Polymer composite material capable of sustainably releasing negative ions, preparation method therefor and use thereof

Abstract

The present invention relates to the technical field of polymer composite materials. The present invention provides a polymer composite material capable of sustainably releasing negative ions, wherein the polymer composite material is mainly prepared from the following raw materials in parts by weight: 75-90 parts of a matrix, 3-15 parts of a functional composite powder, 2-8 parts of a release additive, and 3-8 parts of an attenuation-compensating composite additive. The polymer composite material further comprises 1-2 parts of other additives. The present invention further provides a method for preparing the polymer composite material capable of sustainably releasing negative ions. On the basis of the same inventive concept, the present invention further provides a use of the polymer composite material capable of sustainably releasing negative ions in the fields of air purification, healthcare, thermoplastic elastomer product fabrication, textile production, and plastic product manufacturing. In the present invention, by using multiple functional composite powders and various composite components, microchannel-based release mechanisms and attenuation-compensating mechanisms are formed on a series of polymer matrices, thereby enabling the prepared polymer composite material to achieve the remarkable effect of sustainably releasing high concentrations of negative air ions.

Description

A polymer composite material for sustainably releasing negative ions, its preparation method and application Technical Field

[0001] This invention belongs to the field of polymer composite material technology, specifically relating to a polymer composite material that sustainably releases negative ions, its preparation method, and its application. Background Technology

[0002] Negative ions are ions carrying a negative charge and have various beneficial effects such as purifying air, sterilizing, and relieving fatigue. 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. Among these, tourmaline is a natural mineral and the most commonly used, possessing piezoelectric and pyroelectric properties, and can continuously release negative ions.

[0003] However, the application of functional tourmaline and its composite powder in polymer materials has always faced two major technical challenges: First, how to make functional tourmaline and its composite powder able to contact and ionize with water and air on the plastic surface after being combined with polymer materials, thereby forming a large concentration of negative air ions; Second, since negative ions are easily destroyed by rapid reaction with positive ions and are unstable, how to make the formed polymer composite material sustainably release a certain amount of negative air ions, thereby ensuring its practical application effect.

[0004] Existing patented technologies, such as Chinese patent CN1386550A, provide a technique, process, and formula for preparing a high-efficiency composite powder for generating negative air ions. This involves ultrafinely pulverizing natural polar minerals, such as iron tourmaline, magnesium tourmaline, iron-magnesium tourmaline, and lithium tourmaline, and then mechanically and chemically combining them with rare earth composite salts (or rare earth composite oxides) and nano-semiconductor materials; or surface-treating polar mineral tourmaline (e.g., heat treatment at 100–900℃, surface acid-base treatment) and then combining it with rare earth salts and nano-photocatalytic semiconductor materials to prepare a high-efficiency composite material for generating negative air ions. This patented technology's composite powder for generating negative air ions is more than twice as effective as that of pure tourmaline and other materials in generating negative air ions, i.e., by using a composite functional powder specifically designed to address the low concentration of negative ions released by single tourmaline, it aims to increase the amount of negative ions released. For example, Chinese patent CN112795094A provides a PP alloy material that can release negative oxygen ions, its preparation method, and its application. This PP alloy material that can release negative oxygen ions comprises the following components by weight: carrier resin 65... 75 portions, 8 fillers 30 portions, compatibilizer 0.5g 2 copies, POE 2 15 portions, negative ion powder 3 5 parts, lubricant 0.5 parts 2 parts, wherein the carrier resin is composed of PP resin and PE resin, wherein the weight of added PE does not exceed 10% of the weight of the carrier resin, and the function of releasing negative oxygen ions can be given by changing the material of the corresponding components; Chinese Patent CN106750906A, this invention provides a polyolefin composition with enhanced negative ion release, which is composed of the following raw materials in parts by weight: polyolefin mixture (copolymer PP, etc.) 60 90 portions; 5 fillers 30 portions; negative ion releasing agent 1 5 parts; conductive agent 1 part 10 portions; 1 auxiliary agent 3 parts; lubricant 0.1 0.3 parts; antioxidant 0.2 parts 0.5 parts; weather resistant agent 0.2 parts 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 is increased by adding different proportions of tourmaline and negative ion powder to PP as the base material. However, neither of them has solved the two major technical problems mentioned above, resulting in a negative ion release of only 2,000 ions / cm³. 3 The following may have a short duration or do not involve sustainable release.

[0005] Therefore, existing technologies urgently need improvement in order to enable the practical application of polymer materials that sustainably release high concentrations of negative air ions. Summary of the Invention

[0006] This invention aims to address the shortcomings of existing technologies by providing a polymer composite material for the sustainable release of negative ions, its preparation method, and its applications. The objective of this invention is to achieve a large negative ion release volume, a long release time, and sustainable release.

[0007] To address the above problems, the present invention provides the following technical solution:

[0008] A polymer composite material that sustainably releases negative ions 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 aid, and 3-8 parts of attenuation compensation composite aid.

[0009] The polymer composite material for sustainably releasing negative ions as described above also includes other additives, which include any one or a mixture of two or more of lubricants, antioxidants, dispersants, compatibilizers, or processing aids. Preferably, the other additives include a mixture of lubricants and antioxidants.

[0010] Preferably, a sustainable negative ion-releasing polymer composite material is mainly prepared from the following raw materials in parts by weight: 80-85 parts of base material, 8-13 parts of functional composite powder, 2-4 parts of release aid, 3-5 parts of attenuation compensation composite aid, and 0.5-1 parts of other aids. Most preferably, a sustainable negative ion-releasing polymer composite material is mainly prepared from the following raw materials in parts by weight: 80 parts of base material, 13 parts of functional composite powder, 4 parts of release aid, 5 parts of attenuation compensation composite aid, 0.5 parts of lubricant, and 0.5 parts of antioxidant. Under these conditions, its air negative ion release concentration is 10300 (ions / cm³), and the 10-year negative ion release attenuation value is 16.3%, exhibiting the best overall effect.

[0011] In the aforementioned sustainably negative ion-releasing polymer composite material, the lubricant is selected from any one or a mixture of several of calcium stearate, zinc stearate, stearic acid, and EBS. Preferably, the lubricant is selected from any one of calcium stearate and zinc stearate. Most preferably, the lubricant is selected from calcium stearate.

[0012] In the aforementioned sustainably negative ion-releasing polymer composite material, the antioxidant is selected from any one or a mixture of several of antioxidants 1010, 3114, 1078, 618, and 168. Preferably, the antioxidant is selected from any one or a mixture of two of antioxidants 1010 and 168. Most preferably, the antioxidant is selected from a mixture of antioxidants 1010 and 168 in a weight ratio of 2:1.

[0013] Of course, the polymer composite material for continuously releasing negative ions of the present invention may also contain other additives, such as dispersants, compatibilizers, processing aids, etc.

[0014] Preferably, the dispersant is selected from any one of maleic anhydride-grafted polypropylene, polyethylene wax, and ethylene bis-stearamide.

[0015] 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.

[0016] Preferably, the processing aid is selected from any one of polyethylene wax, ethylene bis-stearamide, oxidized polyethylene wax, silicone oil, and erucamide.

[0017] The aforementioned sustainable negative ion-releasing polymer composite material, wherein the functional composite powder is selected from any one or a mixture of several of the following: iron tourmaline, iron-magnesium tourmaline, lithium tourmaline, magnesium tourmaline, sodium-manganese tourmaline, rare earth oxides, rare earth composite salts, and photocatalytic oxides.

[0018] In this invention, the components in the functional composite powder possess autonomous lattice instability, generating a voltage difference that ionizes water and air in the air, producing negative air ions. Simultaneously, certain components in the functional composite powder, such as rare earth oxides and rare earth composite salts containing rare earth elements, improve the spontaneous polarization properties of tourmaline through doping with the tourmaline in the functional powder, thereby enhancing the negative oxygen ion release performance of tourmaline. Furthermore, the photocatalytic oxides in the functional composite powder, as described above, possess photocatalytic activity, accelerating the generation of negative ions under light conditions; additionally, they can act as catalysts, promoting the decomposition of water molecules in the air, further generating negative ions. However, the formation of some negative air ions can also result in their annihilation by combining with external positive ions; these components alone are insufficient to ensure a high concentration of negative air ions and the continuous generation of such a high concentration.

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

[0021] In some embodiments of the present invention, the functional composite powder is selected from a mixture of magnesium tourmaline, rare earth oxides, and photocatalytic oxides, wherein the weight ratio of magnesium tourmaline, rare earth oxides, and photocatalytic oxides is 5:1:1 or 4:2:1.

[0022] In some embodiments of the present invention, preferably, the rare earth oxide is selected from any one or a mixture of two of CeO2, Ce2O3, La2O3, and Nd2O3. 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 or a mixture of several of LaPO4, La(NO3)3, CePO4, Ce(NO3)3, NdPO4, and Nd(NO3)3. 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 or a mixture of several of TiO2, ZnO, Fe2O3, tungsten oxide, and tin oxide. Optionally, the photocatalytic oxide is selected from any one of TiO2, ZnO, tungsten oxide, or tin oxide.

[0023] The sustainably releasing negative ion polymer composite material described above uses a substrate selected from any one or a mixture of several of PP, PE, PVC, ABS, PS, PA6, PA66, POM, PBT, PET, PC, TPE, TPU, and TPV. Preferably, the substrate is selected from any one of PP, ABS, TPE, PA6, or PBT. Under this condition, on the one hand, the substrate provides a stable physical structure for the sustainably releasing negative ion polymer composite material, ensuring its mechanical strength and durability during use; on the other hand, the selection of the substrate ensures that the components can be uniformly dispersed and achieve optimal effects. Simultaneously, the substrate has good processing properties, facilitating the manufacture of products in various shapes. Most preferably, the substrate is selected from PP.

[0024] The sustainably negative ion-releasing polymer composite material described above uses a release aid selected from any one or a mixture of several 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. Preferably, the release aid is selected from any one or a mixture of several of expanded graphite, diatomaceous earth, zeolite powder, shell powder, oyster powder, shrimp shell powder, and activated carbon. Under these conditions, the release aid provides ionization channels with external air and moisture. Most preferably, the release aid is a mixture of diatomaceous earth and oyster powder, with a weight ratio of diatomaceous earth to oyster powder of 1:1.

[0025] The continuously releasing negative ion polymer composite material described above uses an attenuation compensation composite additive selected from any one or a mixture of several of the following: white negative ion powder, cerium lanthanum phosphate 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 absorbers. Under these conditions, the attenuation compensation composite additive can protect the functional composite powder and the releasing additive, preventing them from aging or failing due to environmental factors (such as temperature, humidity, and light) during long-term use. This helps extend the service life of the negative ion releasing product.

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

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

[0028] In some embodiments of the present invention, the attenuation compensation composite additive is selected from a mixture of monazite powder, water-soluble negative ion powder, and UV absorber, wherein the weight ratio of the monazite powder, water-soluble negative ion powder, and UV absorber is 100:50:1 or 100:30:2.

[0029] Most preferably, the attenuation compensation composite additive is a mixture of monazite powder, white negative ion powder, and UV absorber in a weight ratio of 100:50:1.

[0030] Optionally, the UV absorber is any one of 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-methoxy-5-sulfonic benzophenone, sodium 2-hydroxy-4-methoxy-5-sulfonic acid benzophenone, and 2-hydroxy-4-n-octyloxybenzophenone. Most preferably, the UV absorber is 2,2'-dihydroxy-4,4'-dimethoxybenzophenone.

[0031] In this invention, the functional composite powder can directly ionize with air and moisture to generate negative ions, while the release aid further enhances the generation and release of negative ions by increasing the ionization channels with external air and water. The attenuation compensation composite aid, on the one hand, slows down the aging process of the functional composite powder, maintaining its long-term stable negative ion release capacity, and on the other hand, produces a good synergistic effect with the functional composite powder and the release aid, increasing the continuous ionization capacity. The substrate provides a physical carrier and protection for each active ingredient, while other additives improve the processing and mechanical properties of the composite material. Through the multi-level synergistic effect of the functional composite powder, release aid, attenuation compensation composite aid, substrate, and other additives such as lubricants and antioxidants, this polymer composite material achieves a large negative ion release capacity, long-term release, and sustainable release effect.

[0032] Based on the same inventive concept, this invention provides a method for preparing a polymer composite material that sustainably releases negative ions, comprising the following steps:

[0033] (1) According to the 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;

[0034] (2) According to the set ratio, add the functional composite powder, substrate, release agent, attenuation compensation composite agent prepared in step (1), and other additives into a high-speed mixer to obtain a mixture;

[0035] (3) The mixture in step (2) is placed in a high-speed mixer and mixed for 5-10 minutes. The mixture is then discharged and fed into a twin-screw extruder through the feed port for melting, extrusion, cooling, and granulation. The twin-screw extruder operates at a speed of 200-500 R / min. The temperatures from the feed to the die head are set to 120-180℃, 150-200℃, 160-220℃, 170-250℃, 180-270℃, 170-270℃, 160-250℃, 160-250℃, and 160-250℃, respectively. The vacuum degree is ≤0.06 MPa, thus obtaining a polymer composite material that continuously releases negative ions. Preferably, the twin-screw extruder operates at a speed of 350-450 R / min. Preferably, the temperatures of the twin-screw extruder from feed to die head are set to 125–180℃, 160–200℃, 180–220℃, 185–250℃, 180–260℃, 180–250℃, 170–210℃, 160–250℃, and 170–230℃, respectively, with a vacuum degree ≤0.06 MPa. Most preferably, the rotational speed of the twin-screw extruder is 450 R / min. Preferably, the temperatures of the twin-screw extruder from feed to die head are set to 180℃, 190℃, 200℃, 210℃, 210℃, 200℃, 185℃, 180℃, and 180℃, respectively, with a vacuum degree of 0.06 MPa.

[0036] Based on the same inventive concept, this invention provides a method for preparing a polymer composite material that sustainably releases negative ions, and the application of the negative ion polymer composite material prepared by the method described above in the fields of air purification, medical care, thermoplastic elastomer product preparation, textile preparation, and plastic product preparation.

[0037] Compared with existing technologies, the effects and advantages of this invention are:

[0038] 1. This invention provides a polymer composite material that sustainably releases negative ions. It uses a variety of composite functional powders and composite components to form a micro-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 concentrations of negative air ions.

[0039] 2. The polymer composite material for continuously releasing negative ions prepared by the preparation method provided by the present invention can release more than 10,000 negative ions per cm³; the polymer composite material for releasing negative ions can last for more than 10 years. Embodiments of the present invention

[0040] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0041] Unless otherwise defined, all technical and scientific terms used in this specification have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used in this specification is for the purpose of describing particular embodiments only and is 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.

[0042] Unless otherwise specified, the experimental methods used in the following examples are conventional methods.

[0043] Unless otherwise specified, all materials and reagents used in the following examples are commercially available.

[0044] PP, polypropylene, model: T30S, purchased from Maoming Petrochemical Company;

[0045] ABS, acrylonitrile-butadiene-styrene copolymer, model: ABS121, purchased from Ningbo LG Yongxing Chemical Co., Ltd.;

[0046] TPE, thermoplastic elastomer, model: EPK, purchased from Kunshan Kexin Polymer Materials Co., Ltd.

[0047] PA6, polyamide six, model: PA-2700, purchased from Guangdong Hengshenmeida New Material Co., Ltd.

[0048] PBT, polybutylene terephthalate, model: KH2083, purchased from Hengli Petrochemical Co., Ltd.

[0049] Antioxidant 1010 and Antioxidant 168 were purchased from BASF, Germany.

[0050] Iron-magnesium tourmaline, lithium tourmaline, and magnesium tourmaline were purchased from Shijiazhuang Tourmaline Mineral Products Co., Ltd., 800 mesh.

[0051] The monazite powder was purchased from Yixuan Mineral Products Processing Plant in Lingshou County, 200 mesh.

[0052] Rare earth negative ion powder was purchased from Shanghai Anna Environmental Technology Co., Ltd., 600 mesh;

[0053] White negative ion powder and soluble negative ion powder were purchased from Dongguan Yanteng Negative Ion Technology Co., Ltd., 800 mesh.

[0054] Example 1:

[0055] This embodiment provides a sustainable negative ion-releasing polymer composite material, mainly prepared from the following raw materials in parts by weight: 80 parts of substrate, 8 parts of functional composite powder, 2 parts of release aid, 3 parts of attenuation compensation composite aid, 0.5 parts of lubricant, and 0.5 parts of antioxidant. In this embodiment, the substrate is PP; the functional composite powder is a mixture of iron-magnesium 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 compensation 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.

[0056] The preparation method of a polymer composite material that sustainably releases negative ions according to this embodiment includes the following steps:

[0057] (1) Monazite powder, rare earth negative ion powder and 2-hydroxy-4-methoxybenzophenone were mixed by mechanical mixing in a weight ratio of 100:50:1 to prepare a degradation compensation composite additive.

[0058] (2) According to the set ratio, the functional composite powder, substrate, release aid, attenuation compensation composite aid prepared in step (1), lubricant and antioxidant are added to the high-speed mixer to obtain a mixture;

[0059] (3) The mixture is placed in a high-speed mixer and mixed for 10 minutes. The mixture is discharged and fed into a twin-screw extruder through the feed port for melting, extrusion, cooling, and granulation. The rotation speed of the twin-screw extruder is 450 R / min. The temperature of the twin screw from the feed to the die head is set to 180℃, 190℃, 200℃, 210℃, 210℃, 200℃, 185℃, 180℃, and 180℃ respectively. The vacuum degree is 0.06 MPa. The resulting polymer composite material with sustainable negative ion release is obtained.

[0060] Example 2:

[0061] This embodiment provides a sustainable negative ion-releasing polymer composite material, mainly prepared from the following raw materials in parts by weight: 80 parts of substrate, 13 parts of functional composite powder, 4 parts of release aid, 5 parts of attenuation compensation composite aid, 0.5 parts of lubricant, and 0.5 parts of 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 shell powder in a weight ratio of 1:1; the attenuation compensation 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.

[0062] The preparation method of a polymer composite material that sustainably releases negative ions according to this embodiment includes the following steps:

[0063] (1) Monazite powder, white negative ion powder and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone were mixed by mechanical mixing in a weight ratio of 100:50:1 to prepare a degradation compensation composite additive;

[0064] (2) According to the set ratio, the functional composite powder, substrate, release aid, attenuation compensation composite aid prepared in step (1), lubricant and antioxidant are added to the high-speed mixer to obtain a mixture;

[0065] (3) The mixture is placed in a high-speed mixer and mixed for 10 minutes. The mixture is discharged and fed into a twin-screw extruder through the feed port for melting, extrusion, cooling, and granulation. The rotation speed of the twin-screw extruder is 450 R / min. The temperature of the twin screw from the feed to the die head is set to 180℃, 190℃, 200℃, 210℃, 210℃, 200℃, 185℃, 180℃, and 180℃ respectively. The vacuum degree is 0.06 MPa. The resulting polymer composite material with sustainable negative ion release is obtained.

[0066] Example 3:

[0067] This embodiment provides a sustainable negative ion-releasing polymer composite material, mainly prepared from the following raw materials in parts by weight: 85 parts of substrate, 12 parts of functional composite powder, 4 parts of release aid, 5 parts of attenuation compensation composite aid, 0.5 parts of lubricant, and 0.5 parts of antioxidant. In this embodiment, the substrate is ABS; the functional composite powder is a mixture of iron-magnesium tourmaline, CeO2, and tungsten oxide in a weight ratio of 4:2:1; the release aid is a mixture of zeolite powder and oyster shell powder in a weight ratio of 1:1; the attenuation compensation 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.

[0068] The preparation method of a polymer composite material that sustainably releases negative ions according to this embodiment includes the following steps:

[0069] (1) Monazite powder, water-soluble negative ion powder and 2-hydroxy-4-methoxy-2'-carboxybenzophenone were mixed by mechanical mixing in a weight ratio of 100:30:2 to prepare a degradation compensation composite additive;

[0070] (2) According to the set ratio, the functional composite powder, substrate, release aid, attenuation compensation composite aid prepared in step (1), lubricant and antioxidant are added to the high-speed mixer to obtain a mixture;

[0071] (3) The mixture is placed in a high-speed mixer and mixed for 10 minutes. The mixture is discharged and fed into a twin-screw extruder through the feed port for melting, extrusion, cooling, and granulation. The rotation speed of the twin-screw extruder is 450 R / min. The temperature of the twin screw from the feed to the die head is set to 180℃, 190℃, 200℃, 210℃, 220℃, 230℃, 200℃, 200℃, and 200℃ respectively. The vacuum degree is 0.06 MPa. The resulting polymer composite material with sustainable negative ion release is obtained.

[0072] Example 4:

[0073] This embodiment provides a sustainable negative ion-releasing polymer composite material, mainly prepared from the following raw materials in parts by weight: 85 parts of substrate, 10 parts of functional composite powder, 4 parts of release aid, 5 parts of attenuation compensation composite aid, 0.5 parts of lubricant, and 0.5 parts of antioxidant. In this embodiment, the substrate is TPE; the functional composite powder is a mixture of magnesium tourmaline, LaPO4, and TiO2 in a weight ratio of 5:1:1; the release aid is a mixture of zeolite powder and oyster shell powder in a weight ratio of 1:1; the attenuation compensation 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.

[0074] The preparation method of a polymer composite material that sustainably releases negative ions according to this embodiment includes the following steps:

[0075] (1) Monazite powder, white negative ion powder and 2-hydroxy-4-methoxy-5-sulfonic acid benzophenone were mixed by mechanical mixing in a weight ratio of 100:50:1 to prepare a degradation compensation composite additive.

[0076] (2) According to the set ratio, the functional composite powder, substrate, release aid, attenuation compensation composite aid prepared in step (1), lubricant and antioxidant are added to the high-speed mixer to obtain a mixture;

[0077] (3) The mixture is placed in a high-speed mixer and mixed for 10 minutes. The mixture is discharged and fed into a twin-screw extruder through the feed port for melting, extrusion, cooling, and granulation. The rotation speed of the twin-screw extruder is 350 R / min. The temperature of the twin screw from the feed to the die head is set to 125℃, 160℃, 180℃, 185℃, 180℃, 180℃, 170℃, 170℃, and 170℃ respectively. The vacuum degree is 0.06 MPa. The resulting polymer composite material with sustainable negative ion release is obtained.

[0078] Example 5:

[0079] This embodiment provides a sustainable negative ion-releasing polymer composite material, mainly prepared from the following raw materials in parts by weight: 80 parts of substrate, 10 parts of functional composite powder, 4 parts of release aid, 5 parts of attenuation compensation composite aid, 0.5 parts of lubricant, and 0.5 parts of 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 attenuation compensation composite aid is a mixture of monazite powder, water-soluble negative ion powder, and sodium benzophenone 2-hydroxy-4-methoxy-5-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.

[0080] The preparation method of a polymer composite material that sustainably releases negative ions according to this embodiment includes the following steps:

[0081] (1) Monazite powder, water-soluble negative ion powder, sodium benzoate 2-hydroxy-4-methoxy-5-sulfonate were mixed by mechanical mixing in a weight ratio of 100:30:2 to prepare a degradation compensation composite additive.

[0082] (2) According to the set ratio, the functional composite powder, substrate, release aid, attenuation compensation composite aid prepared in step (1), lubricant and antioxidant are added to the high-speed mixer to obtain a mixture;

[0083] (3) The mixture is placed in a high-speed mixer and mixed for 10 minutes. The mixture is discharged and fed into a twin-screw extruder through the feed port for melting, extrusion, cooling, and granulation. The rotation speed of the twin-screw extruder is 350 R / min. The temperature of the twin screw from the feed to the die head is set to 180℃, 200℃, 220℃, 250℃, 260℃, 250℃, 210℃, 230℃, and 230℃ respectively. The vacuum degree is 0.06 MPa. The resulting polymer composite material can continuously release negative ions.

[0084] Example 6:

[0085] This embodiment provides a sustainable negative ion-releasing polymer composite material, mainly prepared from the following raw materials in parts by weight: 80 parts of substrate, 10 parts of functional composite powder, 4 parts of release aid, 5 parts of attenuation compensation composite aid, 0.5 parts of lubricant, and 0.5 parts of 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 shell powder in a weight ratio of 2:1; the attenuation compensation 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.

[0086] The preparation method of a polymer composite material that sustainably releases negative ions according to this embodiment includes the following steps:

[0087] (1) Monazite powder, rare earth negative ion powder and 2-hydroxy-4-n-octyloxybenzophenone were mixed by mechanical mixing in a weight ratio of 100:50:1 to prepare a degradation compensation composite additive.

[0088] (2) According to the set ratio, the functional composite powder, substrate, release aid, attenuation compensation composite aid prepared in step (1), lubricant and antioxidant are added to the high-speed mixer to obtain a mixture;

[0089] (3) The mixture is placed in a high-speed mixer and mixed for 10 minutes. The mixture is discharged and fed into a twin-screw extruder through the feed port for melting, extrusion, cooling, and granulation. The rotation speed of the twin-screw extruder is 400 R / min. The temperature of the twin screw from the feed to the die head is set to 180℃, 190℃, 200℃, 210℃, 210℃, 200℃, 185℃, 180℃, and 180℃ respectively. The vacuum degree is 0.06 MPa. The resulting polymer composite material can continuously release negative ions.

[0090] Comparative Example 1:

[0091] This comparative example provides a negative ion-releasing polymer composite material, mainly prepared from the following raw materials in parts by weight: 80 parts of substrate, 7 parts of functional composite powder, 12 parts of release aid, 0.5 parts of lubricant, and 0.5 parts of 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 shell 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.

[0092] The comparative example provides a method for preparing a negative ion-releasing polymer composite material, which includes the following steps:

[0093] (1) According to the set ratio, add the functional composite powder, substrate, release aid, lubricant and antioxidant into the high-speed mixer to obtain a mixture;

[0094] (2) The mixture is placed in a high-speed mixer and mixed for 10 minutes. The mixture is discharged and fed into a twin-screw extruder through the feed port for melting, extrusion, cooling, and granulation. The rotation speed of the twin-screw extruder is 450 R / min. The temperature of the twin screw from the feed to the die head is set to 180℃, 190℃, 200℃, 210℃, 210℃, 200℃, 185℃, 180℃, and 180℃ respectively. The vacuum degree is 0.06 MPa. The negative ion-releasing polymer composite material is obtained.

[0095] Comparative Example 2:

[0096] This comparative example provides a negative ion-releasing polymer composite material, mainly prepared from the following raw materials in parts by weight: 80 parts of substrate, 5 parts of functional composite powder, 3 parts of attenuation compensation composite additive, 0.5 parts of lubricant, and 0.5 parts of antioxidant. In this embodiment, the substrate is PP; the functional composite powder is a mixture of iron-magnesium tourmaline, Nd2O3, and ZnO in a weight ratio of 5:1:1; the attenuation compensation 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.

[0097] The preparation method of the negative ion-releasing polymer composite material of this comparative example includes the following steps:

[0098] (1) Monazite powder, rare earth negative ion powder and 2-hydroxy-4-methoxybenzophenone were mixed by mechanical mixing in a weight ratio of 100:50:1 to prepare a degradation compensation composite additive.

[0099] (2) According to the set ratio, the functional composite powder, the substrate, the attenuation compensation composite additive prepared in step (1), the lubricant and the antioxidant are added to the high-speed mixer to obtain a mixture;

[0100] (3) The mixture is placed in a high-speed mixer and mixed for 10 minutes. The mixture is discharged and fed into a twin-screw extruder through the feed port for melting, extrusion, cooling, and granulation. The rotation speed of the twin-screw extruder is 450 R / min. The temperature of the twin screw from the feed to the die head is set to 180℃, 190℃, 200℃, 210℃, 210℃, 200℃, 185℃, 180℃, and 180℃ respectively. The vacuum degree is 0.06 MPa. The negative ion-releasing polymer composite material is obtained.

[0101] Comparative Example 3:

[0102] This comparative example provides a sustainable negative ion-releasing polymer composite material, mainly prepared from the following raw materials in parts by weight: 85 parts of base material, 1 part of functional composite powder, 10 parts of release aid, 5 parts of attenuation compensation composite aid, 0.5 parts of lubricant, and 0.5 parts of antioxidant. In this comparative example, the base material is ABS; the functional composite powder is a mixture of iron-magnesium tourmaline, CeO2, and tungsten oxide in a weight ratio of 4:2:1; the release aid is a mixture of zeolite powder and oyster shell powder in a weight ratio of 1:1; the attenuation compensation 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.

[0103] The comparative example provides a method for preparing a polymer composite material that sustainably releases negative ions, comprising the following steps:

[0104] (1) Monazite powder, water-soluble negative ion powder and 2-hydroxy-4-methoxy-2'-carboxybenzophenone were mixed by mechanical mixing in a weight ratio of 100:30:2 to prepare a degradation compensation composite additive;

[0105] (2) According to the set ratio, the functional composite powder, substrate, release aid, attenuation compensation composite aid prepared in step (1), lubricant and antioxidant are added to the high-speed mixer to obtain a mixture;

[0106] (3) The mixture is placed in a high-speed mixer and mixed for 10 minutes. The mixture is discharged and fed into a twin-screw extruder through the feed port for melting, extrusion, cooling, and granulation. The rotation speed of the twin-screw extruder is 450 R / min. The temperature of the twin screw from the feed to the die head is set to 180℃, 190℃, 200℃, 210℃, 220℃, 230℃, 200℃, 200℃, and 200℃ respectively. The vacuum degree is 0.06 MPa. The negative ion-releasing polymer composite material is obtained.

[0107] The test methods and results of Examples 1-6 and Comparative Examples 1-3 are as follows:

[0108] I. Detection of Air Negative Ion Release Concentration

[0109] The concentration of negative air ions released was determined using the following test method.

[0110] 1. After fully charging the detector, turn it on, zero it, and place it vertically on a level table. Let it stand for ten minutes until the machine is running normally.

[0111] 2. Invert the sealed chamber above the testing instrument to create a sealed environment simulating the situation inside a vehicle. Ensure adequate lighting during this process. Let it stand for 30 minutes until the airflow inside the chamber stabilizes and the readings are uniform (the error of five consecutive readings should not exceed 10%). Then, continuously read and record the value P on the instrument ten times. 0,1 -P 0,10 Its average value This refers to the initial concentration of negative ions in the air, expressed in units of (ions / cm³). 3 ).

[0112] 3. Lift the sealed box and maintain airflow for 1 minute. Place the sample to be tested, with its maximum surface area facing upwards, on the tray or weighing paper; if it is granular material, spread it out as evenly as possible. Place the prepared sample 10cm away from the detector, and then cover both the detector and the sample with the sealed box.

[0113] 4. Let it stand for 30 minutes until the airflow inside the chamber stabilizes and the readings are uniform (the error of five consecutive readings should not exceed 10%), then continuously record the value P on the instrument. A,1 -P A,10 The average value was calculated. .but Let m be the concentration of negative ions induced in the air of a sample A with mass m in a closed space of (L*W*H), expressed in units of (ions / cm³). 3 ).

[0114] The concentration of negative ions induced by a unit mass of sample A in a unit enclosed space is calculated according to formula (1), and the result is the arithmetic mean of 5 samples.

[0115]

[0116] In the formula:

[0117] N – The concentration of induced negative ions in the sample in air, expressed in units of (ions / cm³). 3 );

[0118] —The reading of negative air ions after the test sample is placed in the test environment;

[0119] —The reading of negative ions in the raw air in the test environment without the test sample placed inside;

[0120] m — the mass of the test sample, in grams (g);

[0121] L—Length inside the test chamber, in millimeters (mm);

[0122] W — Width inside the test chamber, in millimeters (mm);

[0123] H – Height inside the test chamber, in millimeters (mm).

[0124] Examples 1-6 and Comparative Examples 1-3 each involved 1 kg of sample. Five samples were tested in each group within a 0.5 cubic meter space. The arithmetic mean was taken to obtain the concentration of negative air ions released.

[0125] II. 10-Year Release Attenuation Value Detection

[0126] The release efficiency of negative ions from the sample was measured over a long period of time at room temperature, and the release attenuation value over 10 years was calculated based on the following principle.

[0127]

[0128] Wherein, C: percentage of functional compound powder

[0129] D: Percentage of release aid

[0130] E: Percentage of attenuation compensation composite additive

[0131] Day: Number of days

[0132] This section describes the roles of functional composite powder (C) and attenuation-compensating composite additive (E) in composite materials. Functional composite powder typically increases the generation and release of negative air ions, while attenuation-compensating composite additive helps mitigate the attenuation of negative air ion release caused by environmental factors such as humidity and temperature changes. This indicates that the effect of the attenuation-compensating composite additive is twice that of the functional composite powder, meaning that E contributes more than twice to the release amount compared to C. This reflects the crucial enhancing role of attenuation-compensating additives in composite materials, particularly in counteracting the effects of external environmental factors.

[0133] This section reflects the negative impact of releasing agents (D) on the release of negative air ions. As the content of the releasing agent increases, the release amount changes negatively. This is because the addition of the releasing agent affects the stability or release process of negative air ions, thus reducing the effective release amount. In formulation design, an appropriate amount of releasing agent needs to be used to balance its effects to avoid adversely affecting the overall performance.

[0134] This section describes the decay pattern of negative air ion release over time (days). The release of negative air ions decreases with increasing time, and the decay rate is proportional to the logarithm of time. e^6.6 is a decay constant that determines the magnitude of the decay rate. A logarithmic decay model is used here, indicating that the initial release is relatively rapid, while the decay rate gradually slows down over time. This decay behavior reflects the stability of negative air ion release and the performance degradation of composite materials during long-term use.

[0135] 10-year release decay value (%) = (1 - Air negative ion release in year 10 / Initial release) × 100%

[0136] The test results of Examples 1-6 and Comparative Examples 1-3 are shown in Table 1.

[0137] Table 1 Test results of Examples 1-6 and Comparative Examples 1-3

[0138]

[0139] As can be seen from Table 1, the concentration of negative air ions released in Examples 1-6 was 5200-10300 ions / cm³. 3The PP composite materials obtained in the above examples achieve very high negative ion concentrations, and their 10-year negative ion release attenuation values ​​are all <20%, meaning they still have a high release amount after 10 years. Therefore, they can be used in air purification, healthcare, thermoplastic elastomer product preparation, textile preparation, and plastic product preparation, exhibiting high negative ion release concentration, long lifespan, and good durability, meeting the needs of practical applications. Comparative Example 1, compared to Example 2, does not contain the attenuation compensation composite additive, and its 10-year release attenuation value relative to the initial release amount is higher, and its air negative ion release concentration is lower. This indicates that the presence of the attenuation compensation composite additive of the present invention can not only significantly reduce the rate of attenuation of negative ion release over time in the prepared PP composite material, but also maintain a high air negative ion release concentration, providing a more stable and durable negative ion release effect. Comparative Example 2, compared to Example 1, does not contain the release additive, and its air negative ion release concentration is lower. This indicates that the release additives, such as diatomaceous earth, shell powder, and activated carbon, can enable the functional powders on the plastic surface to form ionization channels that contact water and oxygen in the outside air, thereby increasing the negative ion release amount. Compared to Example 3, Comparative Example 3 shows a change in the ratio of functional composite powder to releasing agent. It can be seen that in this invention, the functional composite powders containing iron tourmaline, iron-magnesium tourmaline, lithium tourmaline, magnesium tourmaline, sodium-manganese tourmaline, rare earth oxides, rare earth composite salts, and photocatalytic oxides have a weakened ability to directly generate negative ions if their content is too low. With a higher content of releasing agent, the initial negative ion release may be higher due to the presence of a porous structure. However, over time, the opportunity for reaction with external positive ions increases, and the negative ion release decreases rapidly, leading to faster decay.

[0140] In summary, the above components and their contents, including the base material, functional composite powder, release aid, attenuation compensation composite aid, and other additives of this invention, must be used in combination to achieve better overall air negative ion release concentration and 10-year release attenuation value. Omitting or replacing the contents of the components will not achieve the excellent effects of this invention.

[0141] It should be noted that the specific embodiments are merely representative examples of the present invention, and the technical solution of the present invention is obviously not limited to the above embodiments, and there can be many variations. Those skilled in the art who obtain the present invention based on its explicit disclosure or without objection from the written description should consider it to be within the scope of protection of this patent.

Claims

1. A polymer composite material that sustainably releases negative ions, characterized in that, It 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 agent, and 3-8 parts of attenuation compensation composite agent.

2. The polymer composite material for sustainably releasing negative ions according to claim 1, characterized in that, It also includes other additives, which include any one or a mixture of two or more of lubricants, antioxidants, dispersants, compatibilizers, or processing aids.

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

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

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

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

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

8. The polymer composite material for sustainably releasing negative ions according to claim 1, characterized in that, The attenuation compensation composite additive is selected from any one or a mixture of several of the following: white negative ion powder, cerium lanthanum phosphate 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.

9. The preparation method of any one of the continuously releasing negative ion polymer composite materials according to claims 1 to 8, characterized in that, Includes the following steps: (1) According to the 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) According to the set ratio, add the functional composite powder, substrate, release agent, attenuation compensation composite agent prepared in step (1), and other additives into a high-speed mixer 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 then discharged and fed into a twin-screw extruder through the feed port for melting, extrusion, cooling, and granulation. The rotation speed of the twin-screw extruder is 200 to 500 R / min. The temperature of the twin screw from the feed to the die head is set to 120 to 180°C, 150 to 200°C, 160 to 220°C, 170 to 250°C, 180 to 270°C, 170 to 270°C, 160 to 250°C, 160 to 250°C, 160 to 250°C, and the vacuum degree is ≤0.06 MPa. This yields a polymer composite material that can continuously release negative ions.

10. The negative ion polymer composite material prepared by any one of the methods for preparing a sustainable negative ion release polymer composite material according to claims 1 to 8, or the negative ion polymer composite material according to claim 9, in the fields of air purification, medical care, thermoplastic elastomer product preparation, textile preparation, and plastic product preparation.

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