CN107287682B

CN107287682B - Graphene-containing stone needle composite fiber and preparation method and application thereof

Info

Publication number: CN107287682B
Application number: CN201710551686.7A
Authority: CN
Inventors: 唐地源; 张金柱; 刘顶
Original assignee: Shandong Shengquan New Material Co Ltd
Current assignee: Shandong Shengquan New Material Co Ltd
Priority date: 2017-07-07
Filing date: 2017-07-07
Publication date: 2019-12-13
Anticipated expiration: 2037-07-07
Also published as: CN107287682A

Abstract

The invention provides a graphene-containing stone needle composite fiber and a preparation method and application thereof. A graphene-containing stone needle composite fiber is mainly prepared from the following components: fiber carrier slices, stone needles and graphene materials; the graphene material is a material with a graphene lamellar structure and comprises any one or a combination of at least two of graphene, graphene oxide and a graphene derivative. According to the invention, the graphene material is introduced into the composite fiber prepared from the stone needle and the fiber slices so as to improve the dispersibility between the stone needle and the fiber, and meanwhile, the strength, far infrared function, thermoelectric property and stability of the fiber are improved by utilizing various excellent characteristics of the graphene material.

Description

Graphene-containing stone needle composite fiber and preparation method and application thereof

Technical Field

The invention relates to the field of textile materials, in particular to a graphene-containing stone needle composite fiber and a preparation method and application thereof.

Background

In recent years, with the continuous improvement of people's life and the rapid development of science and technology, textile fibers with various health care functions and products thereof, such as anion far infrared fibers, biological magnetic fibers and products thereof, emerge in large numbers. The clothes made of the functional fibers have certain health care and physical therapy effects and are widely applied at present. The stone needle contains more than forty kinds of microelements and mineral substances which are beneficial to human bodies and more than 20 kinds of anti-aging elements such as calcium, magnesium, zinc, chromium, strontium, selenium and the like which are necessary for human bodies. The stone needle has a singular energy field, can generate far infrared radiation when acting on the skin of a human body, and has a very wide frequency band and a far infrared frequency reaching range of 7-20 mu m. The stone needle achieves some treatment and health care through microcrystalline infrared and pulse wave bands, and if the stone needle can be effectively introduced into fibers to be made into functional fibers, the efficacy of the stone needle can be exerted persistently.

For example, patent application CN102586923A discloses a stone needle functional fiber and a processing process thereof, which is composed of stone needle functional master batches and polypropylene fiber-grade resin, wherein the stone needle functional master batches comprise the following components in percentage by weight: 1-15% of stone needle powder additive, 2.5-9% of coupling agent, 15-25% of dispersing agent and 52-67% of carrier resin. A large amount of conventional coupling agents and dispersing agents are needed when the stone needle functional master batch is prepared, the used dispersing agents comprise PE high-molecular wax, PP molecular wax or EVA, the used coupling agents comprise silane, titanate, aluminate and aluminum-titanium composite coupling agents, and the additives can dilute carrier resin and reduce the strength of the prepared fiber.

Patent application CN105970327A discloses a health-care regenerated cellulose fiber containing stone needles, which is composed of stone needles and regenerated fibers, and conventional dispersing agents and thickening agents are added, wherein the used dispersing agents comprise sodium polypropylene salt, sodium polymetaphosphate, sodium pyrophosphate, zinc stearate, sodium hexametaphosphate, polyethylene glycol, triethylhexylphosphoric acid and nano titanium dioxide, the used thickening agents are sodium carboxymethylcellulose, the additives also reduce the original strength of the regenerated cellulose, the dry breaking strength only reaches 2.4-4.6 cN/dtex, and the heat retention rate reaches 93% at most.

In view of the above, the present invention is particularly proposed.

disclosure of Invention

The invention aims to provide a graphene-containing stone needle composite fiber, which solves the technical problem that the strength of the fiber is reduced after the stone needle is introduced into the existing product.

The second purpose of the invention is to provide the preparation method of the graphene-containing stone needle composite fiber, which is simple in process and small in difference between the process and the existing product, so that the difficulty in workshop reconstruction during product upgrading is reduced.

The third purpose of the invention is to provide the application of the graphene-containing stone needle composite fiber, which is widely applied and mainly used in the textile field, such as the manufacture of yarns, fabrics, non-woven fabrics, filter materials or thermal wadding fillers.

In order to solve the technical problems, the invention provides the following technical scheme:

A graphene-containing stone needle composite fiber is mainly prepared from the following components: fiber carrier slices, stone needles and graphene materials;

The graphene material is a material with a graphene lamellar structure and comprises any one or a combination of at least two of graphene, graphene oxide and a graphene derivative.

The graphene provided by the invention is prepared from graphite by a stripping method. The graphene oxide can be prepared by reduction, or the graphite can be prepared by oxidation reduction, or the carbon-containing gas can be prepared by a CVD method, or the graphene oxide can be prepared by taking biomass as a raw material by a high-temperature cracking method.

according to the invention, the graphene material is introduced into the composite fiber made of the stone needle and the fiber, so that the dispersibility between the stone needle and the fiber is improved, and meanwhile, the high-strength characteristic of the graphene material is utilized to improve the fiber strength.

the specific principle of the invention is as follows: inside the composite fiber, the microscopic morphology appears as: the fiber carrier slices, the stone needles and the graphene materials are mutually dispersed, namely the stone needles are uniformly dispersed in a two-dimensional lamellar structure of the graphene materials and coated on the surface of the graphene materials, so that the phenomenon that self ions are accumulated or agglomerated to cause the phenomenon that the stone needles cannot be uniformly dispersed in fibers is avoided, and the agglomeration of graphene materials is effectively prevented. Therefore, in the invention, the graphene substance and the stone needle are mutually used as dispersion media, so that the functional effect of the stone needle in the fiber is improved, and the breaking strength, the breaking elongation and the thermoelectric property of the composite fiber are improved by utilizing the good strength, flexibility and hot spot property of the graphene substance.

Through detection, the breaking strength of the stone needle composite fiber is not reduced by introducing stone needles and other substances, but can be improved by more than 20 percent, even by 50 percent, the far infrared normal emissivity of the stone needle composite fiber can reach more than 0.91, and the bacteriostasis rate of the stone needle composite fiber can reach more than 90 percent.

The graphene can be commercially available graphene, and can also be obtained by different preparation methods, such as a mechanical stripping method, an epitaxial growth method, a chemical vapor deposition method and a graphite oxidation-reduction method. However, some methods have difficulty in large-scale preparation of strictly theoretical graphene, for example, some of the graphene prepared by the prior art may have some impurity elements, other allotropes of carbon elements, or graphene structures with non-single-layer or even multi-layer layers (for example, 3 layers, 5 layers, 10 layers, 20 layers, etc.), and the graphene used in the present invention also includes the above-mentioned non-strictly theoretical graphene.

The graphene oxide can be commercially available graphene oxide, can also be a product obtained by oxidizing graphene prepared by partial reduction crosslinking, can also be a product obtained by oxidizing graphene prepared by a PECVD method, can also be obtained by oxidizing graphite, can be obtained by preparing carbon-containing gas by a CVD method, and can also be obtained by preparing biomass as a raw material by a high-temperature cracking method.

The stone needle composite fiber can be further improved to improve various performances of the stone needle composite fiber, such as:

preferably, the weight portions of the fiber carrier slice are 100, the stone needle is 1-3 and the graphene material is 0.5-3.

after the proportion of the raw materials is optimized, the strength of the product can be improved, and the far infrared function, particularly the heat retention rate, of the product can be improved.

Likewise, it is further preferred that: 100 parts of fiber carrier slice, 1-2 parts of stone needle and 1.5-3 parts of graphene material.

Preferably, the particle size of the stone needle is below 1 μm.

The particle size of the stone needle is too large to facilitate spinning, and the particle size is preferably less than 1 μm in consideration of the factor that the spinneret orifice is blocked or the filaments are broken.

Preferably, the particle size of the graphene material is 8 μm or less.

The particle size of the graphene material is too large and easy to agglomerate. Further, since the particle size is too small or too concentrated, the particle size of the graphene material is preferably dispersed in a different range, for example, the particle size is in a partial proportion of 1 to 5 μm, in a partial proportion of 5 to 8 μm, or in a state where the lower limit value and the upper limit value of the particle size distribution are greatly different.

Preferably, the mass of the graphene material with the particle size of more than 1 μm is more than or equal to 1/4 of the mass of the stone needle.

Considering the microscopic forms of the graphene material and the stone needle and the change of the spinning process to the particle form, the finding shows that when the mass of the graphene material with the particle size of more than 1 μm is more than or equal to 1/4 of the mass of the stone needle, the dispersion effect is better, and the comprehensive performance of the product is better.

Likewise, it is further preferred that: the mass of the graphene material with the particle size of more than 1 mu m is less than or equal to the total mass of the stone needle.

Preferably, the fiber carrier slice is selected from one or more of polyester fiber, acrylic fiber, nylon fiber, polypropylene fiber and spandex fiber, and preferably from one or more of polyester fiber, acrylic fiber and nylon fiber.

The polyester fiber, the acrylic fiber, the polyamide fiber, the polypropylene fiber and the spandex fiber can obtain better product performance after being matched with the stone needle and the graphene, and particularly the polyester fiber, the acrylic fiber and the polyamide fiber.

The composite fiber obtained by all the schemes of the invention can achieve the following performances:

the dry breaking strength of the graphene-containing stone needle composite fiber can be improved by more than 20%, even 50%, for example, the dry breaking strength of the graphene-containing stone needle composite polyester fiber can reach more than 6.8cN/dtex, while the dry breaking strength of the conventional polyester fiber is about 4.2 cN/dtex; the dry breaking strength of the graphene-containing stone needle composite nylon fiber can reach more than 7.0cN/dtex, while the dry breaking strength of the conventional nylon fiber is about 5.2 cN/dtex.

preferably, the far infrared normal emissivity of the stone needle composite fiber is above 0.91.

preferably, the bacteriostasis rate of the stone needle composite fiber is more than 90%.

Preferably, the tourmaline is also contained.

after tourmaline is added, the far infrared function of the composite fiber can be improved, and the effect is better when the total amount is 1-3 parts, namely:

By weight, 100 parts of fiber carrier slice, 1-3 parts of stone needle, 0.5-3 parts of graphene material and 1-3 parts of tourmaline.

Preferably, the particle size of the tourmaline is below 1 μm, preferably 200nm-500 nm.

too large particle size of tourmaline is not beneficial to spinning, and can block spinneret orifices or cause yarn breakage. In view of this, the particle size of tourmaline is preferably 1 μm or less, and preferably 200nm to 500 nm.

Preferably, the total mass of the tourmaline and the stone needle is less than or equal to 5 parts by weight.

the excessive total amount of tourmaline and stone needle can adversely affect spinning and further reduce the tensile property of the composite fiber.

The preparation method of the graphene-containing stone needle composite fiber comprises the following steps:

mixing the stone needle, the graphene material and a part of the fiber carrier slices to prepare master batches;

And mixing the master batch with the rest fiber carrier slices for spinning.

In the method, the types of the fiber carrier slices used for preparing the master batch and spinning can be the same or different.

Preferably, tourmaline is also added during the preparation of the master batch, 1-3 parts of tourmaline is preferably added, and the total mass of the tourmaline and the stone needle is preferably less than or equal to 5 parts.

As described above, the far infrared function of the composite fiber can be improved after tourmaline is added.

Preferably, the graphene material contains particles having a particle size of 1 μm or more and particles having a particle size of less than 1 μm.

Preferably, when the master batch is prepared, the graphene material with the particle size of more than 1 μm is mixed with the stone needle to obtain a mixture A; mixing a graphene material with the particle size of less than 1 mu m with the fiber carrier slice to obtain a mixture B; and mixing the mixture A and the mixture B to prepare master batches.

due to the repulsion among different substances, the stone needle is firstly coated on the periphery of the graphene with the large particle size, so that the effect of dispersing the graphene can be achieved, self dispersion is facilitated, the stone needle can be coated on the periphery of the graphene to form large particles, and aggregation with other graphene particles is further prevented.

In the above steps, the graphene materials of 1 μm or more and 1 μm or less overlap each other in particle size of 1 μm, but the present invention is not particularly limited thereto, that is, the graphene materials of 1 μm may be mixed with the stone needle or the fibrous carrier chips.

Preferably, tourmaline is also added when the mixture A is prepared, 1-3 parts of tourmaline is preferably added, and the total mass of the tourmaline and the stone needle is preferably less than or equal to 5 parts.

As mentioned above, the composite fiber provided by the invention has outstanding fracture strength, far infrared function, thermoelectric property, chemical stability, processability and the like, so that the composite fiber is widely applied and can be used for manufacturing textiles such as yarns, fabrics, non-woven fabrics, filter materials or thermal insulating flock fillers.

In summary, compared with the prior art, the invention achieves the following technical effects:

(1) The mechanical properties of the stone needle composite fiber are improved, especially the breaking strength, the breaking elongation and the like.

(2) The far infrared function of the stone needle composite fiber is improved, so that the heat retention rate and other health care effects are improved.

(3) The thermoelectric property of the stone needle composite fiber is improved.

Detailed Description

the technical solutions of the present invention will be described clearly and completely with reference to the following detailed description, but those skilled in the art will understand that the following described examples are some, not all, of the examples of the present invention, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. 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. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.

The graphene materials provided by the invention are of the following types:

Graphene A: "model number: electrically and thermally conductive graphene of SE1231 ".

and graphene B: "model number: SE1430 "enhanced graphene series.

And (3) graphene C: the biomass graphene is prepared by the method of example 1 in a method for preparing biomass graphene by using CN104724699A as a raw material.

Example 1

Taking polyester fiber as an example below, a graphene-containing stone needle composite polyester fiber is prepared

Taking materials:

100 g of polyester chips, 2 g of stone needle (with the particle size distribution of 0.5-1 mu m) and 1.5 g of graphene B (with the particle size distribution of 0.5-3 mu m), wherein the amount of the graphene B with the particle size of more than 1 mu m is 0.5 g.

Preparing master batch:

Firstly, mixing a graphene material with the particle size of more than 1 mu m with a stone needle to obtain a mixture A; mixing a graphene material with the particle size of less than 1 mu m with 1/4 of polyester chips to obtain a mixture B; and mixing and heating the mixture A and the mixture B, kneading at a high speed, blending and extruding by a double screw, cooling and granulating to obtain master batches.

spinning:

And mixing the master batch with the rest polyester chips, performing melt extrusion spinning, and performing post-treatment to obtain the composite fiber.

example 2

the difference from the example 1 is only that the mixture ratio of the raw materials is different as follows:

100 g of polyester chips, 3 g of stone needle (with the particle size distribution of 0.5-1 mu m) and 3 g of graphene B (with the particle size distribution of 0.5-3 mu m), wherein the amount of the graphene B with the particle size of more than 1 mu m is 1 g.

Example 3

100 g of polyester chips, 1 g of stone needle (with the particle size distribution of 0.5-1 mu m) and 0.5 g of graphene B (with the particle size distribution of 0.5-3 mu m), wherein the amount of the graphene B with the particle size of more than 1 mu m is 0.25 g.

Examples 4 to 5

The difference from example 1 is only in the type of graphene, and graphene a (example 4) and graphene C (example 5) have particle size distributions of 1 to 8 μm.

Example 6

The difference from the embodiment 1 is that the process for preparing the master batch is simple, and specifically:

And simultaneously mixing and heating the stone needle, the graphene B and the polyester slices, kneading at a high speed, blending and extruding by a double screw, cooling and granulating to obtain the master batch.

The procedure is as in example 1.

Example 7

The difference from example 1 is only the particle size of the stone needle, which is distributed between 1 μm and 3 μm.

Example 8

the only difference from example 6 is that 1 gram of tourmaline (particle size distribution between 200nm and 500nm) was added to the starting material and was added at the time of preparation of mixture A.

Example 9

The difference from example 8 is only that the amount of tourmaline added is 3 g of tourmaline.

comparative example 1

See patent application CN102586923A, the specific process is as follows:

Taking materials according to weight percentage, 10 percent of stone needle particles with the particle size of less than 2 mu m, 5 percent of silane, 25 percent of PE polymer wax and 60 percent of PP resin. Mixing and heating all the raw materials, kneading at a high speed, blending and extruding by a double screw, cooling, and granulating to obtain the master batch.

Adding 2.5 times of polypropylene fiber into the master batch, uniformly mixing, performing melt extrusion spinning, and performing post-treatment to obtain the composite fiber.

Comparative example 2

The difference from example 1 is that the stone needle is 10 g.

Comparative example 3

The difference from the embodiment 1 is that the particle sizes of the stone needle and the graphene B are both larger than 5 μm.

Comparative example 4

The conventional polyester fiber is manufactured by Yangzhou Tianlun fiber Co.

The properties of the composite fibers of all the above examples and comparative examples are shown in Table 1.

TABLE 1 Properties of different Stone needle composite fibers

Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. The graphene-containing stone needle composite fiber is characterized by being prepared from the following components in parts by weight: 100 parts of fiber carrier slices, 1-3 parts of stone needles and 0.5-3 parts of graphene materials;

The graphene material is a material with a graphene lamellar structure and comprises any one or a combination of at least two of graphene, graphene oxide and a graphene derivative;

The mass of the graphene material with the particle size of more than 1 mu m is more than or equal to 1/4 of the mass of the stone needle.

2. The graphene-containing stone needle composite fiber according to claim 1, wherein the fiber carrier is 100 parts by weight, the stone needle is 1-2 parts by weight, and the graphene substance is 1.5-3 parts by weight.

3. The graphene-containing stone needle composite fiber according to claim 1, wherein the particle size of the stone needle is below 1 μm.

4. The graphene-containing stone needle composite fiber according to claim 1, wherein the particle size of the graphene material is below 8 μm.

5. The graphene-containing stone needle composite fiber according to claim 1, wherein the mass of the graphene material with the particle size of more than 1 μm is less than or equal to the total mass of the stone needle.

6. the graphene-containing stone needle composite fiber according to claim 1, wherein the fiber carrier chip is selected from one or more of polyester fiber, acrylic fiber, nylon fiber, polypropylene fiber and spandex fiber.

7. The graphene-containing stone needle composite fiber according to claim 6, wherein the fiber carrier chip is selected from one or more of polyester fiber, acrylic fiber and nylon fiber.

8. The graphene-containing stone needle composite fiber according to claim 1, wherein the far infrared normal emissivity of the stone needle composite fiber is above 0.91.

9. The graphene-containing stone needle composite fiber according to claim 1, wherein the bacteriostasis rate of the stone needle composite fiber is above 90%.

10. The graphene-containing stone needle composite fiber is characterized by being prepared from the raw material of the graphene-containing stone needle composite fiber according to any one of claims 1 to 9 and tourmaline.

11. The graphene-containing stone needle composite fiber according to claim 10, wherein the particle size of tourmaline is below 1 μm.

12. the graphene-containing stone needle composite fiber according to claim 11, wherein the particle size of the tourmaline is 200nm to 500 nm.

13. The graphene-containing stone needle composite fiber according to claim 10, wherein the graphene-containing stone needle composite fiber comprises 100 parts by weight of fiber carrier slice, 1-3 parts by weight of stone needle, 0.5-3 parts by weight of graphene material and 1-3 parts by weight of tourmaline.

14. The graphene-containing stone needle composite fiber according to claim 10, wherein the total mass of tourmaline and stone needle is less than or equal to 5 parts by weight.

15. The preparation method of the graphene-containing stone needle composite fiber according to any one of claims 1 to 9, which is characterized by comprising the following steps:

And mixing the master batch with the rest fiber carrier slices for spinning.

16. The preparation method of the graphene-containing stone needle composite fiber according to any one of claims 10 to 14, which is characterized by comprising the following steps:

Mixing the master batch with the rest fiber carrier slices for spinning;

tourmaline is also added when the master batch is prepared.

17. The preparation method according to claim 16, wherein the graphene material contains particles having a particle size of 1 μm or more and a particle size of less than 1 μm.

18. The preparation method according to claim 17, characterized in that during preparation of the master batch, graphene materials with particle sizes of more than 1 μm are mixed with the stone needle to obtain a mixture A; mixing a graphene material with the particle size of below 1 mu m with the fiber carrier slice to obtain a mixture B; mixing the mixture A and the mixture B to prepare master batches;

And adding tourmaline when preparing the mixture A.

19. Use of the graphene-containing stone needle composite fiber according to any one of claims 1 to 14 for the production of yarns, fabrics, nonwovens, filter materials or thermal wadding fillers.