CN115726187A - Fiber composite material and preparation method and application thereof - Google Patents
Fiber composite material and preparation method and application thereof Download PDFInfo
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- CN115726187A CN115726187A CN202111016708.2A CN202111016708A CN115726187A CN 115726187 A CN115726187 A CN 115726187A CN 202111016708 A CN202111016708 A CN 202111016708A CN 115726187 A CN115726187 A CN 115726187A
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Landscapes
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The invention relates to a fiber composite material and a preparation method and application thereof, wherein the fiber composite material contains a fiber material and carbon quantum dots, the particle size of the carbon quantum dots is less than 10nm, the content of oxygen on the surface of the carbon quantum dots is 10-50 wt%, and the content of carbon on the surface of the carbon quantum dots is 50-90 wt%. The fiber composite material has a good effect of removing free radicals.
Description
Technical Field
The invention relates to a fiber composite material and a preparation method and application thereof.
Background
The fiber is a substance composed of continuous or discontinuous filaments, and is widely applied in the fields of home furnishing, buildings, aviation, automobiles, national defense, military industry and the like. The fiber mainly comprises chemical fiber and natural fiber, wherein the chemical fiber is made by chemical treatment and mainly comprises artificial fiber, regenerated fiber, synthetic fiber and inorganic fiber. The artificial fiber comprises viscose fiber, acetate fiber and cuprammonium fiber; the regenerated fiber comprises regenerated cellulose fiber, regenerated protein fiber, regenerated starch fiber and regenerated synthetic fiber; the synthetic fiber includes polyester fiber, polyamide fiber, polyvinyl alcohol fiber, polyacrylonitrile fiber, polypropylene fiber, etc.; inorganic fibers include glass fibers, metal fibers and carbon fibers. Natural fibers are fibers that are present in nature and can be directly obtained, and are mainly classified into plant fibers and animal fibers. The plant fiber is a natural composite nano new material, and is also called wood fiber and cellulose fiber. The animal fiber is obtained from animal hair or gland secretion of insect, and comprises hair fiber and gland fiber, and the main chemical component of the animal fiber is protein, so it is also called protein fiber. Furthermore, natural fibers also include mineral fibers, which are fibers obtained from mineral rocks of fibrous structure.
Free radicals are the main culprit of human body aging, and how to destroy and remove the free radicals is an important research direction for scientific and technological workers in recent years. The existing fibers for daily life such as home furnishing and the like are mainly animal and plant fibers and synthetic fibers, such as fibers for wearing such as various cloth materials, mask cloth and the like, but the fibers have poor effect of removing free radicals.
Disclosure of Invention
The invention aims to provide a fiber composite material, a preparation method and application thereof.
In order to achieve the above object, a first aspect of the present invention provides a fiber composite material comprising a fiber material and carbon quantum dots, the particle size of the carbon quantum dots being 10nm or less, the content of oxygen element on the surface of the carbon quantum dots being 10 to 50 wt%, and the content of carbon element on the surface being 50 to 90 wt%.
Optionally, the particle size of the carbon quantum dots is 2-10nm, the content of oxygen element on the surface of the carbon quantum dots is 20-40 wt%, and the content of carbon element on the surface of the carbon quantum dots is 60-80 wt%.
Optionally, the carbon-oxygen double bond on the surface of the carbon quantum dot is C = O: the molar ratio of the carbon-oxygen single bond C-O is 1: (0.5-2).
Optionally, the carbon quantum dots are present in an amount of 0.0001 to 1 wt%, preferably 0.0005 to 0.01 wt%, based on the total weight of the fiber composite;
the deviation of the number of distribution of the carbon quantum dots per unit area on the surface of the fiber composite material is 0 to 50%, preferably 0 to 30%.
Optionally, the fibrous material comprises chemical fibers and natural fibers;
preferably, the fiber material is selected from one or more of rayon, regenerated fiber, synthetic fiber, inorganic fiber, plant fiber and animal fiber;
more preferably, the fibrous material is a plant fiber and/or an animal fiber.
In a second aspect, the present invention provides a method of making a fibrous composite material provided by the first aspect of the present invention, the method comprising: the fiber material is contacted and compounded with the solution containing the carbon quantum dots, and the fiber material contacted and compounded with the solution containing the carbon quantum dots is subjected to heat treatment at 120-280 ℃.
Optionally, the solution containing the carbon quantum dots is prepared by the following steps: carrying out hydrothermal treatment on an aqueous solution containing organic acid at 150-300 ℃ for 1-48h in a heat-resistant closed container;
the content of organic acid in the aqueous solution is 1-60 wt%; the organic acid is selected from citric acid, tartaric acid, oxalic acid, quinic acid, salicylic acid, malic acid or ascorbic acid, or a combination of two or three of them.
Optionally, the conditions of the contacting include: the temperature is 30-100 deg.C, the pressure is 0-2MPa, and the time is 2-60min;
the conditions of the heat treatment include: the temperature is 120-280 deg.C, and the time is 1-240min.
Optionally, the solution containing carbon quantum dots is used in an amount of 10 to 1000 parts by weight relative to 100 parts by weight of the fiber material; the concentration of the solution containing the carbon quantum dots is 0.0001-10g/L;
the solvent of the solution containing the carbon quantum dots is one or more of water, methanol, ethanol, acetone and acetic acid.
In a third aspect, the present invention provides a use of the fiber composite material in the first aspect for preparing knitted fabric and/or nonwoven fabric.
Through the technical scheme, the preparation method can highly disperse the carbon quantum dots on the fibers under mild conditions, and the prepared fiber composite material containing the carbon quantum dots has good performance of removing free radicals, and can be used in knitted fabrics and/or non-woven fabrics.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes the embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The invention provides a fiber composite material, which comprises a fiber material and carbon quantum dots, wherein the particle size of the carbon quantum dots is less than 10nm, the content of oxygen element on the surface of the carbon quantum dots is 10-50 wt%, and the content of carbon element on the surface of the carbon quantum dots is 50-90 wt%. The fiber composite material has better free radical scavenging performance.
In the present invention, the particle size refers to the maximum three-dimensional length of the carbon quantum dot particle, i.e., the corresponding distance between two points on the carbon quantum dot particle having the largest distance. The measurement of the particle size can be carried out by methods known to the person skilled in the art, for example by transmission electron microscopy.
In a preferred embodiment, the particle size of the carbon quantum dots is 2 to 10nm, and when the particle size of the carbon quantum dots is within the above range, the fiber composite material has more excellent radical scavenging properties.
According to the bookThe invention has the advantages that the carbon quantum dots in the fiber composite material are uniformly distributed, and the surface (such as 1-5000 mu m) of the fiber composite material in unit area 2 ) The deviation in the number of the distribution of the upper carbon quantum dots is 0 to 50%, preferably 0 to 30%. The distribution quantity deviation can reflect the distribution uniformity of the carbon quantum dots on the fiber composite material, and the distribution quantity deviation can be obtained by respectively testing the quantity of the carbon quantum dots in any two different areas with the same area on the surface of the fiber composite material through a scanning electron microscope and then calculating according to the difference of the quantity of the carbon quantum dots compared twice.
In order to further optimize the performance of the fiber composite material, in a preferred embodiment of the present invention, the content of oxygen on the surface of the carbon quantum dots is 20 to 40 wt%, the content of carbon on the surface is 60 to 80 wt%, and the content of the surface elements of the carbon quantum dots can be measured by XPS. More preferably, when the carbon-oxygen double bond C = O on the surface of the carbon quantum dot: the molar ratio of the carbon-oxygen single bond C-O is 1: (0.5-2), the obtained fiber composite material has better free radical scavenging performance.
The content of carbon quantum dots according to the invention can vary within wide limits, for example from 0.0001 to 1% by weight, preferably from 0.0005 to 0.01% by weight, based on the total weight of the fiber composite. When the weight of the carbon quantum dots is within the range, the weight ratio of the carbon quantum dots to the fibers is proper, the carbon quantum dots on the composite fibers are better in dispersity, and the fiber composite material has better free radical scavenging performance.
Fibrous materials are well known to those skilled in the art and may include chemical fibers and natural fibers; preferably, the fiber material is selected from one or more of rayon, regenerated fiber, synthetic fiber, inorganic fiber, plant fiber and animal fiber; more preferably, the fibrous material is a plant fiber and/or an animal fiber.
The kind and source of the carbon quantum dots are not particularly limited, and the carbon quantum dots can be obtained by commercial or self-preparation, and can be polymer dots, graphene dots and the like. In one embodiment, the carbon quantum dots are prepared by a method comprising the steps of: in a heat-resistant closed container, carrying out hydrothermal treatment on an organic acid aqueous solution at 150-300 ℃ for 1-48h, wherein the pressure of the hydrothermal reaction can be a reaction autogenous pressure or an external pressure, and when the pressure is the external pressure, the pressure is 1-5MPa. According to the invention, the content of organic acid in the aqueous solution can vary within wide limits and can be, for example, from 1 to 60% by weight, preferably from 5 to 30% by weight. The organic acid can be organic acid contained in natural plant such as fruit, specifically selected from citric acid, tartaric acid, oxalic acid, quinic acid, salicylic acid, malic acid or ascorbic acid, or their combination.
In a second aspect, the present invention provides a method of making a fibrous composite material provided by the first aspect of the present invention, the method comprising: the fiber material is contacted and compounded with the solution containing the carbon quantum dots, and the fiber material contacted and compounded with the solution containing the carbon quantum dots is subjected to heat treatment at 120-280 ℃.
In the invention, the strong adsorbability of the carbon quantum dots and the heat treatment process are utilized in the contact process of the fiber material and the solution containing the carbon quantum dots, so that the fiber material and the carbon quantum dots are effectively compounded. The method is simple and easy to implement, the conditions are mild, and the prepared fiber composite material has good free radical scavenging performance.
The present invention is not particularly limited in kind and source of the carbon quantum dots, and can be obtained by commercial or self-preparation. In one embodiment, the carbon quantum dots are prepared by a method comprising: in a heat-resistant closed container, carrying out hydrothermal treatment on an aqueous solution containing organic acid at 150-300 ℃ for 1-48h, wherein the pressure of the hydrothermal reaction can be the autogenous pressure of the reaction or the applied pressure, and when the pressure is the applied pressure, the pressure is 1-5MPa. According to the invention, the content of organic acid in the aqueous solution can vary within wide limits and can be, for example, from 1 to 60% by weight, preferably from 5 to 30% by weight. The organic acid may be an organic acid contained in natural fruits, and may be selected from, for example, citric acid, tartaric acid, oxalic acid, quinic acid, salicylic acid, malic acid, or ascorbic acid, or a combination of two or three thereof.
In order to make the fiber material and the carbon quantum dots better contact-compounded, according to the present invention, in step S1, the contact conditions may include: the temperature is 30-100 deg.C, preferably 50-80 deg.C, the pressure is 0-2MPa, preferably 0-1MPa, and the time is 2-60min, preferably 5-30min.
According to the present invention, the heat treatment may be carried out in an open system, that is, in an environmental system such as a heat treatment apparatus communicating with the atmosphere, for example, a conventional heat treatment apparatus; the heat treatment may be carried out in a closed system, that is, in an environmental system such as a heat treatment facility not open to the atmosphere, and various closed reaction heating facilities may be used. The atmosphere for the heat treatment is not required, and may be an air atmosphere or a nitrogen atmosphere, for example. The conditions of the heat treatment may include: the temperature is 120-280 deg.C, preferably 130-240 deg.C, and the time is 1-240min, preferably 10-60min.
In one embodiment of the present invention, the solution containing carbon quantum dots is used in an amount of 10 to 1000 parts by weight, preferably 50 to 500 parts by weight, with respect to 100 parts by weight of the fiber material. The carbon quantum dot content of the fiber composite material prepared in the dosage range is proper, and the fiber composite material has good free radical scavenging performance.
According to the present invention, the concentration of the carbon quantum dot-containing solution may vary within a wide range, and may be, for example, 0.0001 to 10g/L, preferably 0.001 to 1g/L. When the concentration of the solution containing the carbon quantum dots is within the range, the carbon quantum dots are favorably and fully contacted with the fiber material, so that the prepared fiber composite material has better free radical scavenging performance. The solvent of the solution containing the carbon quantum dots is not particularly limited, and may be, for example, one or more of water, methanol, ethanol, acetone, and acetic acid.
In a third aspect, the present invention provides a use of the fiber composite material provided in the first aspect of the present invention in the preparation of knitted fabrics and/or nonwoven fabrics.
The invention is further illustrated by the following examples, but is not to be construed as being limited thereto.
The method for measuring the content of the carbon quantum dots in the fiber composite material and the content of the fiber material in the embodiment is as follows: 2g of the fiber material was weighed using a five-position electronic balance (XS 105DU, metler-Tollido, switzerland), the content of the carbon quantum dots and the content of the fiber material in the fiber material were calculated from the mass difference before and after the addition of the carbon quantum dots, and the measurement was repeated three times, and the average value was taken as the final data result.
The particle size of the carbon quantum dots is measured by a transmission electron microscope method, and the content of surface elements and the molar ratio of C = O of carbon-oxygen double bonds to C-O of carbon-oxygen single bonds are obtained by XPS test.
Example 1
(1) Preparation of carbon Quantum dots
An aqueous solution containing carbon quantum dots was obtained by mixing 25g of a 20 wt% citric acid aqueous solution and 25g of a 10 wt% ascorbic acid aqueous solution at normal temperature and pressure, and then treating the mixture under hydrothermal conditions at 210 ℃ under autogenous pressure for 40 hours. Through detection, the concentration of the carbon quantum dots in the aqueous solution containing the carbon quantum dots is 6.1g/L.
(2) Preparation of fiber composite material containing carbon quantum dots
After diluting an appropriate amount of the aqueous solution containing the carbon quantum dots obtained in the step (1) (the concentration of the diluted carbon quantum dots is about 0.04 g/L), contacting and compounding 10g of dispersed viscose fibers at the temperature of 55 ℃ and under the pressure of 0.1MPa, wherein the weight ratio of the diluted carbon quantum dot solution to the fibers is 5:1, contacting for 30min, and then carrying out heat treatment on the viscose fiber obtained by compounding for 1h in the air at the temperature of 200 ℃ to obtain the fiber composite material containing the carbon quantum dots.
It was determined that, based on the total weight of the fibrous composite material containing carbon quantum dots, the content of the carbon quantum dots was 0.007% by weight, the deviation of the number of the distribution of the carbon quantum dots per unit area of the surface of the fibrous composite material was 15%, the particle size of the carbon quantum dots was 3nm, the content of oxygen on the surface was 26% by weight, the content of carbon on the surface was 74% by weight, and the carbon-oxygen double bonds on the surface of the carbon quantum dots C = O: the molar ratio of the carbon-oxygen single bond C-O is 1:1.2.
example 2
A fiber composite was prepared in the same manner as in example 1, except that, in step (2), the adhesive fiber was replaced with tencel fiber.
It was determined that, based on the total weight of the fiber composite material containing carbon quantum dots, the content of the carbon quantum dots was 0.009 wt%, the deviation of the distribution number of the carbon quantum dots per unit area on the surface of the fiber composite material was 11%, the particle size of the carbon quantum dots was 3nm, the content of oxygen elements on the surface was 27 wt%, the content of carbon elements on the surface was 73 wt%, and the surface carbon-oxygen double bonds of the carbon quantum dots C = O: the molar ratio of the carbon-oxygen single bond C-O is 1:1.3.
example 3
A fiber composite material was prepared in the same manner as in example 1, except that, in the step (1), the concentration of the citric acid aqueous solution was 40 wt%, the concentration of the ascorbic acid aqueous solution was 20 wt%, and the hydrothermal temperature was 280 ℃.
Through detection, based on the total weight of the fiber composite material containing the carbon quantum dots, the content of the carbon quantum dots is 0.009 wt%, the distribution quantity deviation of the carbon quantum dots on the surface of the fiber composite material per unit area is 20%, the particle size of the carbon quantum dots is 8nm, the content of oxygen elements on the surfaces of the carbon quantum dots is 56 wt%, the content of carbon elements on the surfaces is 44 wt%, and the carbon-oxygen double bonds on the surfaces of the carbon quantum dots C = O: the molar ratio of carbon to oxygen single bond C-O is 1:0.4.
example 4
A fiber composite material was produced in the same manner as in example 1, except that in the step (2), the concentration of the carbon quantum dots after dilution was about 1.1g/L.
Through detection, based on the total weight of the fiber composite material containing the carbon quantum dots, the content of the carbon quantum dots is 0.2 wt%, the distribution quantity deviation of the carbon quantum dots on the surface of the fiber composite material in unit area is 18%, the particle size of the carbon quantum dots is 3nm, the content of oxygen elements on the surfaces of the carbon quantum dots is 26 wt%, the content of carbon elements on the surfaces is 74 wt%, and the carbon-oxygen double bonds on the surfaces of the carbon quantum dots C = O: the molar ratio of carbon to oxygen single bond C-O is 1:1.3.
example 5
A fiber composite material was produced in the same manner as in example 1, except that in step (2), the concentration of the diluted carbon quantum dots was about 0.0002g/L.
Through detection, based on the total weight of the fiber composite material containing the carbon quantum dots, the content of the carbon quantum dots is 0.0004 wt%, the distribution quantity deviation of the carbon quantum dots on the surface of the fiber composite material in unit area is 32%, the particle size of the carbon quantum dots is 3nm, the content of oxygen on the surface of the carbon quantum dots is 27 wt%, the content of carbon on the surface is 73 wt%, and the carbon-oxygen double bonds on the surface of the carbon quantum dots C = O: the molar ratio of carbon to oxygen single bond C-O is 1:1.2.
example 6
A fiber composite material was prepared in the same manner as in example 1, except that, in the step (2), the contact temperature was 150 ℃ and the contact time was 1440min, the pressure was 2.5MPa, and the heat treatment temperature was 280 ℃ and the contact time was 240min.
It was determined that, based on the total weight of the fiber composite material containing carbon quantum dots, the content of the carbon quantum dots was 0.01 wt%, the deviation of the number of the distribution of the carbon quantum dots on the surface of the fiber composite material per unit area was 38%, the particle size of the carbon quantum dots was 10nm, the content of oxygen element on the surface was 35 wt%, the content of carbon element on the surface was 65 wt%, and the carbon-oxygen double bond C = O on the surface of the carbon quantum dots: the molar ratio of the carbon-oxygen single bond C-O is 1:0.3.
comparative example 1
The method of example 1 was employed except that the aqueous solution containing carbon quantum dots was replaced with an aqueous solution of equal content of nanocarbon particles (average particle diameter 60 nm) to obtain a fibrous composite material containing nanocarbon particles. The content of the nanocarbon particles was determined to be 0.03% by weight, based on the total weight of the fiber composite.
Test example
(1) The fiber materials of the examples and comparative examples were subjected to radical scavenging (DPPH method) tests:
the DPPH concentration is detected in a Biotek microplate reader by means of an ultraviolet-visible absorption spectrophotometer in the wavelength range from 450 to 600 nm. Immersing the fiber material in a freshly prepared absolute methanol solution of DPPH (100. Mu.M) and standing for 1h in the dark; parallel tests were not run into the fibrous material. The measurement was repeated three times and the average value was taken as the final result, wherein the larger the data result of DPPH radical scavenging rate, the better the radical scavenging performance is shown in Table 1.
The DPPH radical clearance (%) after the reaction was measured and calculated by the following formula:
DPPH radical clearance (%) = (a) 0 -A i )/A 0 X 100%, wherein A i Absorbance at 450-600nm of a solution of DPPH (100. Mu.M) in anhydrous methanol after immersion in a fiber sample, A 0 The absorbance of the DPPH solution without immersion of the fiber, i.e., the absorbance of the DPPH radical solution.
TABLE 1
| Clearance of free radicals,% | |
| Example 1 | 36 |
| Example 2 | 39 |
| Example 3 | 32 |
| Example 4 | 28 |
| Example 5 | 25 |
| Example 6 | 21 |
| Comparative example 1 | 11 |
| Viscose fiber | 8 |
| Tencel fiber | 12 |
From the results of the above examples and comparative examples, it can be seen that the fiber composite material of the present invention has good radical scavenging properties.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. A fiber composite material comprises a fiber material and carbon quantum dots, wherein the particle size of the carbon quantum dots is less than 10nm, the content of oxygen element on the surface of the carbon quantum dots is 10-50 wt%, and the content of carbon element on the surface of the carbon quantum dots is 50-90 wt%.
2. The fiber composite material according to claim 1, wherein the particle size of the carbon quantum dots is 2-10nm, the content of oxygen element on the surface of the carbon quantum dots is 20-40 wt%, and the content of carbon element on the surface is 60-80 wt%.
3. The fibrous composite material according to claim 1 wherein the carbon quantum dots have surface carbon-oxygen double bonds C = O: the molar ratio of the carbon-oxygen single bond C-O is 1: (0.5-2).
4. The fiber composite of claim 1, wherein the carbon quantum dots are present in an amount of 0.0001 to 1 wt. -%, preferably 0.0005 to 0.01 wt. -%, based on the total weight of the fiber composite;
the deviation of the number of distribution of the carbon quantum dots per unit area on the surface of the fiber composite material is 0 to 50%, preferably 0 to 30%.
5. The fibrous composite of claim 1 wherein the fibrous material comprises chemical fibers and natural fibers;
preferably, the fiber material is selected from one or more of rayon, regenerated fiber, synthetic fiber, inorganic fiber, plant fiber and animal fiber;
more preferably, the fibrous material is a plant fiber and/or an animal fiber.
6. A method of making a fibrous composite according to any of claims 1 to 5, the method comprising:
the fiber material is contacted and compounded with a solution containing carbon quantum dots, and the fiber material which is contacted and compounded with the solution containing the carbon quantum dots is subjected to heat treatment at 120-280 ℃.
7. The method of claim 6, wherein the solution containing carbon quantum dots is prepared by a method comprising: carrying out hydrothermal treatment on an aqueous solution containing organic acid at 150-300 ℃ for 1-48h in a heat-resistant closed container;
the content of organic acid in the aqueous solution is 1-60 wt%; the organic acid is selected from citric acid, tartaric acid, oxalic acid, quinic acid, salicylic acid, malic acid or ascorbic acid, or a combination of two or three of them.
8. The method of claim 6, wherein the conditions of the contacting comprise: the temperature is 30-100 deg.C, the pressure is 0-2MPa, and the time is 2-60min;
the conditions of the heat treatment include: the temperature is 120-280 deg.C, and the time is 1-240min.
9. The method of claim 6, wherein the solution containing carbon quantum dots is used in an amount of 10-1000 parts by weight relative to 100 parts by weight of the fiber material; the concentration of the solution containing the carbon quantum dots is 0.0001-10g/L;
the solvent of the solution containing the carbon quantum dots is one or more of water, methanol, ethanol, acetone and acetic acid.
10. Use of the fibrous composite material according to any of claims 1 to 5 for the production of knitted and/or nonwoven fabrics.
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