阅读说明：本技术 一种超疏水性纳米纤维及其应用 (Super-hydrophobic nanofiber and application thereof ) 是由 潘玉明 董勤霞 潘豪炜 王婷 于 2020-11-19 设计创作，主要内容包括：本发明公开了一种超疏水性纳米纤维,所述超疏水性纳米纤维经过原料配比、制作功能性母粒、经过拉丝工艺制备成纳米纤维,通过在二氧化硅溶胶中整理得到超疏水性纳米纤维,由于表面附着二氧化硅,增大了静态接触角θ,提高了纤维的疏水性,且无毒无害,环保安全,经久耐用。本发明还提供了一种超疏水亲肤面料,采用上述超疏水性纳米纤维编织,无毒无害、疏水性强,内层采用多种天然纤维混纺纱编织而成,亲肤透气、吸水排汗,适合贴身穿着,在改善疏水面料硬度大、不亲肤的同时不破坏疏水面料原本的功能性。(The invention discloses a super-hydrophobic nanofiber, which is prepared into a nanofiber by raw material proportioning, functional master batch preparation and a wire drawing process, the super-hydrophobic nanofiber is obtained by finishing in silica sol, and as silica is attached to the surface of the super-hydrophobic nanofiber, a static contact angle theta is increased, the hydrophobicity of the fiber is improved, and the super-hydrophobic nanofiber is non-toxic, harmless, environment-friendly, safe and durable. The invention also provides a super-hydrophobic skin-friendly fabric which is woven by adopting the super-hydrophobic nano fibers, is non-toxic, harmless and strong in hydrophobicity, is formed by weaving various natural fiber blended yarns in the inner layer, is skin-friendly, breathable, water-absorbing and sweat-releasing, is suitable for close-fitting wearing, is improved in hardness and is not skin-friendly, and the original functionality of the hydrophobic fabric is not damaged.)

1. The super-hydrophobic nanofiber is characterized by being prepared by the following method:

s1: mixing terephthalic acid and ethylene glycol, adding a dispersing agent, and uniformly stirring to prepare slurry; adding the prepared slurry into an esterification reaction kettle for carrying out a first esterification reaction, and adding sorbitol and polyethylene glycol for carrying out a second esterification reaction when the collection amount of byproducts reaches 82-95% of a theoretical value; after the esterification reaction is finished, carrying out polycondensation reaction on the prepared esterified substance to obtain a polyester slice;

s2: uniformly mixing the polyester chips obtained in the step S1 with nano silver nitrate powder, nano zinc oxide powder and nano iron oxide powder, adding a stabilizer, a dispersant and a smoothing agent, uniformly stirring, and then performing melt granulation to obtain functional master batches;

s3: drying the functional master batch obtained in the step S2 until the average water content of the functional master batch is not more than 0.01%, and drawing the dried functional master batch to obtain the nano fiber;

s4: and soaking the nano-fibers into silica sol for finishing, and drying to obtain the super-hydrophobic nano-fibers.

2. The superhydrophobic nanofiber according to claim 1, wherein in step S1, the dispersant is polyisobutylene polysuccinimide; the smoothing agent is one or more of food-grade white oil, palm oil, soybean oil, rapeseed oil, cottonseed oil, corn oil, rice bran oil, sunflower oil, peanut oil, castor oil, sesame oil, zanthoxylum seed oil, tea oil, coconut oil, olive oil, pistacia chinensis oil, palm oil and turpentine oil.

3. The superhydrophobic nanofiber according to claim 1, wherein the temperature required for the melt granulation in step S2 is 260-300 ℃.

4. The superhydrophobic nanofiber according to claim 1, wherein in step S1, the molar ratio of phthalic acid to ethylene glycol is 1: 1.05-2.

5. The superhydrophobic nanofiber according to claim 1, wherein in step S2, the mass ratio of the polyester chip, the nano silver nitrate powder, the nano zinc oxide powder and the nano iron oxide powder is 1000:8:5: 3.

6. the superhydrophobic nanofiber according to claim 1, wherein the drying temperature in step S3 is 150-180 ℃.

7. The super-hydrophobic skin-friendly fabric is characterized by comprising an inner layer and a hydrophobic layer from inside to outside in sequence; the hydrophobic layer is woven by yarns spun by the super-hydrophobic nano fibers prepared by the method according to any one of claims 1 to 7, and the inner layer is woven by blended yarns of cotton-flax fibers, modal fibers, silk fibers and polyester fibers; the inner layer and the hydrophobic layer are connected by polyester filaments through a tucking process.

8. The superhydrophobic skin-friendly fabric according to claim 7, wherein the blending ratio of the cotton-flax fibers, the modal fibers, the silk fibers and the polyester fibers is 50:35:10: 5.

9. the superhydrophobic skin-friendly fabric according to claim 5, wherein the gram weight of the superhydrophobic skin-friendly fabric is 100-260g/m²。

Technical Field

The invention relates to the field of novel materials, in particular to a super-hydrophobic nanofiber and application thereof.

Background

Along with social progress and development, the material and cultural living standard of people is improved year by year, and the clothing consumption level is also changed fundamentally. The traditional single clothes can not meet the requirements of people on the variety diversification of clothes any more, but pay more attention to the organic combination of practicability, comfort, health care and safety. At present, the clothing industry has entered an era that is won by new materials, new technologies, new processes and new products, and the fashion trend and change of clothing will change along with the innovation and development of fabrics.

In 1805, Young proposed that the contact angle θ can be measured by the equilibrium relationship of the liquid drop on the surface of a planar solid under the tension of three interfaces, and if the contact angle θ is larger than 150 °, it is defined as hydrophobicity. The smoother the surface, the smaller the contact angle theta, and the hydrophilicity is presented; the rougher the surface, the larger the contact angle θ, and the more likely to be rendered hydrophobic. Traditional hydrophobicity surface fabric adopts to plate a layer hydrophobic layer on finished product surface fabric usually, reaches the purpose of hydrophobicity, but traditional hydrophobic fibre only relies on the surface coating to play hydrophobic effect, very easily plays static, balling up has the fold, not only uncomfortable and can make the coating on surface drop after using for a long time, and at this moment, the hydrophobic layer also can lose original effect and become hydrophobic no longer.

Aiming at the defects that a coating film of a hydrophobic coating adopted by the traditional hydrophobic fabric is easy to fall off, the raw materials are not skin-friendly and uncomfortable, and the use experience is poor, the novel super-hydrophobic fiber and the super-hydrophobic skin-friendly fabric are invented, the hydrophobic characteristic is met, the skin-friendly and breathable performance is achieved, and the application occasions are enlarged.

Disclosure of Invention

The technical problem to be solved by the invention is to provide a super-hydrophobic nanofiber and a super-hydrophobic skin-friendly fabric using the super-hydrophobic nanofiber, aiming at the defects of the prior art.

The invention adopts the following technical scheme for solving the technical problems:

the first aspect of the invention provides a super-hydrophobic nanofiber, which is prepared by the following method:

s1: mixing terephthalic acid and ethylene glycol, adding a dispersing agent, and uniformly stirring to prepare slurry; adding the prepared slurry into an esterification reaction kettle for carrying out a first esterification reaction, and adding sorbitol and polyethylene glycol for carrying out a second esterification reaction when the collection amount of byproducts reaches 82-95% of a theoretical value; after the esterification reaction is finished, carrying out polycondensation reaction on the prepared esterified substance to obtain a polyester slice;

s2: uniformly mixing the polyester chips obtained in the step S1 with nano silver nitrate powder, nano zinc oxide powder and nano iron oxide powder, adding a stabilizer, a dispersant and a smoothing agent, uniformly stirring, and then performing melt granulation to obtain functional master batches;

s3: drying the functional master batch obtained in the step S2 until the average water content of the functional master batch is not more than 0.01%, and drawing the dried functional master batch to obtain the nano fiber;

s4: and (4) soaking the nano-fiber prepared in the step (S3) into silica sol for finishing, and drying to obtain the super-hydrophobic nano-fiber.

Further, in step S1, the dispersant is polyisobutylene succinimide; the smoothing agent is one or more of food-grade white oil, palm oil, soybean oil, rapeseed oil, cottonseed oil, corn oil, rice bran oil, sunflower oil, peanut oil, castor oil, sesame oil, zanthoxylum seed oil, tea oil, coconut oil, olive oil, pistacia chinensis oil, palm oil and turpentine oil.

Further, the temperature required for the melt granulation in the step S2 is 260-300 ℃.

Further, in step S1, the molar ratio of phthalic acid to ethylene glycol is 1: 1.05-2.

Further, in step S2, the mass ratio of the polyester chips, the nano silver nitrate powder, the nano zinc oxide powder, and the nano iron oxide powder is 1000:8:5: 3.

further, in step S3, the drying temperature is 150 ℃ to 180 ℃.

The second aspect of the invention provides a super-hydrophobic skin-friendly fabric, which sequentially comprises an inner layer and a hydrophobic layer from inside to outside; the hydrophobic layer is woven by yarns spun by the super-hydrophobic nano fibers prepared by the method, and the inner layer is woven by blended yarns of cotton-flax fibers, modal fibers, silk fibers and polyester fibers; the inner layer and the hydrophobic layer are connected by polyester filaments through a tucking process.

Further, the blending ratio of the cotton-flax fibers, the modal fibers, the silk fibers and the polyester fibers is 50:35:10: 5.

further, the gram weight of the super-hydrophobic skin-friendly fabric is 100-260g/m²。

Compared with the prior art, the invention has the following advantages:

according to the invention, the super-hydrophobic nano-fiber is obtained by finishing in the silica sol, and the surface is attached with silica, so that the static contact angle theta is increased, the hydrophobicity of the fiber is improved, and the super-hydrophobic nano-fiber is non-toxic, harmless, environment-friendly, safe and durable.

According to the super-hydrophobic skin-friendly fabric, the hydrophobic layer is woven by the super-hydrophobic nano fibers prepared by the preparation method, the fabric is non-toxic, harmless and strong in hydrophobicity, the inner layer is woven by various natural fiber blended yarns, the fabric is skin-friendly, breathable, water-absorbing and sweat-releasing, suitable for close-fitting wearing, large in hardness and not skin-friendly of the hydrophobic fabric, and the original functionality of the hydrophobic fabric is not damaged.

Detailed Description

The present invention is further illustrated by the following examples, which are not to be construed as limiting the invention.

It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.

Example 1

The embodiment provides a preparation method of a super-hydrophobic nanofiber, which comprises the following steps:

s1: mixing terephthalic acid and ethylene glycol according to a molar ratio of 1:1.05, adding a dispersing agent, and uniformly stirring to prepare slurry; adding the prepared slurry into an esterification reaction kettle for carrying out a first esterification reaction, and adding sorbitol and polyethylene glycol for carrying out a second esterification reaction when the collection amount of byproducts reaches 95% of a theoretical value; after the esterification reaction is finished, carrying out polycondensation reaction on the prepared esterified substance to prepare polyester chips;

s2: and (2) mixing the polyester chips prepared in the step (S1) with nano silver nitrate powder, super-hydrophobic zinc oxide powder and super-hydrophobic iron oxide powder according to the ratio of 1000:8:5:3, adding a stabilizer, a dispersant and a smoothing agent, uniformly stirring, and then performing melt granulation at the temperature of 260 ℃ to obtain functional master batches:

s3: drying the functional master batch prepared in the step S2 at the temperature of 150 ℃ until the average water content of the functional master batch is not more than 0.01%; drawing the dried functional master batch to prepare nano fiber;

s4: and (5) soaking the nano-fibers prepared in the step (S3) into silica sol for finishing, and drying to obtain the super-hydrophobic nano-fibers.

Example 2

The embodiment provides a preparation method of a super-hydrophobic nanofiber, which comprises the following steps:

s1: mixing terephthalic acid and ethylene glycol according to a molar ratio of 1:1.1, adding a dispersing agent, and uniformly stirring to prepare slurry; adding the prepared slurry into an esterification reaction kettle for carrying out a first esterification reaction, and adding sorbitol and polyethylene glycol for carrying out a second esterification reaction when the collection amount of byproducts reaches 90% of a theoretical value; after the esterification reaction is finished, carrying out polycondensation reaction on the prepared esterified substance to prepare polyester chips;

s2: and (2) mixing the polyester chips prepared in the step (S1) with nano silver nitrate powder, nano zinc oxide powder and nano iron oxide powder according to the ratio of 1000:8:5:3, adding a stabilizer, a dispersant and a smoothing agent, uniformly stirring, and then performing melt granulation at the temperature of 270 ℃ to obtain functional master batches:

s3: drying the functional master batch prepared in the step S2 at 160 ℃ until the average water content of the functional master batch is not more than 0.01%; drawing the dried functional master batch to prepare nano fiber;

s4: and (5) soaking the nano-fibers prepared in the step (S3) into silica sol for finishing, and drying to obtain the super-hydrophobic nano-fibers.

Example 3

The preparation method of the superhydrophobic nanofiber comprises the following steps:

s1: mixing terephthalic acid and ethylene glycol according to a molar ratio of 1:1.2, adding a dispersing agent, and uniformly stirring to prepare slurry; adding the prepared slurry into an esterification reaction kettle for carrying out a first esterification reaction, and adding sorbitol and polyethylene glycol for carrying out a second esterification reaction when the collection amount of byproducts reaches 85% of a theoretical value; after the esterification reaction is finished, carrying out polycondensation reaction on the prepared esterified substance to prepare polyester chips;

s2: and (2) finishing the polyester chip prepared in the step (S1) with nano silver nitrate powder, nano zinc oxide powder and nano iron oxide powder according to the proportion of 1000:8:5:3, adding a stabilizer, a dispersant and a smoothing agent, uniformly stirring, and then performing melt granulation at 290 ℃ to obtain the functional master batch:

s3: drying the functional master batch prepared in the step S2 in a heating environment at the temperature of 170 ℃ until the average water content of the functional master batch is not more than 0.01%; drawing the dried functional master batch to prepare nano fiber;

s4: and (5) soaking the nano-fibers prepared in the step (S3) into silica sol for finishing, and drying to obtain the super-hydrophobic nano-fibers.

Example 4

The embodiment provides a super-hydrophobic skin-friendly fabric, which sequentially comprises an inner layer and a hydrophobic layer from inside to outside; the hydrophobic layer is woven by yarns spun by the super-hydrophobic nano fibers in the embodiments 1 to 3, and the inner layer is woven by blended yarns of cotton-flax fibers, modal fibers, silk fibers and polyester fibers; the inner layer and the hydrophobic layer are connected by polyester filaments through a tucking process.

The blending ratio of the cotton-flax fibers, the modal fibers, the silk fibers and the polyester fibers is 50:35:10: 5.

Application example

Three types of super-hydrophobic skin-friendly fabrics prepared in example 4 and a hydrophobic fabric with a commercial model of XH-330 were tested: three types of super-hydrophobic skin-friendly fabrics prepared in example 4 and hydrophobic fabrics with the type XH-330 on the market are respectively adhered to the surface of a glass slide by a square centimeter, then the glass slide is fixed on a sample stage of a JY-82B video contact angle measuring instrument, water with the volume of 0.25ml is dripped on the surface of a sample, and the static contact angle theta at the junction of three phases is measured. The measurements were repeated three times at different positions on the surface of the sample, and the average values were averaged, and the average value of the static contact angle θ is shown in table 1:

TABLE 1

	Mean contact Angle (°)
		Example 1	165.17
Example 2	164.72
		Example 3	169.01
XH-330 hydrophobic fabric	159.23

The larger the static contact angle theta is, the better the hydrophobicity of the fabric is, and as can be seen from the results in table 1, the hydrophobicity of the skin-friendly fabric prepared by the super-hydrophobic nanofibers prepared in examples 1 to 3 is obviously improved compared with the hydrophobic fabric of XH-330, mainly because the surface roughness of the super-hydrophobic fibers is increased by plating a layer of silica film on the surfaces of the hydrophobic fibers by the sol-gel method, so that the nanofibers have better hydrophobic performance.

The foregoing detailed description of the preferred embodiments of the invention has been presented. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Therefore, the technical solutions that can be obtained by a person skilled in the art through logic analysis, reasoning or limited experiments based on the prior art according to the concept of the present invention should be within the scope of the claims of the present invention.