Polymer composite material capable of continuously releasing negative ions as well as preparation method and application of polymer composite material

Abstract

The invention relates to the technical field of polymer composite materials. The invention provides a polymer composite material capable of continuously releasing negative ions. The polymer composite material is mainly prepared from the following raw materials in parts by weight: 75-90 parts of a base material, 3-15 parts of functional composite powder, 2-8 parts of a release auxiliary agent, 3-8 parts of an attenuation compensation composite auxiliary agent and 1-2 parts of other auxiliary agents. The invention also provides a preparation method of the polymer composite material capable of continuously releasing negative ions. Based on the same inventive concept, the invention also provides application of the polymer composite material capable of continuously releasing negative ions in the fields of air purification, medical care, thermoplastic elastomer product preparation, textile preparation and plastic product preparation. A microcosmic channel release mechanism and an attenuation compensation mechanism are formed on a series of polymer base materials by adopting a plurality of composite functional powders and a plurality of composite components, so that the prepared polymer composite material achieves the outstanding effect of continuously releasing high-concentration negative ions in air.

Description

Technical Field

[0001] The present invention belongs to the technical field of polymer composite materials, and in particular relates to a polymer composite material that can sustainably release negative ions, and a preparation method and application thereof. Background Art

[0002] Negative ions are negatively charged ions with numerous beneficial effects, including air purification, sterilization, and fatigue relief. By combining negative ion-releasing materials with polymer matrices (such as plastics, rubber, and fibers), composite materials with specific functions can be formed. Commonly used negative ion-releasing materials include functional tourmaline and its composite powders, including tourmaline, negative ion powder, barium titanate, and zinc oxide. Tourmaline, a naturally occurring mineral, is the most commonly used, exhibiting piezoelectric and pyroelectric properties and capable of continuously releasing negative ions.

[0003] However, the application of functional tourmaline and its composite powder in polymer materials has always been subject to two major technical difficulties: first, how to make the functional tourmaline and its composite powder contact and ionize with water and air on the plastic surface after being compounded with the polymer material, thereby forming a large concentration of negative air ions; second, since negative ions easily react with positive ions and disappear quickly, they are unstable. How to make the formed polymer composite material sustainably release a certain amount of negative air ions to ensure its actual application effect.

[0004] Among existing patented technologies, for example, Chinese patent CN1386550A provides a technique, process, and formula for preparing composite powders that efficiently generate negative air ions. Natural polar minerals, such as iron tourmaline, magnesium tourmaline, iron-magnesium tourmaline, and lithium tourmaline, are ultrafinely ground and mechanochemically compounded with rare earth composite salts (or rare earth composite oxides) and nano-semiconductor materials. Alternatively, the polar mineral tourmaline is surface-treated (e.g., heat-treated at 100-900°C, surface acid-base treated) and then compounded with rare earth salts and nano-photocatalytic semiconductor materials to prepare a composite material that efficiently generates negative air ions. This patented technical solution achieves a composite powder that generates negative air ions more than twice as efficiently as tourmaline and other materials alone. This composite powder, developed to address the low concentration of negative ions released by single tourmaline, aims to increase the amount of negative ions released. Another example is Chinese patent CN112795094A, which provides a PP alloy material capable of releasing negative oxygen ions, and its preparation method and application. The PP alloy material capable of releasing negative oxygen ions comprises the following components by weight: 65-75 parts of carrier resin, 8-30 parts of filler, 0.5-2 parts of compatibilizer, 2-15 parts of POE, 3-5 parts of negative ion powder, and 0.5-2 parts of lubricant. The carrier resin is composed of PP resin and PE resin, wherein the weight of the added PE does not exceed 10% of the weight of the carrier resin. The function of releasing negative oxygen ions can be imparted by replacing the material of the corresponding components; Chinese patent CN106750906A, which provides a polyolefin composition with enhanced negative ion release, which comprises the following raw materials by weight: 60-90 parts of polyolefin mixture (copolymer PP, etc.); 5-30 parts of filler; negative ion Release agent 1-5 parts; conductive agent 1-10 parts; auxiliary agent 1-3 parts; lubricant 0.1-0.3 parts; antioxidant 0.2-0.5 parts; weathering agent 0.2-0.5 parts; wherein the auxiliary agent is diethanolamine with a long-chain alkyl group. In the above Chinese patents CN112795094A and CN106750906A, the negative ion release amount is increased by adding different proportions of tourmaline and negative ion powder to PP as the base material, but the above two technical problems are not solved, so the negative ion release amount obtained is 2,000 / cm 3 The following either have a short duration or do not involve sustained release.

[0005] Therefore, in order to make the polymer materials that can release high concentrations of negative air ions sustainably available for practical application, the existing technology needs to be improved urgently. Summary of the Invention

[0006] The present invention aims to address the deficiencies of the prior art and provide a polymer composite material for sustainable negative ion release, a preparation method thereof, and an application thereof. The present invention aims to release a large amount of negative ions, a long release time, and sustainable release.

[0007] In order to solve the above problems, the present invention provides the following technical solutions: A polymer composite material capable of sustainably releasing negative ions is mainly prepared from the following raw materials in parts by weight: 75-90 parts of a base material, 3-15 parts of a functional composite powder, 2-8 parts of a release auxiliary agent, 3-8 parts of an attenuation-compensating composite auxiliary agent, and 1-2 parts of other auxiliary agents.

[0008] A preferred polymer composite material for sustained negative ion release is primarily composed of the following raw materials in parts by weight: 80-85 parts substrate, 8-13 parts functional composite powder, 2-4 parts release aid, 3-5 parts attenuation-compensating composite aid, and 0.5-1 part other additives. Most preferably, a polymer composite material for sustained negative ion release is primarily composed of the following raw materials in parts by weight: 80 parts substrate, 13 parts functional composite powder, 4 parts release aid, 5 parts attenuation-compensating composite aid, 0.5 part lubricant, and 0.5 part antioxidant. Under these conditions, the material achieves an air negative ion release concentration of 10,300 (ions / cm³) and a 10-year negative ion release attenuation value of 16.3%, achieving optimal overall performance.

[0009] In the above-mentioned sustainable negative ion-releasing polymer composite material, other additives include any one of lubricants, antioxidants, dispersants, compatibilizers or processing aids, or a mixture of two or more thereof. Preferably, the other additives include a mixture of lubricants and antioxidants.

[0010] In the above-mentioned sustainable negative ion-releasing polymer composite material, the lubricant is selected from any one of calcium stearate, zinc stearate, stearic acid, and EBS, or a mixture thereof. Preferably, the lubricant is selected from any one of calcium stearate and zinc stearate. Most preferably, the lubricant is selected from calcium stearate.

[0011] In the above-described sustained-release negative ion polymer composite material, the antioxidant is selected from any one of antioxidant 1010, antioxidant 3114, antioxidant 1078, antioxidant 618, and antioxidant 168, or a mixture thereof. Preferably, the antioxidant is selected from any one of antioxidant 1010 and antioxidant 168, or a mixture thereof. Most preferably, the antioxidant is selected from a combination of antioxidant 1010 and antioxidant 168, with the weight ratio of the antioxidants being 2:1.

[0012] Of course, the polymer composite material capable of sustainably releasing negative ions of the present invention may also contain other additives, such as diffusing agents, compatibilizers, processing aids, and the like.

[0013] Preferably, the dispersant is selected from any one of maleic anhydride grafted polypropylene, polyethylene wax, and ethylene bisstearamide.

[0014] Preferably, the compatibilizer is selected from any one of maleic anhydride grafted polypropylene, ethylene-vinyl acetate copolymer, ethylene-octene copolymer, styrene-butadiene-styrene block copolymer, and styrene-isoprene-styrene block copolymer.

[0015] Preferably, the processing aid is selected from any one of polyethylene wax, ethylene bisstearamide, oxidized polyethylene wax, silicone oil, and erucamide.

[0016] The sustainable negative ion-releasing polymer composite material as described above, wherein the functional composite powder is selected from any one of iron tourmaline, ferromagnesium tourmaline, lithium tourmaline, magnesium tourmaline, sodium manganese tourmaline, rare earth oxides, rare earth composite salts, and photocatalytic oxides, or a mixture of several of them.

[0017] In the present invention, the components in the functional composite powder have autonomous lattice instability and generate a voltage difference, which can cause the water and air in the air to be ionized and generate air negative ions. At the same time, certain components in the functional composite powder, such as rare earth oxides and rare earth composite salts containing rare earth elements, can improve the spontaneous polarization performance of tourmaline through the doping effect with the tourmaline in the functional powder, and can enhance the negative oxygen ion release performance of tourmaline. For example, the photocatalytic oxide in the functional composite powder as described above has photocatalytic activity and can accelerate the generation of negative ions under light conditions; in addition, it can also act as a catalyst to promote the decomposition of water molecules in the air and further generate negative ions. However, the formation of some air negative ions will also be destroyed by combining with external positive ions. These components alone are not enough to ensure a high concentration of air negative ions and the continuous generation of high concentrations of air negative ions.

[0018] In some embodiments of the present invention, the functional composite powder is selected from a mixture of ferromagnesian tourmaline, rare earth oxides, and photocatalytic oxides, and the weight ratio of the ferromagnesian tourmaline, rare earth oxides, and photocatalytic oxides is 5:1:1 or 4:2:1.

[0019] In some embodiments of the present invention, the functional composite powder is selected from a mixture of lithium tourmaline, rare earth composite salt, and photocatalytic oxide, and the weight ratio of the lithium tourmaline, rare earth composite salt, and photocatalytic oxide is 5:1:1 or 4:2:1.

[0020] In some embodiments of the present invention, the functional composite powder is selected from a mixture of magnesia tourmaline, rare earth oxides, and photocatalytic oxides, and the weight ratio of the magnesia tourmaline, rare earth oxides, and photocatalytic oxides is 5:1:1 or 4:2:1.

[0021] In some embodiments of the present invention, preferably, the rare earth oxide is selected from any one of CeO2, Ce2O3, La2O3, Nd2O3, or a mixture of two thereof. Optionally, the rare earth oxide is selected from any one of CeO2 or Nd2O3. Preferably, the rare earth composite salt is selected from any one of LaPO4, La(NO3)3, CePO4, Ce(NO3)3, NdPO4, or Nd(NO3)3, or a mixture thereof. Preferably, the rare earth composite salt is selected from any one of LaPO4, CePO4, or Ce(NO3)3. Preferably, the photocatalytic oxide is selected from any one of TiO2, ZnO, Fe2O3, tungsten oxide, or tin oxide, or a mixture thereof. Optionally, the photocatalytic oxide is selected from any one of TiO2, ZnO, tungsten oxide, or tin oxide.

[0022] In the above-described sustainable negative ion-releasing polymer composite material, the substrate is selected from any one of PP, PE, PVC, ABS, PS, PA6, PA66, POM, PBT, PET, PC, TPE, TPU, and TPV, or a mixture thereof. Preferably, the substrate is selected from any one of PP, ABS, TPE, PA6, or PBT. Under these conditions, on the one hand, the substrate provides a stable physical structure for the sustainable negative ion-releasing polymer composite material, ensuring its mechanical strength and durability during use; on the other hand, the choice of substrate ensures that all components are evenly dispersed and achieve optimal results. Furthermore, the substrate has good processing properties, making it easy to manufacture into products of various shapes. Most preferably, the substrate is selected from PP.

[0023] In the above-described sustainable negative ion-releasing polymer composite material, the release aid is selected from any one of expanded graphite, diatomaceous earth, molecular sieves, zeolite powder, shell powder, oyster powder, shrimp shell powder, activated carbon, silica powder, MOFs, and carbonate rock powder, or a mixture of several of them. Preferably, the release aid is selected from any one of expanded graphite, diatomaceous earth, zeolite powder, shell powder, oyster powder, shrimp shell powder, and activated carbon, or a mixture of several of them. Under these conditions, the release aid provides an ionization channel with external air and moisture. Most preferably, the release aid is selected from a mixture of diatomaceous earth and oyster powder, and the weight ratio of the diatomaceous earth to oyster powder is 1:1.

[0024] In the above-described sustainable negative ion-releasing polymer composite material, the attenuation-compensating composite additive is selected from any one of white negative ion powder, lanthanum phosphate ore powder, rare earth phosphate ore powder, bastnaesite powder, thorium ore powder, rare earth ceramic powder, monazite powder, rare earth negative ion powder, water-soluble negative ion powder, and UV absorbers, or a mixture thereof. Under these conditions, the attenuation-compensating composite additive can protect the functional composite powder and the release additive, preventing them from aging or failure due to environmental factors (such as temperature, humidity, and light) during long-term use, thereby helping to extend the service life of the negative ion-releasing product.

[0025] In some embodiments of the present invention, the attenuation compensation composite auxiliary agent is selected from a mixture of monazite powder, rare earth negative ion powder, and UV absorber, and the weight ratio of the monazite powder, rare earth negative ion powder, and UV absorber is 100:50:1 or 100:30:2.

[0026] In some embodiments of the present invention, the attenuation compensation composite auxiliary agent is selected from a mixture of monazite powder, white negative ion powder, and UV absorber, and the weight ratio of the monazite powder, white negative ion powder, and UV absorber is 100:50:1 or 100:30:2.

[0027] In some embodiments of the present invention, the attenuation compensation composite auxiliary agent is selected from a mixture of monazite powder, water-soluble negative ion powder, and UV absorber, and the weight ratio of the monazite powder, water-soluble negative ion powder, and UV absorber is 100:50:1 or 100:30:2.

[0028] Most preferably, the attenuation compensation composite auxiliary agent is a mixture of monazite powder, white negative ion powder, and UV absorber in a weight ratio of 100:50:1.

[0029] Optionally, the UV absorber is any one of 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxylbenzophenone, 2-hydroxy-4-methoxy-5-sulfonic acid benzophenone, 2-hydroxy-4-methoxy-5-sodium sulfonate benzophenone, and 2-hydroxy-4-n-octyloxybenzophenone. Most preferably, the UV absorber is 2,2'-dihydroxy-4,4'-dimethoxybenzophenone.

[0030] In the present invention, the functional composite powder can directly ionize with air and water to directly generate negative ions, and the release auxiliary agent further enhances the generation and release effect of negative ions by increasing the ionization channel with the external air and water; the attenuation compensating composite auxiliary agent, on the one hand, delays the aging process of the functional composite powder and maintains its long-term stable negative ion release ability, and on the other hand, produces a good synergistic effect with the functional composite powder and the release auxiliary agent to increase the continuous ionization ability. The substrate provides a physical carrier and protection for each active ingredient, while other auxiliary agents improve the processing performance and mechanical properties of the composite material. Through the multi-level synergistic effect of the above functional composite powder, release auxiliary agent, attenuation compensating composite auxiliary agent, substrate and other auxiliary agents such as lubricants and antioxidants, the polymer composite material achieves the effect of large negative ion release, long-term release and sustainable release.

[0031] Based on the same inventive concept, the present invention provides a method for preparing a polymer composite material capable of sustainably releasing negative ions, comprising the following steps: (1) According to a set ratio, the raw material components of the attenuation compensation composite additive are mechanically mixed or ground with water as a medium to prepare the attenuation compensation composite additive; (2) adding the functional composite powder, the base material, the release agent, the attenuation compensation composite agent prepared in step (1), and other additives into a high-speed mixer according to a set ratio to obtain a mixture; (3) The mixture in step (2) is placed in a high-speed mixer and mixed for 5 to 10 minutes. The mixture is discharged and introduced into a twin-screw extruder through a feed port for melting, extrusion, cooling, and granulation. The speed of the twin-screw extruder is 200 to 500 R / min, and the temperature of the twin-screw from the feed to the die is set to 120 to 180°C, 150 to 200°C, 160 to 220°C, 170 to 250°C, 180 to 270°C, 180 to 270°C, 160 to 250°C, 160 to 250°C, and 160 to 250°C, respectively. The vacuum degree is ≤ 0.06 MPa, thereby obtaining a polymer composite material capable of continuously releasing negative ions. Preferably, the speed of the twin-screw extruder is 350 to 450 R / min. Preferably, the temperature of the twin screw from feeding to the die is set to 125-180°C, 160-200°C, 180-220°C, 185-250°C, 180-260°C, 180-250°C, 170-210°C, 160-250°C, 170-230°C, and the vacuum degree is ≤0.06Mpa. Most preferably, the speed of the twin screw extruder is 450 R / min. Preferably, the temperature of the twin screw from feeding to the die is set to 180°C, 190°C, 200°C, 210°C, 210°C, 200°C, 185°C, 180°C, 180°C, and the vacuum degree is 0.06Mpa.

[0032] Based on the same inventive concept, the present invention provides a method for preparing a negative ion polymer composite material that can sustainably release negative ions, a negative ion polymer composite material prepared therefrom, or the application of the negative ion polymer composite material as described above in the fields of air purification, medical care, thermoplastic elastomer product preparation, textile preparation, and plastic product preparation.

[0033] Compared with the existing technology, the effects and advantages of the present invention are: 1. The present invention provides a polymer composite material that can sustainably release negative ions. It adopts a variety of composite functional powders and a variety of composite components to form a microscopic channel release mechanism and attenuation compensation mechanism on a series of polymer substrates, so that the prepared polymer composite material can achieve the outstanding effect of sustainably releasing high-concentration air negative ions.

[0034] 2. The polymer composite material for sustainable negative ion release prepared by the preparation method provided by the present invention can release air negative ions at a concentration of more than 10,000 air negative ions per cm³; the polymer composite material can release air negative ions for more than 10 years. DETAILED DESCRIPTION

[0035] The following will be combined with the contents of the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0036] Unless otherwise defined, all technical and scientific terms used in this specification have the same meanings as those commonly understood by those skilled in the art to which this invention pertains. The terms used in this specification are intended solely for the purpose of describing specific embodiments and are not intended to limit the invention. The term "and / or" as used in this specification includes any and all combinations of one or more of the associated listed items.

[0037] Unless otherwise specified, the experimental methods used in the following examples are conventional methods.

[0038] Unless otherwise specified, the materials and reagents used in the following examples can be obtained from commercial sources.

[0039] Ferromagnesian tourmaline, lithium tourmaline, and magnesium tourmaline were purchased from Shijiazhuang Tourmaline Mineral Products Co., Ltd., 800 mesh; Monazite powder was purchased from Yixuan Mineral Products Processing Plant in Lingshou County, 200 mesh; Rare earth anion powder was purchased from Shanghai Annao Environmental Technology Co., Ltd., 600 mesh; White negative ion powder and soluble negative ion powder were purchased from Dongguan Yanteng Negative Ion Technology Co., Ltd., 800 mesh.

[0040] Example 1: This embodiment provides a polymer composite material for sustained negative ion release, primarily composed of the following raw materials in parts by weight: 80 parts substrate, 8 parts functional composite powder, 2 parts release aid, 3 parts attenuation-compensating composite aid, 0.5 parts lubricant, and 0.5 parts antioxidant. In this embodiment, the substrate is PP; the functional composite powder is a mixture of ferromagnesian tourmaline, Nd2O3, and ZnO in a weight ratio of 5:1:1; the release aid is a mixture of diatomaceous earth, shell powder, and activated carbon in a weight ratio of 2:2:1; the attenuation-compensating composite aid is a mixture of monazite powder, rare earth negative ion powder, and 2-hydroxy-4-methoxybenzophenone in a weight ratio of 100:50:1; the lubricant is calcium stearate; and the antioxidant is a mixture of antioxidant 1010 and antioxidant 168 in a weight ratio of 2:1.

[0041] The method for preparing a polymer composite material capable of sustainably releasing negative ions in this embodiment comprises the following steps: (1) Monazite powder, rare earth anion powder, and 2-hydroxy-4-methoxybenzophenone are mechanically mixed in a weight ratio of 100:50:1 to prepare an attenuation compensation composite additive; (2) adding the functional composite powder, the base material, the release aid, the attenuation compensation composite aid prepared in step (1), the lubricant, and the antioxidant into a high-speed mixer according to a set ratio to obtain a mixture; (3) The mixture was placed in a high-speed mixer and mixed for 10 minutes. The mixture was discharged and introduced into a twin-screw extruder through a feed port for melting, extrusion, cooling, and granulation. The speed of the twin-screw extruder was 450R / min, and the temperatures of the twin-screw from the feed to the die were set to 180°C, 190°C, 200°C, 210°C, 210°C, 200°C, 185°C, 180°C, and 180°C, respectively. The vacuum degree was 0.06Mpa, thereby obtaining a polymer composite material capable of continuously releasing negative ions.

[0042] Example 2: This embodiment provides a polymer composite material for sustained negative ion release, primarily composed of the following raw materials in parts by weight: 80 parts substrate, 13 parts functional composite powder, 4 parts release aid, 5 parts attenuation-compensating composite aid, 0.5 parts lubricant, and 0.5 parts antioxidant. In this embodiment, the substrate is PP; the functional composite powder is a mixture of lithium tourmaline, CePO4, and tungsten oxide in a weight ratio of 5:1:1; the release aid is a mixture of diatomaceous earth and oyster powder in a weight ratio of 1:1; the attenuation-compensating composite aid is a mixture of monazite powder, white negative ion powder, and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone in a weight ratio of 100:50:1; the lubricant is calcium stearate; and the antioxidant is a mixture of antioxidant 1010 and antioxidant 168 in a weight ratio of 2:1.

[0043] The method for preparing a polymer composite material capable of sustainably releasing negative ions in this embodiment comprises the following steps: (1) Monazite powder, white negative ion powder, and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone are mechanically mixed in a weight ratio of 100:50:1 to prepare an attenuation compensation composite additive; (2) adding the functional composite powder, the base material, the release aid, the attenuation compensation composite aid prepared in step (1), the lubricant, and the antioxidant into a high-speed mixer according to a set ratio to obtain a mixture; (3) The mixture was placed in a high-speed mixer and mixed for 10 minutes. The mixture was discharged and introduced into a twin-screw extruder through a feed port for melting, extrusion, cooling, and granulation. The speed of the twin-screw extruder was 450R / min, and the temperatures of the twin-screw from the feed to the die were set to 180°C, 190°C, 200°C, 210°C, 210°C, 200°C, 185°C, 180°C, and 180°C, respectively. The vacuum degree was 0.06Mpa, thereby obtaining a polymer composite material capable of continuously releasing negative ions.

[0044] Example 3: This embodiment provides a polymer composite material for sustained negative ion release, which is primarily prepared from the following raw materials in parts by weight: 85 parts of a substrate, 12 parts of a functional composite powder, 4 parts of a release aid, 5 parts of a decay-compensating composite aid, 0.5 parts of a lubricant, and 0.5 parts of an antioxidant. In this embodiment, the substrate is ABS; the functional composite powder is a mixture of ferromagnesian tourmaline, CeO2, and tungsten oxide in a weight ratio of 4:2:1; the release aid is a mixture of zeolite powder and oyster powder in a weight ratio of 1:1; the decay-compensating composite aid is a mixture of monazite powder, water-soluble negative ion powder, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone in a weight ratio of 100:30:2; the lubricant is zinc stearate; and the antioxidant is a mixture of antioxidant 1010 and antioxidant 168 in a weight ratio of 2:1.

[0045] The method for preparing a polymer composite material capable of sustainably releasing negative ions in this embodiment comprises the following steps: (1) Monazite powder, water-soluble negative ion powder, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone are mechanically mixed in a weight ratio of 100:30:2 to prepare an attenuation compensation composite additive; (2) adding the functional composite powder, the base material, the release aid, the attenuation compensation composite aid prepared in step (1), the lubricant, and the antioxidant into a high-speed mixer according to a set ratio to obtain a mixture; (3) The mixture was placed in a high-speed mixer and mixed for 10 minutes. The mixture was discharged and introduced into a twin-screw extruder through a feed port for melting, extrusion, cooling, and granulation. The speed of the twin-screw extruder was 450R / min, and the temperatures of the twin-screw from the feed to the die were set to 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, 200°C, 200°C, and 200°C, respectively. The vacuum degree was 0.06Mpa, thereby obtaining a polymer composite material capable of continuously releasing negative ions.

[0046] Example 4: This embodiment provides a polymer composite material for sustained negative ion release, which is primarily prepared from the following raw materials in parts by weight: 85 parts of a substrate, 10 parts of a functional composite powder, 4 parts of a release aid, 5 parts of a decay-compensating composite aid, 0.5 parts of a lubricant, and 0.5 parts of an antioxidant. In this embodiment, the substrate is TPE; the functional composite powder is a mixture of magnesia tourmaline, LaPO4, and TiO2 in a weight ratio of 5:1:1; the release aid is a mixture of zeolite powder and oyster powder in a weight ratio of 1:1; the decay-compensating composite aid is a mixture of monazite powder, white negative ion powder, and 2-hydroxy-4-methoxy-5-sulfonic acid benzophenone in a weight ratio of 100:50:1; the lubricant is calcium stearate; and the antioxidant is a mixture of antioxidant 1010 and antioxidant 168 in a weight ratio of 2:1.

[0047] The method for preparing a polymer composite material capable of sustainably releasing negative ions in this embodiment comprises the following steps: (1) Monazite powder, white negative ion powder, and 2-hydroxy-4-methoxy-5-sulfonic acid benzophenone are mechanically mixed in a weight ratio of 100:50:1 to prepare an attenuation compensation composite additive; (2) adding the functional composite powder, the base material, the release aid, the attenuation compensation composite aid prepared in step (1), the lubricant, and the antioxidant into a high-speed mixer according to a set ratio to obtain a mixture; (3) The mixture was placed in a high-speed mixer and mixed for 10 minutes. The mixture was discharged and introduced into a twin-screw extruder through a feed port for melting, extrusion, cooling, and granulation. The speed of the twin-screw extruder was 350R / min, and the temperatures of the twin-screw from the feed to the die were set to 125°C, 160°C, 180°C, 185°C, 180°C, 180°C, 170°C, 170°C, and 170°C, respectively. The vacuum degree was 0.06Mpa, thereby obtaining a polymer composite material capable of continuously releasing negative ions.

[0048] Example 5: This embodiment provides a polymer composite material for sustained negative ion release, which is primarily prepared from the following raw materials in parts by weight: 80 parts of a substrate, 10 parts of a functional composite powder, 4 parts of a release aid, 5 parts of a decay-compensating composite aid, 0.5 parts of a lubricant, and 0.5 parts of an antioxidant. In this embodiment, the substrate is PA6; the functional composite powder is a mixture of lithium tourmaline, CePO4, and tin oxide in a weight ratio of 5:1:1; the release aid is a mixture of diatomaceous earth and shrimp shell powder in a weight ratio of 1:1; the decay-compensating composite aid is a mixture of monazite powder, water-soluble negative ion powder, and 2-hydroxy-4-methoxy-5-sodium benzophenone sulfonate in a weight ratio of 100:30:2; the lubricant is calcium stearate; and the antioxidant is a mixture of antioxidant 1010 and antioxidant 168 in a weight ratio of 2:1.

[0049] The method for preparing a polymer composite material capable of sustainably releasing negative ions in this embodiment comprises the following steps: (1) Monazite powder, water-soluble negative ion powder, and 2-hydroxy-4-methoxy-5-sodium sulfonate benzophenone are mechanically mixed in a weight ratio of 100:30:2 to prepare an attenuation compensation composite additive; (2) adding the functional composite powder, the base material, the release aid, the attenuation compensation composite aid prepared in step (1), the lubricant, and the antioxidant into a high-speed mixer according to a set ratio to obtain a mixture; (3) The mixture was placed in a high-speed mixer and mixed for 10 minutes. The mixture was discharged and introduced into a twin-screw extruder through a feed port for melting, extrusion, cooling, and granulation. The speed of the twin-screw extruder was 350R / min, and the temperatures of the twin-screw from the feed to the die were set to 180°C, 200°C, 220°C, 250°C, 260°C, 250°C, 210°C, 230°C, and 230°C, respectively. The vacuum degree was 0.06Mpa, thereby obtaining a polymer composite material capable of continuously releasing negative ions.

[0050] Example 6: This embodiment provides a polymer composite material for sustained negative ion release, which is primarily prepared from the following raw materials in parts by weight: 80 parts of a substrate, 10 parts of a functional composite powder, 4 parts of a release aid, 5 parts of an attenuation-compensating composite aid, 0.5 parts of a lubricant, and 0.5 parts of an antioxidant. In this embodiment, the substrate is PBT; the functional composite powder is a mixture of lithium tourmaline, Ce(NO3)3, and tungsten oxide in a weight ratio of 4:2:1; the release aid is a mixture of expanded graphite and oyster powder in a weight ratio of 2:1; the attenuation-compensating composite aid is a mixture of monazite powder, rare earth negative ion powder, and 2-hydroxy-4-n-octyloxybenzophenone in a weight ratio of 100:50:1; the lubricant is calcium stearate; and the antioxidant is a mixture of antioxidant 1010 and antioxidant 168 in a weight ratio of 2:1.

[0051] The method for preparing a polymer composite material capable of sustainably releasing negative ions in this embodiment comprises the following steps: (1) Monazite powder, rare earth anion powder, and 2-hydroxy-4-n-octyloxybenzophenone are mechanically mixed in a weight ratio of 100:50:1 to prepare an attenuation compensation composite additive; (2) adding the functional composite powder, the base material, the release aid, the attenuation compensation composite aid prepared in step (1), the lubricant, and the antioxidant into a high-speed mixer according to a set ratio to obtain a mixture; (3) The mixture was placed in a high-speed mixer and mixed for 10 minutes. The mixture was discharged and introduced into a twin-screw extruder through a feed port for melting, extrusion, cooling, and granulation. The speed of the twin-screw extruder was 400 R / min, and the temperatures of the twin-screw from the feed to the die were set to 180°C, 190°C, 200°C, 210°C, 210°C, 200°C, 185°C, 180°C, and 180°C, respectively. The vacuum degree was 0.06 MPa, thereby obtaining a polymer composite material capable of continuously releasing negative ions.

[0052] Comparative Example 1: This comparative example provides a negative ion-releasing polymer composite material, primarily composed of the following raw materials in parts by weight: 80 parts of a substrate, 7 parts of a functional composite powder, 12 parts of a release aid, 0.5 parts of a lubricant, and 0.5 parts of an antioxidant. In this embodiment, the substrate is PP; the functional composite powder is a mixture of lithium tourmaline, CePO4, and tungsten oxide in a weight ratio of 5:1:1; the release aid is a mixture of diatomaceous earth and oyster powder in a weight ratio of 1:1; the lubricant is calcium stearate; and the antioxidant is a mixture of antioxidant 1010 and antioxidant 168 in a weight ratio of 2:1.

[0053] This comparative example provides a method for preparing a negative ion-releasing polymer composite material, comprising the following steps: (1) Add the functional composite powder, base material, release agent, lubricant, and antioxidant into a high-speed mixer according to a set ratio to obtain a mixture; (2) The mixture was placed in a high-speed mixer and mixed for 10 minutes. The mixture was discharged and introduced into a twin-screw extruder through a feed port for melting, extrusion, cooling, and granulation. The speed of the twin-screw extruder was 450R / min, and the temperatures of the twin-screw from the feed to the die were set to 180°C, 190°C, 200°C, 210°C, 210°C, 200°C, 185°C, 180°C, and 180°C, respectively. The vacuum degree was 0.06Mpa, and thus a negative ion-releasing polymer composite material was obtained.

[0054] Comparative Example 2: This comparative example provides a negative ion-releasing polymer composite material, primarily composed of the following raw materials in parts by weight: 80 parts of a substrate, 5 parts of a functional composite powder, 3 parts of an attenuation-compensating composite additive, 0.5 parts of a lubricant, and 0.5 parts of an antioxidant. In this embodiment, the substrate is PP; the functional composite powder is a mixture of ferromagnesian tourmaline, Nd2O3, and ZnO in a weight ratio of 5:1:1; the attenuation-compensating composite additive is a mixture of monazite powder, rare earth negative ion powder, and 2-hydroxy-4-methoxybenzophenone in a weight ratio of 100:50:1; the lubricant is calcium stearate; and the antioxidant is a mixture of antioxidant 1010 and antioxidant 168 in a weight ratio of 2:1.

[0055] The preparation method of a negative ion-releasing polymer composite material of this comparative example comprises the following steps: (1) Monazite powder, rare earth anion powder, and 2-hydroxy-4-methoxybenzophenone were mechanically mixed in a weight ratio of 100:50:1 to prepare an attenuation compensation composite additive; (2) adding the functional composite powder, the base material, the attenuation compensation composite additive prepared in step (1), the lubricant, and the antioxidant into a high-speed mixer according to a set ratio to obtain a mixture; (3) The mixture was placed in a high-speed mixer and mixed for 10 minutes. The mixture was discharged and introduced into a twin-screw extruder through a feed port for melting, extrusion, cooling, and granulation. The speed of the twin-screw extruder was 450R / min, and the temperatures of the twin-screw from the feed to the die were set to 180°C, 190°C, 200°C, 210°C, 210°C, 200°C, 185°C, 180°C, and 180°C, respectively. The vacuum degree was 0.06Mpa, and thus a negative ion-releasing polymer composite material was obtained.

[0056] Comparative Example 3: This comparative example provides a polymer composite material for sustained negative ion release, which is primarily prepared from the following raw materials in parts by weight: 85 parts of a substrate, 1 part of a functional composite powder, 10 parts of a release aid, 5 parts of an attenuation-compensating composite aid, 0.5 parts of a lubricant, and 0.5 parts of an antioxidant. In this comparative example, the substrate is ABS; the functional composite powder is a mixture of ferromagnesian tourmaline, CeO2, and tungsten oxide in a weight ratio of 4:2:1; the release aid is a mixture of zeolite powder and oyster powder in a weight ratio of 1:1; the attenuation-compensating composite aid is a mixture of monazite powder, water-soluble negative ion powder, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone in a weight ratio of 100:30:2; the lubricant is zinc stearate; and the antioxidant is a mixture of antioxidant 1010 and antioxidant 168 in a weight ratio of 2:1.

[0057] This comparative example provides a method for preparing a polymer composite material capable of sustainably releasing negative ions, comprising the following steps: (1) Monazite powder, water-soluble negative ion powder, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone are mechanically mixed in a weight ratio of 100:30:2 to prepare an attenuation compensation composite additive; (2) adding the functional composite powder, the base material, the release aid, the attenuation compensation composite aid prepared in step (1), the lubricant, and the antioxidant into a high-speed mixer according to a set ratio to obtain a mixture; (3) The mixture was placed in a high-speed mixer and mixed for 10 minutes. The mixture was discharged and introduced into a twin-screw extruder through a feed port for melting, extrusion, cooling, and granulation. The speed of the twin-screw extruder was 450 R / min, and the temperatures of the twin-screw from the feed to the die were set to 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, 200°C, 200°C, and 200°C, respectively. The vacuum degree was 0.06 MPa, thereby obtaining a negative ion-releasing polymer composite material.

[0058] The test methods and results of Examples 1 to 6 and Comparative Examples 1 to 3 are as follows: 1. Air negative ion release concentration detection The concentration of air negative ions released is tested using the following test method.

[0059] 1. After fully charging the detector, turn it on, adjust the zero, and place it vertically on a level table. Let it sit for ten minutes until the machine operates normally.

[0060] 2. Place the airtight box upside down on the detector to create a closed environment to simulate the situation inside the car. At this time, ensure that there is light. Let it stand for 30 minutes. After the airflow in the box is stable and the readings are uniform (the error of five consecutive readings is no more than 10%), read the value on the instrument ten times in a row. P 0,1 -P 0,10 Its average value , which is the original negative ion concentration in the air, the unit is (pieces / cm 3 ).

[0061] 3. Lift the sealed box and keep the air flowing for 1 min. m Place the sample to be tested on a tray or weighing paper with the largest surface facing upward. If it is a granular material, spread it out as flat as possible. Place the prepared sample 10 cm away from the tester and cover both the tester and the sample with a sealed box.

[0062] 4. Wait for 30 minutes until the airflow in the box is stable and the readings are uniform (the error of five consecutive readings is no more than 10%), and then continuously record the values ​​on the instrument. P A,1 -P A,10 Calculate the average value .but For quality m The negative ion concentration of sample A in the air of a closed space of (L*W*H) is expressed in units of (particles / g / cm 3 ).

[0063] The negative ion concentration induced by a unit mass of sample A in a unit closed space is calculated according to formula (1), and the result is the arithmetic mean of 5 samples.

[0064] Where: N——Negative ion concentration induced by the sample in the air, in units of gram per cubic centimeter [ / (g·cm 3 )]; ——Negative air ion reading (-) after the test sample is placed in the test environment; ——Negative ion reading (-) in the original air of the test environment without any test sample placed in it; m——mass of the test sample, in grams (g); L - the length of the test chamber, in millimeters (mm); W - width of the test chamber, in millimeters (mm); H - the height of the test chamber, in millimeters (mm).

[0065] 1 kg of sample was sampled in Example 1-Example 6 and Comparative Examples 1-3. Five samples were tested in each group in a 0.5 cubic space, and the arithmetic mean was taken to obtain the air negative ion release concentration.

[0066] 2. 10-year release attenuation value detection The negative ion release efficiency of the sample was measured at room temperature for a long time, and the release attenuation value within 10 years was calculated according to the following principle.

[0067] Negative air ion release in the 10th year = 500⋅(C+2E)−50⋅D−(log(Day))⋅e^6.6 Where, C: percentage of functional composite powder D: Percentage of released additive E: Percentage of attenuation compensation compound additive Day: number of days 500⋅(C+2E): This component expresses the contribution of the functional composite powder (C) and the attenuation-compensating composite additive (E) within the composite material. The functional composite powder generally increases the generation and release of negative air ions, while the attenuation-compensating composite additive helps mitigate the attenuation of negative air ion release caused by environmental factors (such as humidity and temperature fluctuations). This figure shows that the attenuation-compensating composite additive has twice the impact of the functional composite powder, meaning that E contributes more than twice as much to the release as C. This reflects the critical role of the attenuation-compensating composite additive in improving the composite material's performance, particularly in combating environmental influences.

[0068] 50⋅D: This component reflects the negative impact of the release aid (D) on the release of negative air ions. As the release aid content increases, the release amount shows a negative correlation. This is because the addition of the release aid affects the stability or release process of negative air ions, thereby reducing the effective release amount. In formulation design, the appropriate amount of release aid needs to be balanced to avoid adversely affecting overall performance.

[0069] (log(Day))⋅e^6.6: This term describes the decay of negative air ion release over time (days). Over time, the release of negative air ions decreases, and the rate of decay is proportional to the logarithm of time. e^6.6 is a decay constant that determines the decay rate. A logarithmic decay model is used here, indicating a rapid initial release followed by a gradual slowing of the decay rate over time. This decay behavior reflects the stability of negative air ion release and the performance degradation of the composite material over time.

[0070] 10-year release attenuation value (%) = (1-10th year air negative ion release / initial release) × 100% The test results of Examples 1 to 6 and Comparative Examples 1 to 3 are shown in Table 1.

[0071] Table 1 Test results of Examples 1 to 6 and Comparative Examples 1 to 3

[0072] As can be seen from Table 1, the air negative ion release concentration of Examples 1 to 6 is 5200-10300 / cm 3, achieving very high negative ion concentrations. Furthermore, the PP composite materials obtained in the above examples all exhibited a 10-year negative ion release attenuation value of less than 20%, meaning they still released a high amount after 10 years. Consequently, they can be used in air purification, healthcare, thermoplastic elastomer product preparation, textile preparation, and plastic product preparation, featuring high negative ion release concentration, long lifespan, and excellent durability, meeting the needs of practical applications. Comparative Example 1, which does not contain a decay-compensating composite additive, exhibits a higher 10-year release attenuation value relative to the initial release, and a lower air negative ion release concentration. This demonstrates that the presence of the decay-compensating composite additive not only significantly reduces the rate at which the negative ion release of the prepared PP composite material decays over time, but also maintains a high air negative ion release concentration, providing a more stable and long-lasting negative ion release effect. Comparative Example 2, which does not contain a release additive, exhibits a lower air negative ion release concentration than Example 1, demonstrating that release additives, such as diatomaceous earth, shell powder, and activated carbon, enable the functional powder on the plastic surface to form ionization channels through the release additive that contact water and oxygen in the external air, thereby increasing negative ion release. Comparative Example 3 shows a change in the ratio of the functional composite powder to the release aid compared to Example 3. It can be seen that in the present invention, the functional composite powders such as ferromagnesian tourmaline, lithium tourmaline, magnesium tourmaline, sodium manganese tourmaline, rare earth oxides, rare earth composite salts, and photocatalytic oxides are used. If the content is too low, the ability to directly generate negative ions is weakened. In the case of a high amount of release aid, a higher amount of negative ion release may be initially exhibited due to the presence of a porous structure. However, over time, the chance of reaction with external positive ions increases, and the amount of negative ion release decreases rapidly, resulting in faster attenuation.

[0073] In summary, the substrate, functional composite powder, release aid, attenuation compensation composite aid, other additives and other components and contents of the present invention must be used in combination to make the overall air negative ion release concentration and 10-year release attenuation value of the material better. Omitting or replacing the component content cannot achieve the excellent effect of the present invention.

[0074] It should be noted that the specific embodiments are only representative examples of the present invention. Obviously, the technical solutions of the present invention are not limited to the above embodiments and may be subject to many variations. Those skilled in the art who are clear about the disclosure of the present invention or who can unambiguously derive the invention from the written description of the document should be considered to be within the scope of protection of this patent.

Claims

1. A polymer composite material capable of sustainably releasing negative ions, characterized in that: The invention is mainly prepared from the following raw materials in parts by weight: 75-90 parts of base material, 3-15 parts of functional composite powder, 2-8 parts of release auxiliary agent, 3-8 parts of attenuation compensation composite auxiliary agent and 1-2 parts of other auxiliary agents.

2. The sustainable negative ion releasing polymer composite material according to claim 1, characterized in that: Other additives include any one of lubricants, antioxidants, dispersants, compatibilizers or processing aids, or a mixture of two or more thereof.

3. The sustainable negative ion releasing polymer composite material according to claim 2, characterized in that: The lubricant is selected from any one of calcium stearate, zinc stearate, stearic acid, and EBS, or a mixture of several of them.

4. The sustainable negative ion releasing polymer composite material according to claim 2, characterized in that: The antioxidant is selected from any one of antioxidant 1010, antioxidant 3114, antioxidant 1078, antioxidant 618, and antioxidant 168, or a mixture of several of them.

5. The sustainable negative ion releasing polymer composite material according to claim 1, characterized in that: The functional composite powder is selected from any one of iron tourmaline, ferromagnesium tourmaline, lithium tourmaline, magnesium tourmaline, sodium manganese tourmaline, rare earth oxides, rare earth composite salts, and photocatalytic oxides, or a mixture of several of them.

6. The polymer composite material for sustainable negative ion release according to claim 1, characterized in that: The substrate is selected from any one of PP, PE, PVC, ABS, PS, PA6, PA66, POM, PBT, PET, PC, TPE, TPU, and TPV, or a mixture of several thereof.

7. The sustainable negative ion releasing polymer composite material according to claim 1, characterized in that: The release aid is selected from any one of expanded graphite, diatomaceous earth, molecular sieve, zeolite powder, shell powder, oyster powder, shrimp shell powder, activated carbon, silica powder, MOFs, and carbonate rock powder, or a mixture of several of them.

8. The sustainable negative ion releasing polymer composite material according to claim 1, characterized in that: The attenuation compensation composite auxiliary agent is selected from any one of white negative ion powder, cerium phosphate lanthanum ore powder, rare earth phosphate ore powder, fluorocarbon cerium ore powder, thorium ore powder, rare earth ceramic powder, monazite powder, rare earth negative ion powder, water-soluble negative ion powder, and UV absorber, or a mixture of several of them.

9. The method for preparing a polymer composite material capable of sustainably releasing negative ions according to any one of claims 1 to 8, characterized in that: The following steps are involved: (1) According to a set ratio, the raw material components of the attenuation compensation composite additive are mechanically mixed or ground with water as a medium to prepare the attenuation compensation composite additive; (2) adding the functional composite powder, the base material, the release agent, the attenuation compensation composite agent prepared in step (1), and other additives into a high-speed mixer according to a set ratio to obtain a mixture; (3) The mixture in step (2) is placed in a high-speed mixer and mixed for 5 to 10 minutes. The mixture is discharged and introduced into a twin-screw extruder through a feed port for melting, extrusion, cooling, and granulation. The speed of the twin-screw extruder is 200 to 500 R / min, and the temperature of the twin-screw from the feed to the die is set to 120 to 180°C, 150 to 200°C, 160 to 220°C, 170 to 250°C, 180 to 270°C, 180 to 270°C, 160 to 250°C, 160 to 250°C, and 160 to 250°C, respectively. The vacuum degree is ≤0.06 MPa, thereby obtaining a polymer composite material capable of continuously releasing negative ions.

10. Use of the negative ion polymer composite material prepared by the method for preparing a negative ion-sustaining polymer composite material according to any one of claims 1 to 8 or the negative ion polymer composite material according to claim 9 in the fields of air purification, medical care, preparation of thermoplastic elastomer products, preparation of textiles, and preparation of plastic products.

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