阅读说明：本技术 碳量子点在制备防晒的纺织材料中的应用 (Application of carbon quantum dots in preparation of sun-proof textile material ) 是由 胡广齐 姜红 于 2021-07-29 设计创作，主要内容包括：本发明提供碳量子点在制备防晒的纺织材料中的应用：纺织材料包括柔性基材和以柔性基材作为载体的碳量子点；碳量子点的合成方法如下：向十八烯中加入碳源和钝化剂,采用溶剂热法,使反应物在260～330℃的温度下反应2～7h,反应过程中提供N2作为保护气氛,反应生成碳量子点；碳源包括被至少一个氨基所取代的硅烷、柠檬酸中的至少一种,钝化剂包括十二胺、十六胺、十八胺中的至少一种。按照上述方法制备的碳量子点为油溶性碳量子点,其与纺织材料具有较高的相容性,并能够吸收广谱的紫外线。将上述碳量子点作为紫外线吸收剂掺入纺织材料中,能够对纺织材料起到有效的紫外线防护效果,显著减少了纺织材料出现由紫外线辐射导致的脆化、破裂等情况。(The invention provides an application of carbon quantum dots in preparing a sun-proof textile material, which comprises the following steps: the textile material comprises a flexible substrate and carbon quantum dots taking the flexible substrate as a carrier; the synthesis method of the carbon quantum dots comprises the following steps: adding a carbon source and a passivating agent into octadecene, reacting reactants for 2-7 hours at the temperature of 260-330 ℃ by adopting a solvothermal method, and providing N2 as a protective atmosphere in the reaction process to react to generate carbon quantum dots; the carbon source comprises at least one of silane and citric acid substituted by at least one amino group, and the passivating agent comprises at least one of dodecylamine, hexadecylamine and octadecylamine. The carbon quantum dots prepared by the method are oil-soluble carbon quantum dots which have high compatibility with textile materials and can absorb broad-spectrum ultraviolet rays. The carbon quantum dots are doped into the textile material as the ultraviolet absorbent, so that the effective ultraviolet protection effect can be achieved on the textile material, and the situations of embrittlement, cracking and the like caused by ultraviolet radiation of the textile material are obviously reduced.)

1. The application of the carbon quantum dots in the preparation of the sun-proof textile material is characterized in that:

the textile material comprises a flexible substrate and carbon quantum dots taking the flexible substrate as a carrier;

the synthesis method of the carbon quantum dots comprises the following steps: adding a carbon source and a passivating agent into octadecylene, and reacting reactants for 2-7 hours at the temperature of 260-330 ℃ by adopting a solvothermal method to provide N in the reaction process₂As a protective atmosphere, reacting to generate the carbon quantum dots;

the carbon source comprises at least one of silane and citric acid substituted by at least one amino group, and the passivating agent comprises at least one of dodecylamine, hexadecylamine and octadecylamine.

2. Use of carbon quantum dots according to claim 1 for the preparation of a sunscreen textile material, characterized in that: citric acid is used as the carbon source, and octadecylamine is used as the passivating agent.

3. Use of carbon quantum dots according to claim 2 for the preparation of a sunscreen textile material, wherein in the synthesis of the carbon quantum dots:

calculating the mass ratio of citric acid to octadecylamine to be 4: 3;

the reaction temperature was 280 ℃.

4. Use of carbon quantum dots according to claim 1 for the preparation of sun-resistant textile material species, characterized in that: the silane substituted with at least one amino group is gamma-aminopropyltriethoxysilane.

5. Use of carbon quantum dots according to claim 4 for the preparation of a sunscreen textile material, characterized in that: gamma-aminopropyltriethoxysilane is used as the carbon source, and octadecylamine is used as the passivating agent.

6. Use of carbon quantum dots according to claim 5 for the preparation of a sunscreen textile material, wherein in the synthesis of the carbon quantum dots:

calculated according to the mass ratio of the fed materials, the gamma-aminopropyl triethoxysilane to octadecylamine is 5: 4;

the reaction temperature was 300 ℃.

7. Use of carbon quantum dots according to claim 4 for the preparation of a sunscreen textile material, characterized in that: the carbon source consists of citric acid and gamma-aminopropyltriethoxysilane, and the passivating agent is compounded from dodecylamine and hexadecylamine.

8. Use of carbon quantum dots according to claim 7 for the preparation of a sunscreen textile material, wherein in the synthesis of the carbon quantum dots:

calculated according to the mass ratio of the materials fed, the citric acid is gamma-aminopropyl triethoxysilane, the dodecylamine is hexadecylamine, and the ratio is 5:4:3:5

9. Use of carbon quantum dots according to any of claims 1 to 8 for the preparation of a sunscreen textile material, characterized in that: in the textile material, the carbon quantum dots are uniformly distributed within the flexible substrate.

10. Use of carbon quantum dots according to claim 9 for the preparation of a sunscreen textile material, characterized in that: the flexible substrate comprises at least one of polyethylene terephthalate and polyamide.

Technical Field

The invention belongs to the field of functional materials, and particularly relates to application of carbon quantum dots in preparation of a sunscreen textile material.

Background

The textile material mainly refers to polyester polymer material, and polymer material after polymerization, such as polyethylene terephthalate (PET) and Polyamide (PA). Textile products using textile materials as raw materials have been widely introduced into the market based on the excellent thermal stability and moldability of the textile materials. However, textile materials contain a large amount of chemical bonds such as C-C, C-N, C-H and the like, and when the textile materials are irradiated under sunlight for a long time, the chemical bonds are broken due to high energy of Ultraviolet (UV), so that the textile products are embrittled, cracked and the like. Losses to the textile industry due to UV radiation damage are as high as billions of dollars annually, worldwide.

In order to reduce the losses of the textile material caused by solar radiation, it is common practice to add UV absorbers to the textile material. The commercial UV absorbers currently in widespread use are mainly classified into organic type UV absorbers and inorganic type UV absorbers. Among them, organic UV absorbers have the defects of short-term effectiveness and toxicity; as for the inorganic type UV absorber, although UV radiation can be shielded for a long time, the efficiency and wavelength range of UV absorption are limited, the protection ability is weak, and the compatibility of the inorganic type UV absorber with the film substrate is poor, and the transparency of the textile product doped with the inorganic type UV absorber is generally low.

Solar radiation includes about 5% of UV radiation in the wavelength range of 200nm-400nm, which can be divided into three regions: 320-400 nm (UV-A), 290-320 nm (UV-B) and 200-290 nm (UV-C). Most UVC is absorbed by the ozone layer and does not reach the earth, but both UVA and UVB can pass through the atmosphere. In conclusion, it is a practical matter for the textile industry to prepare an ultraviolet absorber capable of absorbing a broad spectrum of UV (including UVA and UVB) over a long period of time.

Disclosure of Invention

The invention aims to provide an application of carbon quantum dots in preparation of a sun-proof textile material so as to effectively reduce loss of solar UV radiation to the textile material.

According to one aspect of the present invention, there is provided the use of carbon quantum dots in the preparation of a textile material for protection against sunlight: the textile material comprises a flexible substrate and carbon quantum dots taking the flexible substrate as a carrier; the synthesis method of the carbon quantum dots comprises the following steps: adding carbon source and passivating agent into octadecene, and adopting solventThermal method, reacting the reactant at 260-330 ℃ for 2-7 h, and providing N in the reaction process₂As a protective atmosphere, reacting to generate carbon quantum dots; the carbon source comprises at least one of silane and citric acid substituted by at least one amino group, and the passivating agent comprises at least one of dodecylamine, hexadecylamine and octadecylamine.

Alternatively, citric acid is used as a carbon source and octadecylamine is used as a passivating agent.

Preferably, in the method for synthesizing the carbon quantum dots: calculating the mass ratio of citric acid to octadecylamine to be 4: 3; the reaction temperature was 280 ℃.

Optionally, the silane substituted with at least one amino group is γ -aminopropyltriethoxysilane.

Preferably, gamma-aminopropyltriethoxysilane is used as the carbon source and octadecylamine is used as the passivating agent.

Preferably, in the method for synthesizing the carbon quantum dots: calculated according to the mass ratio of the fed materials, the gamma-aminopropyl triethoxysilane to octadecylamine is 5: 4; the reaction temperature was 300 ℃.

Preferably, the carbon source is composed of citric acid and gamma-aminopropyltriethoxysilane, and the passivating agent is compounded from dodecylamine and hexadecylamine.

Preferably, in the method for synthesizing the carbon quantum dots: calculated according to the mass ratio of the materials fed, the citric acid is gamma-aminopropyl triethoxysilane, the dodecylamine is hexadecylamine, and the ratio is 5:4:3:5

Preferably, in the textile material, the carbon quantum dots are evenly distributed within the flexible substrate.

Preferably, the flexible substrate comprises at least one of polyethylene terephthalate, polyamide. Based on the carbon quantum dots, the ultraviolet can be absorbed efficiently and durably, the carbon quantum dots are doped into the textile material as an ultraviolet absorbent, an effective ultraviolet protection effect can be achieved on the textile material, and the situations of embrittlement, cracking and the like caused by ultraviolet radiation of the textile material are obviously reduced. Meanwhile, the textile material containing the ultraviolet absorbent has excellent sun-proof effect, can be applied to sun-proof articles such as sun umbrellas, sun-proof clothes and the like, and widens the application range of the textile material. Particularly, the carbon quantum dots prepared by the method are oil-soluble carbon quantum dots which have high compatibility with textile materials, so that the prepared textile materials have the characteristics of softness and smoothness and have good skin-friendly feeling. In addition, the carbon quantum dots can absorb broad-spectrum ultraviolet rays, so that a sunscreen product using the carbon quantum dots can provide an all-round sunscreen effect for a user. Specifically, the method comprises the following steps: according to the invention, gamma-aminopropyltriethoxysilane is used as a carbon source, so that the prepared carbon quantum dots can absorb short-wave ultraviolet rays strongly; the octadecene is used for providing a reaction environment of a solvothermal method and providing N2 protection in the reaction process, and the effects of widening the ultraviolet absorption range and improving the ultraviolet absorption intensity can also be achieved.

Drawings

FIG. 1 is a comparison graph of the transmission spectra of the carbon quantum dots obtained from treatment 1A, treatment 1B and control treatment groups of example 1;

FIG. 2 is a comparison graph of the transmission spectra of the carbon quantum dots obtained from the treatment 2A group, the treatment 2B group and the control treatment group of example 1;

FIG. 3 is a comparison graph of the transmission spectra of the carbon quantum dots obtained from the treatment 3A group, the treatment 3B group and the control treatment group of example 1;

FIG. 4 is a comparison of the transmission spectra of carbon quantum dots produced by comparative treatment group A of comparative example 1 and treatment 2A of example 1;

FIG. 5 is a comparison of the transmission spectra of carbon quantum dots produced by comparative treatment group B of comparative example 1 and treatment 2A of example 1;

FIG. 6 is a comparison of the transmission spectra of carbon quantum dots produced by comparative treatment group C of comparative example 1 and treatment 2A of example 1;

FIG. 7 is a comparison of the transmission spectra of carbon quantum dots produced by comparative treatment D set of comparative example 1 and treatment 2A of example 1;

FIG. 8 is a comparison of the transmission spectra of carbon quantum dots produced by comparative treatment E set of comparative example 1 and treatment 2A of example 1;

FIG. 9 is a comparison of the transmission spectra of carbon quantum dots produced by comparative treatment group F of comparative example 1 and treatment 2A of example 1;

FIG. 10 is a comparison of the transmission spectra of carbon quantum dots produced by comparative treatment group G of comparative example 1 and treatment 2A of example 1.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

In this example, 7 treatment groups are designated as treatment group 1A, treatment group 1B, treatment group 2A, treatment group 2B, treatment group 3A, treatment group 3B and control treatment group, and carbon quantum dots were prepared by using different raw materials and reaction parameters for each treatment group.

1. Treatment of group 1A

2g of anhydrous citric acid and 1.5g of dodecylamine are put into 25mL of octadecene, mixed uniformly and added into a reaction kettle to provide N₂Heating to 300 ℃ as protective atmosphere and preserving heat for 5 hours; and after the reaction is finished, naturally cooling to room temperature, then taking out the reaction liquid, dialyzing by using a dialysis bag with the molecular weight of 1000, and carrying out reduced pressure distillation on the liquid obtained by dialysis to obtain residues, namely the carbon quantum dots of the fluid.

2. Treatment of group 1B

Putting 2g of anhydrous citric acid and 1.5g of dodecylamine into 25mL of octadecene, uniformly mixing, adding into a reaction kettle, heating to 300 ℃, and keeping the temperature for 5 hours; and after the reaction is finished, naturally cooling to room temperature, then taking out the reaction liquid, dialyzing by using a dialysis bag with the molecular weight of 1000, and carrying out reduced pressure distillation on the liquid obtained by dialysis to obtain residues, namely the carbon quantum dots of the fluid.

3. Treatment of group 2A

1.5g of gamma-aminopropyltriethoxysilane and 1.2g of octadecylamine are added into 25mL of octadecene, mixed uniformly and added into a reaction kettle to provide N₂Heating to 280 ℃ as protective atmosphere and preserving heat for 5 hours; after the reaction is finishedNaturally cooling to room temperature, then taking out the reaction liquid, dialyzing by using a dialysis bag with the molecular weight of 1000, and distilling the liquid obtained by dialysis under reduced pressure to obtain residues, namely the carbon quantum dots of the fluid.

4. Treatment of group 2B

1.5g of gamma-aminopropyltriethoxysilane and 1.2g of octadecylamine are put into 25mL of octadecene, mixed uniformly and then added into a reaction kettle, the temperature is raised to 280 ℃, and the temperature is kept for 5 hours; and after the reaction is finished, naturally cooling to room temperature, then taking out the reaction liquid, dialyzing by using a dialysis bag with the molecular weight of 1000, and carrying out reduced pressure distillation on the liquid obtained by dialysis to obtain residues, namely the carbon quantum dots of the fluid.

5. Treatment of group 3A

1g of anhydrous citric acid, 0.8g of gamma-aminopropyltriethoxysilane, 0.6g of dodecylamine and 1.0g of hexadecylamine are put into 25mL of octadecene, mixed uniformly and added into a reaction kettle to provide N₂Heating to 300 ℃ as protective atmosphere and preserving heat for 5 hours; and after the reaction is finished, naturally cooling to room temperature, then taking out the reaction liquid, dialyzing by using a dialysis bag with the molecular weight of 1000, and carrying out reduced pressure distillation on the liquid obtained by dialysis to obtain residues, namely the carbon quantum dots of the fluid.

6. Treatment of group 3B

1g of anhydrous citric acid, 0.8g of gamma-aminopropyltriethoxysilane, 0.6g of dodecylamine and 1.0g of hexadecylamine are put into 25mL of octadecene, mixed uniformly and then added into a reaction kettle, and the temperature is raised to 300 ℃ and kept for 5 hours; and after the reaction is finished, naturally cooling to room temperature, then taking out the reaction liquid, dialyzing by using a dialysis bag with the molecular weight of 1000, and carrying out reduced pressure distillation on the liquid obtained by dialysis to obtain residues, namely the carbon quantum dots of the fluid.

7. Control treatment group

Dissolving 1.5g of anhydrous citric acid in 35mL of distilled water, adding 0.8mL of ethylenediamine, uniformly mixing, adding into a reaction kettle, heating to 210 ℃, and preserving heat for 6 hours; and after the reaction is finished, naturally cooling to room temperature, then taking out the reaction liquid, dialyzing by using a dialysis bag with the molecular weight of 1000, and carrying out reduced pressure distillation on the liquid obtained by dialysis to obtain residues, namely the carbon quantum dots of the fluid.

The carbon quantum dots of the fluid obtained from the treatment groups 1A, 1B, 2A, 2B, 3A, 3B and the control group of this example were all freeze-dried to obtain solid carbon quantum dots.

The liquid carbon quantum dots prepared in each treatment group of this example were diluted to 1 μ g/g with water and subjected to transmission spectrum detection, and the transmission spectrogram of each treatment group is shown in fig. 1 to 3. The carbon quantum dots prepared by the control treatment group have obvious absorption on ultraviolet rays with the wavelength of 250-380 nm, wherein the absorption effect on the ultraviolet rays with the wavelength of 345-380 nm is particularly obvious. The carbon quantum dots prepared by treatment 1A, treatment 1B, treatment 2A, treatment 2B, treatment 3A and treatment 3B had a wider uv absorption spectrum range than the carbon quantum dots prepared by the control treatment. On the other hand, comparing the treatment 1A group and the treatment 1B group, the treatment 2A group and the treatment 2B group, and the treatment 3A group and the treatment 3B group, respectively, it was found that N was provided in the process of producing carbon quantum dots by the solvothermal method₂The carbon quantum dots as the protective gas have wider ultraviolet absorption range and more complete ultraviolet absorption capacity. The carbon quantum dots prepared by treating the group 1A can almost completely absorb ultraviolet rays with the wavelength of 320-410 nm, the carbon quantum dots prepared by treating the group 2A can almost completely absorb ultraviolet rays with the wavelength of 280-380 nm, and the carbon quantum dots prepared by treating the group 3A can almost completely absorb ultraviolet rays with the wavelength of 280-410 nm.

Comparative example 1

In this example, 7 sets of comparison treatment groups, which are respectively labeled as comparison treatment group a, comparison treatment group B, comparison treatment group C, comparison treatment group D, comparison treatment group E, comparison treatment group F, and comparison treatment group G, are set with treatment group 2A of example 1 as a reference to investigate: the carbon quantum dots are prepared by adopting a solvothermal method, and the selected solvent type influences the ultraviolet absorption performance of the synthesized carbon quantum dots.

1. Comparative treatment group A

1.5g of gamma-aminopropyltriethoxysilane and 1.2g of octadecylamine are put into 25mL of water, mixed uniformly and then added into a reaction kettle, heated to 280 ℃ and kept warm for 5 hours; and after the reaction is finished, naturally cooling to room temperature, then taking out the reaction liquid, dialyzing by using a dialysis bag with the molecular weight of 1000, and carrying out reduced pressure distillation on the liquid obtained by dialysis to obtain residues, namely the carbon quantum dots of the fluid.

2. Comparative treatment of group B

1.5g of gamma-aminopropyltriethoxysilane and 1.2g of octadecylamine are put into 25mL of ethanol, mixed uniformly and then added into a reaction kettle, heated to 280 ℃ and kept warm for 5 hours; and after the reaction is finished, naturally cooling to room temperature, then taking out the reaction liquid, dialyzing by using a dialysis bag with the molecular weight of 1000, and carrying out reduced pressure distillation on the liquid obtained by dialysis to obtain residues, namely the carbon quantum dots of the fluid.

3. Comparative treatment of group C

1.5g of gamma-aminopropyltriethoxysilane and 1.2g of octadecylamine are put into 25mL of acetone, mixed uniformly and then added into a reaction kettle, heated to 280 ℃ and kept warm for 5 hours; and after the reaction is finished, naturally cooling to room temperature, then taking out the reaction liquid, dialyzing by using a dialysis bag with the molecular weight of 1000, and carrying out reduced pressure distillation on the liquid obtained by dialysis to obtain residues, namely the carbon quantum dots of the fluid.

4. Comparative treatment of group D

Putting 1.5g of gamma-aminopropyltriethoxysilane and 1.2g of octadecylamine into 25mL of carbon tetrachloride, uniformly mixing, adding into a reaction kettle, heating to 280 ℃, and preserving heat for 5 hours; and after the reaction is finished, naturally cooling to room temperature, then taking out the reaction liquid, dialyzing by using a dialysis bag with the molecular weight of 1000, and carrying out reduced pressure distillation on the liquid obtained by dialysis to obtain residues, namely the carbon quantum dots of the fluid.

5. Comparative treatment E group

Putting 11.5g of gamma-aminopropyltriethoxysilane and 1.2g of octadecylamine into 25mL of glycerol, uniformly mixing, adding into a reaction kettle, heating to 280 ℃, and keeping the temperature for 5 hours; and after the reaction is finished, naturally cooling to room temperature, then taking out the reaction liquid, dialyzing by using a dialysis bag with the molecular weight of 1000, and carrying out reduced pressure distillation on the liquid obtained by dialysis to obtain residues, namely the carbon quantum dots of the fluid.

6. Comparative treatment F group

1.5g of gamma-aminopropyltriethoxysilane and 1.2g of octadecylamine are put into 25mL of N, N' -dimethylformamide, mixed uniformly and then added into a reaction kettle, and the temperature is raised to 280 ℃ and kept for 5 hours; and after the reaction is finished, naturally cooling to room temperature, then taking out the reaction liquid, dialyzing by using a dialysis bag with the molecular weight of 1000, and carrying out reduced pressure distillation on the liquid obtained by dialysis to obtain residues, namely the carbon quantum dots of the fluid.

7. Comparative treatment of group G

1.5g of gamma-aminopropyltriethoxysilane and 1.2g of octadecylamine are put into 25mL of dimethyl sulfoxide, mixed uniformly and then added into a reaction kettle, the temperature is raised to 280 ℃, and the temperature is kept for 5 hours; and after the reaction is finished, naturally cooling to room temperature, then taking out the reaction liquid, dialyzing by using a dialysis bag with the molecular weight of 1000, and carrying out reduced pressure distillation on the liquid obtained by dialysis to obtain residues, namely the carbon quantum dots of the fluid.

The liquid carbon quantum dots prepared in each treatment group of this example were diluted to 1 μ g/g with water and subjected to transmission spectrum detection, and the transmission spectra of the carbon quantum dots prepared in each treatment group are shown in fig. 4 to 10 in comparison with the carbon quantum dots prepared in treatment 2A group of example 1. The shapes of ultraviolet projection spectrograms of the quantum dots prepared by the comparison treatment groups of the comparative example are relatively close, and the quantum dots can completely absorb ultraviolet rays with the wavelength of 350-410 nm. However, when the transmission spectra of the carbon quantum dots prepared in the treatment 2A group of example 1 were compared with the transmission spectra of the carbon quantum dots prepared in the comparative treatment groups of this comparative example, it was found that the carbon quantum dots prepared by solvothermal method in the reaction environment provided by octadecene were allowed to have a wider ultraviolet absorption range, and in particular, were significantly more strongly absorbed in short-wavelength ultraviolet.

Example 2

This example prepared sunscreen textile materials using the carbon quantum dots prepared from treatment 1A, treatment 2A and treatment 3A of example 1, respectively.

Preparation of No. 1 sunscreen textile material:

weighing 100g of PA particles, weighing the carbon quantum dots prepared by treating the group 1A in the example 1 according to the mass percent of 5%, and fully mixing the two; and then placing the raw material mixture in an oven, heating at 110 ℃ for 2h, and naturally cooling to room temperature to obtain the No. 1 sun-proof textile material.

The No. 1 sun-proof textile material can efficiently absorb ultraviolet rays with the wavelength of 320-410 nm.

Preparation of No. 2 sun-proof textile material:

weighing 100g of PA particles, weighing the carbon quantum dots prepared by the treatment group 2A in the example 1 according to the mass percent of 5%, and fully mixing the two; and then placing the raw material mixture in an oven, heating at 120 ℃ for 2h, and naturally cooling to room temperature to obtain the No. 2 sun-proof textile material.

Preparation of No. 3 sun-proof textile material:

weighing 100g of PA particles, weighing the carbon quantum dots prepared by treating the group 3A in the example 1 according to the mass percent of 8%, and fully mixing the two; and then placing the raw material mixture in an oven, heating at 130 ℃ for 3h, and naturally cooling to room temperature to obtain the No. 3 sun-proof textile material.

The 3 kinds of sunscreen textile materials prepared in this example are flat and uniform, and no area with abnormally dense or sparse carbon quantum dots distribution is found on the sunscreen textile material. Wherein: the No. 1 sun-proof textile material can efficiently absorb ultraviolet rays with the wavelength range of 320-410 nm; the No. 2 sun-proof textile material can efficiently absorb ultraviolet rays with the wavelength range of 280-380 nm, and has high light transmittance in the visible light range of 400-780 nm; the No. 3 sun-proof textile material can efficiently absorb ultraviolet rays with the wavelength of 280-410 nm, and has a high broad-spectrum sun-proof effect.

Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the true spirit and scope of the present invention.