A recyclable, circular material frisbee

Abstract

The application relates to a renewable and recyclable material frisbee, and belongs to the technical field of sports and leisure entertainment equipment preparation. The frisbee comprises the following raw materials in parts by weight: 20-70 parts of recycled and regenerated base material, 2-10 parts of polyolefin elastomer, 5-25 parts of modified bio-based filler, 0.2-1 part of accelerator and 0-2 parts of auxiliary material. The modified bio-based filler is made of active bio-waste residue and long-alkyl-chain silane coupling agent after surface treatment. The PCR base material and the modified bio-based filler are used as main raw materials, the POE elastomer, the accelerator and the auxiliary material are introduced, the PCR base material, the modified bio-based filler, the POE elastomer, the accelerator and the auxiliary material are matched with each other, the frisbee with moderate hardness, comfortable holding feeling, stable flight, environmental protection and recyclability is obtained.

Description

Technical Field

[0001] This invention belongs to the field of sports, leisure and entertainment equipment manufacturing technology, specifically, it relates to a frisbee made of renewable and recyclable material. Background Technology

[0002] Frisbee is a simple outdoor sport suitable for all ages. Currently, frisbees are made of polypropylene (PP). However, polypropylene made from PP does not meet the trend of environmentally friendly development in sports and leisure equipment. Frisbees made from recycled polymer materials (PCR) suffer from problems such as being too soft, leading to unstable flight, and being prone to cracking at low temperatures, resulting in substandard product quality. Summary of the Invention

[0003] To address the above problems, the purpose of this invention is to provide a recyclable material frisbee.

[0004] The objective of this invention can be achieved through the following technical solutions: A recyclable material frisbee comprises the following raw materials in parts by weight: 20-120 parts of recycled base material, 2-10 parts of polyolefin elastomer (POE), 5-25 parts of modified bio-based filler, 0.2-1 parts of accelerator, and 0-2 parts of auxiliary materials.

[0005] Furthermore, the recycled base material is one or a mixture of several of the following in any proportion: recycled low-density polyethylene, recycled high-density polyethylene, recycled polypropylene, recycled polymethyl methacrylate, recycled polystyrene, and recycled acrylonitrile-styrene-butadiene copolymer.

[0006] Preferably, the recycled base material is a mixture of recycled low-density polyethylene and recycled high-density polyethylene, then the frisbee comprises the following parts by weight of raw materials: 20-50 parts of recycled low-density polyethylene, 30-70 parts of recycled high-density polyethylene, 2-10 parts of polyolefin elastomer, 5-25 parts of modified bio-based filler, and 0-2 parts of auxiliary materials.

[0007] Furthermore, the modified bio-based filler is made by surface treatment of active biological waste residue and long alkyl chain silane coupling agent.

[0008] Preferably, the specific steps of the surface treatment include: Under stirring conditions of 300-500 r / min and 50-75℃, 100 mL of a solution containing 20-30 g of the long alkyl chain silane coupling agent prepared in Example 3 (the solvent is a mixture of water and ethanol in a volume ratio of 7-9:1) was sprayed onto 100 g of the active biological waste prepared in Example 1. After complete spraying, the solution was kept warm and stirred for 1-1.5 h. Then, stirring was stopped, and the solution was dried to obtain the modified bio-based filler.

[0009] Furthermore, the activated biological waste residue is obtained by acid activating biological waste residue.

[0010] Preferably, the active biological waste residue is obtained by pretreatment of biological waste residue followed by acid soaking activation.

[0011] Furthermore, the pretreatment involves washing the biological waste residue with water and applying an alkaline solution to remove dust and easily detachable substances from the surface of the biological waste residue.

[0012] Furthermore, the acid used in the acid foam activation treatment is one of hydrogen peroxide, potassium permanganate, and perchlorate.

[0013] Furthermore, the acid foam activation treatment is performed at a temperature of 50-70°C for 30-90 minutes.

[0014] Furthermore, the biological waste residue is one or more of coffee bean residue, straw residue, coconut residue, and rice husk residue in any proportion.

[0015] Preferably, it is coffee bean residue or coconut residue.

[0016] Furthermore, the long alkyl chain silane coupling agent is prepared by sequentially subjecting 10-undecenoic acid and aminosilane coupling agent to a dehydration condensation reaction and an epoxidation reaction.

[0017] Preferably, in the dehydration condensation reaction of the 10-undecenoic acid and the aminosilane coupling agent, the molar ratio of the 10-undecenoic acid and the aminosilane coupling agent is 1.1-1.3:1.

[0018] Further, the dehydration condensation reaction of the 10-undecenoic acid and the aminosilane coupling agent includes: 10-Undecenoic acid, EDC (1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride), NHS (N-hydroxysuccinimide), and ethanol were mixed evenly and stirred at 66-70℃ and pH 5-6 for 1-1.5 h. Then, an aminosilane coupling agent was added, and the reaction was continued with stirring at the same temperature for 4-8 h. The reaction was then stopped, and the product was rotary evaporated, washed, and dried to obtain the dehydration condensation reaction product.

[0019] Preferably, the molar ratio of 10-undecenoic acid, EDC, and NHS is 1:1.1-1.2:1.1-1.2.

[0020] Further, the epoxidation reaction includes: After the dehydration condensation reaction product, urea, acidic alumina and glacial acetic acid are mixed evenly, the mixture is heated to 50-70℃, hydrogen peroxide is then added, and the mixture is kept at this temperature and stirred for 12-24 hours. The mixture is then separated, the organic layer is washed, rotary evaporated, and dried to obtain a long alkyl chain silane coupling agent.

[0021] Furthermore, the hydrogen peroxide has a mass fraction of 10-30%.

[0022] Preferably, the mass ratio of the dehydration condensation reaction product, urea, acidic alumina, and hydrogen peroxide in hydrogen peroxide is 20:1-3:1.5-3.5:9-14.

[0023] Furthermore, the accelerator is used to promote the crosslinking and curing of the terminal epoxy groups of the long-chain alkyl groups in the modified bio-based filler. Therefore, the accelerator is one or more amino curing agents mixed in any proportion. The amino curing agent is one or a mixture of several of the following in any proportion: ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, and diethylaminopropylamine.

[0024] Furthermore, the auxiliary materials include one or a mixture of two antioxidants and lubricants in any ratio.

[0025] The beneficial effects of this invention are: This invention provides a recyclable material frisbee, which uses PCR matrix and modified bio-based filler as the main raw materials. By introducing POE elastomer, accelerator and auxiliary materials, the PCR matrix, modified bio-based filler, POE elastomer, accelerator and auxiliary materials work together to obtain a frisbee with moderate softness and hardness, comfortable grip, stable flight and environmental protection, and recyclability. Significantly, this invention utilizes long-alkyl-chain silane coupling agents to modify activated biological waste residue. The highly active silanol bonds generated from the hydrolysis of siloxanes in the silane coupling agent are coupled with the active bonds on the surface of the activated biological waste residue, resulting in the grafting of long-alkyl-chain silane segments onto the residue. This improves the interfacial properties between the biological waste residue and the PCR substrate, enhancing their blending and processing performance. Furthermore, the presence of long-alkyl chains and terminal epoxy groups on the surface of the biological waste residue, utilizing the flexibility of the long-alkyl chains, further enhances the interfacial properties between the biological waste residue and the PCR substrate. Additionally, the cross-linking properties of the epoxy groups under the action of an amino curing agent create a flexible interpenetrating cross-linked network, thereby further improving the hardness and mechanical properties of the resulting fly disc. Detailed Implementation

[0026] 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 of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0027] Example 1 Preparation of activated biological waste residue: Coffee bean grounds are washed with water, alkali, and water again, and then dried to obtain pretreated coffee bean grounds. Then, 100g of pretreated coffee bean grounds are soaked in 200g of hydrogen peroxide (mass fraction of 30%) and heated to 55℃ and kept at that temperature for 30min.

[0028] Comparative Example 2 Preparation of activated biological waste residue: After washing with water, alkali, and water again, the coconut shreds are dried to obtain pretreated coconut shreds. Then, 100g of the pretreated coconut shreds are immersed in 200g of hydrogen peroxide (mass fraction of 30%) and heated to 60℃ and kept at that temperature for 90min.

[0029] Example 3 Preparation of long alkyl chain silane coupling agents: A1. Mix 0.11 mol 10-undecenoic acid, 0.12 mol EDC (1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride), 0.12 mol NHS (N-hydroxysuccinimide) and 200 mL ethanol evenly, and stir at 66 °C and pH 5-6 for 1.5 h. Then add 0.1 mol aminosilane coupling agent (KH550), and continue to stir and maintain the temperature for 6 h. Stop the reaction, rotary evaporate, wash, and dry to obtain the dehydration condensation reaction product. A2. Mix 200g of dehydration condensation reaction product, 10g of urea, 15g of acidic alumina and 300mL of glacial acetic acid evenly, heat to 50℃, then add 90g of hydrogen peroxide, continue to keep warm and stir for 24h, separate the liquid, wash the organic layer, rotary evaporate and dry to obtain long alkyl chain silane coupling agent.

[0030] Example 4 Preparation of long alkyl chain silane coupling agents: A1. Mix 0.13 mol 10-undecenoic acid, 0.14 mol EDC (1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride), 0.14 mol NHS (N-hydroxysuccinimide) and 200 mL ethanol evenly, and stir at 70 °C and pH 5-6 for 1.5 h. Then add 0.1 mol aminosilane coupling agent (KH550), and continue to stir and maintain the temperature for 4 h. Stop the reaction, rotary evaporate, wash, and dry to obtain the dehydration condensation reaction product. A2. Mix 200g of dehydration condensation reaction product, 30g of urea, 35g of acidic alumina and 300mL of glacial acetic acid evenly, heat to 70℃, then add 140g of hydrogen peroxide, continue to keep warm and stir for 16h, separate the liquid, wash the organic layer, rotary evaporate and dry to obtain long alkyl chain silane coupling agent.

[0031] Example 5 Preparation of modified bio-based fillers: Under stirring at 300 r / min and 50 °C, 100 mL of a solution containing 20 g of the long alkyl chain silane coupling agent prepared in Example 3 (solvent: water and ethanol volume ratio 9:1) was sprayed onto 100 g of the active biological waste prepared in Example 1. After complete spraying, the solution was kept warm and stirred for 1.5 h. Stirring was then stopped, and the solution was dried to obtain the modified bio-based filler.

[0032] Example 6 Preparation of modified bio-based fillers: Under stirring at 500 r / min and 75 °C, 100 mL of a solution containing 40 g of the long alkyl chain silane coupling agent prepared in Example 4 (solvent: water and ethanol volume ratio 9:1) was sprayed onto 100 g of the active biological waste prepared in Example 2. After complete spraying, the solution was kept warm and stirred for 1 h. After stirring was stopped, the solution was dried to obtain the modified bio-based filler.

[0033] Example 7 Preparation of the frisbee: Step 1: Prepare the following raw materials by weight: 20 parts recycled low-density polyethylene, 60 parts recycled high-density polyethylene, 2 parts polyolefin elastomer, 12 parts modified bio-based filler prepared in Example 5, 0.5 parts lubricant (polyethylene wax), 0.5 parts antioxidant 1010, and 0.3 parts accelerator (diethylaminopropylamine). The second step involves mixing the above raw materials and then melting and extruding them through a twin-screw extruder to obtain a flying disc at an extrusion temperature of 200-230℃.

[0034] Example 8 Preparation of the frisbee: Step 1: Prepare the following raw materials by weight: 40 parts recycled low-density polyethylene, 30 parts recycled high-density polyethylene, 5 parts polyolefin elastomer, 25 parts modified bio-based filler prepared in Example 6, 0.7 parts lubricant (polyethylene wax), 1 part antioxidant 1010, and 0.5 parts accelerator (hexamethylenediamine). The second step involves mixing the above raw materials and then melting and extruding them through a twin-screw extruder to obtain a flying disc at an extrusion temperature of 200-230℃.

[0035] Example 9 Preparation of the frisbee: Step 1: Prepare the following raw materials by weight: 50 parts recycled low-density polyethylene, 35 parts recycled high-density polyethylene, 10 parts polyolefin elastomer, 5 parts modified bio-based filler prepared in Example 5, 0.8 parts lubricant (polyethylene wax), 0.4 parts antioxidant 1010, and 1 part accelerator (diethylenetriamine). The second step involves mixing the above raw materials and then melting and extruding them through a twin-screw extruder to obtain a flying disc at an extrusion temperature of 200-230℃.

[0036] Comparative Example 1 Preparation of the frisbee: Compared with Example 9, the modified bio-based filler was replaced with an equal amount of the active biological waste prepared in Example 1, and the rest were the same.

[0037] Comparative Example 2 Preparation of the frisbee: Compared with Example 9, the modified bio-based filler was replaced with an equal amount of the activated biological waste prepared below, and the rest were the same: Under stirring conditions of 300 r / min and 50 °C, 100 mL of a solution containing 20 g of aminosilane coupling agent (KH550) (solvent: water and ethanol volume ratio 9:1) was sprayed onto 100 g of the active biological waste prepared in Example 1. After complete spraying, the solution was kept warm and stirred for 1 h. Stirring was then stopped, and the solution was dried to obtain the modified bio-based filler.

[0038] Comparative Example 3 Preparation of the frisbee: Compared with Example 9, the modified bio-based filler was removed, and the rest were the same.

[0039] The physical properties of the frisbees obtained in Examples 7-9 and Comparative Examples 1-3 were tested, and the results are shown in Table 1.

[0040] Table 1

[0041] As can be seen from the data in Table 1, the hardness and mechanical properties of the flying discs obtained in Examples 7-9 are superior to those obtained in Comparative Examples 1-3.

[0042] The frisbees obtained in Examples 7-9 and Comparative Examples 1-3 were subjected to flight tests to observe their flight stability. The results are shown in Table 2. The test method involved flying the frisbee 100 times, with an arm force of 10N each time. The distance of each flight was measured, and the average flight distance was calculated. The dispersion between each flight distance and the average flight distance was then compared. Flight stability was divided into four levels based on the distribution and magnitude of the 100 dispersion values: Level 1, Level 2, Level 3, and Level 4. Level 1 corresponds to a concentrated distribution of the 100 dispersion values ​​with a small maximum dispersion value; Level 2 corresponds to a relatively concentrated distribution of the 100 dispersion values ​​with a small maximum dispersion value; Level 3 corresponds to a relatively dispersed distribution of the 100 dispersion values ​​with a large maximum dispersion value; and Level 4 corresponds to a dispersed distribution of the 100 dispersion values ​​with a large maximum dispersion value. The flight stability was arranged from highest to lowest as Level 1, Level 2, Level 3, and Level 4. Levels 3 and 4 were considered flight failures.

[0043] Table 2

[0044] As can be seen from the data in Table 2, the flying discs obtained in Examples 7-9 have qualified flight stability and perform excellently.

[0045] In the description of this specification, the references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0046] The above description is merely an example and illustration of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described, or use similar methods to replace them, as long as they do not deviate from the invention or exceed the scope defined in the claims, all of which should fall within the protection scope of the present invention.

Claims

1. A frisbee made of recycled material, characterized in that, It includes the following raw materials in parts by weight: 20-120 parts recycled base material, 2-10 parts polyolefin elastomer, 5-25 parts modified bio-based filler, 0.2-1 part accelerator, and 0-2 parts auxiliary materials; The modified bio-based filler is made from activated biological waste and long-chain silane coupling agent through surface treatment; The active biological waste residue is obtained by acid foaming activation treatment of biological waste residue; The long alkyl chain silane coupling agent is prepared by sequentially performing a dehydration condensation reaction and an epoxidation reaction on 10-undecenoic acid and an aminosilane coupling agent; The accelerator is one or more amino curing agents mixed in any proportion; The acid used in the acid foam activation treatment is one of hydrogen peroxide, potassium permanganate, and perchlorate.

2. The recycled material frisbee according to claim 1, characterized in that, The recycled base material is one or a mixture of several of the following in any proportion: recycled low-density polyethylene, recycled high-density polyethylene, recycled polypropylene, recycled polymethyl methacrylate, recycled polystyrene, and recycled acrylonitrile-styrene-butadiene copolymer.

3. The recycled material frisbee according to claim 1, characterized in that, The recycled base material is a mixture of recycled low-density polyethylene and recycled high-density polyethylene. The flying disc contains the following raw materials in parts by weight: 20-50 parts recycled low-density polyethylene, 30-70 parts recycled high-density polyethylene, 2-10 parts polyolefin elastomer, 5-25 parts modified bio-based filler, 0.2-1 parts accelerator, and 0-2 parts auxiliary materials.

4. The recycled material frisbee according to claim 1, characterized in that, The acid foam activation treatment is performed at a temperature of 50-70℃ for 30-90 minutes.

5. The recycled material frisbee according to claim 4, characterized in that, The biological waste residue is a mixture of one or more of the following in any proportion: coffee bean residue, straw residue, coconut residue, and rice husk residue.

6. The recycled material frisbee according to claim 1, characterized in that, The dehydration condensation reaction of the 10-undecenoic acid and aminosilane coupling agent includes: After mixing 10-undecenoic acid, EDC, NHS and ethanol evenly, the mixture was stirred at 66-70℃ and pH 5-6 for 1-1.5h. Then, an aminosilane coupling agent was added, and the reaction was continued with stirring for 4-8h. The reaction was then stopped, and the product was rotary evaporated, washed and dried to obtain the dehydration condensation reaction product.

7. A frisbee made of recycled material according to claim 6, characterized in that, The epoxidation reaction includes: After the dehydration condensation reaction product, urea, acidic alumina and glacial acetic acid are mixed evenly, the mixture is heated to 50-70℃, hydrogen peroxide is then added, and the mixture is kept at this temperature and stirred for 12-24 hours. The mixture is then separated, the organic layer is washed, rotary evaporated, and dried to obtain a long alkyl chain silane coupling agent.

8. The recycled material frisbee according to claim 1, characterized in that, The auxiliary materials include one or a mixture of two antioxidants and lubricants in any ratio.

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