Novel composite material prepared from waste spinning, plastic and filler and preparation method of novel composite material

Abstract

The invention discloses a novel composite material prepared from waste spinning, plastic and filler and a preparation method of the novel composite material, and belongs to the technical field of composite material preparation. The novel composite material is prepared from the following components in parts by weight: 60-80 parts of waste clothes, 20-40 parts of polyethylene glycol terephthalate, 8-16 parts of calcium carbonate, 2-8 parts of an organic antibacterial agent and 2-7 parts of an anti-ultraviolet agent, the organic antibacterial agent is prepared by taking isoamyl amine, 3-bromobenzoyl chloride, 2-amino-5-pyridine borate and valeryl chloride as main raw materials, and the anti-ultraviolet agent is prepared by taking L-tryptophan, manganese dioxide, 2-benzene bromoethane, selenium dioxide and p-toluenesulfonhydrazide as main raw materials. The novel composite material prepared by the method has excellent antibacterial performance and ultraviolet-proof performance.

Description

Technical Field

[0001] The present invention belongs to the technical field of composite material preparation, and particularly relates to a novel composite material made of waste textiles, plastics and fillers and a preparation method thereof. Background Art

[0002] With the sharp increase in the quantity of global waste textiles and plastic waste, resource recycling and environmental protection have become key issues to be solved urgently. Every year, a large amount of waste textiles and plastics are landfilled or incinerated, which not only occupies land resources but also releases harmful gases, causing serious damage to the ecological environment. Against this background, it is of great practical significance to make novel composite materials from waste textiles, plastics and fillers to achieve the high-value utilization of waste. However, there are obvious short boards in the antibacterial and ultraviolet resistance of such composite materials at present, which limits their wider application. In terms of antibacterial performance, traditional waste textiles and plastics lack antibacterial functions themselves. Microorganisms such as bacteria and molds are likely to breed during the recycling process of waste textiles, affecting the hygiene and safety of materials and shortening their service life. Plastics are more likely to become a breeding ground for microorganisms in a humid and warm environment. In terms of ultraviolet resistance, waste textiles and plastics have weak ultraviolet absorption and reflection capabilities. Ultraviolet rays can cause the materials to age, fade, become brittle, reduce their mechanical properties and service life, and also endanger human health. Therefore, by developing novel antibacterial agents and ultraviolet-resistant additives, it is expected to improve the antibacterial and ultraviolet resistance of composite materials and broaden their application fields.

[0003] Patent CN 114703670A discloses a preparation method of a natural aromatic antibacterial multi-functional composite material. Using melamine-formaldehyde prepolymer and vinyl monomer as the wall monomers of the microcapsule, a double-layer microcapsule is obtained through in-situ polymerization. After injecting a core material with aromatic, antibacterial and antiviral functions into the wall of the double-layer microcapsule, a natural aromatic antibacterial multi-functional composite material is obtained. The home textile fibers and fabrics added with this material have good antibacterial and antiviral properties and fragrance release functions. However, there is still room for improvement in the antibacterial and ultraviolet resistance of the composite material prepared by this method. Summary of the Invention

[0004] The purpose of the present invention is to provide a novel composite material made of waste textiles, plastics and fillers and a preparation method thereof, which are used to solve the technical problem of poor antibacterial and ultraviolet resistance of composite fabrics in the prior art.

[0005] In order to achieve the above purpose, the present invention adopts the following technical solutions:

[0006] The present invention provides a novel composite material made from waste textiles, plastics and fillers, which is composed of the following components in parts by weight: 60-80 parts of waste clothing, 20-40 parts of polyethylene terephthalate, 8-16 parts of calcium carbonate, 2-8 parts of an organic antibacterial agent, and 2-7 parts of an ultraviolet inhibitor. Among them, the organic antibacterial agent is prepared from isopentylamine, 3-bromobenzoyl chloride, 2-amino-5-pyridine borate and valeryl chloride as the main raw materials, and the ultraviolet inhibitor is prepared from L-tryptophan, manganese dioxide, 2-phenylethyl bromide, selenium dioxide and p-toluenesulfonyl hydrazide as the main raw materials.

[0007] Preferably, the preparation method of the organic antibacterial agent includes the following steps:

[0008] Q1: In an ice-water bath environment, isopentylamine, 4-dimethylaminopyridine and triethylamine are successively added to a container filled with dichloromethane, and then dichloromethane solution containing 3-bromobenzoyl chloride is added dropwise, followed by stirring reaction, and then heating reaction. After the reaction is completed, saturated sodium chloride solution is added for extraction, drying, concentration under reduced pressure, dissolution and purification to obtain Intermediate 1.

[0009] Q2: Intermediate 1 and 2-amino-5-pyridine borate are successively added to 1,4-dioxane, stirred and mixed, then potassium carbonate and DPPF palladium dichloride are added, and the temperature is raised for reaction. Then distilled water is added to continue the reaction. After the reaction is completed, it is cooled, the pressure is reduced, dissolved, filtered and purified to obtain Intermediate 2.

[0010] Q3: In an ice-water bath environment, Intermediate 2, 4-dimethylaminopyridine and triethylamine are successively added to a container filled with dichloromethane, and then dichloromethane solution containing valeryl chloride is added dropwise for reaction, and the temperature is raised to continue the reaction. After the reaction is completed, saturated sodium chloride solution is added for extraction, drying, concentration under reduced pressure, dissolution and purification to obtain the organic antibacterial agent.

[0011] In the above process, the synthesis reaction formula of the organic antibacterial agent is as follows:

[0012]

[0013] The mass spectrometry analysis results of Intermediate 1 are: m / z: 269.04(100.0%), 271.04(97.3%), 270.04(13.3%), 272.04(13.0%), 271.05(1.0%); the mass spectrometry analysis results of Intermediate 2 are: m / z: 283.17(100.0%), 284.17(19.8%), 285.18(1.6%); the mass spectrometry analysis results of the organic antibacterial agent are: m / z: 367.23(100.0%), 368.23(24.2%), 369.23(3.4%), 368.22(1.1%).

[0014] Preferably, in Q1, the molar ratio of isopentylamine, 4-dimethylaminopyridine, triethylamine and 3-bromobenzoyl chloride is (6.21 - 7.45):(0.42 - 0.51):(8.91 - 9.31):(4.15 - 5.01), the stirring reaction time is 10 - 15 min, the temperature-raising reaction temperature is 28 - 32 °C, and the temperature-raising reaction time is 60 - 80 min.

[0015] Preferably, in Q2, the molar ratio of intermediate 1, 2-amino-5-pyridine borate, potassium carbonate and DPPF dichloropalladium is (3.12 - 3.81):(4.11 - 4.89):(6.12 - 7.73):(0.31 - 0.38), the temperature-raising reaction temperature is 95 - 105 °C, the reaction time is 1 - 2 h, and the continued reaction time is 2 - 4 h.

[0016] Preferably, in Q3, the molar ratio of intermediate 2, 4-dimethylaminopyridine, triethylamine and valeryl chloride is (0.61 - 0.72):(0.061 - 0.068):(1.11 - 1.53):(0.92 - 1.04), the reaction time is 10 - 15 min, the temperature-raising continued reaction temperature is 29 - 33 °C, and the reaction time is 1 - 1.5 h.

[0017] Preferably, the preparation method of the ultraviolet ray-proof agent comprises the following steps:

[0018] S1: Add L-tryptophan into a container filled with distilled water. After stirring evenly, add dilute sulfuric acid solution and acetaldehyde solution. Stir at room temperature until solids precipitate. Filter by suction, wash, and dry to obtain product 1; Add product 1 into a container filled with distilled water. Stir at room temperature, then heat up. Subsequently, add manganese dioxide. After stirring evenly, drip dilute sulfuric acid solution to continue the reaction. After the reaction ends, stop heating, stir, adjust the pH, extract, and concentrate to obtain product 2;

[0019] S2: Add product 2 and sodium hydride into a container filled with N,N-dimethylformamide. Stir at room temperature, and then add 2-phenylethyl bromide. Stir at room temperature for reaction. After the reaction ends, add the mixed solution into ice water, extract, dry, concentrate, recrystallize, filter by suction, dissolve, adjust the pH, extract, concentrate, and dry to obtain product 3; Add product 3 and acetonitrile into a container. After heating and stirring, add selenium dioxide. After heating under reflux for reaction, purify to obtain product 4;

[0020] S3: Add product 4, p-toluenesulfonyl hydrazide, cesium carbonate and copper iodide into a container filled with toluene in sequence. Heat and stir for reaction. After the reaction ends, add it into distilled water, extract, concentrate and evaporate, and purify to obtain the ultraviolet ray-proof agent.

[0021] In the above process, the synthesis reaction formula of the ultraviolet ray inhibitor is as follows:

[0022]

[0023] The results of mass spectrometry analysis of product 1 are: m / z: 230.11 (100.0%), 231.11 (14.3%), 232.11 (1.4%); the results of mass spectrometry analysis of product 2 are: m / z: 182.08 (100.0%), 183.09 (13.1%); the results of mass spectrometry analysis of product 3 are: m / z: 286.15 (100.0%), 287.15 (21.8%), 288.15 (2.4%); the results of mass spectrometry analysis of product 4 are: m / z: 300.13 (100.0%), 301.13 (21.9%), 302.13 (2.6%); the results of mass spectrometry analysis of the ultraviolet ray inhibitor are: m / z: 312.14 (100.0%), 313.14 (21.8%), 314.14 (2.5%), 313.13 (1.5%).

[0024] Preferably, in S1, the dosage ratio of L-tryptophan, distilled water, dilute sulfuric acid solution and acetaldehyde solution is (18.8 - 22.1) g : (280 - 330) mL : (4.5 - 5.6) mL : (58 - 63) mL; the dosage ratio of product 1, distilled water, manganese dioxide and dilute sulfuric acid solution is (21.2 - 25.3) g : (280 - 330) mL : (25.3 - 27.5) g : (180 - 220) mL, and the temperature is raised to 90 - 110 °C by heating.

[0025] Preferably, in S2, the dosage ratio of product 2, sodium hydride, N,N-dimethylformamide and 2-bromoethylbenzene is (5.2 - 6.1) g : (1.2 - 1.9) g : (190 - 220) mL : (2.1 - 3.5) mL; the dosage ratio of product 3, acetonitrile and selenium dioxide is (1.4 - 2.2) g : (45 - 54) mL : (3.1 - 3.5) g.

[0026] Preferably, in S3, the dosage ratio of product 4, p-toluenesulfonylhydrazide, cesium carbonate, copper iodide and toluene is (0.2 - 0.9) g : (0.62 - 0.88) g : (1.42 - 1.54) g : (0.05 - 0.09) g : (5 - 9) mL, the heating and stirring temperature is 80 - 85 °C, and the reaction time is 8 - 12 h.

[0027] Preferably, a preparation method of a novel composite material made of waste textiles, plastics and fillers includes the following steps:

[0028] Step 1: Wash, disinfect, dry, crush, and granulate waste clothes to obtain waste clothes particles. Wash, melt, and extrude polyethylene terephthalate to obtain recycled particles. Dry calcium carbonate to obtain pretreated filler.

[0029] Step 2: Add the waste clothes particles, recycled particles, and pretreated filler into a high-speed mixer, mix evenly, then add an organic antibacterial agent and an ultraviolet inhibitor, continue to mix, melt blend, extrude, and mold to obtain a new composite material made of waste textiles, plastics, and fillers.

[0030] In summary, due to the adoption of the above technical solutions, the beneficial effects of the present invention are as follows:

[0031] 1. The present invention first prepares an organic antibacterial agent using isoamylamine, 3-bromobenzoyl chloride, 2-amino-5-pyridyl borate, and valeryl chloride as the main raw materials. Subsequently, an ultraviolet inhibitor is prepared using L-tryptophan, manganese dioxide, 2-phenylethyl bromide, selenium dioxide, and p-toluenesulfonyl hydrazide as the main raw materials. During the preparation process of the new composite material, adding the organic antibacterial agent and the ultraviolet inhibitor can effectively improve its antibacterial performance and ultraviolet resistance, thereby broadening the application field of the new composite material in fabrics.

[0032] 2. Adding the prepared organic antibacterial agent to the preparation process of the new composite material can effectively improve its antibacterial performance. The pyridine ring and amide group contained can bind to microbial proteins or enzymes, inhibit enzyme activity, and the hydrophobic alkyl chain contained can insert into the lipid layer of the microbial cell membrane, interfere with membrane stability, and damage the cell membrane, so that the new composite material has long-term antibacterial and mildew-proof effects. At the same time, the hydrophobic group contained can reduce the surface hydrophilicity of the new composite material, reduce water penetration, and improve weather resistance.

[0033] 3. Adding the prepared ultraviolet inhibitor to the preparation process of the new composite material can effectively improve its ultraviolet resistance. The extended conjugated system contained in the ultraviolet inhibitor can not only reduce the penetration and energy accumulation of ultraviolet rays, but also avoid the generation of free radicals, thereby effectively protecting against ultraviolet rays and improving the durability of the new composite material. Specific Embodiments

[0034] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0035] Example 1: This example discloses a preparation method of an organic antibacterial agent, including the following steps:

[0036] Q1: Under an ice-water bath environment, 0.595 g of isopentylamine, 0.058 g of 4-dimethylaminopyridine, and 0.923 g of triethylamine were successively added to a container containing 10 mL of dichloromethane. Then, 20 mL of dichloromethane solution containing 0.987 g of 3-bromobenzoyl chloride was added dropwise, and the mixture was stirred for 10 min. Subsequently, the temperature was raised to 30 °C and the reaction was carried out for 60 min. After the reaction, saturated sodium chloride solution was added, followed by extraction, drying, concentration under reduced pressure, dissolution, and purification to obtain Intermediate 1;

[0037] Q2: 0.863 g of Intermediate 1 and 0.955 g of 2-amino-5-pyridine borate were successively added to 40 mL of 1,4-dioxane, stirred and mixed. Then, 0.923 g of potassium carbonate and 0.245 g of DPPF palladium dichloride were added. The temperature was raised to 100 °C and the reaction was carried out for 1.5 h. Subsequently, 10 mL of distilled water was added and the reaction was continued for 2 h. After the reaction, it was cooled, concentrated under reduced pressure, dissolved, filtered, and purified to obtain Intermediate 2;

[0038] Q3: Under an ice-water bath environment, 0.165 g of Intermediate 2, 0.007 g of 4-dimethylaminopyridine, and 0.133 g of triethylamine were successively added to a container containing 5 mL of dichloromethane. Then, 5 mL of dichloromethane solution containing 0.118 g of valeryl chloride was added dropwise, and the reaction was carried out for 10 min. The temperature was raised to 30 °C and the reaction was continued for 1.5 h. After the reaction, 30 mL of saturated sodium chloride solution was added, followed by extraction, drying, concentration under reduced pressure, dissolution, and purification to obtain the organic antibacterial agent.

[0039] This example discloses a preparation method of an ultraviolet inhibitor, comprising the following steps:

[0040] S1: 20.3 g of L-tryptophan was added to a container containing 305 mL of distilled water. After stirring evenly, 5.1 mL of 0.5 mol / L dilute sulfuric acid solution and 60.5 mL of acetaldehyde solution were added. Stirring was carried out at room temperature until a solid precipitated. Then, suction filtration, washing, and drying were carried out to obtain Product 1; 23.2 g of Product 1 was added to a container containing 305 mL of distilled water. After stirring at room temperature, the temperature was raised to 100 °C. Subsequently, 26.4 g of manganese dioxide was added. After stirring evenly, 200 mL of 0.5 mol / L dilute sulfuric acid solution was added dropwise and the reaction was continued. After the reaction, heating was stopped, stirring was carried out, the pH was adjusted, extraction was carried out, and concentration was carried out to obtain Product 2;

[0041] S2: Add 5.6 g of product 2 and 1.5 g of sodium hydride into a container filled with 205 mL of N,N-dimethylformamide, stir at room temperature, then add 2.8 mL of 2-phenylethyl bromide, stir and react at room temperature. After the reaction is completed, add the mixed solution into ice water, extract, dry, concentrate, recrystallize, filter by suction, dissolve, adjust the pH, extract, concentrate, and dry to obtain product 3; Add 1.8 g of product 3 and 49.5 mL of acetonitrile into a container, heat and stir, then add 3.3 g of selenium dioxide, heat under reflux and react, and then purify to obtain product 4;

[0042] S3: Add 0.55 g of product 4, 0.75 g of p-toluenesulfonyl hydrazide, 1.48 g of cesium carbonate, and 0.07 g of cuprous iodide into a container filled with 7 mL of toluene in sequence, heat and stir at 80 °C for 12 h. After the reaction is completed, add it into distilled water, extract, concentrate and evaporate, and purify to obtain the ultraviolet inhibitor.

[0043] This example discloses a new composite material made of waste textiles, plastics and fillers, which is composed of the following components in parts by weight: 70 parts of waste clothing, 30 parts of polyethylene terephthalate, 12 parts of calcium carbonate, 5 parts of organic antibacterial agent, and 4.5 parts of ultraviolet inhibitor.

[0044] This example discloses a preparation method of a new composite material made of waste textiles, plastics and fillers, including the following steps:

[0045] Step 1: Wash, disinfect, dry, crush and granulate the waste clothing to obtain waste clothing particles, wash and melt-extrude the polyethylene terephthalate to obtain recycled particles; Dry the calcium carbonate to obtain the pretreated filler;

[0046] Step 2: Add the waste clothing particles, recycled particles and pretreated filler into a high-speed mixer, mix evenly, then add the organic antibacterial agent and ultraviolet inhibitor, continue to mix, melt-blend, extrude and mold to obtain a new composite material made of waste textiles, plastics and fillers.

[0047] Example 2: This example discloses a preparation method of an organic antibacterial agent, including the following steps:

[0048] Q1: Under an ice-water bath environment, add 0.541 g of isopentylamine, 0.052 g of 4-dimethylaminopyridine and 0.901 g of triethylamine into a container filled with 10 mL of dichloromethane in sequence, then dropwise add 20 mL of dichloromethane dissolved with 0.911 g of 3-bromobenzoyl chloride, stir and react for 10 min, then raise the temperature to 30 °C and react for 60 min. After the reaction is completed, add saturated sodium chloride solution, extract, dry, concentrate under reduced pressure, dissolve, and purify to obtain intermediate 1;

[0049] Q2: 0.777 g of intermediate 1 and 0.904 g of 2-amino-5-pyridine borate were successively added to 40 mL of 1,4-dioxane, stirred and mixed. Subsequently, 0.845 g of potassium carbonate and 0.227 g of DPPF palladium dichloride were added. The temperature was raised to 100 °C and reacted for 1.5 h. Then, 10 mL of distilled water was added and the reaction continued for 2 h. After the reaction was completed, it was cooled, depressurized, dissolved, filtered, and purified to obtain intermediate 2;

[0050] Q3: Under an ice-water bath environment, 0.156 g of intermediate 2, 0.008 g of 4-dimethylaminopyridine, and 0.112 g of triethylamine were successively added to a container containing 5 mL of dichloromethane. Then, 5 mL of dichloromethane dissolved with 0.111 g of valeryl chloride was added dropwise, and the reaction was carried out for 10 min. The temperature was raised to 30 °C and the reaction continued for 1.5 h. After the reaction was completed, 30 mL of saturated sodium chloride solution was added, extracted, dried, concentrated under reduced pressure, dissolved, and purified to obtain the organic antibacterial agent.

[0051] This example discloses a preparation method of an anti-ultraviolet agent, including the following steps:

[0052] S1: 18.8 g of L-tryptophan was added to a container containing 330 mL of distilled water. After stirring evenly, 4.5 mL of 0.5 mol / L dilute sulfuric acid solution and 58 mL of acetaldehyde solution were added. Stirred at room temperature until a solid precipitated, filtered by suction, washed, and dried to obtain product 1; 21.2 g of product 1 was added to a container containing 280 mL of distilled water. After stirring at room temperature, the temperature was raised to 100 °C. Subsequently, 25.3 g of manganese dioxide was added. After stirring evenly, 180 mL of 0.5 mol / L dilute sulfuric acid solution was added dropwise and the reaction continued. After the reaction was completed, heating was stopped, stirred, the pH was adjusted, extracted, and concentrated to obtain product 2;

[0053] S2: 5.2 g of product 2 and 1.2 g of sodium hydride were added to a container containing 220 mL of N,N-dimethylformamide. Stirred at room temperature, and then 2.1 mL of 2-phenylethyl bromide was added. Stirred and reacted at room temperature. After the reaction was completed, the mixed solution was added to ice water, extracted, dried, concentrated, recrystallized, filtered by suction, dissolved, the pH was adjusted, extracted, concentrated, and dried to obtain product 3; 1.4 g of product 3 and 45 mL of acetonitrile were added to a container. After heating and stirring, 3.1 g of selenium dioxide was added. After heating and refluxing the reaction, it was purified to obtain product 4;

[0054] S3: 0.2 g of product 4, 0.62 g of p-toluenesulfonyl hydrazide, 1.42 g of cesium carbonate, and 0.09 g of copper iodide were successively added to a container containing 5 mL of toluene. Heated and stirred at 80 °C for 12 h. After the reaction was completed, it was added to distilled water, extracted, concentrated by evaporation, and purified to obtain the anti-ultraviolet agent.

[0055] This embodiment discloses a novel composite material made of waste textiles, plastics, and fillers, which is composed of the following components by weight: 60 parts of waste clothing, 20 parts of polyethylene terephthalate, 8 parts of calcium carbonate, 8 parts of organic antibacterial agent, and 7 parts of ultraviolet inhibitor.

[0056] This embodiment discloses a preparation method of a novel composite material made of waste textiles, plastics, and fillers, including the following steps:

[0057] Step 1: Wash, disinfect, dry, crush, and granulate the waste clothing to obtain waste clothing particles. Wash and melt-extrude the polyethylene terephthalate to obtain recycled particles. Dry the calcium carbonate to obtain pretreated fillers.

[0058] Step 2: Add the waste clothing particles, recycled particles, and pretreated fillers to a high-speed mixer, mix evenly, then add the organic antibacterial agent and ultraviolet inhibitor, continue to mix, melt-blend, extrude, and mold to obtain a novel composite material made of waste textiles, plastics, and fillers.

[0059] Example 3: This embodiment discloses a preparation method of an organic antibacterial agent, including the following steps:

[0060] Q1: Under an ice-water bath environment, sequentially add 0.649 g of isopentylamine, 0.063 g of 4-dimethylaminopyridine, and 0.942 g of triethylamine to a container containing 10 mL of dichloromethane, then dropwise add 20 mL of dichloromethane dissolved with 1.1 g of 3-bromobenzoyl chloride, stir and react for 10 min, then raise the temperature to 30 °C and react for 60 min. After the reaction, add saturated sodium chloride solution, extract, dry, concentrate under reduced pressure, dissolve, and purify to obtain Intermediate 1.

[0061] Q2: Sequentially add 0.95 g of Intermediate 1 and 1.076 g of 2-amino-5-pyridine borate to 40 mL of 1,4-dioxane, stir and mix, then add 1.068 g of potassium carbonate and 0.278 g of DPPF palladium dichloride, raise the temperature to 100 °C and react for 1.5 h, then add 10 mL of distilled water and continue to react for 2 h. After the reaction, cool, reduce the pressure, dissolve, filter, and purify to obtain Intermediate 2.

[0062] Q3: Under an ice-water bath environment, sequentially add 0.184 g of Intermediate 2, 0.007 g of 4-dimethylaminopyridine, and 0.155 g of triethylamine to a container containing 5 mL of dichloromethane, then dropwise add 5 mL of dichloromethane dissolved with 0.125 g of valeryl chloride, react for 10 min, raise the temperature to 30 °C and continue to react for 1.5 h. After the reaction, add 30 mL of saturated sodium chloride solution, extract, dry, concentrate under reduced pressure, dissolve, and purify to obtain the organic antibacterial agent.

[0063] This embodiment discloses a preparation method of an anti-ultraviolet agent, which includes the following steps:

[0064] S1: Add 22.1 g of L-tryptophan into a container containing 280 mL of distilled water. After stirring evenly, add 5.6 mL of 0.5 mol / L dilute sulfuric acid solution and 63 mL of acetaldehyde solution. Stir at room temperature until solids precipitate. Filter by suction, wash, and dry to obtain Product 1. Add 25.3 g of Product 1 into a container containing 330 mL of distilled water. Stir at room temperature, then heat up to 100 °C. Subsequently, add 27.5 g of manganese dioxide. After stirring evenly, dropwise add 220 mL of 0.5 mol / L dilute sulfuric acid solution to continue the reaction. After the reaction ends, stop heating, stir, adjust the pH, extract, and concentrate to obtain Product 2;

[0065] S2: Add 6.1 g of Product 2 and 1.9 g of sodium hydride into a container containing 190 mL of N,N-dimethylformamide. Stir at room temperature, and then add 3.5 mL of 2-phenylethyl bromide. Stir at room temperature for reaction. After the reaction ends, add the mixture into ice water, extract, dry, concentrate, recrystallize, filter by suction, dissolve, adjust the pH, extract, concentrate, and dry to obtain Product 3. Add 2.2 g of Product 3 and 54 mL of acetonitrile into a container. After heating and stirring, add 3.5 g of selenium dioxide. After heating under reflux for reaction, purify to obtain Product 4;

[0066] S3: Add 0.9 g of Product 4, 0.88 g of p-toluenesulfonyl hydrazide, 1.54 g of cesium carbonate, and 0.05 g of copper(I) iodide into a container containing 9 mL of toluene in sequence. Heat and stir at 80 °C for 12 h. After the reaction ends, add it into distilled water, extract, concentrate and evaporate, and purify to obtain the anti-ultraviolet agent.

[0067] This embodiment discloses a new composite material made of waste textiles, plastics, and fillers, which is composed of the following components by weight: 80 parts of waste clothing, 40 parts of polyethylene terephthalate, 16 parts of calcium carbonate, 2 parts of organic antibacterial agent, and 2 parts of anti-ultraviolet agent.

[0068] This embodiment discloses a preparation method of a new composite material made of waste textiles, plastics, and fillers, which includes the following steps:

[0069] Step 1: Wash, disinfect, dry, crush, and granulate the waste clothing to obtain waste clothing particles. Wash and melt-extrude the polyethylene terephthalate to obtain recycled particles. Dry the calcium carbonate to obtain pretreated fillers;

[0070] Step 2: Add waste clothing particles, recycled particles, and pretreated fillers into a high-speed mixer, mix them evenly, then add an organic antibacterial agent and an ultraviolet inhibitor, continue mixing, melt-blend, extrude, and mold to obtain a new composite material made of waste textiles, plastics, and fillers.

[0071] Example 4: This example discloses a preparation method of an organic antibacterial agent, which includes the following steps:

[0072] Q1: Under an ice-water bath environment, add 0.578 g of isoamylamine, 0.055 g of 4-dimethylaminopyridine, and 0.912 g of triethylamine into a container containing 10 mL of dichloromethane in sequence, then dropwise add 20 mL of dichloromethane dissolving 0.948 g of 3-bromobenzoyl chloride, stir and react for 10 min, then raise the temperature to 30 °C and react for 60 min. After the reaction ends, add saturated sodium chloride solution, extract, dry, concentrate under reduced pressure, dissolve, and purify to obtain Intermediate 1;

[0073] Q2: Add 0.817 g of Intermediate 1 and 0.924 g of 2-amino-5-pyridine borate into 40 mL of 1,4-dioxane in sequence, stir and mix, then add 0.885 g of potassium carbonate and 0.235 g of DPPF palladium dichloride, raise the temperature to 100 °C and react for 1.5 h, then add 10 mL of distilled water and continue to react for 2 h. After the reaction ends, cool, reduce the pressure, dissolve, filter, and purify to obtain Intermediate 2;

[0074] Q3: Under an ice-water bath environment, add 0.159 g of Intermediate 2, 0.008 g of 4-dimethylaminopyridine, and 0.123 g of triethylamine into a container containing 5 mL of dichloromethane in sequence, then dropwise add 5 mL of dichloromethane dissolving 0.115 g of valeryl chloride, react for 10 min, raise the temperature to 30 °C and continue to react for 1.5 h. After the reaction ends, add 30 mL of saturated sodium chloride solution, extract, dry, concentrate under reduced pressure, dissolve, and purify to obtain the organic antibacterial agent.

[0075] This example discloses a preparation method of an ultraviolet inhibitor, which includes the following steps:

[0076] S1: Add 19.5 g of L-tryptophan into a container containing 290 mL of distilled water, stir evenly, then add 4.8 mL of 0.5 mol / L dilute sulfuric acid solution and 59 mL of acetaldehyde solution, stir at room temperature until solids precipitate, filter by suction, wash, and dry to obtain Product 1; add 22.4 g of Product 1 into a container containing 315 mL of distilled water, stir at room temperature, then heat and raise the temperature to 100 °C, then add 26.1 g of manganese dioxide, stir evenly, then dropwise add 190 mL of 0.5 mol / L dilute sulfuric acid solution and continue to react. After the reaction ends, stop heating, stir, adjust the pH, extract, and concentrate to obtain Product 2;

[0077] S2: Add 5.4 g of product 2 and 1.3 g of sodium hydride into a container filled with 200 mL of N,N-dimethylformamide, stir at room temperature, then add 2.4 mL of 2-phenylethyl bromide, stir and react at room temperature. After the reaction is completed, add the mixed solution into ice water, extract, dry, concentrate, recrystallize, filter by suction, dissolve, adjust the pH, extract, concentrate, and dry to obtain product 3; Add 1.6 g of product 3 and 47 mL of acetonitrile into a container, stir while heating, then add 3.4 g of selenium dioxide, reflux and react while heating, and purify to obtain product 4;

[0078] S3: Add 0.3 g of product 4, 0.66 g of p-toluenesulfonyl hydrazide, 1.45 g of cesium carbonate, and 0.06 g of cuprous iodide into a container filled with 6 mL of toluene in sequence, heat and stir at 80 °C for 12 h. After the reaction is completed, add it into distilled water, extract, concentrate and evaporate, and purify to obtain the ultraviolet ray inhibitor.

[0079] This example discloses a novel composite material made from waste textiles, plastics and fillers, which is composed of the following components by weight: 75 parts of waste clothing, 25 parts of polyethylene terephthalate, 10 parts of calcium carbonate, 4 parts of organic antibacterial agent, and 3 parts of ultraviolet ray inhibitor.

[0080] This example discloses a preparation method of a novel composite material made from waste textiles, plastics and fillers, including the following steps:

[0081] Step 1: Wash, disinfect, dry, crush and granulate the waste clothing to obtain waste clothing particles; wash and melt-extrude the polyethylene terephthalate to obtain recycled particles; dry the calcium carbonate to obtain the pretreated filler;

[0082] Step 2: Add the waste clothing particles, recycled particles and pretreated filler into a high-speed mixer, mix evenly, then add the organic antibacterial agent and ultraviolet ray inhibitor, continue to mix, melt-blend, extrude and mold to obtain a novel composite material made from waste textiles, plastics and fillers.

[0083] Comparative Example 1: Compared with Example 1, in the process of preparing the novel composite material in Comparative Example 1, the organic antibacterial agent is not added, and other conditions remain unchanged.

[0084] Comparative Example 2: Compared with Example 1, in the process of preparing the novel composite material in Comparative Example 2, the ultraviolet ray inhibitor is not added, and other conditions remain unchanged.

[0085] Experimental Example: The properties of the novel composite materials prepared in Examples 1-4 and Comparative Examples 1-2 were tested. The antibacterial properties of the samples were tested according to GB / T 20944.1-2007, and the ultraviolet protection properties of the samples were tested according to GB / T 18830-2009. The test results are shown in Table 1:

[0086] Table 1

[0087]

[0088] As can be seen from the test results in Table 1, the novel composite materials prepared in Examples 1-4 of the present invention have excellent antibacterial properties and ultraviolet protection properties. By comparing Comparative Example 1 with Examples 1-4, it can be seen that adding an organic antibacterial agent can effectively improve the antibacterial properties of the novel composite material; by comparing Comparative Example 2 with Examples 1-4, it can be seen that adding an ultraviolet protection agent can effectively improve the ultraviolet protection properties of the novel composite material.

[0089] As described above, the above are only the preferred specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present invention, according to the technical solution of the present invention and its inventive concept, makes equivalent substitutions or changes, and all should be covered within the protection scope of the present invention.

[0090] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the present invention to only the specific embodiments. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can well understand and utilize the present invention. The present invention is only limited by the claims and their full scope and equivalents.

Claims

1. A new composite material made of waste textiles, plastics and fillers, characterized in that, It consists of the following components by weight: 60 - 80 parts of waste clothing, 20 - 40 parts of polyethylene terephthalate, 8 - 16 parts of calcium carbonate, 2 - 8 parts of organic antibacterial agent, and 2 - 7 parts of ultraviolet inhibitor. Among them, the organic antibacterial agent is prepared from isopentylamine, 3 - bromobenzoyl chloride, 2 - amino - 5 - pyridine borate, and valeryl chloride as the main raw materials, and the ultraviolet inhibitor is prepared from L - tryptophan, manganese dioxide, 2 - phenylbromoethane, selenium dioxide, and p - toluenesulfonyl hydrazide as the main raw materials.

2. The novel composite material made of waste textile, plastic and filler according to claim 1, characterized in that, The preparation method of the organic antibacterial agent comprises the following steps: Q1: In an ice - water bath environment, isopentylamine, 4 - dimethylaminopyridine, and triethylamine are successively added to a container filled with dichloromethane, and then dichloromethane solution containing 3 - bromobenzoyl chloride is added dropwise, followed by stirring reaction, and then heating reaction. After the reaction is completed, saturated sodium chloride solution is added for extraction, drying, concentration under reduced pressure, dissolution, and purification to obtain intermediate 1. Q2: Intermediate 1 and 2 - amino - 5 - pyridine borate are successively added to 1,4 - dioxane, stirred and mixed, then potassium carbonate and DPPF dichloropalladium are added, and the temperature is raised for reaction. Subsequently, distilled water is added to continue the reaction. After the reaction is completed, it is cooled, the pressure is reduced, dissolved, filtered, and purified to obtain intermediate 2. Q3: In an ice - water bath environment, intermediate 2, 4 - dimethylaminopyridine, and triethylamine are successively added to a container filled with dichloromethane, and then dichloromethane solution containing valeryl chloride is added dropwise for reaction, and the temperature is raised to continue the reaction. After the reaction is completed, saturated sodium chloride solution is added for extraction, drying, concentration under reduced pressure, dissolution, and purification to obtain the organic antibacterial agent.

3. The novel composite material made of waste textiles, plastics and fillers according to claim 2, wherein In Q1, the molar ratio of isopentylamine, 4 - dimethylaminopyridine, triethylamine, and 3 - bromobenzoyl chloride is (6.21 - 7.45):(0.42 - 0.51):(8.91 - 9.31):(4.15 - 5.01).

4. The novel composite material made from waste textile, plastic and filler according to claim 2, characterized in that, In Q2, the molar ratio of intermediate 1, 2 - amino - 5 - pyridine borate, potassium carbonate, and DPPF dichloropalladium is (3.12 - 3.81):(4.11 - 4.89):(6.12 - 7.73):(0.31 - 0.38).

5. The novel composite material made of waste textiles, plastics and fillers according to claim 2, characterized in that, In Q3, the molar ratio of intermediate 2, 4 - dimethylaminopyridine, triethylamine, and valeryl chloride is (0.61 - 0.72):(0.061 - 0.068):(1.11 - 1.53):(0.92 - 1.04).

6. The novel composite material made of waste textile, plastics and fillers according to claim 1, characterized in that, The preparation method of the ultraviolet inhibitor comprises the following steps: S1: L - tryptophan is added to a container filled with distilled water. After stirring evenly, dilute sulfuric acid solution and acetaldehyde solution are added, and stirred at room temperature until solids precipitate. Then it is filtered by suction, washed, and dried to obtain product 1. Product 1 is added to a container filled with distilled water, stirred at room temperature, then heated and the temperature is raised. Subsequently, manganese dioxide is added, stirred evenly, and then dilute sulfuric acid solution is added dropwise to continue the reaction. After the reaction is completed, heating is stopped, stirred, the pH is adjusted, extracted, and concentrated to obtain product 2. S2: Add product 2 and sodium hydride into a container filled with N,N-dimethylformamide, stir at room temperature, then add 2-bromoethylbenzene, stir and react at room temperature. After the reaction is completed, add the mixed solution into ice water, extract, dry, concentrate, recrystallize, filter by suction, dissolve, adjust the pH, extract, concentrate, and dry to obtain product 3; Add product 3 and acetonitrile into a container, heat and stir, then add selenium dioxide, heat under reflux and react, and then purify to obtain product 4; S3: Add product 4, p-toluenesulfonylhydrazide, cesium carbonate and copper(I) iodide into a container filled with toluene in sequence, heat and stir to react. After the reaction is completed, add it into distilled water, extract, concentrate and evaporate, and purify to obtain the ultraviolet absorber.

7. The novel composite material made from waste textiles, plastics and fillers according to claim 6, characterized in that, In the said S1, the dosage ratio of L-tryptophan, distilled water, dilute sulfuric acid solution and acetaldehyde solution is (18.8 - 22.1) g : (280 - 330) mL : (4.5 - 5.6) mL : (58 - 63) mL; the dosage ratio of product 1, distilled water, manganese dioxide and dilute sulfuric acid solution is (21.2 - 25.3) g : (280 - 330) mL : (25.3 - 27.5) g : (180 - 220) mL.

8. The novel composite material made of waste textiles, plastics and fillers according to claim 6, characterized in that, In the said S2, the dosage ratio of product 2, sodium hydride, N,N-dimethylformamide and 2-bromoethylbenzene is (5.2 - 6.1) g : (1.2 - 1.9) g : (190 - 220) mL : (2.1 - 3.5) mL; the dosage ratio of product 3, acetonitrile and selenium dioxide is (1.4 - 2.2) g : (45 - 54) mL : (3.1 - 3.5) g.

9. The novel composite material made from waste textiles, plastics and fillers according to claim 6, wherein, In the said S3, the dosage ratio of product 4, p-toluenesulfonylhydrazide, cesium carbonate, copper(I) iodide and toluene is (0.2 - 0.9) g : (0.62 - 0.88) g : (1.42 - 1.54) g : (0.05 - 0.09) g : (5 - 9) mL.

10. The preparation method of the novel composite material made of waste spinning, plastics and fillers according to any one of claims 1-9, characterized in that, It includes the following steps: Step 1: Wash, disinfect, dry, crush and granulate the waste clothes to obtain waste clothes particles. Wash and melt-extrude polyethylene terephthalate to obtain recycled particles; Dry calcium carbonate to obtain pretreated filler; Step 2: Add the waste clothes particles, recycled particles and pretreated filler into a high-speed mixer, mix evenly, then add an organic antibacterial agent and an ultraviolet absorber, continue to mix, melt-blend, extrude and mold to obtain a new composite material made of waste textiles, plastics and fillers.

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