Synthetic method of master batch for odor-removing fiber, ES fiber and preparation method of ES fiber
By blending modified MCM-41 mesoporous molecular sieve with resin to prepare fiber materials, the problem of fiber materials being unable to adsorb irritating gases was solved, enabling the application of efficient and safe fiber materials in hygiene products.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-01-26
- Publication Date
- 2026-04-14
AI Technical Summary
Existing fiber materials are unable to effectively adsorb and remove strong irritating gases such as ammonia, hydrogen sulfide, and isovaleric acid generated in biodegradation, industrial production, and daily life, leading to problems such as allergies when in contact with the skin.
MCM-41 mesoporous molecular sieves are used for metal ion exchange, then blended with resin to form masterbatches and fibers. The mesoporous structure and active metal ion centers are used to achieve efficient adsorption of irritating gases. The gases are adsorbed through mechanisms such as surface acid-base interaction, complexation and chemical bonding, and enhanced van der Waals forces.
It achieves highly efficient adsorption of a variety of irritating gases, with a large adsorption capacity and high adsorption efficiency. The material is safe and non-toxic, and is suitable for use in hygiene products that come into contact with human skin. It overcomes the shortcomings of traditional materials in adsorption of macromolecules and in high humidity environments.
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Figure CN121853191A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of fiber material technology, and more particularly to a method for synthesizing masterbatch for deodorizing fibers, ES fibers and their preparation methods. Background Technology
[0002] In various scenarios such as biodegradation, industrial production, and daily life, a variety of gases with strong irritant and malodorous properties are produced, such as ammonia (NH3), trimethylamine ((CH3)3N), hydrogen sulfide (H2S), and isovaleric acid (C5H2O). 10 O2), methanethiol (CH4S), indole (C8H7N), nonanal (C9H 18 O), decanal (C 10 H 20 O), etc. These gases not only cause sensory discomfort, but some are also corrosive or toxic, posing a threat to human health and quality of life. Especially in personal care products such as sanitary napkins and diapers, these gases are produced by microbial decomposition and metabolism, and come into direct contact with the skin, easily causing allergies, dermatitis, and other problems. Therefore, endowing fiber materials with safe and efficient odor-removing functions has become an important research and development direction for the textile industry. Summary of the Invention
[0003] In view of the deficiencies of the existing technology, the present invention aims to provide a method for synthesizing masterbatch for deodorizing fiber, ES fiber and preparation method, which synthesizes molecular sieve adsorbent into masterbatch and prepares fiber material, and the molding method can maintain the mesoporous structure and adsorption performance of molecular sieve adsorbent while meeting the safety requirements for human contact, so as to promote this excellent adsorbent fiber material to the field of hygiene care.
[0004] To achieve the above objectives, the technical solution of the present invention mainly includes the following parts: Part One: This invention provides a method for synthesizing masterbatch for deodorizing fibers, comprising the following steps: S100. Dry the molecular sieve adsorbent and screen the particle size in the range of 0.3-5 micrometers; S200, molecular sieve adsorbent ratio 3%-10%, resin ratio 90%-97%, are mixed together in a mixer so that the molecular sieve adsorbent coats the resin surface. S300: Feed the material into a twin-screw extruder, extrude, and pelletize for the first time. Then feed the pelletized material back into the twin-screw extruder to make the molecular sieve adsorbent evenly dispersed in the resin. Extrude and pelletize to obtain masterbatch. The molecular sieve adsorbent is an MCM-41 mesoporous molecular sieve adsorbent with a MCM-41 topological structure after metal ion exchange, washing, drying, and calcination.
[0005] Furthermore, the metal ions include: Li + K + Mg 2+ Ca 2+ Fe 2+ Zn 2+ Ag 2+ At least one of them.
[0006] Furthermore, the degree of ion exchange in the adsorbent obtained after metal ion exchange is between 50% and 80%.
[0007] Optionally, the degree of ion exchange is selected from any value of 50%, 55%, 60%, 65%, 70%, 75%, or 80%, or a range between any two.
[0008] Furthermore, the silicon-to-aluminum ratio in the MCM-41 mesoporous molecular sieve is 40-80, calculated as the molar ratio of SiO2 to Al2O3.
[0009] Optionally, the silicon-to-aluminum ratio is selected from any value or a range between any two of 40, 42, 45, 48, 50, 54, 56, 58, 60, 64, 66, 70, 72, 75, 78 or 80.
[0010] Furthermore, the calcination temperature is between 300°C and 500°C, and the calcination is carried out in a preset atmosphere or vacuum.
[0011] Optionally, the roasting temperature is selected from any value of 300°C, 350°C, 400°C, 450°C or 500°C or a range between any two.
[0012] Furthermore, the preset atmosphere includes one of nitrogen, air, or an inert gas.
[0013] Furthermore, the roasting time is 2 to 24 hours.
[0014] Optionally, the roasting time is selected from 2h, 5h, 7.5h, 10h, 12.5h, 15h, 17.5h, 20h, 22h or 24h.
[0015] Furthermore, in S100, the molecular sieve adsorbent is dried at 100°C for 24 hours.
[0016] Furthermore, in S200, the resin is one of high-density polyethylene resin, PP resin, and PET resin.
[0017] Furthermore, in S200, the mixture is co-mixed in a mixer for 40-60 minutes.
[0018] The MCM-41 mesoporous molecular sieve described in this invention, as a typical silicon-based nanomaterial, is characterized by its highly ordered two-dimensional hexagonal phase (P6mm) pore structure, tunable nanoscale pore size (2-10 nm), and high specific surface area (>1000 m²). 2 It is known for its large pore volume ( / g). Its regular and uniformly sized mesoporous channels provide unobstructed diffusion paths and ample adsorption space for large molecules such as nonanal, decanal, and indole, fundamentally overcoming the bottleneck of microporous materials in adsorbing large molecules.
[0019] Pure silicon-based MCM-41 has a chemically inert surface and a weak adsorption capacity for polar gas molecules. This invention functionalizes it through metal ion exchange, incorporating Li... + K + Mg 2+ Ca 2+ Fe 2+ Zn 2+ Ag 2+ By introducing these into its framework or pore surface, the material is endowed with specific chemical adsorption active centers.
[0020] Molecular sieve adsorbents can adsorb mixed gases from the air atmosphere, including one or more of the following irritating odor gases: ammonia, trimethylamine, hydrogen sulfide, isovaleric acid, methanethiol, indole, nonanal, and decanal. These irritating odor gases mainly originate from three scenarios: biodegradation, industrial production, and daily life. The adsorption temperature range for molecular sieve adsorbents is 77K~309K, with a more suitable range of 298K~309K. Specifically, the adsorption test temperatures for molecular sieve adsorbents are: liquid nitrogen (77K), liquid argon (87K), liquid oxygen (90K), liquefied natural gas (113K), ice (273K), room temperature (298K), and human body temperature (309K). The adsorption pressure range for molecular sieve adsorbents is 50~3000kPa.
[0021] The adsorption principle and mechanism of this invention are mainly based on the following aspects: First, the surface acid-base interaction introduces metal cations (such as Li) + , K + Ca 2+ Mg 2+ As a Lewis acid site, it can strongly adsorb basic gas molecules with lone pairs of electrons, such as ammonia (NH3) and trimethylamine ((CH3)3N). Simultaneously, skeletal hydroxyl groups generated after ion exchange or basic sites introduced (such as K+) can also adsorb these molecules. + The relevant sites can adsorb acidic gases, such as hydrogen sulfide (H2S) and isovaleric acid; secondly, they can adsorb transition metal ions such as Fe. 2+Zn 2+ Zn can form stable coordination bonds or undergo chemical reactions with sulfur- and nitrogen-containing compounds. 2+ Ag reacts with hydrogen sulfide (H2S) to form ZnS, and with methanethiol (CH3SH) to form Zn(CH3S)2, thus achieving irreversible or highly efficient chemisorption. + It has an extremely high affinity for sulfur-containing compounds and can catalyze their decomposition; finally, there is the enhanced van der Waals force and polarization. The highly dispersed metal ions change the electron cloud density on the pore surface, which enhances the van der Waals force between the adsorbent and gas molecules. In particular, for polar molecules such as aldehydes (nonanal, decanal), the presence of metal ions can induce them to generate stronger dipole moments, thereby improving the physical adsorption capacity through electrostatic interactions.
[0022] This invention balances the hydrophobicity of the framework with the number of exchangeable sites by adjusting the silicon-to-aluminum ratio (40-80); and optimizes the density and distribution of surface active sites by controlling the ion exchange rate (50%-80%), thus preventing pore blockage. Finally, the material, after calcination at a specific temperature (300℃-500℃) and atmosphere, can stabilize its structure and activate adsorption sites, forming a highly efficient composite adsorbent that integrates physical adsorption (mesoporous channels) and chemical adsorption (metal active sites).
[0023] This invention does not simply use the original MCM-41, but creatively combines the advantages of MCM-41's large pore size and high specific surface area with the specific chemical adsorption capacity of metal ions through multi-metal ion exchange and precise process control (exchange degree, silicon-aluminum ratio, calcination conditions), achieving "broad-spectrum" and efficient adsorption of a series of irritating odor gases from inorganic to organic and from small molecules to large molecules.
[0024] Part Two: The present invention also protects a fiber obtained from the masterbatch synthesized by the above-mentioned method for synthesizing odor-removing fiber masterbatch.
[0025] Part Three: This invention provides a method for preparing odor-removing ES fibers, comprising the following steps: S1. ES fiber sheath masterbatch was prepared using the above masterbatch synthesis method. S2, ES fibers are obtained by extrusion.
[0026] Furthermore, step S2 includes using a composite spinning device to melt and extrude the sheath masterbatch and core masterbatch into two sets of screw extruders, and then combining the obtained sheath melt and core melt into filaments through a composite spinning assembly. After being cooled and drawn by side blowing air, the odor-removing ES fiber is obtained.
[0027] Part Four: This invention protects an ES fiber prepared by the above-described method for preparing odor-removing ES fiber.
[0028] Part Five: This invention protects an odor-removing ES fiber used to adsorb irritating odor gases such as ammonia, trimethylamine, hydrogen sulfide, isovaleric acid, methanethiol, indole, nonanal, and decanal from the air atmosphere, so as to remove irritating odors.
[0029] Part Six: This invention protects a hot air fabric made of odor-removing ES fiber, which can be used in sanitary napkins and diaper pads.
[0030] This invention successfully introduces mesoporous molecular sieve materials, originally widely used in industrial fields such as catalysis and macromolecular separation, into the field of hygiene products that come into direct contact with human skin. This requires materials to not only possess highly efficient adsorption properties but also meet stringent requirements such as safety, non-toxicity, and high biocompatibility. This invention achieves this technological breakthrough by selecting appropriate metal ions and synthesis processes.
[0031] Compared with traditional activated carbon and zeolite, the adsorbent provided by this invention exhibits comprehensive performance advantages in terms of adsorption capacity (especially for larger and polar molecules), adsorption rate (thanks to the mesoporous structure), and stability under high humidity conditions, providing a novel and efficient material solution for solving the problem of complex multi-component odor adsorption.
[0032] Compared with the prior art, the beneficial effects of the present invention are as follows: 1) The masterbatch provided by the present invention retains the adsorption characteristics of molecular sieve adsorbents, and has a greater adsorption capacity and higher adsorption efficiency for irritating odor gases including ammonia, trimethylamine, hydrogen sulfide, isovaleric acid, methanethiol, indole, nonanal, and decanal.
[0033] 2) The masterbatch method for preparing fiber materials provided by this invention perfectly integrates mesoporous molecular sieves into the fiber materials, thus fully preserving the adsorption capacity of the molecular sieve adsorbent.
[0034] 3) The fiber material prepared by the masterbatch method provided by this invention is the first successful introduction of mesoporous molecular sieve materials into the field of hygiene products that come into direct contact with human skin. This requires the material to not only have high adsorption performance, but also to meet stringent requirements such as safety, non-toxicity, and high biocompatibility. This invention achieves this technological breakthrough by selecting appropriate metal ions and synthesis processes.
[0035] 4) This invention provides a novel and efficient material solution for solving the problem of complex multi-component odor adsorption. Attached Figure Description
[0036] Figure 1In Example 1 of this invention, the zinc ion (Zn) 2+ (Image of the exchanged MCM-41 molecular sieve adsorbent) Figure 2 This is a scanning electron microscope (SEM) image of the mesoporous molecular sieve of Example 1 of the present invention; Figure 3 This is a scanning electron microscope (SEM) image of the ES fibers prepared by the masterbatch method used in Example 1 of the present invention. Figure 4 The image shows the test results of ES fiber adsorption and removal of trimethylamine obtained by the masterbatch method used in Example 1 of this invention. Figure 5 The image shows the adsorption and removal test results of isovaleric acid by ES fibers prepared by the masterbatch method used in Example 1 of this invention. Figure 6 Scanning electron microscope (SEM) image of the original fibers without the addition of molecular sieve adsorbent; Figure 7 The image shows a scanning electron microscope (SEM) image of the fibers prepared by adding molecular sieve adsorbent using the oil-based method in Comparative Example 1. Figure 8 The image shows the test results of fiber adsorption for the removal of trimethylamine in Comparative Example 1, prepared by adding molecular sieve adsorbent to oil-based method. Detailed Implementation
[0037] The present invention will now be described in detail with reference to the embodiments, but the present invention is not limited to these embodiments.
[0038] Unless otherwise specified, all raw materials used in the embodiments of this invention were purchased commercially. Experimental methods in the following embodiments that do not specify particular conditions were generally performed under conventional conditions.
[0039] The X-MCM-41 molecular sieve powder used in the embodiments of this invention is prepared through the following steps: (1) Preparation of MCM-41 raw powder: An appropriate amount of hexadecyltrimethylammonium bromide (DTAB) was added to 4.8 L of distilled water to form a homogeneous solution under stirring. 35 mL of sodium hydroxide (2 M) solution was added to the solution, and the mixture was stirred continuously at 80 °C for 5 minutes. Subsequently, an appropriate amount of tetraethyl orthosilicate (TEOS) was added, and the reaction was continued to be stirred at 80 °C for 10 h. After the reaction was completed, the product was collected, washed with distilled water, and dried at 60 °C for 24 h. Finally, the obtained MCM-41 material was calcined at 550 °C for 5 h to completely remove the surfactant, and dried MCM-41 raw powder was obtained. (2) Preparation of MCM-41 molecular sieve adsorbent: Using appropriate concentrations of Li... + K + Mg 2+ Ca 2+ Fe 2+Zn 2 + Ag + The solution was used to perform ion exchange on the MCM-41 raw powder obtained in (1) to obtain mesoporous molecular sieve adsorbent powders with different ion exchanges.
[0040] Example 1 Preparation of zinc ions (Zn 2+ The exchanged MCM-41 molecular sieve adsorbent is as follows: 50 g of hexadecyltrimethylammonium bromide (DTAB) was added to 4.8 L of distilled water to form a homogeneous solution under stirring. 35 mL of sodium hydroxide (2 M) solution was added to this solution, and the mixture was stirred continuously at 80 °C for 5 minutes. Then, 250 mL of tetraethyl orthosilicate (TEOS) was added, and the reaction was continued at 80 °C for 10 hours. After the reaction was complete, the product was collected, washed with distilled water, and dried at 60 °C for 24 hours. Finally, the obtained MCM-41 mesoporous molecular sieve was calcined at 550 °C for 5 hours to completely remove the surfactant, yielding dried MCM-41 raw powder. The silica-alumina ratio of the MCM-41 raw powder was determined using XRF, and a silica-alumina ratio of 40-80 was selected.
[0041] The obtained MCM-41 raw powder (selected with a silicon-to-aluminum ratio of SiO2 / Al2O3=60) was subjected to zinc ion (Zn) treatment. 2+ After exchange (zinc ion exchange degree of 75%), activation is achieved by calcination at 350℃ under vacuum for 10 hours to obtain zinc ions (Zn). 2+ The exchanged MCM-41 molecular sieve adsorbent powder, such as Figure 1 .
[0042] Prepared zinc ions (Zn 2+ The exchanged MCM-41 molecular sieve adsorbent was synthesized into masterbatch through the following steps: S100: Dry the molecular sieve adsorbent at 100℃ for 24 hours, and screen the particle size range of 0.3-5 micrometers; S200, molecular sieve adsorbent ratio 3%-10%, resin ratio 90%-97%, are mixed together in a mixer for 40-60 minutes to allow the molecular sieve adsorbent to coat the resin surface. S300: Feed the material into a twin-screw extruder, extrude, and pelletize for the first time. Then feed the pelletized material back into the twin-screw extruder to uniformly disperse the molecular sieve adsorbent in the resin. Extrude and pelletize to obtain masterbatch.
[0043] The masterbatch mentioned above can be used as a sizing material for ES fibers, or it can be used alone to make single-component fibers.
[0044] In this embodiment, the masterbatch synthesized in the above process is used as the ES fiber sheath masterbatch. Using a composite spinning equipment, the sheath masterbatch and the core masterbatch are fed into two sets of screw extruders for melt extrusion. The obtained sheath melt and core melt are combined into filaments by the composite spinning assembly, and then cooled and stretched by side blowing air to obtain the odor-removing ES fiber.
[0045] The core layer masterbatch uses conventional materials, such as commonly used polypropylene (PP), or polyester, polyamide, polylactic acid, etc., for specific functional requirements.
[0046] The obtained ES fibers were scanned by electron microscopy, and the results are shown in the appendix. Figure 3 The ES fiber surface is uniform, and the molecular sieve adsorbent and fiber have a good fusion effect.
[0047] ES fiber effectively adsorbs and removes irritating odors; results are shown in the appendix. Figure 4-5 And Table 1.
[0048] Table 1. Test results of ES fiber prepared by masterbatch method for odor removal adsorption.
[0049] ES fibers can be used to adsorb one or more mixed gases from the air atmosphere, including ammonia, trimethylamine, hydrogen sulfide, isovaleric acid, methanethiol, indole, nonanal, decanal, etc., to remove irritating odors. These irritating odor gases mainly come from three scenarios: biodegradation, industrial production, and daily life.
[0050] The ES fibers obtained by the masterbatch method were made into hot air fabric. The hot air fabric was subjected to safety testing in accordance with the hygiene requirements for disposable sanitary products in GB15979-2024. The test results are shown in Table 2.
[0051] Table 2. Safety test results of hot air fabric
[0052] The ES fiber of this invention, when made into a hot air fabric, has high adsorption capacity for substances such as ammonia, trimethylamine, hydrogen sulfide, isovaleric acid, methanethiol, indole, nonanal, and decanal, and has high skin contact safety. It can be applied to products involving skin contact, such as sanitary napkins and diaper pads.
[0053] Comparative Example 1 ES fibers were prepared using the oiling method. A molecular sieve adsorbent was added to the pre-spinning oil, and the scanning electron microscopy (SEM) results of the fibers are shown below. Figure 7 Molecular sieves agglomerate, resulting in uneven fiber surfaces.
[0054] The effect of ES fibers prepared by the oil-based method on removing trimethylamine was tested, and the test results are as follows: Figure 8 .
[0055] Results analysis: Adding molecular sieve adsorbent to the pre-spinning oil to make the molecular sieve adsorbent completely exposed on the fiber surface resulted in poor adsorption and odor removal effect because the pores of the molecular sieve adsorbent were blocked by the oil.
[0056] It should be noted that the parts of this invention not described in detail are prior art.
[0057] The above examples are merely preferred embodiments of the present invention. Obviously, the present invention is not limited to the above embodiments, and many variations are possible. All variations that can be directly derived or conceived by those skilled in the art from the disclosure of the present invention should be considered within the scope of protection of the present invention.
Claims
1. A method for synthesizing masterbatch for odor-removing fibers, characterized in that: S100. Dry the molecular sieve adsorbent and screen the particle size in the range of 0.3-5 micrometers; S200, molecular sieve adsorbent ratio 3%-10%, resin ratio 90%-97%, are mixed together in a mixer so that the molecular sieve adsorbent coats the resin surface. S300: Feed the material into a twin-screw extruder, extrude, and pelletize for the first time. Then feed the pelletized material back into the twin-screw extruder to make the molecular sieve adsorbent evenly dispersed in the resin. Extrude and pelletize to obtain masterbatch. The molecular sieve adsorbent is an MCM-41 mesoporous molecular sieve adsorbent with a MCM-41 topological structure after metal ion exchange, washing, drying, and calcination.
2. The method for synthesizing masterbatch for deodorizing fibers according to claim 1, characterized in that: The metal ions include: Li + K + Mg 2+ Ca 2+ Fe 2+ Zn 2+ Ag 2+ At least one of the following; the degree of ion exchange in the adsorbent obtained after metal ion exchange is 50% to 80%.
3. The method for synthesizing masterbatch for deodorizing fibers according to claim 1, characterized in that: The silicon-aluminum ratio in the MCM-41 mesoporous molecular sieve is 40~80, calculated as the molar ratio of SiO2 to Al2O3; the calcination temperature is 300℃~500℃, and the calcination is carried out in a preset atmosphere or vacuum. The preset atmosphere includes one of nitrogen, air, or an inert gas; the calcination time is 2 to 24 hours.
4. The method for synthesizing masterbatch for deodorizing fibers according to claim 1, characterized in that: In S100, the molecular sieve adsorbent is dried at 100°C for 24 hours; In S200, the resin is one of high-density polyethylene resin, PP resin, and PET resin; it is co-mixed in a mixer for 40-60 minutes.
5. A method for preparing odor-removing ES fibers, characterized in that, Includes the following steps: S1. Preparation of cortex masterbatch: ES fiber sheath masterbatch was prepared by the masterbatch synthesis method as described in any one of claims 1-4; S2, ES fibers are obtained by extrusion.
6. The method for preparing odor-removing ES fiber according to claim 5, characterized in that: Step S2 includes using a composite spinning device to melt and extrude the sheath masterbatch and core masterbatch into two sets of screw extruders, respectively. After the obtained sheath melt and core melt are combined into filaments by a composite spinning assembly, they are cooled and stretched by side blowing air to obtain odor-removing ES fiber.
7. An odor-removing fiber, characterized in that, The fiber is obtained by the masterbatch synthesis method for deodorizing fiber according to any one of claims 1-3.
8. An odor-removing ES fiber, characterized in that, ES fiber prepared by the method for preparing odor-removing ES fiber as described in claim 4 or 5.
9. An odor-removing ES fiber as described in claim 8, used to adsorb irritating odor gases such as ammonia, trimethylamine, hydrogen sulfide, isovaleric acid, methanethiol, indole, nonanal, and decanal from the air atmosphere to achieve the purpose of removing irritating odors.
10. A hot air cloth made of odor-removing ES fiber as described in claim 8, for use in sanitary napkins and diaper pads.