CN115197470A

CN115197470A - Pearl powder-containing multifunctional master batch, pearl powder-containing multifunctional fiber and preparation method of pearl powder-containing multifunctional master batch and pearl powder-containing multifunctional fiber

Info

Publication number: CN115197470A
Application number: CN202210722781.XA
Authority: CN
Inventors: 张兴光; 胡乐程; 鄢军; 王威
Original assignee: Aseptic Era Composite New Materials Suzhou Co ltd
Current assignee: Aseptic Era Composite New Materials Suzhou Co ltd
Priority date: 2022-06-24
Filing date: 2022-06-24
Publication date: 2022-10-18

Abstract

The invention discloses a pearl powder-containing multifunctional master batch, a pearl powder-containing multifunctional master batch fiber and a preparation method of the pearl powder-containing multifunctional master batch fiber. The pearl powder-containing multifunctional master batch comprises the following raw materials in parts by weight: 50-80 parts of matrix resin, 10-40 parts of pearl powder, 5-10 parts of porous carbon material, 1-5 parts of phase change material, 0.0001-0.0005 part of heat stabilizer, 0.5-3 parts of binder and 1-3 parts of dispersant, wherein the absolute dry mass parts of the raw materials are 100 parts.

Description

Pearl powder-containing multifunctional master batch, pearl powder-containing multifunctional fiber and preparation method of pearl powder-containing multifunctional master batch and pearl powder-containing multifunctional fiber

Technical Field

The invention belongs to the technical field of functional materials, and particularly relates to a pearl powder-containing multifunctional master batch, a pearl powder-containing multifunctional master batch fiber and a preparation method of the pearl powder-containing multifunctional master batch fiber.

Background

According to GB/T36930-2018, pearl powder is a powdery substance which is formed by mechanically processing pearls. The Chinese pharmacopoeia, ben Cao gang mu, and Chinese pharmacopoeia, etc. describe the efficacy of pearl powder. The pearl powder contains more than 90 percent of aragonite calcium carbonate, more than 20 amino acids, more than 30 trace elements and other substances, and can be widely applied to the fields of medicines and cosmetics such as oral administration or external application and the like. The pearl master batch is a mixture which is prepared by uniformly mixing micro-nano pearl powder, matrix resin, dispersing auxiliary agent and the like according to a certain mass ratio and uniformly dispersing the pearl powder in the matrix resin through melting processing. During spinning, the pearl master batches with a certain mass ratio are uniformly added into matrix resin, and the obtained fiber is called pearl fiber.

The cellulose fiber has excellent skin-friendly performance, and the addition of the pearl powder endows the cellulose fiber with additional active calcium, amino acid and various trace elements. The Donghua university and the novel Shanghai spinning center cooperate together, and the ultra-fining technology is applied to the novel viscose fiber for the first time in 200410067962.5 applied in 2004, so that the sequence chapter of the pearl fiber is opened. When people wear the fabric made of the pearl fibers, the pearl necklace is worn on the skin as if the pearl necklace is worn on the skin, natural elements beneficial to the human body are released in a micro and slow manner through the sliding friction between the fabric and the skin, and the pearl necklace can remove hot pox viruses on the surface of the skin and has the health-care functions of removing freckles, beautifying and protecting the skin, calming the nerves and arresting convulsion and delaying senility. In contrast, chemical fibers have the problems of poor serviceability, poor thermal comfort and the like during use, and are particularly obvious in underwear.

The micro-nano pearl powder is applied to the field of chemical fibers, so that the chemical fibers have excellent skin-friendly performance, the smoothness, the flexibility and the hygroscopicity of the fibers are improved, the performances of wrinkle resistance, dyeing and the like are further improved, and the application prospect is extremely wide. Downstream products of pearl fiber include: civil clothing, such as underwear, thermal clothing, underwear, and socks; the clothes such as jeans, western-style clothes and the like with poor comfort are used; infant products. Household textiles, for example: bed sheets, quilt covers, pillow cases, home wear, pajamas, etc.; the quilt is filled with short fibers, flocculus and the like; skin-friendly sleeping bag. Other textiles, such as accessories or medical masks.

Through the research of documents and related technical data, some enterprises, experts and the like have already made related researches on the aspects of developing pearl master batches, fibers and the like, and the specific steps are as follows:

1. application No.: CN 201410022954.2; the name is as follows: pearl yarn. The preparation method of the pearl yarn comprises the following steps: preparing a pearl powder aqueous solution, wherein the content of pearl powder is 25% of the total mass, the water content is 75% of the total mass, and grinding the pearl powder into water to obtain the pearl powder aqueous solution; mixing caprolactam with the pearl powder aqueous solution, and then adding carboxylic acid, ammonia, 6-aminocaproic acid and nylon monomer salt for polymerization; wherein, the pure caprolactam accounts for 90-95% of the weight, the pearl powder aqueous solution accounts for 1-3%, the carboxylic acid accounts for 2-3%, the ammonia accounts for 2-3%, and the 6-aminocaproic acid accounts for 2-3%; heating caprolactam to 240-270 ℃ for hydrolytic ring opening to generate 6-aminocaproic acid, and adding carboxylic acid to accelerate hydrolytic ring opening; also comprises the generation of amide exchange reaction and equilibrium reactions such as acidolysis, aminolysis and the like; washing the polymerized caprolactam slices with water to remove monomers and oligomers, and drying in vacuum to obtain pearl nylon master batches; and (3) pumping the pearl nylon master batch to obtain the pearl yarn.

The main defects are as follows: the pearl powder is added in the polymerization process of the polymer monomer to prepare the pearl nylon master batch by using a grafting method, the process is complex, and the method is only suitable for preparing the nylon pearl yarn; meanwhile, the strength of the finished fiber is greatly influenced by the addition amount of the powder, so that the content of the functional powder is greatly limited, and the function is single.

2. Application No.: CN202010129009.8; name: a functional slurry containing jade powder and pearl powder for blending textile fiber and its preparation method are provided. The functional slurry for blending the textile fibers comprises the following components in parts by weight: 2-6 parts of pearl powder, 4-12 parts of jade powder, 50-100 parts of dispersion solution, 1-1.5 parts of dispersing agent, 3-16 parts of anion powder and 0.3-1.2 parts of antibacterial agent, wherein the particle size of the pearl powder is 9000-11000 meshes, the particle size of the jade powder is 10000-12500 meshes, the dispersion solution is one or more of deionized water, distilled water or softened water, and the antibacterial agent is one or two of nano silver oxide and nano zinc oxide; the preparation method comprises the following steps of S1, screening and preparing materials; s2, primary crushing; s3, secondary crushing; s4, grinding the pearl powder particles; s5, grinding jade particles; s6, mixing and grinding; and S7, mixing and blending.

The main defects are as follows: the pearl powder is combined with jade powder by utilizing the characteristic of cold nature of the pearl, and meanwhile, the pearl powder is compounded with anion powder, an antibacterial agent and the like to prepare multifunctional slurry, so that the pearl powder is an after-finishing process for yarns or fabrics, and the preparation of master batches is not involved. The functional sizing agent has almost no binding force between fibers such as chemical fibers, which have compact structures and almost no hydrophilic groups, and needs to be attached by means of sodium alginate adhesives, but the problems of poor fiber air permeability, reduced flexibility and the like can be caused.

3. Application No.: CN202010257821.9; the name is as follows: a temperature-regulating antibacterial pearl regenerated cellulose fiber and a preparation method thereof. The preparation steps are as follows: preparing a temperature-controlled pearl microcapsule; preparing an additive mother solution; preparing blended spinning solution; spinning; and performing post-treatment to obtain the temperature-regulating antibacterial pearl regenerated cellulose fiber. The temperature control health microcapsule consists of a composite core material formed by blending and adsorbing pearl powder and paraffin and a wall material formed by high molecular polymers; the mass ratio of the composite core material to the wall material is 0.3-3:1; the average particle size of the pearl powder is less than or equal to 1.2 mu m; the average grain diameter of the microcapsule is less than or equal to 3 mu m.

The main defects are as follows: the wet spinning process for preparing the regenerated cellulose fiber is not suitable for preparing chemical fibers, and meanwhile, a large amount of research is carried out, so that most of phase-change paraffin microcapsules suitable for human bodies in the market are poor in temperature resistance, not suitable for a melt spinning process, or expensive in price and difficult to produce in batches.

4. Application No.: CN201910083108.4; name: a method for preparing normal temperature and pressure dyeable polyester pearl fiber. The preparation method of the normal temperature and pressure dyeable polyester pearl fiber comprises the following steps: cutting and grinding pearls to obtain crude pearl powder, mixing the crude pearl powder with water according to the weight ratio of 1; uniformly mixing the pearl powder and a compatilizer at normal temperature according to the weight ratio of 1.1-0.5, adding the mixture into normal-temperature normal-pressure dyeable polyester chips, wherein the weight content of the mixture in the normal-temperature normal-pressure dyeable polyester chips is 10-30%, and granulating by using a double-screw extruder to obtain nano pearl polyester chips; blending with polyester chips dyeable at normal temperature and normal pressure for spinning.

The main defects are as follows: the pearl powder is crushed by a wet grinding process, a large amount of water is added in the crushing process, and a drying process is additionally added, so that the drying process not only consumes a large amount of energy, but also easily causes the problem of re-agglomeration among particles in the drying process; the prepared nano pearl fiber has single function and does not meet the current demand for the multifunctional integrated fiber.

5. Application No.: CN202010257821.9; name: a polyolefin fiber and a method for producing the same. The fiber is composed of natural pearl powder with the grain diameter less than 2 microns, tourmaline and zeolite contained in polyolefin fiber. The preparation method comprises refining natural pearl powder, tourmaline and zeolite, mixing with dispersant, mixing with polyolefin slices, granulating to obtain master batch, mixing the master batch with polyolefin slices, and melt spinning.

The main defects are as follows: as is well known, the functionality of the powder is closely related to the particle size and the dispersion performance of the powder, the smaller the particle size of the functional powder is, the larger the specific surface area is, the higher the activity is, and meanwhile, the agglomeration among the powder can be reduced by a proper dispersion process, so that the powder functionality can be exerted to a greater extent. The particle size of the pearl powder and other functional powder is less than 2 microns, which not only influences the functional performance efficiency, but also causes the problems of low double A rate of the spun superfine denier filament and the like, and causes production difficulty; amino acids in the pearl powder are easy to denature under the production condition that the production temperature is 230-290 ℃, and the exertion of the skin-friendly performance of the finished product is influenced.

Disclosure of Invention

With the development of times, multifunctional textiles are more and more favored by people, and the pearl fiber has unique skin-friendly performance, far infrared emission performance, ultraviolet resistance and other performances. However, although pearl fabric is popular in summer due to cold nature, when the pearl fabric is used in winter, the cool feeling of the pearl fabric is not good for the warmth retention of users, and meanwhile, the low-temperature environment in winter prevents substances such as amino acid in the pearls from overflowing, so that the wearing comfort and the skin-friendly performance of the pearl fabric are affected. Moreover, the amino acid in the pearl has poor thermal stability, and the pearl fiber has serious influence on the skin-friendly performance of the pearl fiber due to denaturation in high-temperature production (for example, the temperature range of the melt of the polyester yarn is 275-290 ℃ and the temperature range of the melt of the nylon yarn is 245-270 ℃), which becomes a great difficulty in blending, melting and spinning the micro-nano pearl powder in the chemical fiber. Therefore, the development of a preparation method for producing stable pearl powder-containing multifunctional master batches and stable pearl powder-containing multifunctional master batches has great significance.

In a first aspect, the present invention provides a pearl powder-containing multifunctional masterbatch. The pearl powder-containing multifunctional master batch comprises the following raw materials in parts by weight: 50-80 parts of matrix resin, 10-40 parts of pearl powder, 5-10 parts of porous carbon material, 1-5 parts of phase change material, 0.0001-0.0005 part of heat stabilizer, 0.5-3 parts of binder and 1-3 parts of dispersant, wherein the absolute dry mass parts of the raw materials are 100 parts.

Preferably, the phase change temperature range of the phase change material is 95-250 ℃.

Preferably, the phase change material is a polyol phase change material.

Preferably, the phase change material is one or more of hexitol, erythritol and pentaerythritol.

Preferably, the binder is one or more selected from anhydrous glycerin, liquid paraffin and white wax.

In a second aspect, the invention provides a preparation method of a pearl powder-containing multifunctional master batch. The preparation method comprises the following steps:

s1, weighing 10-40 parts of pearl powder, 1-5 parts of phase change material and 0.1-1 part of dispersant, and carrying out first dispersion grinding in a dry vibration ball mill pulverizer; then adding 5-10 parts of porous carbon material and 0.0001-0.0005 part of heat stabilizer, and continuously performing second dispersion grinding in a dry vibration ball mill pulverizer to obtain composite powder;

s2, weighing 50-80 parts of matrix resin and the rest of dispersing agent, adding 0.5-3 parts of binder, and uniformly mixing in mixing equipment to obtain a mixture of the matrix resin, the dispersing agent and the binder; adding the composite powder prepared in the step S1, and continuously and uniformly mixing in a mixing device to obtain a mixture of matrix resin, a binder, a dispersing agent and the composite powder;

and S3, adding the mixture of the matrix resin, the binder, the dispersing agent and the composite powder prepared in the step S2 into a screw extruder for granulation, and carrying out high-temperature melting, screw conveying, extrusion, cooling, grain cutting and drying to obtain the pearl powder-containing multifunctional master batch.

Preferably, in step S1, the working frequency of the dry vibration ball mill for the first dispersion grinding and the second dispersion grinding is 1200-1500rpm, and the grinding time of the dry vibration ball mill is 20-240min, preferably 30-50min.

Preferably, in step S2, the rotation speed of the mixing device is 30-3000rpm, and the time is 5-10min.

In a third aspect, the present invention provides a pearl powder-containing multifunctional fiber. The raw material composition of the pearl powder-containing multifunctional fiber comprises the pearl powder-containing multifunctional master batch and the matrix resin slice of any one of claims 1 to 5, preferably, the mass ratio of the pearl powder-containing multifunctional master batch to the matrix resin slice is 1-8; more preferably, the base resin chip of the multifunctional fiber is the same type as the base resin of the multifunctional mother particle.

In a fourth aspect, the invention provides a preparation method of pearl powder-containing multifunctional fiber. Mixing the pearl powder-containing multifunctional master batch with the matrix resin slices, and spinning according to a conventional method.

Drawings

FIG. 1 shows the dried material, which is composed of matrix resin, pearl powder, phase-change material and composite powder from left to right.

FIG. 2 is a diagram showing the interaction between the hydrophilic groups on the surface of pearl powder and the hydroxyl groups on the surface of phase-change material.

In FIG. 3, from left to right, "A particle" in which a binder is spread on the surface of a base resin particle and "B particle" in which "composite powder" is surface-bonded to "A particle" are shown.

FIG. 4 is a schematic diagram of solid-liquid phase change of the phase change material during the production process to improve the high temperature denaturation of amino acid.

FIG. 5 is a sectional scanning electron microscope image of the multifunctional master batch of example 2.

FIG. 6 is a sectional scanning electron microscope image of the multifunctional mother particle of comparative example 2.

Detailed Description

The present invention is further illustrated by the following examples, which are to be understood as merely illustrative of, and not restrictive on, the present invention. Unless otherwise specified, each percentage means a mass percentage.

The pearl powder-containing multifunctional master batch comprises the following raw materials: the composition comprises, by weight, 100 parts of the raw materials, 50-80 parts of matrix resin, 10-40 parts of pearl powder, 5-10 parts of porous carbon material, 1-5 parts of phase change material, 0.0001-0.0005 part of heat stabilizer, 0.5-3 parts of binder and 1-3 parts of dispersant.

The matrix resin can form stable fluid melt after reaching the melting point at the temperature, and is a high molecular polymer for spinning which is basically not decomposed under the spinning condition. The matrix resin includes, but is not limited to, high molecular polymers such as polyesters, polyamides, polyolefins, and the like. For example, polyesters include, but are not limited to, polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), and the like. Polyamides include, but are not limited to, polyamide 6 (PA 6), polyamide 66 (PA 66), polyamide 610 (PA 610), and the like. Polyolefins include, but are not limited to, polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polyacrylonitrile (PAN), polyvinylidene fluoride (PTFE), and the like. Of course, other matrix resins having skin-friendly functional requirements may be selected.

The particle diameter of Margarita powder is preferably controlled at 200-1500nm. The particle size is too small, and a dry grinding and crushing process is required to be added, so that energy loss and waste are caused; too large grain size easily causes difficult spinning, and especially easily causes the problem of low double A rate in the process of spinning superfine denier filaments. The pearl belongs to natural substances, is rich in active calcium, amino acid and a plurality of trace elements beneficial to human bodies, has a plurality of polar hydrophilic groups such as hydroxyl, amino, carboxyl and the like on the surface, can improve the moisture absorption and air permeability of chemical fibers, improves the dyeing performance, can be combined with polar groups of other auxiliary agents by hydrogen bonds, van der waals force and even chemical bonds, has good compatibility, and is beneficial to stable production. The Margarita powder can be prepared by grinding special-shaped Margarita which can not be used directly. The pearl may be seawater or fresh water pearl, preferably fresh water pearl.

The particle size of the porous carbon material is preferably 200-1500nm. The porous carbon material has a highly developed specific surface area and pore structure, and may have a hierarchical pore structure of various sizes ranging from ultrafine nano-scale micro-pores of molecular size to micro-scale micro-pores suitable for the activity of microorganisms. The pore size of the porous carbon material can be divided into micropores (< 2 nm), mesopores (2-50 nm) and macropores (> 50 nm) according to the rules of the pure and applied chemical association (IUPAC), and the mesoporous porous carbon material is preferably used in the present invention. In some embodiments, the porous carbon material is selected from porous carbon black, porous bamboo charcoal, porous coconut charcoal, porous coffee charcoal, and the like. The porous carbon material also has the effects of emitting far infrared rays and negative ions, resisting bacteria and preventing mildew, and has excellent functions of keeping warm, deodorizing, regulating humidity and the like.

The phase-change material utilizes the characteristics of a large amount of heat absorption and release in the phase transition process of solid-liquid, solid-solid, solid-gas and the like of the material to store and manage heat energy, and has the advantages of high energy storage density and small temperature change in the heat absorption and release process. The phase change material provided by the invention meets the following conditions: 1. the phase transition temperature range is 95-250 ℃; 2. the compatibility with pearl powder is good; 3. high safety performance and no side reaction with assistant or matrix resin. Preferably, the phase change material is a polyol (type) phase change material with the phase change temperature of 95-250 ℃ and high energy storage density. Specifically, the solid-liquid phase change occurs in the process of melting the matrix resin of the polyol phase change material, most of heat is absorbed, and meanwhile, the affinity between hydroxyl on the surface of the polyol phase change material and hydrophilic groups on the surface of pearl powder enables the phase change material and the pearl powder to generate a combination effect. Moreover, the polyalcohol phase-change material has good thermal stability and does not react with other components of the pearl master batch. In addition, solid-solid phase change is generated through the transformation of crystal form and other phase structures in the process of taking the polyol phase change material fiber, so that the heat management capability of the fiber is improved. The capacity of a phase change material to absorb or release a large amount of heat per unit mass is expressed in enthalpy (unit: J/g). In some technical schemes, the phase change material is one or more of hexitol (with enthalpy value reaching-290J/g), erythritol (with enthalpy value reaching-350J/g) and pentaerythritol (with enthalpy value reaching-300J/g).

The heat stabilizer includes but is not limited to one or more of barium stearate, zinc stearate, rare earth heat stabilizer, epoxy butyl stearate, phosphite ester heat stabilizer and beta-diketone.

The binder is one or more of anhydrous glycerin (water content < 1%), liquid paraffin (distillation temperature >300 ℃) and white wax (distillation temperature 150-250 ℃). The adhesive is liquid with good fluidity at normal temperature, has a high boiling point, is non-volatile, does not decompose or carbonize at the melting temperature of the polymer, and has stable chemical properties; while having an affinity for the matrix resin. When the matrix resin is melted into a melt, the adhesive has good compatibility and affinity with the melt, and also has good affinity with pearl powder and porous carbon materials, so that the adhesive is easy to uniformly spread on the surfaces of the pearl powder, the porous carbon materials and the like.

The dispersing agent is one or more of polyethylene wax, carboxylated polyethylene wax, oxidized polyethylene wax, stearic acid, calcium stearate, zinc stearate, cadmium stearate and N, N' -ethylene bis stearamide. The proper dispersant is selected to help to improve the compatibility of the pearl powder, the porous carbon material and the matrix resin.

Synthetic fibers occupy an extremely important position in the textile market by virtue of wide raw material sources, excellent properties, and processability, but have limited use in textiles in direct contact with the skin due to problems of poor comfort such as stuffiness and air impermeability caused by dense fiber structures. The use of the pearl powder rich in amino acid and other skin-friendly materials effectively improves the problems, but the amino acid materials are denatured to different degrees in the melting processing process of chemical fibers, thereby seriously reducing the function exertion. The invention utilizes the characteristic that the phase-change material absorbs and releases heat in a large amount in the phase-change process, selects the phase-change material with the phase-change temperature of 95-250 ℃, utilizes the strong affinity between polar groups on the surface of the phase-change material and the surface of pearl powder, absorbs a large amount of heat in the melting processing process, changes the heat from solid state into liquid state, spreads on the surface of the pearl powder, prevents the amino acid from high-temperature denaturation, and the phase-change conversion process is reversible. The application of the phase-change material in the melting process is not limited to the pearl powder material, and the method is also suitable for other problems of denaturation and inactivation possibly generated in the process temperature range. In conclusion, the invention utilizes the phase-change material (the phase-change temperature is 95-250 ℃) and the heat stabilizer to improve the problem of high-temperature denaturation of amino acid, prepares the pearl powder-containing multifunctional master batch by compounding the porous carbon material, and designs a hollow section and the like to prepare the multifunctional pearl fiber.

The function of the powder is exerted not only by the properties of the powder itself but also by the particle size dispersibility of the powder. The problem of poor mixing uniformity exists between substances in different phases and between solid particles with different sizes. The size and physical property difference between different functional powder bodies such as pearl powder and the like and between the functional powder body and matrix resin causes that the functional powder bodies are not easy to be effectively and uniformly mixed, further influences the performance of the functional powder bodies and reduces the utilization rate. The low-melting-point binder is selected to pretreat the matrix resin, and the functional powder is added to ensure that the functional powder is uniformly adhered to the surface of the matrix resin, so that the uniform dispersibility is improved. In addition, some researches have been made on further refining pearl powder by using a wet pulverizing device, but the additional drying process is required, a large amount of energy is consumed, and the problem of re-agglomeration among particles is caused. The invention uses a dry-method vibration ball-milling pulverizer to perform secondary grinding on the powder, wherein pearl powder, a dispersing agent and a phase-change material are ground for the first time, and the interaction among the pearl powder, the dispersing agent and the phase-change material is enhanced; and the porous carbon material and the heat stabilizer are added in the secondary grinding to reduce the integral grain diameter of the powder and improve the mixing uniformity among the powder. The functional powder is uniformly adhered to the surface of the matrix resin by using the low-melting-point binder and adopting a proper dispersion process, so that the problem of non-uniform dispersion is solved, and the phenomenon of dust pollution is improved. Meanwhile, with the help of a proper dispersant, the multifunctional master batch with uniformly dispersed functional powder is finally obtained.

The preparation method of the pearl powder-containing multifunctional master batch of the present invention is exemplified below.

Removing water from matrix resin, margarita powder, porous carbon material, phase change material, and dispersant in drying equipment. The material can be dried to constant weight by selecting a proper drying process according to the physicochemical properties of the material.

10-40 parts of pearl powder, 1-5 parts of phase change material and 0.1-1 part of dispersing agent are weighed and subjected to first dispersing grinding in a dry-method vibration ball-milling grinder. Wherein the working frequency of the dry vibration ball milling pulverizer is 1200-1500rpm, and the pulverizing time of the dry vibration ball milling pulverizer is 20-240min, preferably 30-50min. The first dry vibration dispersing grinding aims at performing dry vibration ball milling grinding on large particles in the pearl powder, and simultaneously enabling the phase-change material and part of the dispersing agent to act on the pearl powder.

And then adding 5-10 parts of porous carbon material and 0.0001-0.0005 part of heat stabilizer, and performing second dispersion grinding in a dry vibration ball mill pulverizer. Wherein the working frequency of the dry vibration ball milling pulverizer is 1200-1500rpm, and the pulverizing time of the dry vibration ball milling pulverizer is 20-240min, preferably 30-50min. The second dry vibration dispersing grinding is used for carrying out dry vibration ball milling crushing on large particles in the porous carbon material, and simultaneously mixing all the pearl powder, the phase change material, part of the dispersing agent, the porous carbon material and the heat stabilizer uniformly. The mixture obtained by the second dispersion grinding is referred to as "composite powder".

As shown in figure 2, in the action process of the dry-method vibration ball-milling pulverizer, the pearl powder and the phase-change material can interact, wherein hydrophilic groups on the surface of the pearl powder interact with hydroxyl groups on the surface of the phase-change material, so that the spreading of the phase-change material on the surface of the pearl powder in the melting process can be improved, and the stability of the pearl powder in high-temperature production is further improved.

Weighing 50-80 parts of dried matrix resin and the rest dispersant, adding 0.5-3 parts of binder, and uniformly mixing in a mixing device to obtain a mixture of matrix resin, dispersant and binder, which is called as particles A. The mixing device is a low-speed mixer or a high-speed mixer. The rotation speed of the mixing equipment can be 30-3000rpm, and the time can be 5-10min. And then adding the dried composite powder, and continuously and uniformly mixing in a mixing device to obtain a mixture of the matrix resin, the binder, the dispersing agent and the composite powder, which is called as B particles. The mixing device is a low-speed mixer or a high-speed mixer. The speed of the mixing device may be 30-3000rpm. The time is 5-10min.

The selected adhesive has good affinity with matrix resin and can be quickly and uniformly spread on the surfaces of matrix resin particles. Particles in which a layer of binder is spread on the surface of the matrix resin particles are called "a particles". This facilitates the bonding of the matrix resin with the dried "composite powder". The surface of the dispersant particles also spreads a layer of binder. After the composite powder is added, the binder can well adhere the composite powder to the surface of the matrix resin, so that the problems of dust flying and material waste caused in the mixing process are reduced or solved. Meanwhile, composite powder particles are uniformly adhered to the surfaces of each polymer matrix resin and each dispersing agent particle, so that the pearl powder and the porous carbon material in the finally obtained master batch are uniformly distributed. Particles in which a layer of the composite powder is bonded to the surface of the particles A are referred to as particles B.

And (3) melting and granulating: and adding the uniform mixture of the matrix resin particles, the binder, the dispersing agent and the composite powder, namely the particles B, obtained by the steps into a screw extruder for granulation, and carrying out processes such as high-temperature melting, screw conveying, extrusion, cooling, grain cutting, drying and the like to obtain the pearl powder-containing multifunctional master batch. The screw extruder is one of a single-screw extrusion granulator, a double-screw extrusion granulator, a banburying matched single-screw extrusion granulator, a banburying matched double-screw extrusion granulator and a double-stage extrusion granulator. The temperature setting of the different heating zones of the extrusion granulator is different according to the kind of the matrix resin used. For example: selecting Polyethylene (PE) and polypropylene (PP) as matrix resins, and setting the temperature to be 120-260 ℃; selecting polyamide 6 (PA 6) as matrix resin, and setting the temperature within the range of 180-260 ℃; polyethylene terephthalate (PET) is selected as matrix resin, and the temperature setting range is 240-280 ℃. In the extrusion process, the material is heated and melted, the phase-change material absorbs most of heat, the partially melted phase-change material is spread on the surface of the pearl powder, and the incompletely melted phase-change material continuously absorbs the heat to protect the amino acid and prevent the amino acid from high-temperature denaturation.

Melt spinning: mixing the prepared pearl powder-containing multifunctional master batch with corresponding matrix resin slices, and spinning according to a conventional method. The mass ratio of the pearl powder-containing multifunctional master batch to the corresponding matrix resin slices can be 1-8. The fiber section includes but is not limited to hollow, trilobal, cross, wang font, five-leaf shaped and other section structures. The structure can also be directly designed into a round structure and the like according to the functional requirements.

The invention provides a preparation method of pearl powder-containing multifunctional master batch and fiber, wherein a phase-change material (with the phase-change temperature of 95-250 ℃) is applied to the production of the multifunctional master batch, proper heat stabilizer, dispersant and other auxiliary agents are selected, a dry-method vibration ball-milling crushing method is adopted for grinding twice, functional particles such as porous carbon materials and the like are compounded, a low-melting-point binder is selected for pretreating a matrix resin, and a proper dispersion process is adopted to enable functional powder such as the pearl powder, the porous carbon materials and the like to be uniformly adhered to the surface of the matrix resin. The prepared multifunctional fiber has excellent skin-friendly, smooth and soft, moisture absorption and ventilation, far infrared emission, antibacterial and mildew-proof performances, and also effectively improves the problem of amino acid denaturation under the high-temperature condition; meanwhile, the hollow equal-fiber section is designed, and the solid-solid phase change process generated by the transformation of the crystal form equal-phase structure is added to the phase change material, so that the heat management capability of the fiber is improved.

Finally, the preparation method of the pearl powder-containing multifunctional master batch and the fiber of the invention changes the micro-nano pearl powder into powder containing amino acid, collagen and the like which can not resist high temperature; replacing micro-nano porous carbon materials with inorganic powders such as jade powder, mica powder, ceramic powder, tourmaline powder, zeolite powder, vermiculite powder, other carbon material powders, metal powder, glass-supported silver, zirconium phosphate-supported silver, cerium oxide powder, zinc oxide powder, copper oxide powder, cuprous oxide powder and the like; the polyol phase change material used in the invention is replaced by: 1. the phase transition temperature range is 95-250 ℃; 2. the compatibility with pearl powder is good; 3. the safety performance is high, the side reaction with the auxiliary agent or the matrix resin is avoided, and other phase change materials meeting the conditions are also applicable to the invention.

The present invention will be described in further detail with reference to examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art in light of the foregoing description are intended to be included within the scope of the invention. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.

Example 1: preparation of pearl powder-containing multifunctional polyamide 6 (PA 6) master batch and fiber

The method comprises the following steps: removing water from matrix resin PA6, pearl powder, porous carbon black, phase change material hexanehexol and dispersant oxidized polyethylene wax in drying equipment.

Step two: preparation of composite powder: weighing 15 parts of pearl powder, 1.5 parts of phase change material hexanehexol and 0.5 part of dispersant oxidized polyethylene wax, and carrying out first dispersion grinding in a dry vibration ball mill pulverizer. Then, 10 parts of porous carbon black and 0.0001 part of phosphite heat stabilizer are added, and the mixture is subjected to secondary dispersion grinding in a dry vibration ball mill pulverizer to obtain uniformly mixed composite powder. The working frequency of the dry vibration ball mill pulverizer is 1400rpm for 30min during each dispersion grinding.

Step three: mixing matrix resin and composite powder: dried 70.5 parts of matrix resin PA6 and 1.4999 parts of dispersant oxidized polyethylene wax are weighed, 1 part of binder anhydrous glycerin is added to be uniformly mixed in a high-speed mixer, and a mixture of the matrix resin PA6, the dispersant and the binder anhydrous glycerin is obtained and is called as 'A particles'. The rotation speed of the mixing device was 3000rpm for 5min. And then adding the dried composite powder, and continuously and uniformly mixing in a high-speed mixer to obtain a mixture of matrix resin PA6, binder anhydrous glycerin, a dispersing agent and the composite powder, namely the particles B. The rotation speed of the mixing device was 3000rpm for 5min.

Step four: melting and granulating: and adding the particles B obtained in the step three into a double-screw extrusion granulator for granulation, and carrying out high-temperature melting, screw conveying, extrusion, cooling, granulation and drying processes to obtain the pearl powder-containing multifunctional PA6 master batch. Wherein, the temperatures of the first section, the second section, the third section, the fourth section and the fifth section of the double-screw extrusion granulator are respectively set as follows: 220 deg.C, 230 deg.C, 250 deg.C, 260 deg.C.

Step five: melt spinning: and (3) mixing the pearl powder-containing multifunctional PA6 master batch prepared in the fourth step with PA6 matrix resin slices in a mass mixing ratio of 5.

Example 2: preparation of pearl powder-containing polyethylene terephthalate (PET) master batch and fibers

The method comprises the following steps: removing water from matrix resin PET, pearl powder, porous coffee carbon, phase-change material pentaerythritol and dispersant N, N' -ethylene bis stearamide in drying equipment.

Step two: preparation of composite powder: weighing 20 parts of pearl powder, 3 parts of phase change material pentaerythritol and 1 part of dispersant N, N' -ethylene bis stearamide, and carrying out first dispersion grinding in a dry vibration ball mill pulverizer. Subsequently, 10 parts of porous coffee carbon and 0.0002 part of a rare earth heat stabilizer were added, and the mixture was subjected to secondary dispersion grinding in a dry vibration ball mill, to obtain a uniformly mixed "composite powder". The working frequency of the dry vibration ball mill pulverizer is 1400rpm for 50min during each dispersion grinding.

Step three: mixing matrix resin and composite powder: 62.5 parts of dried base resin PET and 3242 parts of 1.9998 parts of dispersant N, N' -ethylene bis stearamide were weighed, and 1.5 parts of binder liquid paraffin (distillation temperature >300 ℃) was added thereto and uniformly mixed in a high-speed mixer to obtain "a mixture of base resin PET, dispersant and binder liquid paraffin", which was referred to as "A particles". The rotation speed of the mixing device was 3000rpm for 5min. And then adding the dried composite powder, and continuously and uniformly mixing in a high-speed mixer to obtain a mixture of matrix resin PET, binder liquid paraffin, a dispersing agent and the composite powder, which is called as B particles. The speed of the mixing apparatus was 3000rpm for 5min.

Step four: and (3) melting and granulating: and D, adding the particles B obtained in the step three into a double-screw extrusion granulator for granulation, and carrying out high-temperature melting, screw conveying, extrusion, cooling, granulation and drying processes to obtain the pearl powder-containing multifunctional PET master batch. Wherein, the temperatures of the first section, the second section, the third section, the fourth section and the fifth section of the granulator are respectively set as follows: 262 ℃, 265 ℃, 270 ℃.

Step five: melt spinning: and D, mixing the pearl powder-containing multifunctional PET master batch prepared in the step four with the PET matrix resin slices in a mass mixing ratio of 4.

Example 3: preparation of pearl powder-containing polypropylene (PP) master batch and fibers

The method comprises the following steps: removing water from matrix resin PP, pearl powder, porous coconut charcoal, phase-change material erythritol and dispersant polyethylene wax in drying equipment.

Step two: preparation of composite powder: weighing 30 parts of pearl powder, 5 parts of phase change material erythritol and 1 part of dispersant polyethylene wax, and carrying out first dispersion grinding in a dry vibration ball mill pulverizer. Subsequently, 5 parts of porous coconut carbon and 0.0005 part of rare earth heat stabilizer were added, and the mixture was subjected to secondary dispersion grinding in a dry vibration ball mill pulverizer to obtain a uniformly mixed "composite powder". The working frequency of the dry vibration ball mill pulverizer is 1400rpm for 50min during each dispersion grinding.

Step three: mixing matrix resin and composite powder: 55 parts of dried base resin PET and 1.9995 parts of dispersant polyethylene wax are weighed, 2 parts of binder liquid paraffin (distillation temperature is more than 300 ℃) is added and uniformly mixed in a high-speed mixer, and a mixture of the base resin PP, the dispersant and the binder liquid paraffin is obtained and is called as particles A. The rotation speed of the mixing device was 3000rpm for 5min. And adding the dried composite powder, and continuously and uniformly mixing in a high-speed mixer to obtain a mixture of the matrix resin PP, the binder liquid paraffin, the dispersing agent and the composite powder, which is called as B particles. The rotation speed of the mixing device was 3000rpm for 5min.

Step four: and (3) melting and granulating: and adding the particles B obtained in the step three into a double-screw extrusion granulator for granulation, and carrying out high-temperature melting, screw conveying, extrusion, cooling, granulation and drying processes to obtain the pearl powder-containing multifunctional PP master batch. Wherein, the temperatures of the first section, the second section, the third section, the fourth section and the fifth section of the granulator are respectively set as follows: 180 deg.C, 200 deg.C, 220 deg.C, 250 deg.C.

Step five: melt spinning: and D, mixing the pearl powder-containing multifunctional PP master batch prepared in the step four with PP matrix resin slices in a mass mixing ratio of 4.

Comparative example 1: preparation of pearl powder-containing multifunctional polyamide 6 (PA 6) master batch and fiber

The method comprises the following steps: removing water from the matrix resin PA6, the pearl powder, the porous carbon black and the dispersant oxidized polyethylene wax in drying equipment.

Step two: preparation of composite powder: weighing 15 parts of pearl powder and 0.5 part of dispersant oxidized polyethylene wax, and carrying out first dispersion grinding in a dry vibration ball mill pulverizer. Then, 10 parts of porous carbon black and 0.0001 part of phosphite heat stabilizer are added, and the mixture is subjected to secondary dispersion grinding in a dry vibration ball mill pulverizer to obtain uniformly mixed composite powder. The working frequency of the dry vibration ball mill pulverizer is 1400rpm for 30min during each dispersion grinding.

Step three: mixing matrix resin and composite powder: weighing 72 parts of dried matrix resin PA6 and 1.4999 parts of dispersant oxidized polyethylene wax, adding 1 part of binder anhydrous glycerin, and uniformly mixing in a high-speed mixer to obtain a mixture of the matrix resin PA6, the dispersant and the binder anhydrous glycerin, which is called as particles A. The speed of the mixing apparatus was 3000rpm for 5min. And adding the dried composite powder, and continuously and uniformly mixing in a high-speed mixer to obtain a mixture of matrix resin PA6, binder anhydrous glycerin, a dispersing agent and the composite powder, which is called as B particles. The speed of the mixing apparatus was 3000rpm for 5min.

Step four: melting and granulating: and adding the particles B obtained in the step three into a double-screw extrusion granulator for granulation, and carrying out high-temperature melting, screw conveying, extrusion, cooling, granulation and drying processes to obtain the pearl powder-containing multifunctional PA6 master batch. Wherein, the temperatures of the first section, the second section, the third section, the fourth section and the fifth section of the granulator are respectively set as follows: 220 deg.C, 230 deg.C, 250 deg.C, 260 deg.C.

Step five: melt spinning: and D, mixing the pearl powder-containing multifunctional PA6 master batch prepared in the step four with PA6 matrix resin slices in a mass mixing ratio of 5.

The pearl powder-containing multifunctional master batches prepared in example 1, example 2, example 3 and comparative example 1 were tested for production stability. The stability of the brace and the comparison of peculiar smell in the production process are used as judgment basis. Brace stability is the judgement of making thickness stability and the fracture condition etc. of brace in the production process according to the production experience, through the mode of range estimation. The peculiar smell refers to a unique protein scorched smell generated by the denaturation of amino acid in the high-temperature production of the pearl powder-containing multifunctional master batch, and is detected by referring to 6.7 in GB 18401-2010 national basic safety technical Specification for textile products, and specifically, the smell generated in the production process is recorded and compared by two or more producers. The test results are shown in table 1.

TABLE 1 production stability of pearl powder-containing multifunctional masterbatch

Master batch source	Brace stability	Degree of odor
			Example 1	Stabilization	Light and lightweight
Example 2	Stabilization	Light and lightweight
			Example 3	Stabilization	Light and lightweight
Comparative example 1	Stabilization	Heavy load

The pearl powder-containing multifunctional fibers prepared in example 1, example 2, example 3 and comparative example 1 were tested for the kind and content of amino acids and calcium content. The types and contents of amino acids were determined according to GB 5009.124-2016 standard for determination of amino acids in food safety food. The calcium content is determined according to GB 5009.92-2016 national food safety standard for determination of calcium in food. The test results are shown in table 2.

TABLE 2 amino acid types and contents of pearl powder-containing multifunctional fiber, calcium content test results

As can be seen from table 1, the pearl powder-containing multifunctional master batches prepared in examples 1, 2 and 3 of the present invention have stable bracing stability and less off-flavor in production, compared to comparative example 1. As can be seen from Table 2, the pearl powder-containing multifunctional fiber amino acids prepared in examples 1, 2 and 3 of the present invention were higher in type and content, and calcium content, as compared to comparative example 1.

Comparative example 2: preparation of pearl powder-containing polyethylene terephthalate (PET) master batch and fibers

Step two: mixing matrix resin with auxiliary agents such as pearl powder, porous coffee carbon, dispersing agent and the like: 62.5 parts of dried base resin PET and 3242 parts of 2.9998 parts of dispersant N, N' -ethylene bis stearamide were weighed, and 1.5 parts of binder liquid paraffin (distillation temperature >300 ℃) was added thereto and uniformly mixed in a high-speed mixer to obtain a "mixture of base resin PET and binder liquid paraffin" referred to as "A particles". The speed of the mixing apparatus was 3000rpm for 5min. Then, 20 parts of dried pearl powder, 3 parts of phase change material pentaerythritol, 10 parts of porous coffee carbon and 0.0002 part of rare earth heat stabilizer are added at one time and are continuously and uniformly mixed in a high-speed mixer to obtain a mixture of matrix resin PET, binder liquid paraffin, pearl powder, porous coffee carbon, dispersing agent and other auxiliaries, which is called as B particles. The speed of the mixing apparatus was 3000rpm for 5min.

Step three: melting and granulating: and D, adding the particles B obtained in the step two into a double-screw extrusion granulator for granulation, and carrying out high-temperature melting, screw conveying, extrusion, cooling, granulation and drying processes to obtain the pearl powder-containing multifunctional PET master batch. Wherein, the temperatures of the first section, the second section, the third section, the fourth section and the fifth section of the granulator are respectively set as follows: 262 ℃, 265 ℃, 270 ℃.

Step four: melt spinning: and C, mixing the pearl powder-containing multifunctional PET master batch prepared in the step three with the PET matrix resin slices in a mass mixing ratio of 4.

Fig. 5 is a cross-sectional Scanning Electron Microscope (SEM) image of the multifunctional master batch of example 2. Fig. 6 is a cross-sectional Scanning Electron Microscope (SEM) image of the multifunctional mother particle of comparative example 2. As can be seen from fig. 5 and 6, compared with comparative example 2, the multifunctional master batch prepared in example 2 of the present invention has the advantages that the overall particle size of the pearl powder and the porous carbon material is reduced, and the dispersion and mixing uniformity among the powders is significantly improved.

Detection shows that after the phase change material is added in the dry-method vibration ball milling crushing method and the production process, the pearl powder-containing multifunctional master batch is stable in production, the overall particle size of the pearl powder and the porous carbon material is reduced, the dispersion uniformity in the master batch is improved, and the finally prepared pearl powder-containing multifunctional fiber has high amino acid and active calcium content.

Claims

1. The pearl powder-containing multifunctional master batch is characterized by comprising the following raw materials in parts by weight: 50-80 parts of matrix resin, 10-40 parts of pearl powder, 5-10 parts of porous carbon material, 1-5 parts of phase change material, 0.0001-0.0005 part of heat stabilizer, 0.5-3 parts of binder and 1-3 parts of dispersant, wherein the absolute dry mass parts of the raw materials are 100 parts.

2. The pearl powder-containing multifunctional master batch according to claim 1, wherein the phase transition temperature range of the phase transition material is 95-250 ℃.

3. The pearl powder-containing multifunctional masterbatch according to claim 1 or 2, wherein the phase change material is a polyol phase change material.

4. The pearl powder-containing multifunctional master batch according to any one of claims 1 to 3, wherein the phase change material is one or more of hexitol, erythritol and pentaerythritol.

5. The pearl powder-containing multifunctional masterbatch according to any one of claims 1 to 4, wherein the binder is one or more selected from anhydrous glycerin, liquid paraffin, and white wax.

6. The preparation method of the pearl powder-containing multifunctional master batch according to any one of claims 1 to 5, wherein the preparation method comprises the following steps:

s1, weighing 10-40 parts of pearl powder, 1-5 parts of phase-change material and 0.1-1 part of dispersing agent, and performing first dispersing grinding in a dry-method vibration ball mill pulverizer; then adding 5-10 parts of porous carbon material and 0.0001-0.0005 part of heat stabilizer, and continuously performing second dispersion grinding in a dry vibration ball mill pulverizer to obtain composite powder;

7. The preparation method according to claim 6, wherein in step S1, the working frequency of the dry vibration ball mill pulverizer for the first dispersion grinding and the second dispersion grinding is 1200-1500rpm, and the pulverizing time of the dry vibration ball mill pulverizer is 20-240min, preferably 30-50min.

8. The method according to claim 6 or 7, wherein in step S2, the rotation speed of the mixing device is 30-3000rpm for 5-10min.

9. The pearl powder-containing multifunctional fiber is characterized in that the raw material composition of the pearl powder-containing multifunctional fiber comprises the pearl powder-containing multifunctional master batch and the matrix resin slice of any one of claims 1 to 5, preferably, the mass ratio of the pearl powder-containing multifunctional master batch to the matrix resin slice is 1-8; more preferably, the base resin chip of the multifunctional fiber is the same type as the base resin of the multifunctional mother particle.

10. The method of claim 9, wherein the pearl powder-containing multifunctional fiber is spun by mixing the pearl powder-containing multifunctional master batch with the matrix resin chips according to a conventional method.