sucking the mixed spinning solution into an injector and placing the injector on a multi-stage micro-flow injection pump, setting the liquid outlet rate of the micro-flow pump to be 5mL/h respectively, setting the distance from a needle head to a receiver to be 35cm, blowing air out of a needle hole by an air pump under the pressure of 0.1MPa, and obtaining the composite fiber membrane on the receiver, wherein the ambient temperature is 20 ℃, the humidity is 56%, and the spinning time is 3.5 h.

The infrared lamp is used for irradiating the composite fiber film and the common fiber film at the same time, and the infrared radiation intensity of the visible composite fiber film is reduced by 45 percent compared with that of the common fiber film when the infrared thermal imager is used for observing. The composite fiber film is attached to a human body, and the infrared radiation intensity of the position where the composite fiber film is attached is observed to be reduced by 50% under an infrared thermal imager.

Example 2.

1.4g of tetrabutyltitanate and 0.14g of thioglycolic acid were added to 120g of methanol and stirred magnetically at room temperature for 30 min. Then 7g of deionized water was quickly poured into the solution. The mixed solution was stirred at room temperature for 2.5 h. The precipitate was collected by centrifugation and washed 2 times with ethanolic alcohol to remove excess thioglycolic acid to give TiO2 nanoparticles. 1g of TiO₂The nanoparticles were dispersed in 200g of methanol and poured into a 500mL four-necked flask, and 20g of ammonia water was added and stirred uniformly. 20g of ethanol and 15g of tetraethyl orthosilicate were mixed well to obtain solution A. And uniformly mixing 12g of ethanol, 5g of ammonia water and 3g of deionized water to obtain a solution B. Solution a and solution B were added dropwise to the flask simultaneously, while continuing mechanical stirring at 30 ℃. Reacting for 24h to obtain the product of TiO₂As a core, SiO₂TiO as shell₂@SiO₂A core-shell nanoparticle dispersion. The precipitate was collected by centrifugation and washed several times with ethanol to give TiO₂@SiO₂Core-shell nanoparticles having an average particle size of 180 nm.

10g of polyacrylonitrile was dissolved in 45g N, N-dimethylacetamide to obtain a spinning solution, and 0.45g of TiO was added₂@SiO₂And adding the core-shell nano particles into the polymer spinning solution, and performing ultrasonic mixing to obtain a mixed spinning solution. Sucking the mixed spinning solution into an injector, placing the injector on a multi-stage micro-flow injection pump, and pumping the micro-flow pumpThe liquid outlet rates of the two liquid outlet pipes are respectively set to be 10mL/h, the distance from the needle head to the receiver is set to be 40cm, the air pump blows air from the needle hole under the pressure of 0.15MPa, the ambient temperature is 25 ℃, the humidity is 58%, the spinning time is 4h, and the composite fiber membrane is obtained on the receiver.

The infrared lamp is used for irradiating the composite fiber film and the common fiber film at the same time, and the infrared radiation intensity of the visible composite fiber film is reduced by 60 percent compared with that of the common fiber film when the infrared thermal imager is used for observing. The composite fiber film is attached to a human body, and the infrared radiation intensity of the position where the composite fiber film is attached is observed to be reduced by 65 percent under an infrared thermal imager.

Example 3.

2.4g of tetrabutyltitanate and 0.24g of thioglycolic acid were added to 120g of ethanol and stirred magnetically at room temperature for 30 min. 12g of deionized water were then quickly poured into the solution. The mixed solution was stirred at room temperature for 3 hours. The precipitate was collected by centrifugation and washed 2 times with ethanol to remove excess thioglycolic acid to give TiO2 nanoparticles. 2g of TiO₂The nanoparticles were dispersed in 200g of ethanol and poured into a 500mL four-necked flask, and 15g of ammonia water was added and stirred uniformly. 25g of ethanol and 10g of tetraethyl orthosilicate were mixed well to obtain solution A. 15g of ethanol, 6g of ammonia water and 3g of deionized water were mixed uniformly to obtain a solution B. Solution a and solution B were added dropwise to the flask simultaneously, while continuing mechanical stirring at 20 ℃. Reacting for 36h to obtain the product of TiO₂As a core, SiO₂TiO as shell₂@SiO₂A core-shell nanoparticle dispersion. The precipitate was collected by centrifugation and washed several times with ethanol to give TiO₂@SiO₂Core-shell nanoparticles having an average particle size of 160 nm.

8g of polyvinylpyrrolidone was dissolved in 50g of ethanol to obtain a spinning solution, and 0.15g of TiO was added₂@SiO₂And adding the core-shell nano particles into the polymer spinning solution, and performing ultrasonic mixing to obtain a mixed spinning solution. Sucking the mixed spinning solution into an injector and placing the injector on a multi-stage micro-flow injection pump, setting the liquid outlet speed of the micro-flow pump to be 15mL/h respectively, setting the distance from a needle head to a receiver to be 45cm, blowing air out of a needle hole by an air pump under the pressure of 0.2MPa, wherein the ambient temperature is 32 ℃, the humidity is 63%, and spinning is carried outThe time was 5.5h and a composite fiber membrane was obtained on the receiver.

The infrared lamp is used for irradiating the composite fiber film and the common fiber film at the same time, and the infrared radiation intensity of the visible composite fiber film is reduced by 35 percent compared with that of the common fiber film when the infrared thermal imager is used for observing. The composite fiber film is pasted on a human body, and the infrared radiation intensity of the position pasted with the composite fiber film is observed to be reduced by 40 percent under an infrared thermal imager.