Waste mobile phone circuit board nonmetal component / epoxy resin based composite material and preparation method thereof

Abstract

The invention aims to provide the waste mobile phone circuit board nonmetal component / epoxy resin-based composite material and the preparation method thereof in order to overcome the defects of the existing composite material prepared from the waste circuit board nonmetal component, and the method has the characteristics of simple process, safe operation, cleanness, sustainability, high raw material utilization rate, easy industrial amplification and the like. According to the method, commercially available waste mobile phone circuit boards are used as raw materials, and the composite material is prepared through the steps of preparing waste mobile phone circuit board powder, assembling an ultrasonic-microbubble synergistic strengthening treatment device, preparing waste mobile phone circuit board nonmetal components, preparing the waste mobile phone circuit board nonmetal component / epoxy resin based composite material and the like. The method disclosed by the invention has the characteristics of simple process, safety in operation, convenience in industrial amplification, high raw material utilization rate, low equipment and operation cost and the like. The product prepared by the method can be widely applied to the fields of automobile parts, 3D printing, sports equipment and the like.

Description

Technical Field

[0001] The invention belongs to the technical field of solid waste resource utilization, and specifically relates to a non-metal component / epoxy resin-based composite material of waste mobile phone circuit boards and a preparation method thereof. Background Art

[0002] In recent years, electrical and electronic equipment has experienced rapid growth internationally. At the same time, technological innovation and market competition have intensified, leading to rapid product updates and iterations. As a result, the number of discarded electrical and electronic equipment has surged, and global attention to electronic waste pollution has also increased. Waste mobile phone circuit boards are an important component of waste mobile phones, of which non-metallic components account for about 60-70% of the total mass. Due to the low value of non-metallic components and the difficulty of processing and fully utilizing the glass fiber and resin in them, the reuse of non-metallic components in waste mobile phone circuit boards has rarely received attention, and they are often simply incinerated or landfilled, which not only wastes resources, but also causes harmful substances in non-metallic components to enter the soil and water, posing a serious threat to the environment and human health. The non-metallic components of waste mobile phone circuit boards are mainly composed of glass fiber and resin, which can be used as a promising reinforcing agent and functional filler. In the context of strengthening the recycling of low-value recyclables in recent years, it is urgent to develop a green and sustainable method to realize the resource utilization of non-metallic components in waste mobile phone circuit boards.

[0003] Polymer-based composite materials are based on thermosetting resins (such as epoxy resins, unsaturated polyester resins, etc.), thermoplastics (such as polypropylene, polyvinyl chloride, polyethylene, etc.), rubber and other polymers, supplemented with other fillers for reinforcement, and are compounded through a variety of processes. Compared with traditional materials, this type of composite material can improve the corresponding performance according to the properties of the filler, thereby improving its mechanical properties. Although polymer-based composite materials have excellent mechanical properties and broad application prospects, their high cost, processing difficulty, energy consumption and environmental pollution are still urgent to be solved. Adding non-metallic components of waste mobile phone circuit boards to polymer materials can not only effectively reduce the cost of composite materials, but also improve their comprehensive performance to a certain extent. It is also of great significance to alleviate the environmental pollution caused by the traditional method of recycling non-metallic components.

[0004] There are existing methods for preparing composite materials from non-metallic components of waste circuit boards, such as the invention patent with announcement number CN 113563686A "A method for preparing composite materials from non-metallic powder of waste circuit boards" published on October 29, 2021. The method disclosed in this patent is: circuit boards are obtained by disassembling waste items, and then manually cleaned, crushed, surface modified, and ABS resin and additives are added, and then high-speed mixing and drying are performed to obtain composite materials. The disadvantages of this method are: ① The residual metal is not fully removed during the reuse of non-metallic powders, which not only causes potential metal pollution, but also aggravates the deterioration of the aging performance of polymer composite materials; ② The non-metallic powder modification process is easy to cause the organic matter and other substances therein to deteriorate at a higher temperature, which will cause secondary pollution; ③ The process conditions are strict and the composition of the composite material is complex; ④ The use of the obtained product is limited and cannot meet the needs of the current material manufacturing industry. Summary of the invention

[0005] The purpose of the present invention is to provide a composite material of non-metallic components of waste mobile phone circuit boards / epoxy resin-based composite materials and a preparation method thereof in view of the shortcomings of the existing composite materials prepared from non-metallic components of waste circuit boards. The method has the characteristics of simple process, safe operation, clean and sustainable, high raw material utilization rate, and easy industrial scale-up. The composite material of non-metallic components of waste mobile phone circuit boards / epoxy resin-based composite materials prepared by the method has the characteristics of excellent mechanical properties, high thermal stability, broad market prospects, and wide application.

[0006] The mechanism of the present invention is: the disassembled waste mobile phone circuit board is placed in a closed container, and high-pressure steam is introduced for steam explosion treatment. When the pressure in the container rises to a preset value, a period of pressure maintenance treatment is carried out. After the pressure maintenance process is completed, the high-pressure steam in the container will expand rapidly, thereby effectively working on the waste mobile phone circuit board, and then using strong impact to crush it. The ultrasonic reactor uses a transducer to convert high-frequency sound wave energy into mechanical vibration, which will produce positive and negative alternating sound pressure and ultrasonic cavitation when propagating in the material, and form jets and microjets at the solid and liquid interfaces respectively, thereby destroying the adsorption of fine particles and large metal particles in the waste mobile phone circuit board powder, causing the shedding and peeling of fine microparticle-level particles, and promoting particle separation. At the same time, microbubbles are introduced in the ultrasonic process to form a synergistic enhancement of ultrasound and microbubbles. The microbubbles generated by the jet bubble generator enter the sorting system in the form of a foam flow with the liquid jet, and the bubbles collide with the waste mobile phone circuit board powder. The hydrophobic non-metallic component particles adhere to the bubble surface and reach the upper layer of the system as the bubbles rise, while the metal component particles remain in the lower layer of the system. After the ultrasonic-microbubble synergistic strengthening treatment, the metal and non-metal components of the waste mobile phone circuit board powder showed higher separation efficiency in the centrifugal gravity sorting process. In addition, the glass fiber in the non-metal components of the waste mobile phone circuit board can disperse the load applied to the epoxy resin-based composite material, and the residual additives promote the curing of the composite material, thereby improving the mechanical and thermal properties of the epoxy resin-based composite material, and realizing the high-value reuse of the non-metal components of the waste mobile phone circuit board in the preparation of epoxy resin-based composite materials.

[0007] The object of the present invention is achieved as follows: a non-metallic component of waste mobile phone circuit boards / epoxy resin-based composite material and a preparation method thereof, using commercially available waste mobile phone circuit boards as raw materials, preparing waste mobile phone circuit board powder, assembling an ultrasonic-microbubble synergistic strengthening treatment device, preparing non-metallic components of waste mobile phone circuit boards, preparing non-metallic components of waste mobile phone circuit boards with residual metal removed, preparing modified non-metallic components of waste mobile phone circuit boards, and preparing non-metallic components of waste mobile phone circuit boards / epoxy resin-based composite materials to achieve composite material preparation. The specific method steps are as follows: (1) Preparation of waste mobile phone circuit board powder The commercially available waste mobile phone circuit boards are used as raw materials. After disassembling them into small pieces of 0.5 to 2 cm, the disassembled waste mobile phone circuit boards are placed in an ultrasonic cleaning machine according to the ratio of the mass (g) of the disassembled waste mobile phone circuit boards to the volume (mL) of distilled water of 1:50 to 100, and cleaned for 15 to 30 minutes under the condition of an ultrasonic output power of 50 to 80 W. After the ultrasonic cleaning is completed, the cleaned waste mobile phone circuit boards are placed in a steam explosion device and steam exploded under the conditions of a blasting pressure of 1.5 to 2.0 MPa and a pressure holding time of 300 to 900 seconds. After the steam explosion is completed, the explosion collection is dried at 60°C for 30 to 50 minutes. The powder collected after drying is the waste mobile phone circuit board powder, which is set aside.

[0008] (2) Assembling the ultrasonic-microbubble synergistic enhanced treatment device An electric mechanical stirrer is installed above the ultrasonic reactor, and the stirring paddle of the stirrer is located 15 to 30 mm from the bottom of the inner cavity of the ultrasonic reactor. Then, a jet bubble generator with a water inlet and a water outlet is fixed to the bottom of the inner cavity of the ultrasonic reactor at a horizontal distance greater than 30 mm from the stirring paddle to ensure that the stirring paddle does not touch the jet bubble generator during operation. Then, 10 μm microporous filter membranes are respectively installed on the water inlet and water outlet of the jet bubble generator, thereby assembling an ultrasound-microbubble synergistic enhancement treatment device for the next step of treatment.

[0009] (3) Preparation of non-metallic components from waste mobile phone circuit boards According to the ratio of mass (g) of the waste mobile phone circuit board powder prepared in step (1): volume (mL) of ethanol: mass (g) of polyvinyl butyral in a ratio of 1:5-20:0.1-0.5, the three are placed in the inner cavity of the ultrasonic reactor in the ultrasonic-microbubble synergistic enhanced treatment device assembled in step (2), and the jet bubble generator, electric mechanical stirrer, and ultrasonic reactor in the ultrasonic-microbubble synergistic enhanced treatment device are started in sequence. When the air intake of the jet bubble generator is 0.5-1.5m 3 / h, stirring speed of 100-300r / min, ultrasonic output power of 60-120W, synergistic strengthening treatment is carried out for 20-30min to obtain powder slurry of waste mobile phone circuit boards. After the treatment is completed, the powder slurry of waste mobile phone circuit boards is pumped into the centrifugal gravity sorting device by a peristaltic pump, and gravity sorting is carried out for 10-20min under the condition of a drum speed of 300-500r / min. After the centrifugal gravity sorting is completed, the materials inside the drum and the materials at the discharge port in the centrifugal gravity sorting device are collected respectively. The collected materials inside the drum are mainly metal components of waste mobile phone circuit boards, which can be used to prepare plant nutrient peptide chelated copper. For the collected materials at the discharge port, they mainly contain non-metallic components of waste mobile phone circuit boards. After filtering through a filter equipped with a filter membrane with a pore size of 50μm, the filtrate and filter residue are collected respectively. The collected filtrate is an ethanol solution containing polyvinyl butyral, which can be used for the preparation of powder slurry of waste mobile phone circuit boards in step (3) after being prepared. The collected filter residue is dried at 60°C for 1 to 2 hours to obtain the non-metallic components of waste mobile phone circuit boards, with a recovery rate of 90.2 to 97.6%, which is used for the next step of treatment.

[0010] (4) Preparation of non-metallic components of waste mobile phone circuit boards after removing residual metals The reaction solution is prepared according to the mass (g) of the non-metallic components of the waste mobile phone circuit board prepared in step (3): the volume (mL) of the glutathione solution with a concentration of 0.1 to 0.9 M: the volume (mL) of the hydrogen peroxide solution with a volume fraction of 5 to 8% in the ratio of 1:20 to 100:30 to 100. The reaction solution is placed in an ultrasonic reactor with a stirring device, and the chelation reaction is carried out for 1 to 2 hours under the conditions of a temperature of 40 to 50°C, an ultrasonic output power of 50 to 70W, and a stirring speed of 400 to 500 r / min. After the reaction is completed, the reaction mixture is filtered through a filter, and the reaction mixture filtrate and the reaction mixture filtrate residue are collected respectively. The collected reaction mixture filtrate mainly contains glutathione chelated copper, which can be used as a plant nutrient after crystallization. The collected reaction mixture filtrate residue is dried at 60°C for 10 to 30 minutes to obtain the non-metallic components of the waste mobile phone circuit board with residual metal removed, and the metal residual rate is 0.16 to 0.21%, which is used for the next step of treatment.

[0011] (5) Preparation of non-metallic components of modified waste mobile phone circuit boards according to c -Aminopropyl triethoxysilane (KH-550): anhydrous ethanol in a volume ratio of 1:30 to 100. c-Aminopropyltriethoxysilane (KH-550) is dissolved in anhydrous ethanol, and then the pH is adjusted to 4-6 with acetic acid, and hydrolysis is carried out for 3-6 hours to obtain a silane coupling agent hydrolyzate. According to the ratio of the mass (g) of the non-metallic components of the waste mobile phone circuit board after the residual metal is removed: the volume (mL) of the silane coupling agent hydrolyzate is 1:10-30, the non-metallic components of the waste mobile phone circuit board after the residual metal is removed are placed in the silane coupling agent hydrolyzate to obtain a modified reaction liquid. The modified reaction liquid is subjected to a modification reaction at a temperature of 60-80°C for 1-3 hours. After the reaction is completed, the modified reaction material is washed with anhydrous ethanol 2-5 times the volume of the silane coupling agent hydrolyzate, and the washed liquid and washed solid are collected respectively. For the collected washed liquid, the anhydrous ethanol is recovered by vacuum distillation and can be further used in the preparation of the silane coupling agent hydrolyzate. The collected cleaned solids are dried at 60°C for 30 to 60 minutes to obtain the modified non-metallic components of the waste mobile phone circuit boards for the next step of treatment.

[0012] (6) Preparation of non-metallic components / epoxy resin-based composite materials from waste mobile phone circuit boards According to the mass ratio of E-51 epoxy resin: modified waste mobile phone circuit board non-metallic component prepared in step (5): curing agent: diluent of 1: 0.01-0.3: 0.02-0.08: 0.1-0.15, stir and mix at a temperature of 50°C for 30-60 minutes, then place the mixture in a mold and cure at a temperature of 70-100°C for 1-3 hours to obtain a waste mobile phone circuit board non-metallic component / epoxy resin-based composite material. Among them, the curing agent is 2-methylimidazole or 2-ethyl-methylimidazole or phthalic anhydride, and is not limited to the listed curing agents; the diluent is dimethyl methyl phosphate or dibutyl phthalate or dioctyl phthalate, and is not limited to the listed diluents.

[0013] After the present invention adopts the above technical solution, it mainly has the following effects: 1. The method of the present invention has the characteristics of simple process, safe operation, easy acquisition of raw materials, convenience for industrial scale-up, high raw material utilization rate, and low equipment and operation costs.

[0014] 2. The present invention uses ultrasonic-microbubble synergistic enhanced treatment to separate non-metallic components from waste mobile phone circuit boards. The recovery rate of non-metallic components is increased by more than 30% compared with traditional technologies, significantly improving the utilization rate of raw materials.

[0015] 3. The separation and utilization of metal substances in the non-metal components of waste mobile phone circuit boards in the present invention not only improves the safety of the composite material, but also converts it into high value-added products, further improving production efficiency.

[0016] 4. The non-metallic component / epoxy resin-based composite material of waste mobile phone circuit boards produced by the present invention not only has low production cost, but also has significantly improved performance in various aspects compared with epoxy resin materials prepared without adding non-metallic components of waste mobile phone circuit boards. Among them, the tensile strength is increased by 13.8-51.4%, the compressive strength is increased by 2.3-27.8%, the bending strength is increased by 1.3-47.0%, the hardness is increased by 163.1-174.5%, and the initial curing temperature of the material is reduced by 6.8-24.3°C.

[0017] 5. The present invention utilizes non-metallic components in waste mobile phone circuit boards to prepare composite materials, which not only effectively reduces the potential environmental pollution of non-metallic components, but also realizes the value-added utilization of non-metallic components.

[0018] The products prepared by the method of the present invention can be widely used in the fields of automotive parts, 3D printing, sports equipment, etc. DETAILED DESCRIPTION

[0019] The present invention is further described below in conjunction with specific implementation methods. Example 1

[0020] A non-metal component / epoxy resin-based composite material of waste mobile phone circuit boards and a preparation method thereof, the specific method steps are as follows: (1) Preparation of waste mobile phone circuit board powder Use commercially available waste mobile phone circuit boards as raw materials, disassemble them into 0.5cm small pieces, and place the disassembled waste mobile phone circuit boards in an ultrasonic cleaning machine according to the ratio of mass (g) of the disassembled waste mobile phone circuit boards to volume (mL) of distilled water of 1:50, and clean them for 30 minutes under the condition of ultrasonic output power of 50W. After the ultrasonic cleaning is completed, the cleaned waste mobile phone circuit boards are placed in a steam explosion device, and steam explosion is carried out under the conditions of explosion pressure of 1.5MPa and pressure holding time of 300s. After the steam explosion is completed, the explosion collection is dried at 60℃ for 50min, and the powder collected after drying is the waste mobile phone circuit board powder, which is set aside.

[0021] (2) Assembling the ultrasonic-microbubble synergistic enhanced treatment device An electric mechanical stirrer is installed above the ultrasonic reactor, and the stirring paddle of the stirrer is located 15 mm from the bottom of the inner cavity of the ultrasonic reactor. Then, a jet bubble generator with a water inlet and a water outlet is fixed to the bottom of the inner cavity of the ultrasonic reactor at a horizontal distance greater than 30 mm from the stirring paddle to ensure that the stirring paddle does not touch the jet bubble generator during operation. Then, 10 μm microporous filter membranes are respectively installed on the water inlet and water outlet of the jet bubble generator, thereby assembling an ultrasound-microbubble synergistic enhancement treatment device for the next step of treatment.

[0022] (3) Preparation of non-metallic components from waste mobile phone circuit boards According to the ratio of mass (g) of the waste mobile phone circuit board powder prepared in step (1): volume (mL) of ethanol: mass (g) of polyvinyl butyral (1:5:0.1, the three were placed in the inner cavity of the ultrasonic reactor in the ultrasonic-microbubble synergistic enhanced treatment device assembled in step (2), and the jet bubble generator, electric mechanical stirrer, and ultrasonic reactor in the ultrasonic-microbubble synergistic enhanced treatment device were started in sequence. When the air intake of the jet bubble generator was 0.5m 3 / h, stirring speed of 100r / min, ultrasonic output power of 60W, synergistic strengthening treatment for 20min, to obtain waste mobile phone circuit board powder slurry. After the treatment is completed, the waste mobile phone circuit board powder slurry is pumped into the centrifugal gravity separation device by a peristaltic pump, and gravity separation is carried out for 10min under the condition of a drum speed of 400r / min. After the centrifugal gravity separation is completed, the materials inside the drum and the materials at the discharge port of the centrifugal gravity separation device are collected respectively. The collected materials inside the drum are mainly metal components of waste mobile phone circuit boards, which can be used to prepare plant nutrient peptide chelated copper. The collected materials at the discharge port mainly contain non-metallic components of waste mobile phone circuit boards. After filtering with a filter equipped with a filter membrane with a pore size of 50μm, the filtrate and filter residue are collected respectively. The collected filtrate is an ethanol solution containing polyvinyl butyral, which can be further used for the preparation of waste mobile phone circuit board powder slurry in (3) after being prepared. The collected filter residue, after being dried at 60°C for 1 hour, is the non-metallic component of the waste mobile phone circuit boards with a recovery rate of 90.2%, which is used for the next step of processing.

[0023] (4) Preparation of non-metallic components of waste mobile phone circuit boards after removing residual metals The reaction solution was prepared according to the ratio of mass (g) of the non-metallic components of the waste mobile phone circuit board prepared in step (3): volume (mL) of glutathione solution with a concentration of 0.1M: volume (mL) of hydrogen peroxide solution with a volume fraction of 8% in a ratio of 1:20:30. The reaction solution was placed in an ultrasonic reactor with a stirring device, and the chelation reaction was carried out for 2 hours at a temperature of 40°C, an ultrasonic output power of 50W, and a stirring speed of 500r / min. After the reaction was completed, the reaction mixture was filtered through a filter, and the reaction mixture filtrate and the reaction mixture filtrate residue were collected respectively. The collected reaction mixture filtrate mainly contained glutathione chelated copper, which could be used as a plant nutrient after crystallization. The collected reaction mixture filtrate residue was dried at 60°C for 30 minutes to obtain the non-metallic components of the waste mobile phone circuit board with residual metal removed, and the metal residual rate was 0.21%, which was used for the next step of treatment.

[0024] (5) Preparation of non-metallic components of modified waste mobile phone circuit boards according to c -Aminopropyl triethoxysilane (KH-550): anhydrous ethanol in a volume ratio of 1:30. c -Aminopropyltriethoxysilane (KH-550) was dissolved in anhydrous ethanol, and then the pH was adjusted to 6 with acetic acid, and hydrolysis was carried out for 3 hours to obtain a silane coupling agent hydrolyzate. According to the ratio of the mass (g) of the non-metallic components of the waste mobile phone circuit board from which the residual metal was removed: the volume (mL) of the silane coupling agent hydrolyzate was 1:10, the non-metallic components of the waste mobile phone circuit board from which the residual metal was removed were placed in the silane coupling agent hydrolyzate to obtain a modified reaction solution. The modified reaction solution was subjected to a modification reaction at a temperature of 60°C for 3 hours. After the reaction was completed, the modified reaction material was washed with anhydrous ethanol twice the volume of the silane coupling agent hydrolyzate, and the washed liquid and washed solid were collected respectively. The collected washed liquid was distilled under reduced pressure to recover anhydrous ethanol, which could be further used in the preparation of the silane coupling agent hydrolyzate. The collected washed solids were dried at 60°C for 30 minutes to obtain the modified non-metallic components of the waste mobile phone circuit boards for the next step of treatment.

[0025] (6) Preparation of non-metallic components / epoxy resin-based composite materials from waste mobile phone circuit boards The mass ratio of E-51 epoxy resin: modified non-metallic component of waste mobile phone circuit board prepared in step (5): curing agent: diluent is 1:0.01:0.02:0.1, stirred and mixed at a temperature of 50°C for 30 minutes, and then the mixture is placed in a mold and cured at a temperature of 70°C for 3 hours to obtain a waste mobile phone circuit board non-metallic component / epoxy resin-based composite material with a tensile strength of 24.9 MPa, a compressive strength of 54.0 MPa, a flexural strength of 61.2 MPa, and a hardness of 34.2 N / mm 2 , initial curing temperature 105.1℃. Example 2

[0026] A non-metal component / epoxy resin-based composite material of waste mobile phone circuit boards and a preparation method thereof, the specific method steps are as follows: (1) Preparation of waste mobile phone circuit board powder Use commercially available waste mobile phone circuit boards as raw materials, disassemble them into 2cm small pieces, and place the disassembled waste mobile phone circuit boards in an ultrasonic cleaning machine according to the ratio of mass (g) of the disassembled waste mobile phone circuit boards to volume (mL) of distilled water of 1:100, and clean them for 15 minutes under the condition of ultrasonic output power of 80W. After the ultrasonic cleaning is completed, the cleaned waste mobile phone circuit boards are placed in a steam explosion device, and steam explosion is performed under the conditions of explosion pressure of 2.0MPa and pressure holding time of 900s. After the steam explosion is completed, the explosion collection is dried at 60℃ for 30min, and the powder collected after drying is the waste mobile phone circuit board powder, which is set aside.

[0027] (2) Assembling the ultrasonic-microbubble synergistic enhanced treatment device An electric mechanical stirrer is installed above the ultrasonic reactor, and the stirring paddle of the stirrer is located 25 mm from the bottom of the inner cavity of the ultrasonic reactor. Then, a jet bubble generator with a water inlet and a water outlet is fixed to the bottom of the inner cavity of the ultrasonic reactor at a horizontal distance greater than 30 mm from the stirring paddle to ensure that the stirring paddle does not touch the jet bubble generator during operation. Then, 10 μm microporous filter membranes are respectively installed on the water inlet and water outlet of the jet bubble generator, thereby assembling an ultrasound-microbubble synergistic enhancement treatment device for the next step of treatment.

[0028] (3) Preparation of non-metallic components from waste mobile phone circuit boards According to the ratio of mass (g) of the waste mobile phone circuit board powder prepared in step (1): volume (mL) of ethanol: mass (g) of polyvinyl butyral (1:20:0.5), the three were placed in the inner cavity of the ultrasonic reactor in the ultrasonic-microbubble synergistic enhanced treatment device assembled in step (2), and the jet bubble generator, electric mechanical stirrer, and ultrasonic reactor in the ultrasonic-microbubble synergistic enhanced treatment device were started in sequence. When the air intake of the jet bubble generator was 1.0 m 3 / h, stirring speed of 200r / min, ultrasonic output power of 90W, synergistic strengthening treatment for 25min, to obtain waste mobile phone circuit board powder slurry. After the treatment is completed, the waste mobile phone circuit board powder slurry is pumped into the centrifugal gravity separation device by a peristaltic pump, and gravity separation is carried out for 20min under the condition of a drum speed of 500r / min. After the centrifugal gravity separation is completed, the materials inside the drum and the materials at the discharge port of the centrifugal gravity separation device are collected respectively. The collected materials inside the drum are mainly metal components of waste mobile phone circuit boards, which can be used to prepare plant nutrient peptide chelated copper. The collected materials at the discharge port mainly contain non-metallic components of waste mobile phone circuit boards. After filtering with a filter equipped with a filter membrane with a pore size of 50μm, the filtrate and filter residue are collected respectively. The collected filtrate is an ethanol solution containing polyvinyl butyral, which can be further used for the preparation of waste mobile phone circuit board powder slurry in (3) after being prepared. The collected filter residue, after being dried at 60°C for 1.5h, is the non-metallic component of the waste mobile phone circuit boards with a recovery rate of 93.4%, which is used for the next step of processing.

[0029] (4) Preparation of non-metallic components of waste mobile phone circuit boards after removing residual metals The reaction solution was prepared according to the ratio of 1:100:100 of the mass (g) of the non-metallic components of the waste mobile phone circuit board prepared in step (3): the volume (mL) of the glutathione solution with a concentration of 0.9M: the volume (mL) of the hydrogen peroxide solution with a volume fraction of 6%. The reaction solution was placed in an ultrasonic reactor with a stirring device, and the chelation reaction was carried out for 1 hour at a temperature of 45°C, an ultrasonic output power of 60W, and a stirring speed of 450r / min. After the reaction was completed, the reaction mixture was filtered through a filter, and the reaction mixture filtrate and the reaction mixture filtrate residue were collected respectively. The collected reaction mixture filtrate mainly contained glutathione chelated copper, which could be used as a plant nutrient after crystallization. The collected reaction mixture filtrate residue was dried at 60°C for 10 minutes to obtain the non-metallic components of the waste mobile phone circuit board with residual metal removed, and the metal residual rate was 0.19%, which was used for the next step of treatment.

[0030] (5) Preparation of non-metallic components of modified waste mobile phone circuit boards according to c -Aminopropyl triethoxysilane (KH-550): anhydrous ethanol in a volume ratio of 1:60. c-Aminopropyltriethoxysilane (KH-550) was dissolved in anhydrous ethanol, and then the pH was adjusted to 4 with acetic acid, and hydrolysis was carried out for 4 hours to obtain a silane coupling agent hydrolyzate. According to the ratio of the mass (g) of the non-metallic components of the waste mobile phone circuit board from which the residual metal was removed: the volume (mL) of the silane coupling agent hydrolyzate was 1:20, the non-metallic components of the waste mobile phone circuit board from which the residual metal was removed were placed in the silane coupling agent hydrolyzate to obtain a modified reaction solution. The modified reaction solution was subjected to a modification reaction at a temperature of 80°C for 1 hour. After the reaction was completed, the modified reaction material was washed with anhydrous ethanol 3 times the volume of the silane coupling agent hydrolyzate, and the washed liquid and washed solid were collected respectively. The collected washed liquid was distilled under reduced pressure to recover anhydrous ethanol, which could be further used in the preparation of the silane coupling agent hydrolyzate. The collected cleaned solids were dried at 60°C for 40 minutes to obtain the modified non-metallic components of the waste mobile phone circuit boards for the next step of treatment.

[0031] (6) Preparation of non-metallic components / epoxy resin-based composite materials from waste mobile phone circuit boards The mass ratio of E-51 epoxy resin: modified non-metallic component of waste mobile phone circuit board prepared in step (5): curing agent: diluent is 1:0.15:0.05:0.12, stirred and mixed at a temperature of 50°C for 50 minutes, and then the mixture is placed in a mold and cured at a temperature of 85°C for 2 hours to obtain a waste mobile phone circuit board non-metallic component / epoxy resin-based composite material with a tensile strength of 33.2MPa, a compressive strength of 64.0MPa, a flexural strength of 71.6MPa, and a hardness of 34.4N / mm 2 , the initial curing temperature is 103.9℃. Example 3

[0032] A non-metal component / epoxy resin-based composite material of waste mobile phone circuit boards and a preparation method thereof, the specific method steps are as follows: (1) Preparation of waste mobile phone circuit board powder Use commercially available waste mobile phone circuit boards as raw materials, disassemble them into 1cm small pieces, and place the disassembled waste mobile phone circuit boards in an ultrasonic cleaning machine according to the ratio of mass (g) of the disassembled waste mobile phone circuit boards to volume (mL) of distilled water of 1:70, and clean them for 20 minutes under the condition of ultrasonic output power of 60W. After the ultrasonic cleaning is completed, the cleaned waste mobile phone circuit boards are placed in a steam explosion device, and steam explosion is performed under the conditions of explosion pressure of 1.8MPa and pressure holding time of 600s. After the steam explosion is completed, the explosion collection is dried at 60℃ for 40min, and the powder collected after drying is the waste mobile phone circuit board powder, which is set aside.

[0033] (2) Assembling the ultrasonic-microbubble synergistic enhanced treatment device An electric mechanical stirrer is installed above the ultrasonic reactor, and the stirring paddle of the stirrer is located 30 mm from the bottom of the inner cavity of the ultrasonic reactor. Then, a jet bubble generator with a water inlet and a water outlet is fixed to the bottom of the inner cavity of the ultrasonic reactor at a horizontal distance greater than 30 mm from the stirring paddle to ensure that the stirring paddle does not touch the jet bubble generator during operation. Then, 10 μm microporous filter membranes are respectively installed on the water inlet and water outlet of the jet bubble generator, thereby assembling an ultrasound-microbubble synergistic enhancement treatment device for the next step of treatment.

[0034] (3) Preparation of non-metallic components from waste mobile phone circuit boards According to the ratio of mass (g) of the waste mobile phone circuit board powder prepared in step (1): volume (mL) of ethanol: mass (g) of polyvinyl butyral (1):15:0.3, the three were placed in the inner cavity of the ultrasonic reactor in the ultrasonic-microbubble synergistic enhanced treatment device assembled in step (2), and the jet bubble generator, electric mechanical stirrer, and ultrasonic reactor in the ultrasonic-microbubble synergistic enhanced treatment device were started in sequence. When the air intake of the jet bubble generator was 1.5m 3 / h, stirring speed of 300r / min, ultrasonic output power of 120W, synergistic strengthening treatment for 30min, to obtain waste mobile phone circuit board powder slurry. After the treatment is completed, the waste mobile phone circuit board powder slurry is pumped into the centrifugal gravity separation device by a peristaltic pump, and gravity separation is carried out for 15min under the condition of a drum speed of 300r / min. After the centrifugal gravity separation is completed, the materials inside the drum and the materials at the discharge port of the centrifugal gravity separation device are collected respectively. The collected materials inside the drum are mainly metal components of waste mobile phone circuit boards, which can be used to prepare plant nutrient peptide chelated copper. The collected materials at the discharge port mainly contain non-metallic components of waste mobile phone circuit boards. After filtering with a filter equipped with a filter membrane with a pore size of 50μm, the filtrate and filter residue are collected respectively. The collected filtrate is an ethanol solution containing polyvinyl butyral, which can be further used for the preparation of waste mobile phone circuit board powder slurry in (3) after being prepared. The collected filter residue, after being dried at 60°C for 2 hours, is the non-metallic component of the waste mobile phone circuit boards with a recovery rate of 97.6%, which is used for the next step of processing.

[0035] (4) Preparation of non-metallic components of waste mobile phone circuit boards after removing residual metals The reaction solution was prepared according to the ratio of 1:60:60 of the mass (g) of the non-metallic components of the waste mobile phone circuit board prepared in step (3): the volume (mL) of the glutathione solution with a concentration of 0.5M: the volume (mL) of the hydrogen peroxide solution with a volume fraction of 5%. The reaction solution was placed in an ultrasonic reactor with a stirring device, and the chelation reaction was carried out for 1.5 hours under the conditions of a temperature of 50°C, an ultrasonic output power of 70W, and a stirring speed of 400r / min. After the reaction was completed, the reaction mixture was filtered through a filter, and the reaction mixture filtrate and the reaction mixture filtrate residue were collected respectively. The collected reaction mixture filtrate mainly contained glutathione chelated copper, which could be used as a plant nutrient after crystallization. The collected reaction mixture filtrate residue was dried at 60°C for 20 minutes to obtain the non-metallic components of the waste mobile phone circuit board with residual metal removed, and the metal residual rate was 0.16%, which was used for the next step of treatment.

[0036] (5) Preparation of non-metallic components of modified waste mobile phone circuit boards according to c -Aminopropyl triethoxysilane (KH-550): anhydrous ethanol in a volume ratio of 1:100. c -Aminopropyl triethoxysilane (KH-550) was dissolved in anhydrous ethanol, and then the pH was adjusted to 5 with acetic acid, and hydrolysis was carried out for 6 hours to obtain a silane coupling agent hydrolyzate. According to the ratio of the mass (g) of the non-metallic components of the waste mobile phone circuit board after the residual metal was removed prepared in step (4): the volume (mL) of the silane coupling agent hydrolyzate was 1:30, the non-metallic components of the waste mobile phone circuit board after the residual metal was removed were placed in the silane coupling agent hydrolyzate to obtain a modified reaction liquid. The modified reaction liquid was subjected to a modification reaction at a temperature of 70°C for 2 hours. After the reaction was completed, the modified reaction material was washed with anhydrous ethanol 5 times the volume of the silane coupling agent hydrolyzate, and the washed liquid and washed solid were collected respectively. For the collected washed liquid, the anhydrous ethanol was recovered by vacuum distillation and can be further used in the preparation of the silane coupling agent hydrolyzate. The collected washed solids were dried at 60°C for 60 minutes to obtain the modified non-metallic components of the waste mobile phone circuit boards for the next step of treatment.

[0037] (6) Preparation of non-metallic components / epoxy resin-based composite materials from waste mobile phone circuit boards The mass ratio of E-51 epoxy resin: modified non-metallic component of waste mobile phone circuit board prepared in step (5): curing agent: diluent is 1:0.3:0.08:0.15, stirred and mixed at a temperature of 50°C for 60 minutes, and then the mixture is placed in a mold and cured at a temperature of 100°C for 1 hour to obtain a waste mobile phone circuit board non-metallic component / epoxy resin-based composite material with a tensile strength of 28.8MPa, a compressive strength of 51.2MPa, a flexural strength of 49.3MPa, and a hardness of 35.7N / mm 2 , the initial curing temperature is 87.6℃.

[0038] Comparative Example 1 A method for separating non-metallic components of waste mobile phone circuit boards and preparing epoxy resin materials, the specific method steps are as follows: (1) Preparation of waste mobile phone circuit board powder Use commercially available waste mobile phone circuit boards as raw materials, disassemble them into 1cm small pieces, and place the disassembled waste mobile phone circuit boards in an ultrasonic cleaning machine according to the ratio of mass (g) of the disassembled waste mobile phone circuit boards to volume (mL) of distilled water of 1:70, and clean them for 20 minutes under the condition of ultrasonic output power of 60W. After the ultrasonic cleaning is completed, the cleaned waste mobile phone circuit boards are placed in a steam explosion device, and steam explosion is performed under the conditions of explosion pressure of 1.8MPa and pressure holding time of 600s. After the steam explosion is completed, the explosion collection is dried at 60℃ for 40min, and the powder collected after drying is the waste mobile phone circuit board powder, which is set aside.

[0039] (2) Preparation of non-metallic components from waste mobile phone circuit boards According to the ratio of mass (g) of the waste mobile phone circuit board powder prepared in step (1): volume (mL) of ethanol: mass (g) of polyvinyl butyral in the ratio of 1:15:0.3, the three are placed in the drum of the centrifugal gravity separation device, and gravity separation is carried out for 15 minutes at a drum speed of 300r / min. After the centrifugal gravity separation is completed, the materials inside the drum and the materials at the discharge port of the centrifugal gravity separation device are collected respectively. The collected materials inside the drum are mainly metal components of waste mobile phone circuit boards, which can be used to prepare plant nutrient peptide chelated copper. The collected materials at the discharge port mainly contain non-metallic components of waste mobile phone circuit boards. After filtering with a filter equipped with a filter membrane with a pore size of 50μm, the filtrate and filter residue are collected respectively. The collected filtrate is an ethanol solution containing polyvinyl butyral, which can be further used for the preparation of waste mobile phone circuit board powder slurry in step (3) after being prepared. The collected filter residue, after drying at 60°C for 2 hours, is the non-metallic component of the waste mobile phone circuit boards with a recovery rate of 72.6%, which is used for the next step of processing.

[0040] (3) Preparation of epoxy resin material According to the mass ratio of E-51 epoxy resin: curing agent: diluent of 1:0.05:0.12, stir and mix at a temperature of 50°C for 50 minutes, then place the mixture in a mold and cure it at a temperature of 85°C for 2 hours to obtain an epoxy resin material with a tensile strength of 21.9MPa, a compressive strength of 50.1MPa, a flexural strength of 48.7MPa, and a hardness of 13.0N / mm 2 , the initial curing temperature is 111.9℃.

[0041] Conclusion: From the comparison of the recovery rate of non-metallic components of waste mobile phone circuit boards and the performance of the prepared materials in the above several groups of embodiments and comparative examples, it can be seen that the recovery rate of non-metallic components of waste mobile phone circuit boards after the introduction of ultrasonic-microbubble synergistic strengthening treatment in the process of preparing non-metallic components of waste mobile phone circuit boards in embodiments 1, 2, and 3 is significantly improved compared with comparative example 1. At the same time, in the process of preparing epoxy resin materials, the modified non-metallic components of waste mobile phone circuit boards are added, and the tensile strength, compressive strength, bending strength and hardness of the prepared non-metallic components of waste mobile phone circuit boards / epoxy resin-based composite materials are significantly increased compared with the epoxy resin material prepared in comparative example 1, and the non-metallic components of waste mobile phone circuit boards / epoxy resin-based composite materials have a lower initial curing temperature, which can reduce the manufacturing cost.

[0042] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not limitations on the implementation methods of the present invention. For ordinary technicians in the relevant field, other different forms of changes or modifications can be made based on the above description. It is impossible to list all the implementation methods here. All obvious changes or modifications derived from the technical solution of the present invention are still within the protection scope of the present invention.

Claims

1. A non-metallic component / epoxy resin-based composite material of waste mobile phone circuit boards and a preparation method thereof, wherein the specific steps are as follows: (1) Preparation of waste mobile phone circuit board powder Using commercially available waste mobile phone circuit boards as raw materials, dismantling them into small pieces of 0.5 to 2 cm, placing the dismantled waste mobile phone circuit boards in an ultrasonic cleaning machine according to the mass of the dismantled waste mobile phone circuit boards: the volume ratio of distilled water is 1 g: 50 to 100 mL, and cleaning them for 15 to 30 minutes under the condition of an ultrasonic output power of 50 to 80 W; after the ultrasonic cleaning is completed, placing the cleaned waste mobile phone circuit boards in a steam explosion device, and steam explosion is performed under the conditions of a blasting pressure of 1.5 to 2.0 MPa and a pressure holding time of 300 to 900 seconds. After the steam explosion is completed, the explosion collection is dried at 60° C. for 30 to 50 minutes, and the powder collected after drying is the waste mobile phone circuit board powder, which is reserved; (2) Assembling the ultrasonic-microbubble synergistic enhanced treatment device An electric mechanical stirrer is installed above the ultrasonic reactor, and the stirring paddle of the stirrer is located 15-30 mm from the bottom of the inner cavity of the ultrasonic reactor. Then, a jet bubble generator with a water inlet end and a water outlet end is fixed to the bottom of the inner cavity of the ultrasonic reactor and the horizontal distance from the stirring paddle is greater than 30 mm, ensuring that the stirring paddle does not touch the jet bubble generator during operation. Then, a 10 μm microporous filter membrane is installed on the water inlet end and the water outlet end of the jet bubble generator, respectively, to assemble an ultrasound-microbubble synergistic enhancement treatment device for the next step of treatment; (3) Preparation of non-metallic components from waste mobile phone circuit boards According to the mass ratio of the waste mobile phone circuit board powder prepared in step (1): the volume of ethanol: the mass ratio of polyvinyl butyral is 1g: 5-20mL: 0.1-0.5g, the three are placed in the inner cavity of the ultrasonic reactor in the ultrasonic-microbubble synergistic enhanced treatment device assembled in step (2), and the jet bubble generator, electric mechanical stirrer and ultrasonic reactor in the ultrasonic-microbubble synergistic enhanced treatment device are started in sequence. When the air intake volume of the jet bubble generator is 0.5-1.5m 3 / h, stirring speed of 100-300r / min, ultrasonic output power of 60-120W, synergistic strengthening treatment is carried out for 20-30min to obtain waste mobile phone circuit board powder slurry. After the treatment is completed, the waste mobile phone circuit board powder slurry is pumped into a centrifugal gravity sorting device by a peristaltic pump. Under the condition of a drum speed of 300-500r / min, gravity sorting is carried out for 10-20min. After the centrifugal gravity sorting is completed, the materials inside the drum and the materials at the discharge port of the centrifugal gravity sorting device are collected respectively; the collected materials inside the drum are mainly waste The metal components of the used mobile phone circuit boards can be used to prepare the plant nutrient peptide chelated copper; the collected material at the discharge port mainly contains the non-metal components of the used mobile phone circuit boards, and after filtering with a filter equipped with a filter membrane with a pore size of 50 μm, the filtrate and the filter residue are collected respectively; the collected filtrate is an ethanol solution containing polyvinyl butyral, which can be further used for the preparation of the powder slurry of the used mobile phone circuit boards in (3) after being prepared; the collected filter residue, after drying at 60°C for 1 to 2 hours, is the non-metal components of the used mobile phone circuit boards, and the recovery rate is 90.2 to 97.6%, which is used for the next step of processing; (4) Preparation of non-metallic components of waste mobile phone circuit boards after removing residual metals A reaction solution is prepared according to the mass of the non-metallic components of the waste mobile phone circuit board prepared in step (3): the volume of the glutathione solution with a concentration of 0.1 to 0.9 M: the volume ratio of the hydrogen peroxide solution with a volume fraction of 5 to 8% is 1 g: 20 to 100 mL: 30 to 100 mL. The reaction solution is placed in an ultrasonic reactor with a stirring device. The chelation reaction is carried out for 1 to 2 hours at a temperature of 40 to 50° C., an ultrasonic output power of 50 to 70 W, and a stirring speed of 400 to 500 r / min. After the reaction is completed, the reaction mixture is filtered through a filter to collect the reaction mixture filtrate and the reaction mixture filtrate residue respectively. The collected reaction mixture filtrate mainly contains glutathione chelated copper, which can be used as a plant nutrient after crystallization. The collected reaction mixture filtrate residue is dried at 60° C. for 10 to 30 minutes to obtain the non-metallic components of the waste mobile phone circuit board with residual metal removed, and the metal residual rate is 0.16 to 0.21%, which is used for the next step of treatment. (5) Preparation of non-metallic components of modified waste mobile phone circuit boards according to γ -Aminopropyl triethoxysilane (KH-550): anhydrous ethanol in a volume ratio of 1:30 to 100. γ -aminopropyltriethoxysilane (KH-550) is dissolved in anhydrous ethanol, and then the pH is adjusted to 4-6 with acetic acid, and hydrolysis is carried out for 3-6 hours to obtain a silane coupling agent hydrolyzate; according to the mass ratio of the non-metallic components of the waste mobile phone circuit board from which the residual metal is removed prepared in step (4): the volume ratio of the silane coupling agent hydrolyzate is 1g: 10-30mL, the non-metallic components of the waste mobile phone circuit board from which the residual metal is removed are placed in the silane coupling agent hydrolyzate to obtain a modified reaction solution, and the modified reaction solution is heated at a temperature of 60 ~80℃, carry out the modification reaction for 1~3h. After the reaction is completed, wash the modified reaction material with anhydrous ethanol of 2~5 times the volume of the silane coupling agent hydrolyzate, and collect the washed liquid and the washed solid respectively; for the collected washed liquid, recover the anhydrous ethanol by vacuum distillation, and continue to use it for the preparation of the silane coupling agent hydrolyzate; for the collected washed solid, dry it at 60℃ for 30~60min, and then it is the modified non-metallic component of the waste mobile phone circuit board for the next step of treatment; (6) Preparation of non-metallic components / epoxy resin-based composite materials from waste mobile phone circuit boards The mass ratio of E-51 epoxy resin: modified waste mobile phone circuit board non-metallic component prepared in step (5): curing agent: diluent is 1: 0.01-0.3: 0.02-0.08: 0.1-0.15, stirred and mixed at a temperature of 50°C for 30-60 minutes, and then the mixture is placed in a mold and cured at a temperature of 70-100°C for 1-3 hours to obtain a waste mobile phone circuit board non-metallic component / epoxy resin-based composite material, wherein: The curing agent is 2-methylimidazole or 2-ethyl-methylimidazole or phthalic anhydride, and is not limited to the listed curing agents; the diluent is dimethyl methyl phosphate or dibutyl phthalate or dioctyl phthalate, and is not limited to the listed diluents.