CN113943982B - Volcanic rock thermal insulation fiber and thermal insulation sock - Google Patents

Abstract

The application relates to volcanic rock thermal insulation fibers and thermal insulation socks, and belongs to the technical field of special functional fabrics. The application firstly discloses volcanic rock fiber, the raw materials of volcanic rock fiber include polyester master batch and far infrared master batch, far infrared master batch is prepared by the raw materials of at least the following mass portions: 100 parts of polyester particles; 50-60 parts of infrared ceramic powder; 5-10 parts of volcanic rock powder; 5-8 parts of graphene oxide; 3-5 parts of coupling agent. The application further discloses a thermal sock which is woven by blended yarns, wherein the blended yarns comprise the volcanic rock thermal fiber. The heat insulation and water washing resistance cloth has the effects of good heat insulation effect and water washing resistance.

Description

A kind of volcanic rock thermal insulation fiber and thermal insulation socks

Technical Field

The present application relates to the field of special functional fabrics, and in particular to a volcanic rock thermal insulation fiber and thermal insulation socks.

Background Art

The feet are a weak spot in the blood circulation process and are easily affected by the ambient temperature. For example, in winter, the feet are very easy to get cold. Currently, the most common way to keep the feet warm is to wear thicker socks. Although thicker socks have a better warming effect, too thick socks feel worse. In addition, since consumers' shoes are of a fixed size, wearing too thick socks may compress the feet and affect the blood circulation of the feet.

With the development of society and the improvement of economic level, consumers have higher and higher requirements for the performance of various textiles. Fabrics that simply increase thickness to improve thermal insulation performance are no longer able to meet consumers' increasing needs. Therefore, the preparation of thin and light fabrics with good thermal insulation effect is a major research direction for functional textile fabrics.

At present, in order to prepare special functional fabrics with heat preservation and heating effects, the fabrics are generally post-finished, that is, a special additive with heat storage and heating capabilities is added to the fabrics through a finishing process, so that the thin fabrics have a good heat preservation effect. However, although the fabrics obtained by the additive post-finishing have good heat preservation performance at the beginning, they are not washable, and the heat preservation performance of the fabrics often decreases significantly after multiple washings.

Summary of the invention

In order to improve the defect that the thermal insulation fabrics prepared by the common post-finishing auxiliaries are not resistant to water washing, the present application provides a volcanic rock thermal insulation fiber and thermal insulation socks.

In the first aspect, the present application provides a volcanic rock thermal insulation fiber, which adopts the following technical solution:

A volcanic rock thermal insulation fiber, comprising the following raw materials in percentage by mass:

Polyester masterbatch 85-90%;

Far infrared masterbatch 10-15%;

The far-infrared masterbatch is prepared from at least the following raw materials in parts by weight:

By adopting the above technical solution, compared with the common post-finishing process, this application specifically makes infrared ceramic powder, volcanic rock powder and graphene oxide with far-infrared emission function into far-infrared masterbatch, and mixes conventional polyester masterbatch and far-infrared masterbatch during spinning, so that the thermal insulation fiber obtained has intrinsic far-infrared emission function. No matter how many times it is washed, the far-infrared emission function of the volcanic rock thermal insulation fiber prepared in the manner of this application can still maintain a high level; correspondingly, common studies have shown that the heating performance of the heating fiber obtained by conventional post-finishing process is almost lost after 50 water washings.

Both infrared ceramic powder and volcanic rock have good far-infrared emission performance. The minerals and trace elements of volcanic rock can easily absorb heat and convert the absorbed heat into infrared rays. In addition, volcanic rock can also reflect infrared radiation generated by the human body. Infrared rays can increase the temperature by interacting with water molecules in the human body, thus playing a positive role in keeping warm. In addition, the structure of volcanic rock is an irregular porous structure, which can absorb a large amount of static air. The thermal conductivity of static air is only about 0.025W/(m℃), which is much lower than the thermal conductivity of polyester fiber. Therefore, adding volcanic rock with a porous structure to polyester fiber can produce good heat storage capacity.

The inventors found that the heat storage and heating effect of graphene oxide is better than that of volcanic rock and common infrared ceramics. However, as a nanomaterial, graphene oxide is very easy to agglomerate, which not only easily blocks the spinneret, but also easily causes fiber defects, thereby reducing the fiber's fracture strength. The inventors found that mixing graphene oxide, infrared ceramic powder and volcanic rock powder can significantly improve the fiber's fracture strength. This may be because the infrared ceramic powder can be inserted between the flaky graphene oxide, increasing the steric hindrance of graphene oxide, and the porous volcanic rock powder can adsorb graphene oxide and infrared ceramic powder, making them more orderly arranged around the volcanic rock powder, thereby reducing fiber defects and improving the fiber's fracture strength.

Optionally, the infrared ceramic powder is a mixture of at _{least two of Al2O3} , _TiO2 , _SiO2 , _Cr2O3 , _ZrO2 , _B4C , SiC, ZrC, BN, AlN, _Si3N4 , TiN, _TiSi2 , _WSi2 , _ZrB2 , and _CrB2 .

By adopting the above technical solution, different infrared ceramic powders have different far-infrared emission bands. In order to make the far-infrared emission band more complete, at least two or more infrared ceramic powders can be selected. In addition, those skilled in the art can select the required infrared ceramic powder according to the infrared emission bands of different infrared ceramic powders and the design of actual products.

Optionally, the infrared ceramic powder is activated before use, and the activation process includes the following steps:

A1. Dispersion: first, put the dispersant into water and disperse it evenly, then add the infrared ceramic powder and mix evenly to obtain a suspension;

A2, activation, grinding and activating the suspension obtained in step A1 to obtain an activated solution;

A3, drying, spray drying the activation solution obtained in step A2 to obtain activated infrared ceramic powder.

By adopting the above technical solution, the surface of infrared ceramic powder is prone to form highly hydrophilic hydroxyl groups, and its specific surface area is too large, and the surface free energy decreases, which makes the ceramic powder easy to agglomerate. These agglomerates are often dozens of times larger than the original particles. Therefore, before using the infrared ceramic powder, it is necessary to disperse and activate the infrared ceramic powder to reduce the impact of these agglomerates on the fiber performance.

The dispersibility of infrared ceramic powder can be greatly improved by first dispersing, then grinding and activating, and finally spray drying. The added dispersant can not only reduce the possibility of agglomeration of infrared ceramic powder, but also improve its compatibility with polyester particles, improve the mutual adhesion between infrared ceramic powder and polyester, increase the fluidity of the melt, and improve spinnability.

Optionally, the dispersant is prepared by mixing lysine and sodium tripolyphosphate in a mass ratio of 1:(8-10).

By adopting the above technical scheme, the cations in sodium tripolyphosphate can be adsorbed by the infrared ceramic powder to form a double electric layer, thereby improving the dispersibility of the infrared ceramic powder, and generally speaking, the dispersibility of sodium tripolyphosphate is better under alkaline conditions. The current common method is to add a strong base such as sodium hydroxide to the system and adjust the pH value of the system to alkaline to improve the dispersion effect of sodium tripolyphosphate. However, in the present application, step A3 uses a spray drying method, and spray drying can save subsequent grinding and other steps, but it will also cause sodium tripolyphosphate and alkaline substances to remain on the far-infrared ceramic powder. However, this system contains a large amount of polyester, which is easily decomposed to form internal damage under the action of strong bases such as sodium hydroxide. Therefore, strong bases such as sodium hydroxide cannot be used in this system.

Lysine is specifically added to the dispersant of the present application. Lysine is an alkaline amino acid, and therefore it can improve the dispersing effect of sodium tripolyphosphate. In addition, lysine itself also carries a positive charge after ionization and can be adsorbed onto the surface of the infrared ceramic powder to further increase the charge on the surface of the infrared ceramic powder, thereby further improving the dispersing effect of the infrared ceramic powder.

Optionally, in step A1, the concentration of the dispersant is 20-25 mg/L, and the concentration of the infrared ceramic powder is 0.8-1.2 g/L.

By adopting the above technical solution, the inventors found that although sodium tripolyphosphate has a good dispersing effect on infrared ceramic powders, after replacing part of the sodium tripolyphosphate with lysine, the effect of the dispersant is significantly improved. On the basis of ensuring the overall dispersion effect, the amount of dispersant can be reduced from about 40-50 mg/L to about 20-25 mg/L.

In addition, the concentration of infrared ceramic powder needs to be strictly controlled, because different concentrations of suspension will affect the final crushing effect, resulting in different particle sizes of activated infrared ceramic powder. If the concentration of suspension is too high, problems such as poor fluidity and slow circulation speed will occur during the grinding process.

Optionally, the graphene oxide is modified before adding, and specifically comprises the following steps:

B1. dissolving graphene oxide, i.e., putting graphene oxide into a solvent and dispersing it evenly to obtain a graphene oxide solution;

B2, mixing, adding acrylonitrile and alkali to the graphene oxide solution obtained in step B1 to obtain a mixture;

B3. Modification: Under the protection of an inert gas atmosphere, the mixture is heated to 95±2 and refluxed for reaction, and then filtered and washed to obtain modified graphene oxide.

By adopting the above technical solution, acrylonitrile easily undergoes addition reaction with compounds containing active hydrogen atoms. Under alkaline conditions, acrylonitrile can react with oxygen-containing groups on the surface of graphene oxide, thereby being grafted onto graphene oxide to form a composite powder similar to a core-shell structure, thereby greatly improving the compatibility of graphene oxide with polyester particles. It should be noted that since the modified graphene oxide needs to be washed, even if a strong base such as sodium hydroxide is added in step B2, it will eventually be eluted, so there is no need to consider its effect on the performance of polyester.

In addition, the inventor unexpectedly discovered that compared with adding unmodified graphene oxide, adding modified graphene oxide can make the final thermal insulation fiber have a significantly better warming effect. This may be because after acrylonitrile is grafted onto graphene oxide and mixed into polyester, in the subsequent finishing process, such as alkali reduction, the nitrile group is converted into a carboxylate with hygroscopic and heat-generating properties, thereby making the thermal insulation fiber have a better warming effect.

In addition, the inventors found that compared with mixing the modified graphene oxide with the unactivated infrared ceramic powder, mixing the modified graphene oxide with the activated infrared ceramic powder obviously has better compatibility. This may be because the activated infrared ceramic powder has lysine, and lysine has active hydrogen, which can react with the acrylonitrile on the modified graphene oxide, so that the activated infrared ceramic powder, the modified graphene oxide and the polyester particles have good compatibility.

Optionally, the solvent used in step B1 is a mixture of water and diethylene glycol, and the volume ratio is water:diethylene glycol=(8-10):1.

By adopting the above technical solution, the inventors found that if only water is used as a solvent in the process of modifying graphene oxide, as the modification proceeds, the system gradually turns from light yellow to black, which means that the graphene oxide is gradually reduced. The reduced graphene oxide exhibits a certain hydrophobicity, so these reduced graphene oxides are easy to agglomerate. The mixed solvent obtained by adding a certain amount of diethylene glycol to water can improve the stability of graphene oxide and reduced graphene oxide and reduce the possibility of agglomeration.

It should be noted that, in general, the maximum extrusion granulation temperature of polyester is around 270°C, but due to the addition of high content of infrared ceramic powder, volcanic rock powder and graphene oxide, the apparent viscosity of the melt will increase, the fluidity will decrease, and the melt will have difficulty flowing during extrusion. In order to improve the fluidity of the melt, the spinning temperature needs to be increased to about 280°C, but the increase in spinning temperature is likely to cause polyester degradation.

However, the inventor unexpectedly discovered that adding diethylene glycol to water can not only improve the stability of the entire system, but also improve the rheology of the melt, thereby reducing the final spinning temperature and improving spinnability. This may be because acrylonitrile and diethylene glycol can generate polyether nitrile under alkaline conditions, and polyether nitrile introduces ether bonds into polyester, and the introduction of ether bonds improves the flexibility of polyester, and the entropy change increases during the melting process, so the melting point of polyester is reduced, which improves the low-temperature spinnability on the basis of ensuring the intrinsic viscosity of polyester. And the ether bond also improves the hygroscopicity of the thermal insulation fiber, which in turn makes the carboxylate group introduced by the nitrile group have better hygroscopic heat generation.

Optionally, in step B1, the graphene oxide is placed in a solvent and then ultrasonically dispersed, the dispersion temperature is 35-40° C., and the ultrasonic time is 15-20 min.

By adopting the above technical solution, after graphene oxide is placed in a solvent and then ultrasonically dispersed, the graphene oxide can be better dissolved in the solvent and is not easy to agglomerate into agglomerates.

In a second aspect, the present application provides a thermal socks, which adopts the following technical solution:

A pair of thermal socks are woven from blended yarns, wherein the blended yarns include the above-mentioned volcanic rock thermal fibers.

By adopting the above technical solution, the yarn obtained by blending the above volcanic rock thermal insulation fiber can be thinner and lighter while ensuring the thermal insulation effect. In addition, the volcanic rock powder added to the thermal insulation yarn has good odor absorption performance and good bactericidal effect, and the added graphene oxide has better bactericidal and deodorizing performance, so it is very suitable for use as yarn for socks.

Optionally, it includes a sock body and a tube body, the sock body and the tube body are connected, the sock body is provided with a contraction ring at the arch of the foot, the sock body is provided with a thickened portion at the heel, the tube body includes a low-pressure section and a high-pressure section, the low-pressure section is provided at the calf of the tube body, there are two high-pressure sections and they are located on both sides of the low-pressure section, and the opening of the tube body is provided with a cuff.

By adopting the above technical solution, the tightening ring at the arch of the foot can make the sock body fit the foot better and can further provide anti-slip support for the arch of the foot. The thickened design at the heel of the sock body can not only provide better cushioning and shock absorption effects, but also improve the wear resistance of the heel of the sock body. The segmented pressure setting at the barrel can reduce the possibility of damage to the barrel due to excessive deformation while ensuring the fit between the barrel and the calf. In addition, the segmented pressure setting can also reduce the impact on blood circulation in the legs.

In summary, the present application includes at least one of the following beneficial technical effects:

1. The far-infrared masterbatch is prepared by compounding volcanic rock powder, infrared ceramic powder and graphene oxide into polyester particles, and the far-infrared masterbatch and polyester masterbatch are mixed and spun to obtain volcanic rock thermal insulation fiber, which has good antibacterial, thermal insulation and deodorizing functions. The compounding of volcanic rock powder, infrared ceramic powder and graphene oxide can improve their respective dispersion effects, thereby reducing fiber defects and improving fiber breaking strength;

2. By activating the infrared ceramic powder, the particle size of the infrared ceramic powder can be reduced, and the dispersion performance of the infrared ceramic powder and the compatibility with polyester particles can be improved;

3. By limiting the composition and ratio of the dispersant, the two can work together to achieve significantly better dispersion effects, thereby greatly reducing the concentration of the dispersant, reducing costs and increasing benefits;

4. By modifying graphene oxide, acrylonitrile monomer is grafted onto graphene oxide to form a composite powder similar to a core-shell structure, so as to reduce the possibility of graphene oxide agglomeration and improve the compatibility of graphene oxide with polyester particles. In addition, the modified graphene oxide can also make the final limit have a better temperature increase effect;

5. By limiting the solvent used in modifying graphene oxide, not only can the stability of the system be improved, but also the ether bonds of the soft segments can be introduced into the polyester system. The introduced ether bonds can reduce the final spinning temperature and improve the spinnability of the system, thereby reducing the possibility of polyester degradation during high-temperature spinning;

6. By using the yarn blended with volcanic rock thermal fiber as the raw material of socks, it can be lighter and thinner while ensuring the warmth effect;

7. By specifically designing the structure of the thermal socks, the anti-slip and shock-absorbing effects of the thermal socks are improved, and the service life of the thermal socks is increased.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG1 is a schematic diagram of the structures of thermal socks in Examples 1-18 and Comparative Examples 1-3 of the present application.

Explanation of reference numerals: 1, sock body; 11, shrinkage ring; 12, thickening portion; 2, barrel; 21, low-pressure section; 22, high-pressure section; 23, cuff.

DETAILED DESCRIPTION

The present application is further described in detail below in conjunction with the accompanying drawings, preparation examples and embodiments.

The sources of various raw materials in the preparation examples and embodiments of this application are recorded in the following table:

Except for the raw materials in the above table, unless otherwise specified, the remaining raw materials are conventionally commercially available.

Preparation example of far-infrared masterbatch

Preparation Example 1

In this preparation example, the following raw materials are required in parts by mass for each portion of far-infrared masterbatch:

Since the volcanic rock thermal insulation fiber prepared in this application is ultimately used in thermal socks, the inventors selected a mixture of Cr ₂ O ₃ , ZrO ₂ , Si ₃ N ₄ , and TiSi ₂ in equal mass ratios as infrared ceramic powders according to actual needs. It should be noted that the inventors can also select infrared ceramic powder combinations with different radiation frequency bands according to the needs of different application scenarios.

The coupling agent used is KH-570.

The preparation process of the far-infrared masterbatch specifically includes the following process steps:

Step 1: Mixing: According to the above ratio, polyester particles, infrared ceramic powder, volcanic rock powder and graphene oxide are weighed and mixed and stirred at a stirring speed of 500 r/min and a stirring time of 15 min to obtain a mixture.

Step 2, drying, heating the mixed material in step 1 to 140°C for drying, keeping stirring during the drying process, the stirring speed is 100r/min, the drying time is 12h, and a dried material is obtained.

Step 3, extrusion granulation, take the dried material and coupling agent in step 2, mix them, use a screw extruder to melt extrude them, and water-cool and granulate them to obtain far-infrared masterbatch. The screw temperature of the screw extruder is set from zone 1 to zone 10 as follows: 160℃-250℃-280℃-280℃-280℃-280℃-280℃-270℃-270℃-270℃.

Preparation Example 2-3

The difference between Preparation Example 2-3 and Preparation Example 1 is that the ratio of raw materials required for preparing each portion of far-infrared masterbatch is different, and is recorded in the following table:

Preparation Example 4

Preparation Example 4 is different from Preparation Example 2 in that the infrared ceramic powder is activated before mixing in step 1, and specifically includes the following steps:

A1. Dispersion: First, put the dispersant into water and disperse it evenly. The dispersant is sodium tripolyphosphate to obtain a sodium tripolyphosphate solution with a concentration of 45 mg/L. Then, add the infrared ceramic powder with a concentration of 1 g/L. Mix well to obtain a suspension.

A2, activation, the suspension obtained in step A1 is ground and activated, the speed of the grinder is 2500r/min, the grinding time is 70min, and an activated solution is obtained.

A3, drying, spray drying the activation solution obtained in step A2 to obtain activated infrared ceramic powder.

The inventors found that under this condition, the suspension obtained in step A1 can remain unstratified for about 30 days, and has an excellent dispersion effect.

Preparation Example 5

The difference between Preparation Example 5 and Preparation Example 4 is that in step A1, an equal mass of lysine is used instead of sodium tripolyphosphate as a dispersant.

The inventors found that under this condition, the suspension obtained in step A1 can remain without stratification for about 10 days, and has a good dispersion effect.

Preparation Example 6

The difference between Preparation Example 6 and Preparation Example 4 is that in step A1, the dispersant is a mixture of lysine and sodium tripolyphosphate, the mass ratio of lysine to sodium tripolyphosphate is 1:9, and the final concentration of the dispersant is 23 mg/L.

The inventors found that under this condition, the suspension obtained in step A1 can remain unstratified for about 30 days, and has an excellent dispersion effect.

Preparation Example 7-8

The difference between Preparation Example 7-8 and Preparation Example 6 is that the process parameters in step A1 are different and are recorded in the following table:

The inventors found that under the conditions in Preparation Example 7, the suspension obtained in Step A1 can remain unstratified for about 27 days, and has an excellent dispersion effect.

The inventors found that under the conditions in Preparation Example 8, the suspension obtained in Step A1 can remain unstratified for about 31 days, and has an excellent dispersion effect.

In addition, it should be noted that when the concentration of the infrared ceramic powder exceeds 1.2 g/L, the viscosity of the suspension obtained in step A1 is relatively high, and the grinding machine has difficulty in grinding, so production cannot continue.

Preparation Example 9

Preparation Example 9 is different from Preparation Example 2 in that the graphene oxide is subjected to a modification treatment before mixing in step 1, and specifically includes the following process steps:

B1. Graphene oxide dissolution, that is, graphene oxide is placed in solvent water, and then ultrasonically dispersed at a temperature of 35° C. for 20 minutes with an ultrasonic power of 100 W. During the ultrasonic process, the ultrasonic dispersion needs to be stopped for 30 seconds every 3 minutes to obtain a graphene oxide solution with a concentration of 1 g/L.

B2, mixing, adding acrylonitrile and alkali to the graphene oxide solution obtained in step B1 to obtain a mixture, wherein the concentration of acrylonitrile added is 1 g/L, and the alkali is sodium hydroxide, and the concentration of the added alkali is 0.5 g/L.

B3. Modification: Under the protection of an inert gas nitrogen atmosphere, the mixture was heated to 95±2° C. and refluxed for 24 hours, then filtered, washed three times with DMF and dried to obtain modified graphene oxide.

Preparation Example 10

The difference between Preparation Example 10 and Preparation Example 4 is that the graphene oxide is modified before mixing in step 1, and the modification process is the same as that of Preparation Example 9 and will not be repeated.

Preparation Example 11

The difference between Preparation Example 11 and Preparation Example 5 is that the graphene oxide is modified before mixing in step 1, and the modification process is the same as that of Preparation Example 9 and will not be repeated.

Preparation Example 12

The difference between Preparation Example 12 and Preparation Example 6 is that the graphene oxide is modified before mixing in step 1, and the modification process is the same as that of Preparation Example 9 and will not be repeated.

Preparation Example 13

The difference between Preparation Example 13 and Example 12 is that the solvent used in Step B1 is a mixture of water and diethylene glycol, and the volume ratio of water:diethylene glycol=9:1.

Preparation Examples 14-16

The difference between Preparation Examples 14-16 and Preparation Example 13 is that the process parameters in the modification process of graphene oxide are different, and are recorded in the following table:

Example

Example 1

The present application example first discloses a volcanic rock thermal insulation fiber. The following raw materials in parts by weight are required to prepare each portion of fiber:

Polyester masterbatch 850g;

Far infrared masterbatch 150g;

The far-infrared masterbatch is the far-infrared masterbatch prepared in Preparation Example 1.

The spinning process of the above-mentioned volcanic rock thermal insulation fiber specifically includes the following process steps:

S1. Prepare materials. Take polyester masterbatch according to the ratio, and pre-crystallize it at 170°C for 15 minutes. After the pre-crystallization, dry it at 160°C for 12 hours. Take far-infrared masterbatch according to the ratio, and dry it at 160°C for 12 hours. Mix the dried polyester masterbatch and far-infrared masterbatch to obtain spinning material.

S2, melt extrusion, using a twin-screw extruder to melt extrude the spinning material obtained in step S1 to obtain a spinning solution. The twin-screw extruder has five zones, and the screw temperatures from zone one to zone five are set to: 265°C-275°C-280°C-283°C-285°C.

S3, filtering and spinning, using a 35 μm filter element to filter the spinning solution in step S2 and spinning to obtain semi-finished yarn.

S4, post-processing, namely, blowing cooling, oiling, winding, and elasticizing the semi-finished yarn obtained in step S3 in sequence to obtain volcanic rock thermal insulation fiber.

Referring to Figure 1, the above-mentioned volcanic rock thermal insulation fiber is used to make thermal socks, and the thermal socks are woven from blended yarns, and the blended yarns are blended from 111dtex volcanic rock thermal insulation fiber and 290dtex combed cotton yarn. The thermal socks include a sock body 1 and a barrel 2, and the sock body 1 and the barrel 2 are sewn or woven into one and connected. A contraction ring 11 is provided at the arch of the sock body 1, and a thickening portion 12 is provided at the heel of the sock body 1. The barrel 2 includes a low-pressure section 21 and a high-pressure section 22. The low-pressure section 21 is provided at the calf of the barrel 2, and there are two high-pressure sections 22, which are respectively located on both sides of the low-pressure section 21. A cuff 23 is provided at the opening of the barrel 2.

Example 2-3

The difference between Example 2-3 and Example 1 is that the raw material composition of the volcanic rock thermal insulation fiber is different, and is recorded in the following table:

Embodiment 4-18

The difference between Example 4-18 and Example 3 is that the sources of far-infrared masterbatch are different, and are recorded in the following table:

It should be noted that the twin-screw extruder in step S2 in Examples 15-18 has five zones, and the screw temperatures from zone 1 to zone 5 are set to: 250°C-258°C-263°C-265°C-268°C, respectively.

Comparative Example

Comparative Example 1

The difference between Comparative Example 1 and Example 1 is that when preparing the far-infrared masterbatch, the volcanic rock powder is replaced with an equal mass of graphene oxide.

Comparative Example 2

The difference between Comparative Example 2 and Example 1 is that when preparing the far-infrared masterbatch, the graphene oxide powder is replaced with volcanic rock powder of the same mass.

Comparative Example 3

Comparative Example 3 is a blank control sample, which is different from Example 1 in that when preparing the far-infrared masterbatch, the far-infrared masterbatch is replaced by polyester masterbatch of equal mass.

Performance testing experiments and data

1. Warmth retention and washability

1.1 Warmth effect

1.1.1 Hygroscopic and exothermic properties

The thermal socks prepared in each embodiment and comparative example were tested according to the method described in GB/T 29866-2013 "Test method for moisture absorption and heat generation of textiles". The test temperature was 20°C and the relative humidity was 90%, and the average maximum temperature rise data and average temperature rise data within 30 minutes were recorded.

1.1.2 Infrared heating effect

The thermal socks prepared in each embodiment and comparative example were taken, and the infrared performance of the samples was tested and analyzed according to the method described in GB/T 30127-2013 "Testing and Evaluation of Far Infrared Performance of Textiles".

1.2 Washability

Take the thermal socks prepared in each embodiment and comparative example, and wash the samples 50 times according to the method described in GB/T 8629-2017 "Household washing and drying procedures for textile testing" (4N washing procedure, hanging to dry). The performance of the washed samples was tested using the two detection methods of 1.1.2 infrared warming effect.

2. Fiber breaking strength

The volcanic rock thermal insulation fibers obtained in each preparation example and each comparative example were taken as samples, and tested according to the method described in the standard GB/T 14337-2008 "Test method for tensile properties of chemical staple fibers".

The test results are recorded in the following table:

in conclusion

1. By comparing the dispersibility of the suspension obtained in step A1 of Preparation Example 4 and Preparation Example 5, it can be concluded that at the same concentration, the dispersibility of sodium tripolyphosphate for infrared ceramic powder is significantly better than that of lysine. Further comparing the dispersibility of the suspension obtained in step A1 of Preparation Example 4 and Preparation Examples 6-8, it can be concluded that when the dispersant is a mixture of sodium tripolyphosphate and lysine, there is a significant synergistic effect on the dispersibility of infrared ceramic powder. The compound dispersant only needs a concentration of 23 mg/L to obtain the dispersibility of 45 mg/L sodium tripolyphosphate alone.

2. By comparing the breaking strength of the sample fibers of Preparation Example 4 and Preparation Example 5, it can be concluded that, at the same concentration, compared with the lysine in Preparation Example 5, the sodium tripolyphosphate in Preparation Example 4 has a better dispersing effect on the infrared ceramic powder. Further comparing the breaking strength of the sample fibers of Preparation Example 10 and Preparation Example 11, it is found that the breaking strengths of the two samples are basically the same, and Preparation Example 10 is to modify the graphene oxide on the basis of Preparation Example 4, and Preparation Example 11 is to modify the graphene oxide on the basis of Preparation Example 5. Under the premise that the breaking strength of the sample fiber of Preparation Example 4 is higher than that of the sample fiber of Preparation Example 5, the breaking strengths of the samples of Preparation Example 10 and Preparation Example 11 are basically the same. This may be due to the synergistic effect of the acrylonitrile added when modifying the graphene oxide in Preparation Example 11 and the lysine added when activating the infrared ceramic powder in Preparation Example 5, which improves the dispersibility and compatibility of graphene oxide and infrared ceramic powder.

3. By comparing the breaking strength of the sample fibers of Preparation Example 12 and Preparation Example 13, it can be concluded that compared with directly using water as a solvent for modifying graphene oxide, using a mixed solvent of water and diethylene glycol can improve the dispersibility of graphene oxide.

4. By comparing the process parameters of Example 14 and Examples 15-18, it can be concluded that when modifying graphene oxide, using a mixed solvent of water and diethylene glycol can reduce the final spinning temperature by about 10°C compared to using a pure solvent of water. This may be because the diethylene glycol introduced when modifying graphene oxide can react with the acrylonitrile introduced when activating the infrared ceramic powder to produce a soft segment ether bond, thereby improving the rheological properties of the polyester system.

5. By comparing the experimental data of Example 1, Comparative Example 1 and Comparative Examples 1-3, it can be concluded that compared with infrared ceramic powder, graphene oxide has obviously better infrared heating performance, and correspondingly, graphene oxide has a greater effect on the breaking strength of the fiber. Although the infrared heating effect of infrared ceramic powder is weaker than that of graphene oxide, its effect on the breaking strength of the fiber is obviously smaller. Under the premise of the presence of volcanic rock powder, compounding infrared ceramic powder and graphene oxide can obviously reduce the effect of graphene oxide on the breaking strength of the fiber (the difference in the breaking strength of the sample fibers of Preparation Example 1 and Comparative Example 2 is very small, and Preparation Example 1 adds graphene oxide compared to Comparative Example 2), which shows that there is a synergistic dispersion effect between volcanic rock powder, graphene oxide and infrared ceramic powder.

The above are all preferred embodiments of the present application, and the protection scope of the present application is not limited thereto. Therefore, any equivalent changes made according to the structure, shape, and principle of the present application should be included in the protection scope of the present application.

Claims (7)

1. A volcanic rock thermal insulation fiber, characterized by comprising the following raw materials in percentage by mass: Polyester masterbatch 85-90%; Far infrared masterbatch 10-15%; The far-infrared masterbatch is prepared from at least the following raw materials in parts by weight: Polyester granules 100 parts; Infrared ceramic powder 50-60 parts; Volcanic rock powder 5-10 parts; Graphene oxide 5-8 parts; Coupling agent 3-5 parts; The infrared ceramic powder is a mixture of at least two of Al ₂ O ₃ , TiO ₂ , SiO ₂ , Cr ₂ O ₃ , ZrO ₂ , B ₄ C, SiC, ZrC, BN, AlN, Si ₃ N ₄ , TiN, TiSi ₂ , WSi ₂ , ZrB ₂ , and CrB ₂ ; The infrared ceramic powder is activated before use, and includes the following steps: A1. Dispersion: first, put the dispersant into water and disperse it evenly, then add the infrared ceramic powder and mix evenly to obtain a suspension; A2, activation, grinding and activating the suspension obtained in step A1 to obtain an activated solution; A3, drying, spray drying the activation solution obtained in step A2 to obtain activated infrared ceramic powder; The dispersant is prepared by mixing lysine and sodium tripolyphosphate in a mass ratio of 1:(8-10). 2. The volcanic rock thermal insulation fiber according to claim 1, characterized in that: in the step A1, the concentration of the dispersant is 20-25 mg/L, and the concentration of the infrared ceramic powder is 0.8-1.2 g/L. 3. The volcanic rock thermal insulation fiber according to claim 1, characterized in that: the graphene oxide is modified before adding, and specifically comprises the following steps: B1, dissolving graphene oxide, that is, putting graphene oxide into a solvent and dispersing it evenly to obtain a graphene oxide solution; B2, mixing, adding acrylonitrile and alkali to the graphene oxide solution obtained in step B1 to obtain a mixture; B3. Modification: Under the protection of an inert gas atmosphere, the mixture is heated to 95±2° C. and refluxed for reaction, and then filtered and washed to obtain modified graphene oxide. 4. The volcanic rock thermal insulation fiber according to claim 3, characterized in that the solvent used in step B1 is a mixture of water and diethylene glycol, and the volume ratio of water: diethylene glycol is (8-10): 1. 5. The volcanic rock thermal insulation fiber according to claim 3, characterized in that: in the step B1, the graphene oxide is placed in a solvent and then ultrasonically dispersed, the dispersion temperature is 35-40°C, and the ultrasonic time is 15-20 minutes. 6. A thermal sock, characterized in that it is woven from blended yarn, wherein the blended yarn includes the volcanic rock thermal fiber as claimed in any one of claims 1 to 5. 7. A thermal sock according to claim 6, characterized in that it comprises a sock body (1) and a tube body (2), the sock body (1) and the tube body (2) are connected, a contraction ring (11) is provided at the arch of the sock body (1), a thickened portion (12) is provided at the heel of the sock body (1), the tube body (2) comprises a low-pressure section (21) and a high-pressure section (22), the low-pressure section (21) is provided at the calf of the tube body (2) of claim 3, there are two high-pressure sections (22) and they are located on both sides of the low-pressure section (21), and a cuff (23) is provided at the opening of the tube body (2).