Preparation method and application of micro-nano superfine six-ring stone particles

Abstract

The invention belongs to the technical field of material processing and textile, and discloses a preparation method and application of micro-nano superfine six-ring stone particles, and the preparation method comprises the following steps: firstly, screening six-ring stone particles which are sequentially subjected to ball milling and cleaning by adopting a flotation process to obtain micro-nano superfine six-ring stone particles with the particle size being less than 3 microns; the application comprises the following steps: firstly, preparing a six-ring stone / polyvinyl chloride spinning solution, then carrying out wet spinning by utilizing the six-ring stone / polyvinyl chloride spinning solution to prepare six-ring stone / polyvinyl chloride filaments, and carrying out a spinning process on the six-ring stone / polyvinyl chloride filaments to obtain six-ring stone / polyvinyl chloride yarns, and finally weaving the six-ring stone / polyvinyl chloride yarns to obtain the six-ring stone / polyvinyl chloride functional fabric. The micro-nano superfine six-ring stone particles are small in particle size, uniform in distribution and low in harmful element content, it can be guaranteed that the micro-nano superfine six-ring stone particles are uniformly dispersed in a six-ring stone / polyvinyl chloride spinning solution, and smooth spinning can be achieved under the condition that the addition amount is far higher than that in the prior art.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of material processing and textiles, and relates to a preparation method and application of micro-nano super-fine hexagonal stone particles. BACKGROUND

[0002] Polymer blending, as an important research field of material science, is focused on mixing two or more polymers through physical or chemical methods to prepare new materials with expected properties to meet the needs of different application scenarios. At the same time, functional minerals have wide application prospects in the fields of electronics, optics, and biomedicine due to their unique physical and chemical properties, such as magnetic minerals, conductive minerals, and optical minerals. In this context, combining the excellent properties of polymers with the functional characteristics of minerals to prepare new materials with the advantages of both has become an important research direction in the field of material science.

[0003] However, the functional mineral particles used in the prior art have a large particle size, which can easily cause blockage of the spinneret or needle during spinning, and affect the flatness of the film if used for film coating, which greatly hinders the use of functional mineral particles in spinning, drafting and other processes.

[0004] In document 1 (Preparation of Recycled Micro Powder Based Cementitious Materials from Construction Waste and Its Effect on Phosphogypsum Performance[D]. Southwest University of Science and Technology [2025-04-25].), the mineral particles are first subjected to dry and wet milling processes using a ball mill to reduce their particle size. The dry milling experiment results show that the particle size is reduced by 46.29% compared to the original recycled concrete powder without ball milling, the proportion of particles with a particle size less than 10 μm increases from 21.74% to 37.49%, and the proportion of particles with a particle size less than 75 μm increases from 84.89% to 94.25%. The wet milling experiment results show that the average particle size of the recycled concrete powder particles after ball milling for 30 min is 4.76 μm, and the proportion of particles with a particle size less than 10 μm is 76.71%. However, after ball milling, 24.21% of the recycled concrete particles are still larger than 10 μm, and neither dry milling nor wet milling reduces the particle size to the micro-nano level.

[0005] In document 2 (Different particle size tourmaline and tourmaline-PVDF fiber membrane for photocatalytic degradation of formaldehyde [J]. Journal of Guangxi University (Natural Science Edition), 2023, 48(6): 1395-1403. 1001-7445.2023.1395.), different particle size tourmaline particles and polyvinylidene fluoride (PVDF) were used to prepare composite fiber membranes. Ball milling was used to prepare tourmaline particles with a particle size of 10 μm. The microstructure and crystal structure of the particles were studied. Tourmaline-PVDF fiber membranes were prepared by electrospinning technology, and their photocatalytic degradation of formaldehyde was investigated. However, the particle size of the tourmaline particles prepared by ball milling is still 10 μm, which is relatively large.

[0006] In document 3 (Research on hydration characteristics and strength model of concrete mixed with particle size recombined fly ash [D]. Dalian University of Technology, 2021.), in order to obtain fly ash particles with a small enough particle size, a screen was used to screen the fly ash particles with a diameter of 3 μm. However, the experimental results showed that large-sized fly ash particles would quickly clog the screen. Therefore, the fly ash was dissolved in a special dispersant to form a suspension, and then filtered. However, the particle size distribution of the obtained particles was only 10%, and the process still had some shortcomings.

[0007] In document 4 (Performance research of rotary vibration screen based on ultrasonic vibration system [D]. Jingdezhen Ceramic University, 2023.), it was found that during the material screening process, the friction between the particles and the screen often generates static electricity, which can cause the particles to agglomerate and form clusters, leading to screen clogging and reduced screening efficiency. Therefore, a new screening method combining rotary vibration screening and ultrasonic technology was proposed, and the mechanism of ultrasonic-assisted material screening was discussed in depth. In this study, by comparing the screening rate and clogging rate on the screen surface with and without ultrasonic vibration, the experimental data clearly showed the effectiveness of ultrasonic vibration in solving the screen clogging problem and significantly improving the screening rate. In addition, the discrete element method was used to simulate the screening process of the ultrasonic rotary vibration screen, which verified the feasibility of this method. The results further confirmed that ultrasonic vibration can effectively disperse particle agglomeration, thereby effectively alleviating the clogging problem and significantly improving the screening efficiency. However, this process still has the problem of screen clogging, and as the target particle size decreases to the micro-nano scale, this method is no longer applicable. This is because when micro-nano particles need to be screened out, the screen aperture needs to reach the micro-nano scale. However, at this time, the nano particles are easy to agglomerate, causing screen clogging and making the particles unable to pass through the screen, resulting in screening failure. In addition, this method also cannot guarantee the uniformity of the particle size distribution, and large-sized particles may remain, affecting the subsequent spinning.

[0008] In existing research, minerals such as hexagonal stone, tourmaline, TiO2 powder, etc. are usually processed into powder and mixed with high polymer to produce adhesives, coatings, boards, plastics, etc. for building material processing, and can also be applied to fibers or fabrics for coating to achieve the functions of generating a large number of negative ions, releasing far infrared, antibacterial, etc. However, particle agglomeration phenomenon occurs when blending with high polymer. Currently, there are three main reasons for the agglomeration of ultra-fine powder: intermolecular forces cause ultra-fine powder agglomeration; electrostatic forces between particles cause agglomeration; and particle adhesion in air.

[0009] In addition, the content of functional mineral particles is low, which also has a great influence on the subsequent mechanical properties of filaments and the function of fabrics. For example, in document 5 (Preparation and Performance Research of PEDOT:PSS / PVA Conductive Fiber[D]. Jiangnan University, 2021. DOI: 10.27169 / d.cnki.gwqgu.2020.001098), the content of conductive particles in conductive fibers was increased to 13.4%, but the diameter of the single fiber after spinning was greater than 100 μm, and the elongation at break was reduced from 30.6% to 24.1%, and the fineness and the amount of addition were also not high. In addition, the particle size of the conductive particles used in this document is nano-level particles, but the content is low.

[0010] At the same time, wet spinning technology is also used for blending to prepare fibers due to its simple process, short production cycle, low cost and other advantages. In order to break through the limitation of the intrinsic properties of the material and improve the performance in multiple dimensions, the existing wet spinning technology mainly focuses on process optimization or polymer blending modification, but rarely involves the addition of functional minerals. For example, document 6 (High-strength PVC filament wet spinning process and its performance research [J]. Journal of Textile Science and Engineering, 2022, 39(04): 82-85.) only explored the effects of spinning conditions such as spinning temperature, coagulation bath temperature and draw ratio on the performance of the fiber to prepare a high-strength polyvinyl chloride fiber.

[0011] For another example, document 7 (Preparation and performance of modified casein / carboxymethyl cellulose sodium blended fiber [J]. Synthetic Fiber, 2019, 48(03): 31-35. 2019.03.008.) used wet spinning to prepare modified casein (CLC) / carboxymethyl cellulose sodium (CMC-Na) blended fibers with a mixed solution of ethanol, calcium chloride and hydrochloric acid as the coagulation bath.

[0012] Therefore, it is of great significance to study a preparation method and application of micro-nano ultra-fine hexagonal stone particles to solve the above problems. SUMMARY

[0013] The application aims at solving the problems in the prior art and providing a preparation method and application of micro-nano super-fine hexagonal stone particles.

[0014] To achieve the above-mentioned purposes, the technical scheme adopted by the application is as follows:

[0015] The preparation method of the micro-nano super-fine hexagonal stone particles adopts a flotation process to screen the hexagonal stone particles after ball milling and cleaning, so as to obtain the micro-nano super-fine hexagonal stone particles.

[0016] The particle size of the micro-nano super-fine hexagonal stone particles is less than 3 microns, and the proportion of the particles with a particle size greater than 2 microns is 0.1% to 0.5%, the proportion of the particles with a particle size of 1 to 2 microns is 1.5% to 3.0%, and the proportion of the particles with a particle size less than 1 micron is 96.5% to 98.5%.

[0017] The flotation is performed by using a flotation machine, and the process parameters of the flotation are as follows: the rotating speed of the turbine blade of the flotation machine is 2000 to 2200 r / min, the stirring time is 8 to 12 minutes, and the sedimentation time is 20 to 30 minutes.

[0018] The method of the application can ensure the complete exclusion of particles with a particle size greater than 3 microns, and by controlling different flotation times, particles with different particle sizes can be efficiently screened. Although the prior art can process most particles to the micro-nano scale, the particle size cannot be guaranteed to be free of particles with a larger particle size, and there is still a high possibility of the existence of mineral particles with a larger particle size.

[0019] According to the standard of GB / T 16418-2008 "Particle System Terminology", the particles treated by the application are superior to the indicators of all prior arts.

[0020] 1. Uniformity of particle size distribution: the particles treated by the application have extremely narrow particle size distribution, and all the particles have a particle size of less than 3 microns, showing extremely high particle size uniformity. Specifically, after static flotation, the particle size distribution of the particles is as follows:

[0021] The proportion of the particles with a particle size of 3 microns or more is 0%, indicating that there is no particle exceeding the threshold of 3 microns; the proportion of the particles with a particle size less than 3 microns and greater than 2 microns is only 0.1% to 0.5%, showing that only a few particles are close to the upper limit of 3 microns; the proportion of the particles with a particle size of 1 to 2 microns is 1.5% to 3.0%, further indicating that most particles are distributed in a smaller particle size range; the proportion of the particles with a particle size less than 1 micron is as high as 96.5% to 98.5%, which indicates that most particles are concentrated in this very narrow particle size range.

[0022] The distribution result shows that the average particle size of the treated particles reaches 267-311.2 nm, and the maximum particle size is not more than 3 μm. The change trend of the particle size tends to be flat, indicating that the uniformity of the particle size distribution is very high. Such excellent uniformity of the particle size distribution not only improves the quality and performance of the product, but also provides more accurate and reliable granular materials for specific application fields.

[0023] 2. Stability: The treated particles of the present application have a significant advantage in dispersibility, and the particles can achieve long-term stable dispersion in solvents or matrices without agglomeration, which is superior to the performance of the prior art in dispersibility and stability. As shown in Figure 1 、 Figure 2 : On the one hand, according to the Zeta potential (referring to GB / T 32672-2016 "Evaluation of Nanomaterial Dispersion System Stability by Electrophoretic Light Scattering Method", using Malvern Zetasizer Nano ZS90 potential instrument (Malvern Panalytical) for testing, the sample was ultrasonically dispersed for 10 min, and three parallel experiments were performed), the surface of the hexahedrite is of the same charge (negative charge), and due to the mutual repulsion of the same charge, the agglomeration phenomenon is reduced; on the other hand, in a liquid, smaller particles are more susceptible to Brownian motion, which helps to prevent agglomeration.

[0024] Among them, the strength of Brownian motion can be represented by the diffusion coefficient (D) of the particles, and the relationship with the particle size (d) is:

[0025] k B : Boltzmann constant;

[0026] T: absolute temperature;

[0027] η: liquid viscosity;

[0028] d: particle diameter;

[0029] The smaller the particle size d, the higher the temperature, the larger the diffusion coefficient D, and the more intense the Brownian motion.

[0030] 3. Environmental friendliness and production efficiency: The production process of the present invention is more environmentally friendly, reducing the emission of harmful substances, meeting the relevant requirements of GB / T 16418-2008 for environmental protection. (The use of floatation machine blades to stir and accelerate the dissolution of arsenic compounds in water, and the retention of hexacyclic stone particles by precipitation, removes the supernatant liquid rich in arsenic elements. According to GB / T 6730.45-2006, the test results after treatment show that the content of arsenic (As) in the hexacyclic stone particles is significantly reduced. The content of arsenic (As) is reduced from 514 mg / kg to less than 1 mg / kg, with a removal rate of more than 99%, so that the harmful elements in the hexacyclic stone particles meet the national standards (refer to GB / T 23994-2009 "Limit of Specific Harmful Elements in Coatings for Consumer Products in Contact with the Human Body", semi-quantitative detection of multiple elements in hexacyclic stone particles before and after cleaning using inductively coupled plasma mass spectrometer, and detection of element content, the test results are as shown in Figure 20 This is because some of its compounds have a certain water solubility. Since the hexacyclic stone is composed of calcite and limonite, the arsenic element in the limonite is mainly in the form of arsenate, which has strong hydrophilicity and can be retained in the precipitate by flotation.

[0031] Key process parameters for flotation:

[0032] 1. The rotation speed of the floatation machine turbine blade is 2000-2200 r / min;

[0033] (1) Uniform dispersion: The high-speed rotating turbine blade can generate strong water flow, which helps to uniformly disperse the particles in the water, preventing the particles from settling or agglomerating.

[0034] (2) Centrifugal force effect: The centrifugal force generated by high speed helps to push heavier particles to the edge of the floatation machine, while lighter particles remain in the water, thus promoting the initial separation of particles.

[0035] (3) Increase contact opportunities: High-speed stirring increases the contact opportunities between particles and flotation agents or bubbles, helping to improve the efficiency of flotation.

[0036] 2. Stirring for 8-12 min;

[0037] (1) Sufficient dispersion: The stirring time of 8-12 min is sufficient to ensure that the particles are uniformly dispersed in the water. Uniform dispersion of particles is the key to the success of the flotation process, as it helps to increase the contact opportunities between particles and bubbles, thus improving the separation efficiency.

[0038] (2) Particle and bubble contact time: During the flotation process, particles need a certain amount of time to contact and adhere to bubbles. The stirring time of 8-12 min can ensure that the particles have enough time to interact with the bubbles, thus improving the flotation effect.

[0039] 3. Precipitation time: 20-30 min;

[0040] Allow the particles to settle in water. Depending on the particle size and density, particles will settle at different speeds, allowing separation.

[0041] (1) Particle size classification: Through precipitation, particles of different sizes can be classified.

[0042] (2) Stable suspension: Precipitation time helps stabilize the suspension, making the supernatant and precipitate more clear, facilitating subsequent processing. This step aims to uniformly disperse particles in water through water flow and centrifugal force, initiating the precipitation process.

[0043] As a preferred technical solution:

[0044] The ball-to-material ratio (mass ratio of ball milling beads to hexagonal stone powder) during ball milling is 4-10:1, the ball mill speed is 200-300 r / min, and the ball milling time is 4-8 h.

[0045] The average particle size of the hexagonal stone particles after ball milling is less than or equal to 4 microns, with a particle size of less than or equal to 4 microns accounting for greater than or equal to 90%, and the maximum particle size is less than or equal to 30 microns.

[0046] The present application also provides a preparation method of hexagonal stone / polyvinyl chloride functional fabric. First, a hexagonal stone / polyvinyl chloride spinning solution is prepared, then a hexagonal stone / polyvinyl chloride filament is prepared by wet spinning using the hexagonal stone / polyvinyl chloride spinning solution, the hexagonal stone / polyvinyl chloride filament is then subjected to a spinning process to obtain a hexagonal stone / polyvinyl chloride yarn, and finally the hexagonal stone / polyvinyl chloride yarn is woven to obtain a hexagonal stone / polyvinyl chloride functional fabric.

[0047] The preparation method of the hexagonal stone / polyvinyl chloride spinning solution is as follows: disperse the micro-nano super-fine hexagonal stone particles into an organic solvent, first use a magnetic stirrer to stir at a speed of 500-800 r / min for 1-2 h, then use a high-speed homogenizer to homogenize at a speed of 12000-18000 r / min for 20-40 min, continue to use an ultrasonic machine to ultrasonic for 20-40 min to strengthen particle de-agglomeration, then use a magnetic stirrer to stir at a speed of 500-800 r / min for 36-60 h, then add a plasticizer dioctyl phthalate and continue to stir for 0.5-2 h, then add polyvinyl chloride and stir uniformly using a glass rod, then heat to 70-75℃ and stir at a speed of 400-600 r / min for 12-24 h using a mechanical stirrer to ensure that the polymer is fully dissolved and the particles are uniformly dispersed, obtaining a hexagonal stone / polyvinyl chloride spinning solution.

[0048] The particle size of the micro-nano super-fine hexagonal stone particles is less than 3 microns, and the proportion of the particle size of more than 2 microns is 0.1% to 0.5%, the proportion of the particle size of 1 to 2 microns is 1.5% to 3.0%, and the proportion of the particle size of less than 1 micron is 96.5% to 98.5%;

[0049] The amount of the micro-nano super-fine hexagonal stone particles is 30% to 70% based on the total mass of the micro-nano super-fine hexagonal stone particles and the polyvinyl chloride.

[0050] The reason why the present application can realize smooth spinning under the condition of far higher than the existing technology is that:

[0051] 1. Foam flotation process:

[0052] The settling rate of mineral particles in a liquid is influenced by a variety of factors, including the density, size, shape of the particles, and the viscosity of the liquid. The density of the particles determines the buoyancy in the liquid, while the size and shape of the particles affect the frictional resistance.

[0053] According to Stokes' law: the smaller the particle size, the larger the specific surface area, the greater the friction area, and the greater the frictional resistance, that is, the greater the relative resistance to sinking, and the longer the residence time in the liquid. When the liquid is close to static, larger particles will settle faster and have a greater settling rate. Therefore, the smaller the particle size, the slower the settling. The foam flotation process used in the present application can capture micro-nano scale hexagonal stone particles through the rising foam, and float them together to the uppermost layer of the solution. When the foam breaks, due to the slow settling speed of the nano-scale hexagonal stone particles, they can still be left in the supernatant after 20 to 30 minutes of settling. The above particle size distribution characteristics obtained by flotation provide the following key advantages for the blending of the spinning solution:

[0054] 1. Uniform dispersion: ultra-fine particles (96.5% to 98.5% of the proportion of less than 1 micron) are uniformly distributed in the polyvinyl chloride spinning solution due to active Brownian motion, effectively reducing local agglomeration and particle settling, and avoiding viscosity fluctuations caused by particle aggregation;

[0055] 2. Spinneret adaptability: strict control of the maximum particle size (less than 3 microns) ensures that the particles pass smoothly through the spinneret micropores, reduces the risk of blockage, and ensures the stability of continuous spinning;

[0056] 3. Controllability of fiber structure: narrow particle size distribution (1.6% to 3.5% of the proportion of more than 1 and less than 3 microns) allows the particles to be uniformly dispersed in the fiber cross-section, reducing structural defects caused by particle size differences.

[0057] By adjusting the amount of hexagonal stone added (30-70wt%), the balance of spinning performance is maintained while achieving high functionality. The combination of core parameters of the flotation process is directly related to the enrichment efficiency of ultra-fine particles, providing reliable technical support for the large-scale production of high-content hexagonal stone / polyvinyl chloride composite fibers.

[0058] 2. Spinning solution preparation (extended stirring time): In the organic solvent, the stirring time is increased to 36-60h. Long stirring time allows the surface of hexagonal stone particles to be fully infiltrated and dispersed in the solution. Then, the plasticizer dioctyl phthalate is added and stirred for 0.5-2h to make the stirring uniform and increase the solution viscosity, so that the dispersed particles are not easy to agglomerate. Then, polyvinyl chloride powder is added and heated and stirred to further increase the solution viscosity, so that the resistance between the dispersed hexagonal stone particles is increased, reducing the risk of agglomeration. This is because polyvinyl chloride itself has a large molecular weight, which can form a three-dimensional barrier on the surface of mineral particles, thereby effectively providing a three-dimensional stability barrier to improve the suspension performance and avoid precipitation. In the prior art, mineral particles are stirred with solvents, plasticizers, and polymers. At this time, the hexagonal stone particles have not been fully dispersed, and the movement of the particles in the solution is hindered by the presence of polymers, greatly reducing the dispersion effect, leading to significant agglomeration, making spinning difficult, and easily causing broken filaments. At this time, even if the stirring time is extended, the quality of the spinning solution will be affected (yellowing and reduced spinnability).

[0059] 3. Wet spinning process: In the wet spinning process, on the one hand, according to the Zeta potential, the surface of the hexagonal stone is filled with the same charge, and due to the principle of mutual repulsion of the same charge, the hexagonal stone particles are more uniformly dispersed in the spinning solution. On the other hand, the temperature of the wet spinning process is 70-80℃ (i.e. the temperature of the spinning solution), which intensifies the Brownian motion between molecules, and the collision between hexagonal stone particles is more intense, also reducing the agglomeration of hexagonal stone particles in the spinning solution (attractive force). The synergistic effect of the above two makes the hexagonal stone particles have a high load while being uniformly dispersed in the spinning solution, allowing smooth spinning at a high hexagonal stone particle addition amount. Specifically:

[0060] 1). Weak charge repulsion basis: The surface of the hexagonal stone carries the same negative charge (Zeta potential -7.5±0.5mV), which is not enough to completely inhibit agglomeration, but can delay the particle aggregation rate through short-range electrostatic repulsion, providing initial conditions for kinetic dispersion;

[0061] 2). Dominance of Brownian motion of ultra-fine particles: After flotation, the particle size distribution of hexagonal stone particles is highly concentrated (96.5-98.5% of particles are less than 1μm). Based on the Stokes-Einstein equation, the temperature of the spinning solution at 70℃ can significantly enhance the Brownian motion, offsetting the lack of low charge repulsion, and inhibiting particle settling and agglomeration through continuous random motion;

[0062] 3) Temperature control rheological optimization: due to the decrease of the spinning solution viscosity and the increase of the flowability at 70-80℃, the flow field shear force promotes the dynamic rearrangement of the particles, forming a uniform dispersion system.

[0063] Compared with the traditional process relying on high Zeta potential (|ζ|>30mV) or chemical dispersants, the present application breaks through the technical bottleneck by "physical synergistic path" (ultra-fining + temperature control kinetics), realizes the continuous production of high-content composite fibers under the conditions of low charge and without dispersants, and has the advantages of environmental protection and economy.

[0064] As a preferred technical solution:

[0065] The preparation method of the sixrings / polyvinyl chloride functional fabric as described above, the concentration of the spinning solution is 8.32-18.92wt%, and the mass ratio of dioctyl phthalate to polyvinyl chloride is 1:2.

[0066] The preparation method of the sixrings / polyvinyl chloride functional fabric as described above, the process flow of wet spinning is that the spinning solution is extruded from the spinneret hole to form a stream after metering by a metering pump, the stream is then solidified into a primary fiber in a coagulation bath, and finally the primary fiber is sequentially drawn, shaped and wound; the main process parameters are:

[0067] Spinning solution preparation stage:

[0068] Liquid storage and degassing: the liquid storage tank is kept at a constant temperature of 70-75℃, the degassing pressure is 0.5-0.8MPa, the degassing time is 15-30min, and the air bubbles in the spinning solution are eliminated.

[0069] Spinning stage:

[0070] The flow rate of the metering pump is 0.5-1.0cc / min to control the extrusion stability;

[0071] The spinneret hole diameter is 0.10-0.20mm, the number of holes is 30-50, and the fiber fineness requirement is matched;

[0072] The coagulation bath is distilled water, and the temperature of the coagulation bath is 41.3-50℃;

[0073] The primary fiber drawing speed is 4-6m / min, the secondary drawing speed is 12-15m / min, and the fiber orientation is optimized; the drawing temperature is 45-50℃, and the fiber is cured in two stages to avoid fiber deformation;

[0074] The winding speed of the take-up roller is 12-15m / min, and the transverse spreading rate is 700-800m / min.

[0075] The preparation method of the sixrings / polyvinyl chloride functional fabric as described above, the linear density of the sixrings / polyvinyl chloride filament is 45-100 dtex, the breaking strength is 4-30 cN, and the breaking elongation is 5-10%.

[0076] The preparation method of the sixrings / polyvinyl chloride functional fabric as described above, the fineness of the sixrings / polyvinyl chloride yarn is 40-70 Tex, the breaking strength is 90-114 cN, and the twist is 200-1000 twists / m.

[0077] The preparation method of the sixrings / polyvinyl chloride functional fabric as described above, the sixrings / polyvinyl chloride functional fabric is a plain weave, the warp yarn is 29.5 Tex polyester yarn, the weft yarn is 40-70 Tex sixrings / polyvinyl chloride yarn, the warp density is 200 / 10 cm (i.e. 200 yarns per 10 cm in the warp direction), and the weft density is 280 / 10 cm (i.e. 280 yarns per 10 cm in the weft direction).

[0078] Beneficial effects:

[0079] (1) The present application can effectively separate micro-nano particles and large particles by using the flotation precipitation method, remove large particles, control the particle size of micro-nano ultra-fine sixrings particles in the range of <3 μm, and have high uniformity of particle size distribution, which can reduce the problem of jet hole blockage and improve the quality and performance of the product, and also provides more accurate and reliable particle materials for specific application fields; in addition, the flotation process also significantly reduces the content of harmful elements in the sixrings particles, so that the harmful elements in the product are lower than the national standard, providing a reliable material basis for the application of functional ore in the textile field.

[0080] (2) The present application first precisely controls the particle surface Zeta potential to a stable negative value through the flotation process, forms a homogeneous electrostatic repulsion layer, significantly weakens the agglomeration tendency dominated by van der Waals force, and then uses the high temperature environment in the PVC processing to strengthen the Brownian motion, drives the particles to continuously migrate by thermal kinetic energy, so that even a short contact can quickly separate, especially for the <1 μm sub-micron particles accounting for 96.5-98.5%, the effect is remarkable; in addition, the narrow particle size distribution design (99.5%-99.9% of particles <2 μm) eliminates the "large particles adsorbing small particles" heterogeneous agglomeration phenomenon caused by large particle size span in traditional process, compared with the existing technology relying on single electrostatic regulation or static dispersion strategy, the present application realizes uniform dispersion at a smaller particle size through the "electrostatic repulsion + dynamic thermal motion + particle size homogenization" triple synergistic effect, and takes into account the functionality and processing stability.

[0081] (3)The application can realize smooth spinning under the condition of far higher than the existing technology adding amount, and the breaking strength of the prepared six-ring stone / polyvinyl chloride filament can reach up to 30 cN, and the breaking elongation can reach up to 10%, which is superior to the prior art, the six-ring stone / polyvinyl chloride functional fabric prepared by using the same can also realize the negative ion release amount, and has excellent antibacterial performance, air permeability and far infrared heat storage and air layer heat preservation effect, so that the practicability is increased, and the application potential in the fields of medical treatment, health, sports and the like is also enhanced, and a new direction is provided for the innovation and development of the functional textile market. BRIEF DESCRIPTION OF DRAWINGS

[0082] Figure 1 It is a dispersion schematic diagram of the six-ring stone particles in the spinning solution of the application;

[0083] Figure 2 It is a Zeta potential schematic diagram of the six-ring stone particles after dispersion in the spinning solution of the application;

[0084] Figure 3 It is an SEM diagram of the six-ring stone particle size under different flotation times in Example 1 of the application; in the diagram, a is an SEM diagram of the six-ring stone particle size when the precipitation time is 0 min, b is an SEM diagram of the six-ring stone particle size when the precipitation time is 5 min, c is an SEM diagram of the six-ring stone particle size when the precipitation time is 10 min, d is an SEM diagram of the six-ring stone particle size when the precipitation time is 15 min, and e is an SEM diagram of the six-ring stone particle size when the precipitation time is 20 min;

[0085] Figure 4 It is a particle size distribution interval statistical diagram of the six-ring stone particles under different precipitation times in Example 1 of the application; in the diagram, 0-1 represents the proportion of the particle size <1 μm, 1-2 represents the proportion of the particle size ≥1 μm and <2 μm, 2-3 represents the proportion of the particle size ≥2 μm and <3 μm, 3-4 represents the proportion of the particle size ≥3 μm and <4 μm, and 4-5 represents the proportion of the particle size ≥4 μm and <5 μm;

[0086] Figure 5 It is a process flow diagram for preparing the six-ring stone / polyvinyl chloride filament of the application; in the diagram, a is a process flow diagram for screening the six-ring stone, b is a process flow diagram from preparing the six-ring stone / polyvinyl chloride spinning solution to preparing the six-ring stone / polyvinyl chloride filament, and c is a process flow diagram for preparing the six-ring stone / polyvinyl chloride filament by using the six-ring stone / polyvinyl chloride spinning solution;

[0087] Figure 6 It is a design layout for preparing the six-ring stone / polyvinyl chloride glove of the application;

[0088] Figure 7DSC curve of the hexacyclane / polyvinyl chloride filament prepared in Example 1 of the present application; in the figure, X represents temperature (unit: ℃), and Y represents heat flow rate (unit: W / g);

[0089] Figure 8 Schematic diagram of surface tension and viscosity of the hexacyclane / polyvinyl chloride spinning solution in Examples 1-5 of the present application;

[0090] Figure 9 Schematic diagram of the morphology after different stirring times when preparing the hexacyclane / polyvinyl chloride spinning solution in Example 1 of the present application; in the figure, a is the schematic diagram of the morphology after stirring for 6 h when preparing the hexacyclane / polyvinyl chloride spinning solution, b is the schematic diagram of the morphology after stirring for 48 h when preparing the hexacyclane / polyvinyl chloride spinning solution, and c is the schematic diagram of the morphology after stirring for 48 h and standing for 2 h when preparing the hexacyclane / polyvinyl chloride spinning solution;

[0091] Figure 10 Schematic diagram of the breaking strength and elongation at break of the hexacyclane / polyvinyl chloride filament prepared in Examples 1-5 of the present application;

[0092] Figure 11 Surface morphology and cross-sectional schematic diagram of the hexacyclane / polyvinyl chloride filament prepared in Example 4 of the present application; in the figure, a is the surface morphology of the hexacyclane / polyvinyl chloride filament prepared in Example 4, and b is the cross-sectional schematic diagram of the hexacyclane / polyvinyl chloride filament prepared in Example 4;

[0093] Figure 12 Thermogravimetric curve of the polyvinyl chloride filament prepared in Comparative Example 1 of the present application, the micro-nano super-fine hexacyclane particles prepared in Example 4, and the hexacyclane / polyvinyl chloride filament;

[0094] Figure 13 Fourier infrared spectrum of the polyvinyl chloride filament prepared in Comparative Example 1 of the present application, the micro-nano super-fine hexacyclane particles prepared in Example 4, and the hexacyclane / polyvinyl chloride filament; in the figure, a represents the hexacyclane / polyvinyl chloride filament, b represents the micro-nano super-fine hexacyclane particles, and c represents the polyvinyl chloride filament;

[0095] Figure 14 Surface morphology of the hexacyclane / polyvinyl chloride yarn prepared in Example 1 of the present application and schematic diagram of the yarn breaking strength under different twist degrees; in the figure, a is the surface morphology of the hexacyclane / polyvinyl chloride yarn prepared in Example 1, and b is the schematic diagram of the yarn breaking strength of the hexacyclane / polyvinyl chloride yarn under different twist degrees;

[0096] Figure 15 Schematic diagram of the hexacyclane / polyvinyl chloride filament releasing negative ions;

[0097] Figure 16The figures show the antibacterial effects of the hexagonal stone / polyvinyl chloride functional fabric prepared in Example 1 and the pure polyvinyl chloride fabric prepared in Comparative Example 1 against S. aureus and E. coli strains. In the figures, a represents the antibacterial effect of the hexagonal stone / polyvinyl chloride functional fabric prepared in Example 1 and the polyvinyl chloride fabric prepared in Comparative Example 1 against S. aureus strain, and b represents the antibacterial effect of the hexagonal stone / polyvinyl chloride functional fabric prepared in Example 1 and the polyvinyl chloride fabric prepared in Comparative Example 1 against E. coli strain. A represents the hexagonal stone / polyvinyl chloride functional fabric, and B represents the polyvinyl chloride fabric prepared in Comparative Example 1.

[0098] Figure 17 This diagram illustrates the far-infrared emission mechanism of the present invention, as well as the internal vibrational heat of the polyvinyl chloride filament and the hexagonal stone / polyvinyl chloride filament prepared in Example 1. In the diagram, a is a schematic diagram of the far-infrared emission mechanism of the present invention, b is a schematic diagram of the internal vibrational heat of the polyvinyl chloride filament, and c is a schematic diagram of the internal vibrational heat of the hexagonal stone / polyvinyl chloride filament prepared in Example 1.

[0099] Figure 18 The figures show infrared thermograms of the hexagonal stone / polyvinyl chloride gloves prepared in Example 1 of this invention before and after wearing them indoors and in an indoor constant temperature chamber. In the figures, a is the infrared thermogram when the hexagonal stone / polyvinyl chloride gloves are first worn indoors, b is the infrared thermogram after wearing the hexagonal stone / polyvinyl chloride gloves indoors for 1 hour, c is the infrared thermogram when the hexagonal stone / polyvinyl chloride gloves are not worn indoors, d is the infrared thermogram after wearing the hexagonal stone / polyvinyl chloride gloves indoors for 0.5 hours, e is the infrared thermogram after wearing the hexagonal stone / polyvinyl chloride gloves only on the palm of the hand indoors for 0.5 hours, and f is the infrared thermogram after wearing the hexagonal stone / polyvinyl chloride gloves only on the back of the hand indoors for 0.5 hours.

[0100] Figure 19 The images show infrared thermograms of the hexagonal stone / polyvinyl chloride gloves prepared in Example 1 of this invention before and after wearing them outdoors at -20°C. In the images, a is the infrared thermogram of wearing the hexagonal stone / polyvinyl chloride gloves outdoors for 0 min, b is the infrared thermogram of wearing the hexagonal stone / polyvinyl chloride gloves outdoors for 15 min, c is the infrared thermogram of wearing the hexagonal stone / polyvinyl chloride gloves outdoors for 30 min, d is the infrared thermogram of not wearing the hexagonal stone / polyvinyl chloride gloves outdoors for 0 min, e is the infrared thermogram of not wearing the hexagonal stone / polyvinyl chloride gloves outdoors for 15 min, and f is the infrared thermogram of not wearing the hexagonal stone / polyvinyl chloride gloves outdoors for 30 min.

[0101] Figure 20 This is a schematic diagram showing the content of harmful elements obtained by ICP semi-quantitative testing of the cleaned hexagonal stone particles according to the present invention. DETAILED DESCRIPTION

[0102] The application will be further described below in connection with specific embodiments. It should be understood that these embodiments are only used to illustrate the application and not to limit the scope of the application. Furthermore, it should be understood that those skilled in the art can make various modifications or changes to the application after reading the content taught by the application, and these equivalent forms also fall within the scope defined by the appended claims of the application.

[0103] In order to ensure the performance of the substances used in each embodiment and comparative example, the manufacturer and brand of the substance are specified. The products of other manufacturers and brands that meet the definition of the application are also feasible.

[0104] The test methods of the relevant performance indicators in each of the following embodiments and comparative examples are as follows:

[0105] Particle size distribution: The micro-nano ultra-fine hexagonal stone particles prepared in each embodiment were used as samples, and then the particle size distribution of the samples was determined by using a Bettersize 3000Plus laser particle size analyzer (manufacturer: Dandong Better) according to the GB / T 19077-2016 "Particle Size Analysis-Laser Diffraction Method" standard.

[0106] Viscosity: The hexagonal stone / polyvinyl chloride spinning solution prepared in each embodiment was used as a sample, and then the viscosity of the spinning solution was determined at a temperature of 70°C using an M HG1 intelligent rotational viscometer.

[0107] Surface tension: The hexagonal stone / polyvinyl chloride spinning solution prepared in each embodiment was used as a sample, and then the surface tension of the spinning solution was tested using the flat plate method of a DTAC-21 type dynamic contact angle and tension tester.

[0108] Breaking strength, elongation at break: The hexagonal stone / polyvinyl chloride filaments and hexagonal stone / polyvinyl chloride yarns prepared in each embodiment were used as samples, and then the samples were determined according to the GB / T 14344-2022 "Chemical Filament Filament Tensile Property Test Method" standard to obtain the breaking strength of the hexagonal stone / polyvinyl chloride filaments and hexagonal stone / polyvinyl chloride yarns and the elongation at break of the hexagonal stone / polyvinyl chloride filaments.

[0109] Negative ion release amount: The hexagonal stone / polyvinyl chloride functional fabric prepared in each embodiment was used as a sample, and then the sample was determined using a Qinsun G281 fabric negative ion generation amount tester according to the GB / T 30128-2013 "Textiles-Determination of Negative Ion Generation" standard; wherein the test conditions: temperature 25±2°C, 65%±5% RH, sample size 300mm x 200mm, continuous test for 15 minutes, repeated 5 times to take the average.

[0110] Temperature rise and far-infrared emissivity: Three fabric samples with a diameter of 80 mm were cut from each of the hexagonal stone / polyvinyl chloride functional fabrics prepared in each embodiment as samples. Then, in accordance with GB / T 30127-2013 "Detection and Evaluation of Far-Infrared Properties of Textiles" standard, the far-infrared emissivity and temperature rise of the three samples were measured using a YS-212A far-infrared emissivity tester, and their average values ​​were calculated.

[0111] Antibacterial effect: The hexagonal stone / polyvinyl chloride functional fabrics prepared in each embodiment were used as samples, and then tested according to GB / T20944.1-2007 "Evaluation of antibacterial properties of textiles - Part 1: Agar plate diffusion method". Staphylococcus aureus and Escherichia coli (10 μL) were used in the test. 6 ~10 7 The test bacteria (CFU / mL) were then sterilized with ultraviolet light for 30 minutes and incubated for 24 hours. The width of the inhibition zone was then measured.

[0112] Air permeability: The hexagonal stone / polyvinyl chloride functional fabrics prepared in each embodiment were used as samples. The samples were then tested in accordance with GB / T5453-1997 "Determination of air permeability of textile fabrics". The YG(B)461E air permeability meter (pressure difference 200Pa) was used for the test. The same sample was measured repeatedly at different locations 5 times and the average value was taken.

[0113] Temperature difference: The hexagonal stone / polyvinyl chloride functional gloves prepared in each embodiment were used as samples. Then, the temperature difference before and after wearing the samples for 1 hour in an indoor constant temperature chamber at 20℃ and 5℃, and an outdoor environment at -20℃ was measured using an infrared thermal imager.

[0114] Example 1

[0115] A method for preparing a hexagonal stone / polyvinyl chloride functional fabric, comprising the following steps:

[0116] (1) As Figure 5 As shown in Figure a, small pieces of hexagonal stone with a diameter of less than 0.5 cm were first crushed in a pulverizer at a speed of 3000 r / min for 5 min. Then, the crushed hexagonal stone powder was ball-milled in a ball mill at a speed of 220 r / min for 4 h and then allowed to stand for 0.5 h. The tilt angle of the pulverizer was 45° and the ball-to-material ratio during ball milling was 6:1.

[0117] The average particle size of the ball-milled hexagonal stone particles was 2.34 μm, with 97.5% of the particles having a diameter of less than 4 μm, and the largest particle size was 20.96 μm.

[0118] (2) The hexagonal stone particles after ball milling in step (1) are poured into a single-tank flotation machine, 1L of distilled water is added, then stirred at a speed of 2100r / min for 1h, then stand for 24h and extract the supernatant with a syringe; wherein the cleaning times is 3 times;

[0119] (3) After cleaning in step (2), 1L of deionized water is added to the single-tank flotation machine, then stirred at a speed of 2100r / min for 10min and then precipitated for 20min (the SEM images of the precipitated 0min, 5min, 10min, 15min and 20min are shown in Figure 3 , from which it can be seen that the hexagonal stone particles without precipitation have a large number of large particle size particles and are very uneven, and the particle size of the hexagonal stone mineral particles becomes smaller and more uniform with the extension of the precipitation time), after the precipitation is completed, the supernatant is extracted with a syringe and placed in a drying oven to dry at 80℃ for 48h, then continue to manually grind 5 times using a mortar and pestle, that is, the micro-nano ultra-fine hexagonal stone particles are obtained; wherein the single manual grinding time is 15min, and the manual grinding direction is to rotate alternately clockwise and counterclockwise;

[0120] The particle size of the obtained micro-nano ultra-fine hexagonal stone particles (the proportion of each particle size is shown in Figure 4 ) is <3μm, and the proportion of particle size >2μm is 0.3%, the proportion of particle size 1-2μm is 2.2%, and the proportion of particle size <1μm is 97.5%;

[0121] (4) Preparation of hexagonal stone / polyvinyl chloride spinning solution;

[0122] As shown in b of Figure 5 , the micro-nano ultra-fine hexagonal stone particles are dispersed in DMF, first stirred at a speed of 600r / min for 1.5h using a magnetic stirrer, then homogenized at a speed of 15000r / min for 30min using a high-speed homogenizer, then ultrasonic for 30min using an ultrasonic machine at a power of 80W, and then stirred at a speed of 600r / min for 48h using a magnetic stirrer (as shown in Figure 9As shown in the morphology images of the samples stirred for 6h and 48h using a magnetic stirrer, it can be seen that extending the stirring time and increasing the solution viscosity are effective methods for reducing particle agglomeration and dispersing hexacyrtolite particles. The hexacyrtolite particles can be prevented from being significantly deepened within 2h in the spinning solution system containing polyvinyl chloride, ensuring that the spinning process is not blocked. Then, dioctyl phthalate is added, and stirring is continued for 1h. After adding polyvinyl chloride and stirring uniformly using a glass rod, the temperature is increased to 70℃, and the hexacyrtolite / polyvinyl chloride spinning solution with a concentration of 13.88wt% is obtained by stirring at a speed of 400r / min for 18h using a mechanical stirrer. In the hexacyrtolite / polyvinyl chloride spinning solution, the amount of micro-nano super-fine hexacyrtolite particles is 60% based on the total mass of the micro-nano super-fine hexacyrtolite particles and polyvinyl chloride, and the mass ratio of dioctyl phthalate to polyvinyl chloride is 1:2.

[0123] As shown in Figure 8 , the surface tension of the hexacyrtolite / polyvinyl chloride spinning solution is 32.2mN / m, and the viscosity is 952.8mPa.S.

[0124] (5) As shown in Figure 5 , the hexacyrtolite / polyvinyl chloride spinning solution prepared in step (4) is injected into a spinning machine liquid storage tank for liquid storage and defoaming. The liquid storage tank is kept at a constant temperature of 70℃, the defoaming pressure is 0.6MPa, and the defoaming time is 20min.

[0125] (6) The spinning solution after defoaming in step (5) is metered by a metering pump and then extruded from a spinneret to form a fine stream. The fine stream is then solidified into a primary fiber in a coagulation bath, and then the primary fiber is subjected to a sequence of "primary drawing, primary drying, secondary drawing, and secondary drying" for drawing and setting. Finally, the primary fiber is naturally air-dried for 48h after being wound, to obtain a hexacyrtolite / polyvinyl chloride filament. In the process, the flow rate of the metering pump is 0.75cc / min, the spinneret hole diameter is 0.16mm, the number of holes is 40, the coagulation bath is distilled water, the temperature of the coagulation bath is 41.3℃, the primary drawing speed of the primary fiber is 5.3m / min, the secondary drawing speed is 13.3m / min, the drawing temperature is 47.3℃, the primary drying temperature is 47.3℃, the secondary drying temperature is 47.3℃, the line speed of the take-up roller during winding is 13.3m / min, and the transverse spread rate is 780m / min.

[0126] The obtained hexacyrtolite / polyvinyl chloride filament (the DSC curve of which is shown in Figure 7As shown in FIG. 1, it can be seen from the figure that the DSC derivative curve has a peak appearing near 50℃, which is the glass transition temperature peak. The glass transition temperature is obtained by the inflection point method. The method takes the inflection point Tig (the point of maximum slope) at the time of transition as the glass transition temperature interval of the material. The position of the endothermic peak can be determined from the first derivative function of the curve near the slope change. The midpoint of the peak of the first derivative curve of the heat flow is the glass transition temperature (Tg), which represents the temperature at which the material changes from a hard and brittle glass state to a soft and tough rubber state, i.e. the heat drawing temperature is set as the line density of 50 dtex, as shown in FIG. 2. The surface morphology and cross-sectional schematic diagram of the sixrings / polyvinyl chloride filament are shown in FIG. 3. As shown in the figure, the sixrings particles are successfully added to the inside of the filament, which proves the correctness of the macro mechanical property data. At the same time, the maximum amount of added ultra-fine sixrings particles can be obtained while ensuring that the filament has excellent mechanical properties and good spinnability. Figure 10 The breaking strength is 10.54 cN and the breaking elongation is 6.68%, as shown in FIG. 4. The surface morphology and cross-sectional schematic diagram of the sixrings / polyvinyl chloride filament are shown in FIG. 5. As shown in the figure, the sixrings particles are successfully added to the inside of the filament, which proves the correctness of the macro mechanical property data. At the same time, the maximum amount of added ultra-fine sixrings particles can be obtained while ensuring that the filament has excellent mechanical properties and good spinnability. Figure 11

[0127] (7) The sixrings / polyvinyl chloride filament obtained in step (6) is combined and twisted using a digital small sample spinning machine to obtain sixrings / polyvinyl chloride yarn. The spindle speed is 4000 revolutions / min, the draft ratio is 1.200, and the twist direction is S.

[0128] The fineness of the obtained sixrings / polyvinyl chloride yarn (the surface morphology thereof is shown in FIG. 6) is 46.5 Tex, the breaking strength is 114 cN, and the twist is 600 twists / m. Figure 14

[0129] To explore the effect of twist on the breaking strength of the obtained sixrings / polyvinyl chloride yarn, only the twist in step (7) is changed while other process parameters remain unchanged, and the breaking strength of the sixrings / polyvinyl chloride yarn obtained under different twists is obtained, as shown in FIG. 7. The breaking strength of the sixrings / polyvinyl chloride yarn without twisting is the lowest, and as the twist increases, the breaking strength of the sixrings / polyvinyl chloride yarn also rises, and when the twist is 600 r / m, the breaking strength of the sixrings / polyvinyl chloride yarn is 114 cN. Then, as the twist increases, the breaking strength of the sixrings / polyvinyl chloride yarn begins to decrease, which is due to the fact that excessive twisting causes damage to the sixrings / polyvinyl chloride yarn, and the pre-load borne due to inclined torsion increases and the axial force decreases. Therefore, the critical twist of the sixrings / polyvinyl chloride yarn is 600 r / m, at which point the mechanical properties of the yarn are optimal. Figure 14

[0130] ​​​(8) The six-membered stone / polyvinyl chloride functional fabric was obtained by using the polyester yarn (402 sewing thread, brand name: Guitz) with a specification of 29.5 Tex as the warp yarn and the six-membered stone / polyvinyl chloride yarn prepared in step (7) as the weft yarn, and using a sample weaving machine to weave by the forward weaving method; wherein the reed number was 60, the heddle number was 1, and the harness frame number was 6.

[0131] The final six-membered stone / polyvinyl chloride functional fabric was plain weave, the warp density was 200 threads / 10 cm, the weft density was 280 threads / 10 cm, and the width was 20 cm.

[0132] The negative ion release amount of the six-membered stone / polyvinyl chloride functional fabric (the process of the release of negative ions of the six-membered stone / polyvinyl chloride filament is shown in Figure 15 ) was 1108 / cm 3 , the far infrared emissivity was 0.942, the antibacterial effect was good (compared with the antibacterial effect of pure polyvinyl chloride fabric, the results are shown in Figure 16 , it can be seen from the figure that the pure polyvinyl chloride fabric had no obvious antibacterial effect, while the antibacterial zone width of the six-membered stone / polyvinyl chloride fabric to S. aureus was 5.56±0.1 mm, and the antibacterial zone width to E. coli was 3.21±0.2 mm, which was much larger than the national standard, showing good antibacterial effect, and Staphylococcus aureus was more sensitive to the six-membered stone / polyvinyl chloride material), the air permeability was 338.88 mm / s, and the temperature rise value was 1.7℃.

[0133] Taking the palm length (from the wrist to the fingertips) as 12 cm, the width (the widest part) as 10 cm, and the finger length (from the palm root to the fingertips) as 7 cm as an example, the six-membered stone / polyvinyl chloride functional glove was prepared using the above six-membered stone / polyvinyl chloride functional fabric, and the specific process was as follows: first, the above six-membered stone / polyvinyl chloride functional fabric was cut according to the design layout as shown in Figure 6 , then the cut fabric was stacked along the thick dashed line, ensuring that the edges were aligned, then the sewing thread was used to sew along the thick solid line three times to ensure the firmness of the sewing, and finally the edge was locked along the thick solid line using the edge locking machine, and the six-membered stone / polyvinyl chloride glove was obtained; wherein the stitch distance was 1 mm.

[0134] The infrared thermal images of not wearing the six-membered stone / polyvinyl chloride functional glove, wearing the six-membered stone / polyvinyl chloride functional glove for 0.5 h and 1 h in the indoor and indoor constant temperature box were tested using the above prepared six-membered stone / polyvinyl chloride functional glove, and the results are shown in Figure 18 .

[0135] The test process in the room: under the condition that the indoor environment temperature is 20℃, after wearing the hexagonal stone / polyvinyl chloride gloves on the left hand and the pure polyvinyl chloride gloves on the right hand, the temperature of the fingers of the left hand and the right hand is respectively tested to be 34.6℃, as shown in Fig. 3a; then after wearing for 1h, the temperature of the fingers of the left hand and the right hand is respectively tested again, and it is found that the temperature of the fingers of the left hand is 0.6℃ higher than that of the right hand, and the temperature difference of the same point on the gloves is 0.5℃, as shown in Fig. 3b; finally, after taking off the gloves, the temperature of the left hand and the right hand is respectively measured, and it is found that the temperature of the fingers of the left hand is 0.9℃ higher than that of the right hand, and the temperature of the back of the left hand is 0.8℃ higher than that of the right hand, as shown in Fig. 3c, so it can be illustrated that the hexagonal stone / polyvinyl chloride functional gloves added with hexagonal stone have slightly better warmth retention; Figure 18 Figure 18 Figure 18

[0136] The test process in the room: under the condition that the indoor environment temperature is 20℃, after wearing the hexagonal stone / polyvinyl chloride gloves on the left hand and the pure polyvinyl chloride gloves on the right hand, the temperature of the fingers of the left hand and the right hand is respectively tested to be 34.6℃, as shown in Fig. 3a; then after wearing for 1h, the temperature of the fingers of the left hand and the right hand is respectively tested again, and it is found that the temperature of the fingers of the left hand is 0.6℃ higher than that of the right hand, and the temperature difference of the same point on the gloves is 0.5℃, as shown in Fig. 3b; finally, after taking off the gloves, the temperature of the left hand and the right hand is respectively measured, and it is found that the temperature of the fingers of the left hand is 0.9℃ higher than that of the right hand, and the temperature of the back of the left hand is 0.8℃ higher than that of the right hand, as shown in Fig. 3c, so it can be illustrated that the hexagonal stone / polyvinyl chloride functional gloves added with hexagonal stone have slightly better warmth retention; Figure 18 Figure 18

[0137] The test process in the room: under the condition that the indoor environment temperature is 20℃, after wearing the hexagonal stone / polyvinyl chloride gloves on the left hand and the pure polyvinyl chloride gloves on the right hand, the temperature of the fingers of the left hand and the right hand is respectively tested to be 34.6℃, as shown in Fig. 3a; then after wearing for 1h, the temperature of the fingers of the left hand and the right hand is respectively tested again, and it is found that the temperature of the fingers of the left hand is 0.6℃ higher than that of the right hand, and the temperature difference of the same point on the gloves is 0.5℃, as shown in Fig. 3b; finally, after taking off the gloves, the temperature of the left hand and the right hand is respectively measured, and it is found that the temperature of the fingers of the left hand is 0.9℃ higher than that of the right hand, and the temperature of the back of the left hand is 0.8℃ higher than that of the right hand, as shown in Fig. 3c, so it can be illustrated that the hexagonal stone / polyvinyl chloride functional gloves added with hexagonal stone have slightly better warmth retention;

[0138] Figure 19 Figure 19 Figure 19 Figure 19

[0139] ​​​​​​​​​​It can also be known through the above tests that the sixrings / polyvinyl chloride functional gloves added with sixrings have better heat preservation effect even at extremely low temperature outdoors.

[0140] Comparative Example 1

[0141] A preparation method of polyvinyl chloride functional fabric, which is basically the same as Example 1, except that steps (1)-(3) are not performed; in step (4), no micro-nano ultra-fine sixring particles are used, and dioctyl phthalate is directly added to DMF and stirred, then polyvinyl chloride is added and stirred uniformly, and then heated and stirred by a mechanical stirrer to obtain a polyvinyl chloride spinning solution;

[0142] The surface tension of the polyvinyl chloride spinning solution is 20.4 mN / m, and the viscosity is 316.5 mPa.S;

[0143] In steps (5)-(6), the polyvinyl chloride spinning solution prepared in Comparative Example 1 is used for spinning to obtain polyvinyl chloride filaments;

[0144] The linear density of the obtained polyvinyl chloride filaments is 46.5 dtex, the breaking strength is 15.56 cN, and the breaking elongation is 12.5%;

[0145] According to the far infrared emission mechanism, the internal vibration heat of the sixring / polyvinyl chloride filaments prepared in Comparative Example 1 and the polyvinyl chloride filaments prepared in Comparative Example 1 is compared, and the results are shown in Figure 17 As can be seen from the figure, the redox activity of Fe 3+ / Fe 2+ in the sixring particles cooperates with the catalytic action of Ti 4+ , and the high specific surface area of the nano-sized particles can significantly enhance the lattice vibration energy, drive the material molecules to transition from low energy state to high energy state (L1 path), and release energy through far infrared radiation (L2 path), greatly improving the heat conversion efficiency; the sixring / polyvinyl chloride filaments prepared in Example 1 can precisely match the human cell vibration frequency (8-15 μm) due to the introduction of sixrings, effectively promoting microcirculation and heat accumulation, and also verifying the core value of the mineral composite strategy in the development of high-efficiency far infrared functional textiles, providing theoretical support for the innovative design of intelligent health care materials;

[0146] The hexagonal stone / polyvinyl chloride filaments prepared in Example 1, the hexagonal stone particles and the polyvinyl chloride filaments prepared in Comparative Example 1 were tested by using a thermogravimetric-differential thermal analyzer (test conditions: test in O2 atmosphere, O2 flow rate: 200 mL / min, heating rate: 10 ℃ / min, heating range: 30-1000 ℃) according to GB / T 19466.3-2004 "Plastics-Differential Scanning Calorimetry (DSC)-Part 3: Determination of melting and crystallization temperatures and melting enthalpy", and the thermogravimetric curve as shown in Figure 12 Fig. 1 was obtained. As can be seen from the figure, in the process of thermal drawing, the drawing is carried out at a temperature close to or slightly higher than Tg, which can effectively promote the ordered arrangement of the polymer chains, so as to ensure that the drawing process can promote the straightening of the molecular chains and avoid excessive slipping between the molecular chains, so as to achieve the best drawing effect and obtain the ideal material properties. In addition, when the polyvinyl chloride filaments are used as a control group, the weight loss of the polyvinyl chloride filaments with the increase of the temperature can be observed, the weight loss rate is calculated, and finally the actual content of the micro-nano super-fine hexagonal stone particles is calculated to be 51.3 wt% according to the test results (because the micro-nano super-fine hexagonal stone particles are physically lost in the processes of flotation, spinning solution filtration and spinneret extrusion, which is a common problem in the industry, and the super-fine particles with a particle size of <1 μm are also easily lost with the supernatant due to Brownian motion in the flotation process, which is a controllable technical loss. Therefore, the micro-nano super-fine hexagonal stone particles in the final fiber will be lost.

[0147] The hexagonal stone / polyvinyl chloride filaments prepared in Example 1, the hexagonal stone particles and the polyvinyl chloride filaments prepared in Comparative Example 1 were characterized by using an infrared spectrometer in the range of 400-4000 cm -1 -1, and the results are shown in Figure 13 Fig. 2. As can be seen from the figure, the FT-IR spectrum of the hexagonal stone / polyvinyl chloride filaments has the characteristic absorption peaks of the hexagonal stone particles and the polyvinyl chloride filaments, and no new characteristic peak is present, which indicates that the hexagonal stone particles are loaded in the polyvinyl chloride filaments and the two are only a simple physical mixture without affecting the structures of each other.

[0148] In step (7), the hexagonal stone / polyvinyl chloride filaments are replaced by the polyvinyl chloride filaments of Comparative Example 1.

[0149] In step (8), the hexagonal stone / polyvinyl chloride yarn is replaced by the polyvinyl chloride yarn prepared in Comparative Example 1.

[0150] The finally prepared polyvinyl chloride functional fabric has the same structure as that of Example 1.

[0151] The negative ion release amount of the polyvinyl chloride functional fabric is 694 / cm 3 , the far infrared emissivity is 0.846, the antibacterial effect has no obvious bacteriostatic property, the air permeability is 306.67 mm / s, and the temperature rise value is 1.6 ℃.

[0152] A comparison of Comparative Example 1 and Example 1 reveals that the PVC fabric prepared in Comparative Example 1 exhibits decreased air permeability, negative ion release, antibacterial properties, far-infrared emissivity, and heat retention. This is because the surface of pure PVC filaments is smooth, resulting in small inter-fiber gaps and obstructed airflow. The addition of hexagonal stone particles increases the surface roughness of the fibers, creating micropores that effectively reduce airflow resistance, thereby improving the fabric's air permeability. Furthermore, the variable valence metals such as Fe and Ti contained in hexagonal stone can transform between their oxidation states, namely Fe(II) and Fe(III). In the natural environment, the iron element (Fe) in hexagonal stone can transform between the two oxidation states of Fe(II) and Fe(III), while the titanium (Ti) present within it... 4+ This process catalyzes the oxidation of oxygen and releases electrons. Simultaneously, hexagonal minerals possess a spontaneous polarization effect similar to tourmaline, creating a weak electric field on their surface or within their micropores. When water molecules (H₂O) from the air enter these micropores, they are electrolyzed under the influence of this weak electric field, decomposing into positively charged hydrogen ions (H₂O). + ) and negatively charged hydroxide ions (OH-) - Subsequently, the H produced by electrolysis + Electrons released from the iron oxidation reaction are captured and combined to form hydrogen gas (H2), which then escapes. Finally, the OH- produced by electrolysis... - It undergoes hydration with water molecules, combining to form stable negative oxygen ion clusters (H3O2). - These H2O2 - When diffused into the surrounding air, it forms negative air ions, giving the fabric the function of releasing negative ions, while its Fe... 2+ / Ti 4+ It can also destroy bacterial cell membranes through redox reactions, and the released negative ions interfere with bacterial metabolism. The two work synergistically to achieve antibacterial effects. However, in Comparative Example 1, due to the lack of hexagonal stone, the negative ion release and antibacterial properties of the PVC fabric were significantly reduced. In addition, the calcium carbonate crystals in hexagonal stone emit far-infrared rays efficiently through molecular vibration. In contrast, the molecular chain vibration frequency of pure PVC is low, the radiation ability is weak, and the far-infrared emissivity is low. Since far-infrared radiation can promote subcutaneous microcirculation and increase blood flow, and the static air layer formed by increasing fiber roughness reduces heat loss, it will also lead to a decrease in the heat preservation performance of PVC fabric.

[0153] Example 2

[0154] A method for preparing a hexagonal stone / polyvinyl chloride functional fabric, comprising the following steps:

[0155] (1) first, the small pieces of hexagonite with a diameter less than 0.5 cm are crushed by a crusher at a rotating speed of 3000 r / min for 5 min, and then the crushed hexagonite powder is ball milled by a ball mill at a rotating speed of 250 r / min for 5 h and then is placed for 0.5 h; wherein, the inclination angle of the crusher is 45°, and the ball-to-material ratio is 4:1 during the ball milling;

[0156] The average particle size of the hexagonite particles after the ball milling is 3.16 μm, and the proportion of the particle size less than 4 μm is 91.2%, and the maximum particle size is 22.67 μm;

[0157] (2) the hexagonite particles after the ball milling in step (1) are poured into a single-tank flotation machine, 1 L of distilled water is then added, and then stirred at a rotating speed of 2100 r / min for 1 h, and then is placed for 24 h and the supernatant is extracted by a syringe; wherein, the cleaning times is 4 times;

[0158] (3) after the cleaning in step (2), 1 L of deionized water is added into the single-tank flotation machine, and then stirred at a rotating speed of 2000 r / min for 8 min and then is placed for 20 min, after the sedimentation, the supernatant is extracted by a syringe and is placed in a drying oven to be dried at 80℃ for 48 h, and then is manually ground for 5 times by a mortar and pestle, and then the micro-nano super-fine hexagonite particles are obtained; wherein, the single manual grinding time is 15 min, and the manual grinding direction is alternately rotated clockwise and counterclockwise;

[0159] The particle size of the obtained micro-nano super-fine hexagonite particles is less than 3 μm, and the proportion of the particle size more than 2 μm is 0.5%, the proportion of the particle size between 1 μm and 2 μm is 3%, and the proportion of the particle size less than 1 μm is 96.5%;

[0160] (4) preparing hexagonite / polyvinyl chloride spinning solution;

[0161] The micro-nano super-fine hexagonite particles are dispersed into DMF by using a magnetic stirrer at a rotating speed of 500 r / min for 1 h, and then by using a high-speed homogenizer at a rotating speed of 12000 r / min for 20 min, and then by using an ultrasonic machine at a power of 90 W for 20 min, and then by using a magnetic stirrer at a rotating speed of 500 r / min for 36 h, and then dioctyl phthalate is added and stirred for 0.5 h, and then polyvinyl chloride is added and stirred uniformly by a glass rod, and then heated to 70℃ and stirred by a mechanical stirrer at a rotating speed of 500 r / min for 12 h to obtain hexagonite / polyvinyl chloride spinning solution with a concentration of 11.42 wt%; wherein, the amount of the micro-nano super-fine hexagonite particles is 40% based on the total mass of the micro-nano super-fine hexagonite particles and the polyvinyl chloride, and the mass ratio of the dioctyl phthalate to the polyvinyl chloride is 1:2;

[0162] As Figure 8As shown, the surface tension of the hexagonal stone / polyvinyl chloride spinning solution is 29.1 mN / m, and the viscosity is 435.7 mPa.S;

[0163] (5) The hexagonal stone / polyvinyl chloride spinning solution prepared in step (4) is injected into a spinning machine liquid storage tank for liquid storage and defoaming; wherein the liquid storage tank is kept at a constant temperature of 70°C, the defoaming pressure is 0.5 MPa, and the defoaming time is 15 min;

[0164] (6) The spinning solution after defoaming in step (5) is extruded from the spinneret to form a stream after metering by a metering pump, and the stream is then solidified into a primary fiber in a coagulation bath, and then the primary fiber is subjected to a sequence of "primary drawing, primary drying, secondary drawing, and secondary drying" for drawing and setting, and finally it is wound and naturally air-dried for 48 h to obtain hexagonal stone / polyvinyl chloride filaments; wherein the flow rate of the metering pump is 0.5 cc / min, the spinneret hole diameter is 0.1 mm, the number of holes is 30, the coagulation bath is distilled water, the temperature of the coagulation bath is 43.5°C, the primary drawing speed of the primary fiber is 4 m / min, and the secondary drawing speed is 12 m / min; the drawing temperature is 45°C, the primary drying temperature is 47.3°C, and the secondary drying temperature is 47.3°C; the line speed of the take-up roller during winding is 12 m / min, and the transverse spread rate is 700 m / min;

[0165] The linear density of the obtained hexagonal stone / polyvinyl chloride filaments is 45 dtex, as shown, the breaking strength is 12.86 cN, and the breaking elongation is 7.93%; Figure 10

[0166] (7) The hexagonal stone / polyvinyl chloride filaments obtained in step (6) are twisted by a digital sample spinning machine to obtain hexagonal stone / polyvinyl chloride yarns; wherein the spindle speed is 4000 rpm, the draw ratio is 1.200, and the twist direction is S;

[0167] The fineness of the obtained hexagonal stone / polyvinyl chloride yarns is 40 Tex, the breaking strength is 90 cN, and the twist is 200 twists / m;

[0168] (8) A polyester yarn (402 sewing thread) with a specification of 29.5 Tex is used as the warp yarn, and the hexagonal stone / polyvinyl chloride yarns prepared in step (7) are used as the weft yarn, and a sample weaving machine is used to weave the hexagonal stone / polyvinyl chloride functional fabric by the over-and-under method; wherein the reed number is 60, the heddle number is 1, and the heald frame number is 6.

[0169] The final hexagonal stone / polyvinyl chloride functional fabric is a plain weave with a warp density of 200 threads / 10 cm, a weft density of 280 threads / 10 cm, and a width of 20 cm;

[0170] The negative ion release amount of the hexagonal stone / polyvinyl chloride functional fabric is 980 / cm 3 ​, the far infrared emissivity is 0.890, the antibacterial effect is good, the air permeability is 338.55mm / s, and the temperature rise value is 1.2℃.

[0171] With the palm length (from the wrist to the fingertips) of 12 cm, the width (the widest part) of 10 cm, and the finger length (from the palm root to the fingertips) of 7 cm as an example, the above six-ring stone / polyvinyl chloride functional fabric is used to prepare a six-ring stone / polyvinyl chloride functional glove, and the specific process is as follows: first, the above six-ring stone / polyvinyl chloride functional fabric is cut according to the design layout as shown in Figure 6 , then the cut fabric is stacked along the thick dashed line, the edges are aligned, then the sewing thread is used to sew three times along the thick solid line by an industrial sewing machine to ensure the firmness of the sewing, and finally the edge is locked along the thick solid line by using a lock machine, and the six-ring stone / polyvinyl chloride glove is obtained; wherein the stitch distance is 1mm.

[0172] The temperature difference of the prepared six-ring stone / polyvinyl chloride glove before and after wearing for 1h in an indoor environment of 20℃ is 0.5℃, the temperature difference before and after wearing for 1h in a constant temperature box with a temperature of 5℃ is 2℃, and the temperature difference before and after wearing for 1h in an outdoor environment of-20℃ is 2.2℃.

[0173] Example 3

[0174] A preparation method of a six-ring stone / polyvinyl chloride functional fabric, comprising the following steps:

[0175] (1) first, the six-ring stone small pieces with a diameter of less than 0.5cm are crushed by a crusher at a speed of 3000r / min for 6min, then the crushed six-ring stone powder is ball milled by a ball mill at a speed of 250r / min for 6h, and then it is placed for 0.5h; wherein the inclination angle of the crusher is 45°, and the ball-to-material ratio during ball milling is 8:1;

[0176] The average particle size of the six-ring stone particles after ball milling is 2.35μm, and the proportion of particle size below 4μm is 98.1%, and the maximum particle size is 17.45μm;

[0177] (2) the six-ring stone particles after ball milling in step (1) are poured into a single-tank flotation machine, 1L of distilled water is added, then stirred at a speed of 2100r / min for 1h, then placed for 24h and the supernatant is extracted by a syringe; wherein the cleaning frequency is 5 times;

[0178] (3) After the cleaning in step (2), 1 L of deionized water was added to the single-tank flotation machine, and then stirred at a speed of 2200 r / min for 12 min and precipitated for 25 min. After the precipitation was completed, the supernatant was extracted using a syringe and placed in an oven for drying at 80℃ for 48 h. Then, the micro-nano ultra-fine hexagonal stone particles were obtained by manual grinding with a mortar and pestle for 6 times. The single manual grinding time was 15 min, and the manual grinding direction was alternately rotated clockwise and counterclockwise;

[0179] The particle size of the obtained micro-nano ultra-fine hexagonal stone particles was <3 μm, and the proportion of particle size >2 μm was 0.1%, the proportion of particle size 1-2 μm was 1.5%, and the proportion of particle size <1 μm was 98.4%;

[0180] (4) Preparation of hexagonal stone / polyvinyl chloride spinning solution;

[0181] The micro-nano ultra-fine hexagonal stone particles were dispersed in DMF by first stirring with a magnetic stirrer at a speed of 800 r / min for 2 h, then homogenized with a high-speed homogenizer at 18000 r / min for 40 min, then ultrasonicated with an ultrasonic machine at a power of 100 W for 40 min, and then stirred with a magnetic stirrer at a speed of 800 r / min for 60 h. Then, dioctyl phthalate was added and stirred for 2 h, then polyvinyl chloride was added and stirred uniformly with a glass rod, and then heated to 75℃ and stirred with a mechanical stirrer at a speed of 600 r / min for 24 h to obtain a hexagonal stone / polyvinyl chloride spinning solution with a concentration of 13.88 wt%. The amount of micro-nano ultra-fine hexagonal stone particles was 50% based on the total mass of micro-nano ultra-fine hexagonal stone particles and polyvinyl chloride, and the mass ratio of dioctyl phthalate to polyvinyl chloride was 1:2;

[0182] As shown in Figure 8 , the surface tension of the hexagonal stone / polyvinyl chloride spinning solution was 30.6 mN / m, and the viscosity was 513.3 mPa.S;

[0183] (5) The hexagonal stone / polyvinyl chloride spinning solution prepared in step (4) was injected into the spinning machine liquid tank for liquid storage and defoaming; wherein the liquid tank was kept at a constant temperature of 75℃, the defoaming pressure was 0.8 MPa, and the defoaming time was 30 min;

[0184] (6) the spinning solution after defoaming in step (5) is metered by a metering pump and then extruded from a spinneret to form a stream, the stream is then solidified into a primary fiber in a coagulation bath, and then the primary fiber is subjected to the sequence of "primary drawing, primary drying, secondary drawing, secondary drying", and finally the primary fiber is wound and naturally dried for 48 h to obtain the six-membered ring stone / polyvinyl chloride filament; wherein the flow rate of the metering pump is 1 cc / min, the spinneret hole diameter is 0.2 mm, the number of holes is 50, the coagulation bath is distilled water, the temperature of the coagulation bath is 44.5℃, the primary drawing speed of the primary fiber is 6 m / min, and the secondary drawing speed is 15 m / min; the drawing temperature is 50℃, the primary drying temperature is 47.3℃, and the secondary drying temperature is 47.3℃; the wire speed of the take-up roller during winding is 15 m / min, and the transverse spread rate is 800 m / min;

[0185] The linear density of the obtained six-membered ring stone / polyvinyl chloride filament is 100 dtex, the breaking strength is 11.25 cN, and the elongation at break is 7.38% as shown in Figure 10

[0186] (7) the six-membered ring stone / polyvinyl chloride filament obtained in step (6) is twisted by a digital sample spinning machine to obtain a six-membered ring stone / polyvinyl chloride yarn; wherein the spindle speed is 4000 rpm, the draft ratio is 1.200, and the twist direction is S;

[0187] The fineness of the obtained six-membered ring stone / polyvinyl chloride yarn is 70 Tex, the breaking strength is 114 cN, and the twist is 1000 twists / m;

[0188] (8) a polyester yarn (402 sewing thread) with a specification of 29.5 Tex is used as the warp yarn, and the six-membered ring stone / polyvinyl chloride yarn obtained in step (7) is used as the weft yarn, and a sample weaving machine is used to weave the six-membered ring stone / polyvinyl chloride functional fabric by the overcasting method; wherein the reed number is 60, the heddle number is 1, and the harness frame number is 6.

[0189] The final six-membered ring stone / polyvinyl chloride functional fabric is a plain weave with a warp density of 200 / 10 cm, a weft density of 280 / 10 cm, and a width of 20 cm;

[0190] The six-membered ring stone / polyvinyl chloride functional fabric has a negative ion release amount of 1005 / cm 3 , a far infrared emissivity of 0.92, good antibacterial effect, a ventilation of 328.76 mm / s, and a temperature rise of 1.5℃.

[0191] ​With the palm length (from the wrist to the fingertips) of 12 cm, the width (the widest part) of 10 cm, and the finger length (from the palm root to the fingertips) of 7 cm as an example, the above six-ring stone / polyvinyl chloride functional fabric is used to prepare a six-ring stone / polyvinyl chloride functional glove, and the specific process is as follows: first, the above six-ring stone / polyvinyl chloride functional fabric is cut according to the design layout as shown in Figure 6 , then the cut fabric is stacked along the thick dashed line, the edges are aligned, and then the fabric is sewn along the thick solid line three times by using a sewing machine to ensure the firmness of the sewing, and finally, the edge of the fabric is locked along the thick solid line by using a lock machine, and then a six-ring stone / polyvinyl chloride glove is prepared; wherein the stitch distance is 1 mm.

[0192] The temperature difference of the prepared six-ring stone / polyvinyl chloride glove before and after wearing for 1 h in an indoor environment of 20℃ is 0.7℃, the temperature difference before and after wearing for 1 h in a constant temperature box with a temperature of 5℃ is 3℃, and the temperature difference before and after wearing for 1 h in an outdoor environment of -20℃ is 3.1℃.

[0193] Example 4

[0194] A preparation method of a six-ring stone / polyvinyl chloride functional fabric, and the steps are as follows:

[0195] (1) First, the small pieces of six-ring stone with a diameter of less than 0.5 cm are crushed by a crusher at a speed of 3000 r / min for 4 min, and then the crushed six-ring stone powder is ball milled by a ball mill at a speed of 250 r / min for 7 h and then is placed for 0.5 h; wherein the inclination angle of the crusher is 45°, and the ball-to-material ratio during ball milling is 5:1;

[0196] The average particle size of the six-ring stone particles after ball milling is 3.5 μm, and the proportion of particle sizes less than 4 μm is 92.3%, and the maximum particle size is 25.12 μm;

[0197] (2) The six-ring stone particles after ball milling in step (1) are poured into a single-tank flotation machine, 1 L of distilled water is added, then stirred at a speed of 2100 r / min for 1 h, then placed for 24 h, and the supernatant is extracted by a syringe; wherein the cleaning frequency is 3 times;

[0198] (3) After cleaning in step (2), 1 L of deionized water is added to the single-tank flotation machine, then stirred at a speed of 2100 r / min for 10 min, and then precipitated for 20 min, after the precipitation is completed, the supernatant is extracted by a syringe, and then placed in a drying oven for drying at 80℃ for 48 h, then manually ground for 4 times by using a mortar and pestle, and then micro-nano ultra-fine six-ring stone particles are obtained; wherein the single manual grinding time is 15 min, and the manual grinding direction is alternately rotated clockwise and counterclockwise;

[0199] The particle size of the obtained micro-nano super-fine hexagonal stone particles is <3 μm, and the proportion of particle size >2 μm is 0.4%, the proportion of particle size 1-2 μm is 2.8%, and the proportion of particle size <1 μm is 96.8%;

[0200] (4) preparing hexagonal stone / polyvinyl chloride spinning solution;

[0201] The micro-nano super-fine hexagonal stone particles are dispersed in DMF, first using a magnetic stirrer to stir at a speed of 600 r / min for 1.5 h, then using a high-speed homogenizer to homogenize at 15000 r / min for 30 min, then using an ultrasonic machine to ultrasonic at a power of 80 W for 30 min, and then using a magnetic stirrer to stir at a speed of 600 r / min for 48 h. Then, dioctyl phthalate is added and stirred for 1 h. Then, polyvinyl chloride is added and stirred uniformly with a glass rod. Then, the temperature is raised to 70°C, and the mixture is stirred at a speed of 400 r / min for 18 h to obtain a hexagonal stone / polyvinyl chloride spinning solution with a concentration of 8.32 wt%. In this process, the amount of micro-nano super-fine hexagonal stone particles is 30% based on the total mass of micro-nano super-fine hexagonal stone particles and polyvinyl chloride, and the mass ratio of dioctyl phthalate to polyvinyl chloride is 1:2.

[0202] As shown in Figure 8 , the surface tension of the hexagonal stone / polyvinyl chloride spinning solution is 27.4 mN / m, and the viscosity is 385.3 mPa.S.

[0203] (5) The hexagonal stone / polyvinyl chloride spinning solution prepared in step (4) is injected into a spinning machine liquid storage tank for liquid storage and defoaming. The liquid storage tank is kept at a constant temperature of 70°C, the defoaming pressure is 0.6 MPa, and the defoaming time is 20 min.

[0204] (6) The spinning solution after defoaming in step (5) is metered by a metering pump and then extruded from the spinneret hole to form a fine stream. The fine stream is then solidified into a primary fiber in a coagulation bath. Then, the primary fiber is subjected to a sequence of "primary drawing, primary drying, secondary drawing, and secondary drying" for drawing and setting. Finally, the primary fiber is wound and naturally air-dried for 48 h to obtain a hexagonal stone / polyvinyl chloride filament. In this process, the flow rate of the metering pump is 0.75 cc / min, the spinneret hole diameter is 0.15 mm, the number of holes is 40, the coagulation bath is distilled water, the temperature of the coagulation bath is 42.2°C, the primary drawing speed of the primary fiber is 5 m / min, the secondary drawing speed is 13 m / min, the drawing temperature is 47°C, the primary drying temperature is 47.3°C, the secondary drying temperature is 47.3°C, the line speed of the take-up roller during winding is 13 m / min, and the transverse spread rate is 750 m / min.

[0205] The linear density of the obtained hexagonal stone / polyvinyl chloride filament is 60 dtex, as shown in Figure 10The breaking strength is 15.12 cN, and the elongation at break is 8.63%;

[0206] (7) The hexagonal stone / polyvinyl chloride filaments obtained in step (6) are parallel-wound and twisted by using a digital small sample spinning machine to obtain hexagonal stone / polyvinyl chloride yarn; wherein the spindle speed is 4000 rpm, the draft ratio is 1.200, and the twist direction is S;

[0207] The fineness of the obtained hexagonal stone / polyvinyl chloride yarn is 50 Tex, the breaking strength is 100 cN, and the twist is 500 twists / m;

[0208] (8) The hexagonal stone / polyvinyl chloride functional fabric is obtained by weaving the hexagonal stone / polyvinyl chloride yarn prepared in step (7) as weft yarn and the polyester yarn (402 sewing thread) with a specification of 29.5 Tex as warp yarn by using a small sample weaving machine in a straight-through manner; wherein the reed number is 60, the heddle number is 1, and the heald frame number is 6.

[0209] The final hexagonal stone / polyvinyl chloride functional fabric has a plain weave, a warp density of 200 roots / 10 cm, a weft density of 280 roots / 10 cm, and a width of 20 cm;

[0210] The hexagonal stone / polyvinyl chloride functional fabric has a negative ion release amount of 950 / cm 3 , a far-infrared emissivity of 0.902, good antibacterial effect, a ventilation of 327.74 mm / s, and a temperature rise value of 1℃.

[0211] Taking the palm length (from the wrist to the fingertips) as 12 cm, the width (the widest part) as 10 cm, and the finger length (from the palm root to the fingertips) as 7 cm as an example, the hexagonal stone / polyvinyl chloride functional glove is prepared from the above hexagonal stone / polyvinyl chloride functional fabric, and the specific process is as follows: first, the above hexagonal stone / polyvinyl chloride functional fabric is cut according to the design pattern as shown in Figure 6 , then the cut fabric is stacked along the thick dashed line, ensuring that the edges are aligned, then the sewing thread is used to sew three times along the thick solid line by using an industrial sewing machine to ensure the firmness of the sewing, and finally, the edge is locked along the thick solid line by using a lock machine, and the hexagonal stone / polyvinyl chloride glove is obtained; wherein the stitch distance is 1 mm.

[0212] The temperature difference of the obtained hexagonal stone / polyvinyl chloride glove before and after wearing for 1 h in an indoor environment of 20℃ is 0.2℃, the temperature difference before and after wearing for 1 h in a constant temperature box with a temperature of 5℃ is 0.6℃, and the temperature difference before and after wearing for 1 h in an outdoor environment of -20℃ is 0.8℃.

[0213] Example 5

[0214] A preparation method of a hexagonal stone / polyvinyl chloride functional fabric, the steps are as follows:

[0215] (1) first use a crusher to crush the small pieces of hexagonite with a diameter less than 0.5 cm at a speed of 3000 r / min for 5 min, and then use a ball mill to ball mill the crushed hexagonite powder at a speed of 280 r / min for 8 h and then stand for 0.5 h; wherein the inclination angle of the crusher is 45°, and the ball-to-material ratio during ball milling is 7:1;

[0216] The average particle size of the ball-milled hexagonite particles is 2.36 μm, and the proportion of particle size less than 4 μm is 96.8%, and the maximum particle size is 18.68 μm;

[0217] (2) pour the ball-milled hexagonite particles in step (1) into a single-tank flotation machine, then add 1 L of distilled water, then stir at a speed of 2100 r / min for 1 h, then stand for 24 h and use a syringe to extract the supernatant; wherein the number of cleaning times is 4;

[0218] (3) after cleaning in step (2), add 1 L of deionized water to the single-tank flotation machine, then stir at a speed of 2000 r / min for 8 min and then precipitate for 25 min, after the precipitation is completed, use a syringe to extract the supernatant, and place it in a drying oven to dry at 80℃ for 48 h, then continue to manually grind 5 times using a mortar and pestle, to obtain micro-nano ultra-fine hexagonite particles; wherein the single manual grinding time is 15 min, and the manual grinding direction alternates clockwise and counterclockwise rotation;

[0219] The particle size of the obtained micro-nano ultra-fine hexagonite particles is <3 μm, and the proportion of particle size >2 μm is 0.2%, the proportion of particle size 1-2 μm is 1.8%, and the proportion of particle size <1 μm is 98%;

[0220] (4) prepare hexagonite / polyvinyl chloride spinning solution;

[0221] Disperse the micro-nano ultra-fine hexagonite particles into DMF using a magnetic stirrer at a speed of 700 r / min for 2 h, then use a high-speed homogenizer at a speed of 16000 r / min for 35 min, then use an ultrasonic machine at a power of 90 W for 35 min, then use a magnetic stirrer at a speed of 700 r / min for 50 h, then add dioctyl phthalate, continue to stir for 1.5 h, then add polyvinyl chloride and stir uniformly using a glass rod, then heat to 72℃ and stir at a speed of 500 r / min for 20 h using a mechanical stirrer to obtain a hexagonite / polyvinyl chloride spinning solution with a concentration of 18.92 wt%; wherein, based on the total mass of the micro-nano ultra-fine hexagonite particles and the polyvinyl chloride, the amount of the micro-nano ultra-fine hexagonite particles is 70%, and the mass ratio of dioctyl phthalate to polyvinyl chloride is 1:2;

[0222] AsFigure 8 As shown in the figure, the surface tension of the hexagonal stone / polyvinyl chloride spinning solution is 32.8 mN / m, and the viscosity is 1424.5 mPa.S;

[0223] (5) The hexagonal stone / polyvinyl chloride spinning solution prepared in step (4) is injected into a spinning machine liquid storage tank for liquid storage and defoaming; wherein the liquid storage tank is kept at a constant temperature of 72°C, the defoaming pressure is 0.7 MPa, and the defoaming time is 25 min;

[0224] (6) The spinning solution after defoaming in step (5) is extruded from the spinneret to form a stream after metering by a metering pump, and the stream is then solidified into a primary fiber in a coagulation bath, and then the primary fiber is subjected to a sequence of "primary drawing, primary drying, secondary drawing, and secondary drying" for drawing and setting, and finally it is wound and naturally air-dried for 48 h to obtain hexagonal stone / polyvinyl chloride filaments; wherein the flow rate of the metering pump is 0.9 cc / min, the spinneret hole diameter is 0.18 mm, the number of holes is 45, the coagulation bath is distilled water, the temperature of the coagulation bath is 45°C, the primary drawing speed of the primary fiber is 5.5 m / min, and the secondary drawing speed is 14 m / min; the drawing temperature is 48°C, the primary drying temperature is 47.3°C, and the secondary drying temperature is 47.3°C; the line speed of the take-up roller during winding is 14 m / min, and the transverse spread rate is 780 m / min;

[0225] The linear density of the obtained hexagonal stone / polyvinyl chloride filaments is 80 dtex, as shown in the figure, the breaking strength is 4.3 cN, and the breaking elongation is 3.47%; Figure 10

[0226] (7) The hexagonal stone / polyvinyl chloride filaments obtained in step (6) are twisted by a digital sample spinning machine to obtain hexagonal stone / polyvinyl chloride yarns; wherein the spindle speed is 4000 revolutions / min, the draw ratio is 1.200, and the twist direction is S;

[0227] The fineness of the obtained hexagonal stone / polyvinyl chloride yarns is 60 Tex, the breaking strength is 110 cN, and the twist is 800 twists / m;

[0228] (8) A polyester yarn (402 sewing thread) with a specification of 29.5 Tex is used as the warp yarn, and the hexagonal stone / polyvinyl chloride yarns prepared in step (7) are used as the weft yarn, and a sample weaving machine is used to weave hexagonal stone / polyvinyl chloride functional fabric by the forward weaving method; wherein the reed number is 60, the heddle number is 1, and the heald frame number is 6.

[0229] The final hexagonal stone / polyvinyl chloride functional fabric is plain weave, the warp density is 200 roots / 10 cm, the weft density is 280 roots / 10 cm, and the width is 20 cm;

[0230] The negative ion release amount of the hexagonal stone / polyvinyl chloride functional fabric is 1120 / cm​3 The far infrared emissivity is 0.91, the antibacterial effect is good, the air permeability is 338.56 mm / s, and the temperature rise value is 2°C.

[0231] For example, taking the palm length (from the wrist to the fingertips) as 12 cm, the width (the widest part) as 10 cm, and the finger length (from the palm root to the fingertips) as 7 cm, the above six-ring stone / polyvinyl chloride functional fabric is used to prepare a six-ring stone / polyvinyl chloride functional glove. The specific process is as follows: first, the above six-ring stone / polyvinyl chloride functional fabric is cut according to the design layout as shown in Figure 6 , then the cut fabric is stacked along the thick dashed line, ensuring that the edges are aligned, then the sewing thread is used to sew three times along the thick solid line by an industrial sewing machine to ensure the firmness of the sewing, and finally the edge is locked along the thick solid line using a lock machine, and a six-ring stone / polyvinyl chloride glove is obtained; wherein the stitch distance is 1 mm.

[0232] The temperature difference of the prepared six-ring stone / polyvinyl chloride glove before and after wearing for 1 h in an indoor environment of 20°C is 0.8°C, the temperature difference before and after wearing for 1 h in a constant temperature box with a temperature of 5°C is 2.8°C, and the temperature difference before and after wearing for 1 h in an outdoor environment of -20°C is 3.2°C.

[0233] Example 6

[0234] A method for preparing a six-ring stone / polyvinyl chloride functional fabric, comprising the following steps:

[0235] (1) First, the six-ring stone pieces with a diameter of less than 0.5 cm are crushed at a speed of 3000 r / min for 5 min using a crusher, and then the crushed six-ring stone powder is ball milled at a speed of 250 r / min for 6 h using a ball mill, and then it is left to stand for 0.5 h; wherein the inclination angle of the crusher is 45°, and the ball-to-material ratio during ball milling is 10:1;

[0236] The average particle size of the six-ring stone particles after ball milling is 2.34 μm, and the proportion of particle sizes less than 4 μm is 97.5%, and the maximum particle size is 20.96 μm;

[0237] (2) Pour the six-ring stone particles after ball milling in step (1) into a single-tank flotation machine, then add 1 L of distilled water, then stir at a speed of 2100 r / min for 1 h, then stand for 24 h and extract the supernatant with a syringe; wherein the cleaning frequency is 5 times;

[0238] (3) After cleaning in step (2), 1L of deionized water was added to the single-tank flotation machine, then stirred at 2200r / min for 12min and precipitated for 30min, after the precipitation was completed, the supernatant was extracted using a syringe and placed in an oven for drying at 80℃ for 48h, then the mortar and pestle were used for manual grinding for 5 times, and the micro-nano ultra-fine six-ring stone particles were obtained; wherein, the single manual grinding time was 15min, and the manual grinding direction was clockwise and counterclockwise rotation alternately;

[0239] The particle size of the obtained micro-nano ultra-fine six-ring stone particles was <3μm, and the proportion of particle size >2μm was 0.3%, the proportion of particle size 1-2μm was 2.5%, and the proportion of particle size <1μm was 97.2%;

[0240] (4) Preparation of six-ring stone / polyvinyl chloride spinning solution;

[0241] The micro-nano ultra-fine six-ring stone particles were dispersed in DMF, first using a magnetic stirrer at a speed of 600r / min for 1h, then using a high-speed homogenizer at a speed of 14000r / min for 25min, then using an ultrasonic machine at a power of 100W for 25min, then using a magnetic stirrer at a speed of 600r / min for 42h, then adding dioctyl phthalate, continuing to stir for 0.5h, then adding polyvinyl chloride and stirring uniformly using a glass rod, then heating to 73℃ and stirring at a speed of 600r / min for 16h using a mechanical stirrer to obtain a six-ring stone / polyvinyl chloride spinning solution with a concentration of 18.92wt%; wherein, based on the total mass of the micro-nano ultra-fine six-ring stone particles and the polyvinyl chloride, the amount of the micro-nano ultra-fine six-ring stone particles was 55%, and the mass ratio of dioctyl phthalate to polyvinyl chloride was 1:2;

[0242] The surface tension of the six-ring stone / polyvinyl chloride spinning solution was 31.2mN / m, and the viscosity was 1424.5mPa.S;

[0243] (5) The six-ring stone / polyvinyl chloride spinning solution prepared in step (4) was injected into the spinning machine liquid storage tank for liquid storage and defoaming; wherein, the liquid storage tank was constant temperature at 73℃, the defoaming pressure was 0.55MPa, and the defoaming time was 18min;

[0244] (6) the spinning solution after defoaming in step (5) is metered by a metering pump and then extruded from a spinneret to form a stream, the stream is then solidified into a primary fiber in a coagulation bath, and then the primary fiber is subjected to "primary drawing, primary drying, secondary drawing, secondary drying" in sequence to be drawn and set, and finally it is wound and naturally dried for 48 h to obtain the six-membered ring stone / polyvinyl chloride filament; wherein the flow rate of the metering pump is 0.6 cc / min, the spinneret hole diameter is 0.12 mm, the number of holes is 35, the coagulation bath is distilled water, the temperature of the coagulation bath is 50°C, the primary drawing speed of the primary fiber is 4.5 m / min, and the secondary drawing speed is 12.5 m / min; the drawing temperature is 46°C, the primary drying temperature is 47.3°C, and the secondary drying temperature is 47.3°C; the wire speed of the take-up roller during winding is 12.5 m / min, and the transverse spread rate is 720 m / min;

[0245] The linear density of the obtained six-membered ring stone / polyvinyl chloride filament is 55 dtex, the breaking strength is 10.89 cN, and the breaking elongation is 6.88%;

[0246] (7) the six-membered ring stone / polyvinyl chloride filament obtained in step (6) is twisted by a digital sample spinning machine to obtain a six-membered ring stone / polyvinyl chloride yarn; wherein the spindle speed is 4000 rpm, the draft ratio is 1.200, and the twist direction is S;

[0247] The fineness of the obtained six-membered ring stone / polyvinyl chloride yarn is 45 Tex, the breaking strength is 95 cN, and the twist is 300 twists / m;

[0248] (8) a polyester yarn (402 sewing thread) with a specification of 29.5 Tex is used as the warp yarn, and the six-membered ring stone / polyvinyl chloride yarn prepared in step (7) is used as the weft yarn, and a sample weaving machine is used to weave the six-membered ring stone / polyvinyl chloride functional fabric by the over-and-under method; wherein the reed number is 60, the heddle number is 1, and the harness frame number is 6.

[0249] The final six-membered ring stone / polyvinyl chloride functional fabric is a plain weave with a warp density of 200 threads / 10 cm, a weft density of 280 threads / 10 cm, and a width of 20 cm;

[0250] The six-membered ring stone / polyvinyl chloride functional fabric has a negative ion release amount of 1075 / cm 3 , a far infrared emissivity of 0.932, good antibacterial effect, a ventilation of 330.56 mm / s, and a temperature rise of 1.5°C.

[0251] Taking the palm length (from the wrist to the fingertips) as 12 cm, the width (the widest part) as 10 cm, and the finger length (from the base of the palm to the fingertips) as 7 cm as an example, the six-membered ring stone / polyvinyl chloride functional glove is prepared using the above six-membered ring stone / polyvinyl chloride functional fabric, and the specific process is as follows:Figure 6 The design layout shown is cut, and the cut fabric is stacked along the thick dashed line, ensuring that the edges are aligned, and then sewn three times along the thick solid line using a sewing machine to ensure the firmness of the sewing, and finally, the edge is locked along the thick solid line using a lock machine to obtain the opal / polyvinyl chloride glove; wherein the stitch distance is 1 mm.

[0252] The temperature difference of the opal / polyvinyl chloride glove obtained before and after wearing for 1 h in an indoor environment of 20℃ is 0.8℃, the temperature difference before and after wearing for 1 h in a thermostat with a temperature of 5℃ is 3.1℃, and the temperature difference before and after wearing for 1 h in an outdoor environment of-20℃ is 3.5℃.

Claims

1. A method for preparing micro / nano-scale ultrafine hexagonal quartz particles, characterized in that: The micro-nano super-fine hexagonite particles are obtained by screening the hexagonite particles which are sequentially subjected to ball milling and cleaning through a flotation process. The particle size of the micro-nano super-fine hexagonite particles is less than 3 microns, and the proportion of the particle size greater than 2 microns is 0.1% to 0.5%, the proportion of the particle size of 1 to 2 microns is 1.5% to 3.0%, and the proportion of the particle size less than 1 micron is 96.5% to 98.5%. The process parameters of the flotation are as follows: the rotating speed of the turbine blade of the flotation machine is 2000 to 2200 r / min, the stirring time is 8 to 12 minutes, and the sedimentation time is 20 to 30 minutes.

2. The method according to claim 1, wherein the method is characterized by, The ball-to-material ratio during the ball milling is 4 to 10:1, the rotating speed of the ball miller is 200 to 300 r / min, and the ball milling time is 4 to 8 hours.

3. The method according to claim 1, wherein the method is characterized by, The average particle size of the hexagonite particles after the ball milling is less than 4 microns, and the proportion of the particle size less than 4 microns is greater than or equal to 90%, and the maximum particle size is less than 30 microns.

4. A method for producing a hexacyclic / polyvinyl chloride functional fabric, characterized by: Firstly, the hexagonite / polyvinyl chloride spinning solution is prepared, then the hexagonite / polyvinyl chloride filament is prepared by using the hexagonite / polyvinyl chloride spinning solution through a wet spinning process, the hexagonite / polyvinyl chloride filament is subjected to a spinning process to obtain the hexagonite / polyvinyl chloride yarn, and finally the hexagonite / polyvinyl chloride yarn is woven to obtain the hexagonite / polyvinyl chloride functional fabric. The preparation method of the hexagonite / polyvinyl chloride spinning solution is as follows: the micro-nano super-fine hexagonite particles are dispersed into an organic solvent, first stirred by using a magnetic stirrer at a rotating speed of 500 to 800 r / min for 1 to 2 hours, then homogenized by using a high-speed homogenizer at a rotating speed of 12000 to 18000 r / min for 20 to 40 minutes, then ultrasonically treated by using an ultrasonic machine for 20 to 40 minutes, then continuously stirred for 36 to 60 hours, then added with dioctyl phthalate, continuously stirred for 0.5 to 2 hours, then added with polyvinyl chloride, heated to 70 to 75℃, and stirred for 12 to 24 hours to obtain the hexagonite / polyvinyl chloride spinning solution. The particle size of the micro-nano super-fine hexagonite particles is less than 3 microns, and the proportion of the particle size greater than 2 microns is 0.1% to 0.5%, the proportion of the particle size of 1 to 2 microns is 1.5% to 3.0%, and the proportion of the particle size less than 1 micron is 96.5% to 98.5%. The amount of the micro-nano super-fine hexagonite particles is 30% to 70% based on the total mass of the micro-nano super-fine hexagonite particles and the polyvinyl chloride.

5. The method for preparing a hexagonal stone / polyvinyl chloride functional fabric according to claim 4, characterized in that, The concentration of the spinning solution is 8.32 to 18.92 wt%, and the mass ratio of the dioctyl phthalate to the polyvinyl chloride is 1:

2.

6. The method for preparing a hexagonal stone / polyvinyl chloride functional fabric according to claim 4, characterized in that, The process flow of the wet spinning is as follows: the spinning solution is metered by a metering pump, then extruded from a spinneret hole to form a stream, then the stream is solidified into a primary fiber in a coagulation bath, and finally the primary fiber is sequentially subjected to drafting, setting and winding; the main process parameters are as follows: The temperature of the liquid storage tank is 70 to 75℃, the defoaming pressure is 0.5 to 0.8 MPa, and the defoaming time is 15 to 30 minutes; The flow rate of the metering pump is 0.5 to 1.0 cc / min; The spinneret hole diameter is 0.10 to 0.20 mm, and the number of holes is 30 to 50 holes; The coagulation bath is distilled water, and the temperature of the coagulation bath is 41.3 to 50℃; The primary fiber drafting speed is 4 to 6 m / min, and the secondary drafting speed is 12 to 15 m / min; and the drafting temperature is 45 to 50℃. The winding speed of the take-up roller is 12-15 m / min, and the transverse spreading speed is 700-800 m / min.

7. The method for preparing a hexagonal stone / polyvinyl chloride functional fabric according to claim 6, characterized in that, The linear density of the hexagonite / polyvinyl chloride filament is 45-100 dtex, the breaking strength is 4-30 cN, and the breaking elongation is 5-10%.

8. The method for preparing a hexagonal stone / polyvinyl chloride functional fabric according to claim 4, characterized in that, The fineness of the hexagonite / polyvinyl chloride yarn is 40-70 Tex, the breaking strength is 90-114 cN, and the twist is 200-1000 twists / m.

9. The method for preparing a hexagonal stone / polyvinyl chloride functional fabric according to claim 4, characterized in that, The hexagonite / polyvinyl chloride functional fabric is in plain weave, the warp yarn is 29.5 Tex polyester yarn, the weft yarn is 40-70 Tex hexagonite / polyvinyl chloride yarn, the warp density is 200 per 10 cm, and the weft density is 280 per 10 cm.

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