CN109232970B - Method for recovering epoxy resin in waste circuit board - Google Patents
Method for recovering epoxy resin in waste circuit board Download PDFInfo
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- CN109232970B CN109232970B CN201811262793.9A CN201811262793A CN109232970B CN 109232970 B CN109232970 B CN 109232970B CN 201811262793 A CN201811262793 A CN 201811262793A CN 109232970 B CN109232970 B CN 109232970B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
- B29B17/02—Separating plastics from other materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
- B29B17/04—Disintegrating plastics, e.g. by milling
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/44—Amides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5033—Amines aromatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/56—Amines together with other curing agents
- C08G59/60—Amines together with other curing agents with amides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/40—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes epoxy resins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
- B29B17/02—Separating plastics from other materials
- B29B2017/0213—Specific separating techniques
- B29B2017/0262—Specific separating techniques using electrical caracteristics
- B29B2017/0265—Electrostatic separation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
- Y02P20/143—Feedstock the feedstock being recycled material, e.g. plastics
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/52—Mechanical processing of waste for the recovery of materials, e.g. crushing, shredding, separation or disassembly
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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- Physics & Mathematics (AREA)
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Abstract
The invention provides a method for recovering epoxy resin in a waste circuit board, belonging to the technical field of electronic material recovery and comprising the following steps: s1: various components are detached from the surface of the waste circuit board; s2: crushing the circuit board obtained in the step S1 to obtain fine powder; s3: sorting the fine powder obtained in the step S2, and removing the metal fine powder to obtain non-metal fine powder; s4: adding dilute nitric acid into the nonmetal fine powder obtained in the step S3, heating in a water bath, carrying out primary filtration, collecting filter residue I, washing the filter residue I with ethyl acetate until an organic phase is colorless, combining ethyl acetate solutions, carrying out secondary filtration, removing filter residue II, washing the filter residue II with a sodium carbonate solution until the filter residue is neutral, distilling, and removing ethyl acetate to obtain epoxy resin; s5: and (4) modifying the epoxy resin obtained in the step (S4) to obtain a modified epoxy resin. The invention has high recovery rate of the epoxy resin, and excellent comprehensive performance by modifying the epoxy resin.
Description
Technical Field
The invention relates to the technical field of electronic material recovery, in particular to a method for recovering epoxy resin in a waste circuit board.
Background
The electronic information industry is the fastest-developing industry at present, electronic products are ubiquitous, along with the continuous development of high and new technologies and the improvement of the consumption level of people, the updating frequency of the electronic products is continuously accelerated, the life cycle of the electronic products is shorter and shorter, and therefore a large number of obsolete electronic and electric products are generated and are called as electronic wastes or electronic garbage. The number of waste wiring boards is large. Because the circuit board is the foundation of the electronic industry, is an important component of various electronic products and is widely applied to computers, communication equipment, control and measurement instruments and household electrical appliance products, the circuit board is located where the electronic product is located, the electronic waste is located where the electronic waste is located, and the waste circuit board is located where the electronic waste is located. In addition, a large amount of leftover materials and waste products are generated in the manufacturing process of the circuit board, and a large amount of leftover materials of the circuit board can be generated while the circuit board industry is rapidly developed.
The waste circuit board is one of the most difficult parts to be recycled and disposed of in electronic waste. The circuit board is a complex composed of high molecular polymer (resin), reinforcing material and metal (copper foil), and the composition mode of the material is complex, so that effective separation of various materials is not easy to realize; in addition, the circuit board also contains substances which have serious harm to the environment, such as heavy metal lead, brominated flame retardant and the like, and if the substances are not properly treated, the substances can cause serious harm to the environment.
The recycling of the non-metal powder of the waste circuit board is attracting wide attention. Firstly, the powder contains some dissociated glass fibers and a small amount of resin lumps, but most of the powder is thermosetting epoxy resin coated glass fiber particles, and is easily compared with fillers such as sawdust, talcum powder, calcium carbonate and the like, so that a great deal of research is carried out on preparing building materials and composite materials by using the nonmetal powder as the filler to reinforce the thermoplastic resin. Since the compatibility of the non-metal powder with the organic polymer material and the inorganic polymer material is poor, the compatibility of the non-metal powder with the organic polymer material and the inorganic polymer material needs to be improved at a high cost, so that the cost advantage of the composite material is sacrificed.
Patent document No. CN102181127A discloses a preparation method of a glass fiber reinforced epoxy resin composite material modified by recycled circuit board powder. Modifying glass fiber by a coupling agent to obtain a surface-active glass fiber reinforcement; performing active treatment on the surface of the dried circuit board recovery powder, and mixing the circuit board recovery powder with epoxy resin to obtain a circuit board recovery powder filling modified epoxy resin matrix; and finally, compounding the coupling agent modified glass fiber reinforcement and the epoxy resin matrix modified by the circuit board recovered powder filling to obtain the circuit board recovered powder modified glass fiber reinforced epoxy resin composite material. However, the method has the disadvantages of complex steps, harsh reaction conditions, high cost and low utilization rate of the epoxy resin in the reclaimed materials in the circuit board.
Patent document CN106947109A discloses a method for recovering epoxy resin from waste circuit boards, which comprises removing electronic components on the surface of the waste circuit board, and cutting the waste circuit board into small pieces; then placing the small circuit board into a closed reactor, adding a mixed solution of polyethylene glycol 400 and polypropylene glycol 500, controlling the solid-liquid ratio to be 1: 10-1: 12g/mL, and adding the polyethylene glycol 400 and the polypropylene glycol 500 according to the mass ratio of 2: 1-6: 1; then adding potassium hydroxide with the addition amount of 1-5 g/L; then closing the closed reactor, and raising the temperature to 120-180 ℃ for reaction for 1-2 hours; and after the reaction is finished, opening the closed reactor, separating the liquid-phase product, and finally rectifying to recover the polyethylene glycol 400 and the polypropylene glycol 500 in the liquid-phase product, wherein the residue left after rectification is the recovered epoxy resin. However, it has been verified that the method has a low recovery rate of the epoxy resin, contains many impurities such as metals, and has a low purity, and the recovered epoxy resin is not suitable for the reproduction of the wiring board.
Disclosure of Invention
In view of the above, the invention provides a method for recovering epoxy resin from waste circuit boards, which has the advantages of high recovery rate of epoxy resin, modification of epoxy resin and excellent comprehensive performance.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a method for recovering epoxy resin in a waste circuit board comprises the following steps:
s1: various components are detached from the surface of the waste circuit board;
s2: crushing the circuit board obtained in the step S1 to obtain fine powder;
s3: sorting the fine powder obtained in the step S2, and removing the metal fine powder to obtain non-metal fine powder;
s4: adding dilute nitric acid into the nonmetal fine powder obtained in the step S3, heating in a water bath, carrying out primary filtration, collecting filter residue I, washing the filter residue I with ethyl acetate until an organic phase is colorless, combining ethyl acetate solutions, carrying out secondary filtration, removing filter residue II, washing the filter residue II with a sodium carbonate solution until the filter residue is neutral, distilling, and removing ethyl acetate to obtain epoxy resin;
s5: and (4) modifying the epoxy resin obtained in the step (S4) to obtain a modified epoxy resin.
Preferably, in the step S3, the sorting method is electrostatic sorting, the voltage of the electric sorter is 20-25V, the rotating speed of the roller is 50-60r/min, and the distance between the corona electrode and the roller is 5.5-7.5 cm.
Preferably, in the step S4, the mass fraction of the dilute nitric acid is 40-50%.
Preferably, in step S4, the ratio of the non-metal fine powder to the dilute nitric acid is 10 g: 50-55 ml.
Preferably, in the step S4, the water bath heating time is 80-90 ℃ and the time is 10-15 h; the distillation temperature is 75-80 deg.C, and the distillation time is 12-15 h.
Preferably, in step S5, the method for modifying the epoxy resin includes: mixing 10g of epoxy resin and 1-4g of boron phenolic resin, heating in a water bath at 85-90 ℃ for 10-30min, adding 5-6g of filler and 1-2g of coupling agent, stirring at 85-90 ℃ for 1-2h at the rotation speed of 300-400r/min, then adding 2-3g of curing agent, stirring at room temperature at the rotation speed of 200-300r/min for 5-10min, and curing at normal temperature for 10-12 h.
Preferably, in step S5, the filler is a mixture of silica and mica powder, and the weight ratio of silica: the ratio of mica powder is 1: 3-5.
Preferably, in step S5, the curing agent is a mixture of polyamide and m-phenylenediamine, and the weight ratio of polyamide: the ratio of m-phenylenediamine to m-phenylenediamine is 1: 0.2-0.4.
Preferably, in step S5, the coupling agent is KH550 or KH 560.
The invention has the beneficial effects that:
demolish various components and parts from abandonment circuit board surface, the recovery processing of the circuit board of being convenient for demolishs the back with components and parts simultaneously, on can reuse other products through detecting qualified components and parts, improve the utilization ratio. And (4) crushing the circuit board obtained in the step (S1) to obtain fine powder, so as to conveniently separate metal and nonmetal from the fine powder, wherein common circuit board crushing equipment mainly comprises a chopper, a rotary crusher, a hammer mill and the like, and the granularity of the fine powder is 50-200 meshes.
Sorting the fine powder obtained in the step S2, and removing the metal fine powder to obtain non-metal fine powder; the sorting method is electrostatic sorting, the voltage of the electric sorting machine is 20-25V, the rotating speed of the roller is 50-60r/min, and the distance between the corona electrode and the roller is 5.5-7.5 cm. According to the difference of discharge speed of metal particles and non-metal particles in the high-voltage electric field, the metal fine powder and the non-metal fine powder are separated. In the invention, the recovery rate of nonmetal reaches 96-98%, and the purity is more than 99%.
Adding dilute nitric acid into the nonmetal fine powder obtained in the step S3, heating in a water bath, carrying out primary filtration, collecting filter residue I, washing the filter residue I with ethyl acetate until an organic phase is colorless, combining ethyl acetate solutions, carrying out secondary filtration, removing filter residue II, washing the filter residue II with a sodium carbonate solution until the filter residue is neutral, distilling, and removing ethyl acetate to obtain epoxy resin; the mass fraction of the dilute nitric acid is 40-50%. The adding proportion of the non-metal fine powder and the dilute nitric acid is 10 g: 50-55 ml. Heating in water bath at 80-90 deg.C for 10-15 hr; the distillation temperature is 75-80 deg.C, and the distillation time is 12-15 h.
And (3) oxidizing and removing impurities in the nonmetal fine powder by dilute nitric acid, washing the filter residue I containing components such as epoxy resin, glass fiber and the like by using ethyl acetate, extracting the epoxy resin in the filter residue I, and separating the epoxy resin from the glass fiber. And (4) performing secondary filtration to obtain solid impurities, so as to improve the purity.
The obtained epoxy resin is modified to obtain the modified epoxy resin with better comprehensive performance. The boron phenolic resin can effectively improve the impact strength of the epoxy resin, improve the toughness of the epoxy resin and improve the flame retardant property and the peel strength. The filler silicon dioxide improves the high temperature resistance of the epoxy resin, and the mica powder has extremely high electrical insulation, acid and alkali corrosion resistance, elasticity, toughness and sliding property, and improves the electrical insulation property and mechanical property of the epoxy resin. The coupling agents KH550 and KH560 are organically combined with the boron phenolic resin and the filler, so that the bonding property is enhanced. The curing agent polyamide and m-phenylenediamine improve the curing degree, and are organically combined with silicon dioxide to improve the high temperature resistance of the epoxy resin.
The invention firstly crushes the circuit board and then uses static sorting to obtain nonmetal fine powder, then uses dilute nitric acid to acidify and remove impurities, ethyl acetate is used for washing, and then distillation is carried out to obtain epoxy resin, the recovery rate reaches 95-97%, the purity is more than 99, and the obtained epoxy resin is modified, thus improving the mechanical property, the high temperature resistance, the electric insulation property and the like, obtaining the modified epoxy resin with excellent comprehensive performance, being suitable for the reproduction of the circuit board, reducing the waste and pollution of resources, improving the utilization rate of materials, saving energy and protecting environment.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention are clearly and completely described below. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention, are within the scope of the invention.
Example 1
The embodiment provides a method for recovering epoxy resin in a waste circuit board, which comprises the following steps:
s1: various components are detached from the surface of the waste circuit board;
s2: crushing the circuit board obtained in the step S1 by using a hammer crusher with the power of 110Kw to obtain 50-200 meshes of fine powder;
s3: sorting the fine powder obtained in the step S2, removing metal fine powder to obtain non-metal fine powder, wherein the sorting method is electrostatic sorting, the voltage of an electric sorting machine is 20V, the rotating speed of a roller is 60r/min, and the distance between a corona electrode and the roller is 5.5 cm;
s4: adding dilute nitric acid with the mass fraction of 40% into the non-metal fine powder obtained in the step S3, wherein the adding ratio of the non-metal fine powder to the dilute nitric acid is 10 g: 55ml, heating in water bath at 80 ℃ for 15h, filtering for the first time, collecting filter residue I, washing with ethyl acetate until the organic phase is colorless, combining ethyl acetate solutions, filtering for the second time, removing filter residue II, washing with sodium carbonate solution until the organic phase is neutral, distilling at 75 ℃ for 15h, and removing ethyl acetate to obtain epoxy resin;
s5: modifying the epoxy resin obtained in the step S4 to obtain a modified epoxy resin, wherein the modification method of the epoxy resin comprises the following steps: mixing 10g of epoxy resin and 1g of boron phenolic resin, heating in a water bath at 85 ℃ for 30min, adding 5g of filler and 1g of coupling agent, stirring at 85 ℃ for 2h at the rotating speed of 300r/min, then adding 2g of curing agent, stirring at room temperature at the rotating speed of 200r/min for 10min, and curing at normal temperature for 10 h. The filler is a mixture of silicon dioxide and mica powder, and the weight ratio of the silicon dioxide to the mica powder is 1: 3. The curing agent is a mixture of polyamide and m-phenylenediamine, and the weight ratio of the polyamide: the ratio of m-phenylenediamine is 1: 0.2. The coupling agent is KH 550.
Example 2
The embodiment provides a method for recovering epoxy resin in a waste circuit board, which comprises the following steps:
s1: various components are detached from the surface of the waste circuit board;
s2: crushing the circuit board obtained in the step S1 by using a hammer crusher with the power of 110Kw to obtain 50-200 meshes of fine powder;
s3: sorting the fine powder obtained in the step S2, removing metal fine powder to obtain non-metal fine powder, wherein the sorting method is electrostatic sorting, the voltage of an electric sorting machine is 21V, the rotating speed of a roller is 58r/min, and the distance between a corona electrode and the roller is 6 cm;
s4: adding dilute nitric acid with the mass fraction of 42% into the non-metal fine powder obtained in the step S3, wherein the adding ratio of the non-metal fine powder to the dilute nitric acid is 10 g: 54ml, heating in water bath at 82 ℃ for 14 hours, filtering for the first time, collecting filter residue I, washing the filter residue I with ethyl acetate until an organic phase is colorless, combining ethyl acetate solutions, filtering for the second time, removing filter residue II, washing with a sodium carbonate solution until the filter residue is neutral, distilling at 76 ℃ for 14 hours, and removing the ethyl acetate to obtain epoxy resin;
s5: modifying the epoxy resin obtained in the step S4 to obtain a modified epoxy resin, wherein the modification method of the epoxy resin comprises the following steps: mixing 10g of epoxy resin and 2g of boron phenolic resin, heating in 86 ℃ water bath for 28min, adding 5g of filler and 1g of coupling agent, stirring at 86 ℃ for 2h at the rotating speed of 300r/min, then adding 2g of curing agent, stirring at room temperature at the rotating speed of 200r/min for 10min, and curing at normal temperature for 10 h. The filler is a mixture of silicon dioxide and mica powder, and the weight ratio of the silicon dioxide to the mica powder is 1: 3. The curing agent is a mixture of polyamide and m-phenylenediamine, and the weight ratio of the polyamide: the ratio of m-phenylenediamine is 1: 0.2. The coupling agent is KH 560.
Example 3
The embodiment provides a method for recovering epoxy resin in a waste circuit board, which comprises the following steps:
s1: various components are detached from the surface of the waste circuit board;
s2: crushing the circuit board obtained in the step S1 by using a hammer crusher with the power of 110Kw to obtain 50-200 meshes of fine powder;
s3: sorting the fine powder obtained in the step S2, removing metal fine powder to obtain non-metal fine powder, wherein the sorting method is electrostatic sorting, the voltage of an electric sorting machine is 22V, the rotating speed of a roller is 55r/min, and the distance between a corona electrode and the roller is 6.5 cm;
s4: adding dilute nitric acid with the mass fraction of 45% into the non-metal fine powder obtained in the step S3, wherein the adding ratio of the non-metal fine powder to the dilute nitric acid is 10 g: 53ml, heating in water bath at 85 ℃ for 13 hours, filtering for the first time, collecting filter residue I, washing the filter residue I with ethyl acetate until an organic phase is colorless, combining ethyl acetate solutions, filtering for the second time, removing filter residue II, washing the filter residue II with a sodium carbonate solution until the filter residue is neutral, distilling at the distillation temperature of 78 ℃ for 14 hours, and removing the ethyl acetate to obtain epoxy resin;
s5: modifying the epoxy resin obtained in the step S4 to obtain a modified epoxy resin, wherein the modification method of the epoxy resin comprises the following steps: mixing 10g of epoxy resin and 2g of boron phenolic resin, heating in water bath at 87 ℃ for 20min, adding 5g of filler and 1g of coupling agent, stirring at 87 ℃ for 1.5h at the rotating speed of 350r/min, then adding 2g of curing agent, stirring at room temperature at the rotating speed of 250r/min for 8min, and curing at room temperature for 11 h. The filler is a mixture of silicon dioxide and mica powder, and the weight ratio of the silicon dioxide to the mica powder is 1: 3. The curing agent is a mixture of polyamide and m-phenylenediamine, and the weight ratio of the polyamide: the ratio of m-phenylenediamine is 1: 0.2. The coupling agent is KH 550.
Example 4
The embodiment provides a method for recovering epoxy resin in a waste circuit board, which comprises the following steps:
s1: various components are detached from the surface of the waste circuit board;
s2: crushing the circuit board obtained in the step S1 by using a hammer crusher with the power of 110Kw to obtain 50-200 meshes of fine powder;
s3: sorting the fine powder obtained in the step S2, removing metal fine powder to obtain non-metal fine powder, wherein the sorting method is electrostatic sorting, the voltage of an electric sorting machine is 23V, the rotating speed of a roller is 58r/min, and the distance between a corona electrode and the roller is 7 cm;
s4: adding dilute nitric acid with the mass fraction of 48% into the non-metal fine powder obtained in the step S3, wherein the adding ratio of the non-metal fine powder to the dilute nitric acid is 10 g: 52ml of the mixture is heated for 12 hours in water bath at 88 ℃, and then filtered for the first time, the filter residue I is collected and washed by ethyl acetate until the organic phase is colorless, the ethyl acetate solution is combined, secondary filtration is carried out, the filter residue II is removed, the filter residue II is washed by sodium carbonate solution until the filter residue is neutral, distillation is carried out, the distillation temperature is 78 ℃, the time is 14 hours, and the ethyl acetate is removed, so that the epoxy resin is obtained;
s5: modifying the epoxy resin obtained in the step S4 to obtain a modified epoxy resin, wherein the modification method of the epoxy resin comprises the following steps: mixing 10g of epoxy resin and 3g of boron phenolic resin, heating in 88 ℃ water bath for 15min, adding 5g of filler and 1g of coupling agent, stirring at 88 ℃ for 1.5h at the rotating speed of 350r/min, then adding 2g of curing agent, stirring at room temperature at the rotating speed of 250r/min for 8min, and curing at room temperature for 11 h. The filler is a mixture of silicon dioxide and mica powder, and the weight ratio of the silicon dioxide to the mica powder is 1: 3. The curing agent is a mixture of polyamide and m-phenylenediamine, and the weight ratio of the polyamide: the ratio of m-phenylenediamine is 1: 0.2. The coupling agent is KH 560.
Example 5
The embodiment provides a method for recovering epoxy resin in a waste circuit board, which comprises the following steps:
s1: various components are detached from the surface of the waste circuit board;
s2: crushing the circuit board obtained in the step S1 by using a hammer crusher with the power of 110Kw to obtain 50-200 meshes of fine powder;
s3: sorting the fine powder obtained in the step S2, removing metal fine powder to obtain non-metal fine powder, wherein the sorting method is electrostatic sorting, the voltage of an electric sorting machine is 25V, the rotating speed of a roller is 50r/min, and the distance between a corona electrode and the roller is 7.5 cm;
s4: adding dilute nitric acid with the mass fraction of 50% into the non-metal fine powder obtained in the step S3, wherein the adding ratio of the non-metal fine powder to the dilute nitric acid is 10 g: 50ml, heating in water bath at 90 ℃ for 10 hours, filtering for the first time, collecting filter residue I, washing the filter residue I with ethyl acetate until an organic phase is colorless, combining ethyl acetate solutions, filtering for the second time, removing filter residue II, washing with a sodium carbonate solution until the filter residue is neutral, distilling at the distillation temperature of 80 ℃ for 12 hours, and removing the ethyl acetate to obtain epoxy resin;
s5: modifying the epoxy resin obtained in the step S4 to obtain a modified epoxy resin, wherein the modification method of the epoxy resin comprises the following steps: mixing 10g of epoxy resin and 4g of boron phenolic resin, heating in a water bath at 90 ℃ for 10min, adding 6g of filler and 2g of coupling agent, stirring at 90 ℃ for 1h at the rotating speed of 400r/min, adding 3g of curing agent, stirring at room temperature at the rotating speed of 300r/min for 5min, and curing at room temperature for 12 h. The filler is a mixture of silicon dioxide and mica powder, and the weight ratio of the silicon dioxide to the mica powder is 1: 5. The curing agent is a mixture of polyamide and m-phenylenediamine, and the weight ratio of the polyamide: the ratio of m-phenylenediamine is 1: 0.4. The coupling agent is KH 550.
Example 6
This embodiment provides a method for recycling epoxy resin from waste circuit boards, which includes the following steps, the same as embodiment 4, but different from embodiment 4, in this embodiment, in step S5, the filler is a mixture of silica and mica powder, and the weight ratio of silica to mica powder is 1: 4. The curing agent is a mixture of polyamide and m-phenylenediamine, and the weight ratio of the polyamide: the ratio of m-phenylenediamine is 1: 0.3. The coupling agent is KH 550.
Example 7
This example provides a method for recycling epoxy resin from waste circuit boards, which comprises the following steps similar to example 6, but differs from example 6 in that in step S4, the waste acid remained after filtrate I obtained by primary filtration is extracted with ethyl acetate can be recycled and is not discharged into the environment.
S5: modifying the epoxy resin obtained in the step S4 to obtain a modified epoxy resin, wherein the modification method of the epoxy resin comprises the following steps: mixing 10g of epoxy resin and 3g of boron phenolic resin, heating in 88 ℃ water bath for 15min, adding 5g of filler, 1g of coupling agent and 1g of glyceryl monostearate, stirring at 88 ℃ for 1.5h at the rotating speed of 350r/min, then adding 2g of curing agent, stirring at the rotating speed of 250r/min at room temperature for 8min, and curing at normal temperature for 11 h. The filler is a mixture of silicon dioxide and mica powder, and the weight ratio of the silicon dioxide to the mica powder is 1: 3. The curing agent is a mixture of polyamide and m-phenylenediamine, and the weight ratio of the polyamide: the ratio of m-phenylenediamine is 1: 0.2. The coupling agent is KH 560.
Example 8
This example provides a method for recycling epoxy resin from waste circuit boards, which comprises the following steps similar to example 6, but differs from example 6 in that in step S4, the waste acid remained after filtrate I obtained by primary filtration is extracted with ethyl acetate can be recycled and is not discharged into the environment.
S5: modifying the epoxy resin obtained in the step S4 to obtain a modified epoxy resin, wherein the modification method of the epoxy resin comprises the following steps: mixing 10g of epoxy resin and 3g of boron phenolic resin, heating in 88 ℃ water bath for 15min, adding 5g of filler, 1g of coupling agent and 1.5g of glyceryl monostearate, stirring at 88 ℃ for 1.5h at the rotating speed of 350r/min, then adding 2g of curing agent, stirring at the rotating speed of 250r/min for 8min at room temperature, and curing at normal temperature for 11 h. The filler is a mixture of silicon dioxide and mica powder, and the weight ratio of the silicon dioxide to the mica powder is 1: 3. The curing agent is a mixture of polyamide and m-phenylenediamine, and the weight ratio of the polyamide: the ratio of m-phenylenediamine is 1: 0.2. The coupling agent is KH 560.
Comparative example 1
This comparative example provides a method for recovering epoxy resin from a waste wiring board, which is different from example 1 in that: in this comparative example, S4: adding dilute nitric acid with the mass fraction of 40% into the non-metal fine powder obtained in the step S3, wherein the adding ratio of the non-metal fine powder to the dilute nitric acid is 10 g: 55ml, heating in water bath at 80 ℃ for 15h, filtering once, collecting filter residue I, washing the filter residue I with ethyl acetate until the organic phase is colorless, combining ethyl acetate solutions, washing the filter residue I with a sodium carbonate solution until the organic phase is neutral, distilling the mixture at the distillation temperature of 75 ℃ for 15h, and removing the ethyl acetate to obtain the epoxy resin.
Comparative example 2
This comparative example provides a method for recovering epoxy resin from a waste wiring board, which is different from example 1 in that: in this comparative example, S5: modifying the epoxy resin obtained in the step S4 to obtain a modified epoxy resin, wherein the modification method of the epoxy resin comprises the following steps: mixing 10g of epoxy resin and 1g of boron phenolic resin, heating in a water bath at 85 ℃ for 30min, adding 1g of coupling agent, stirring at 85 ℃ for 2h at the rotating speed of 300r/min, adding 2g of curing agent, stirring at room temperature at the rotating speed of 200r/min for 10min, and curing at room temperature for 10 h. The curing agent is a mixture of polyamide and m-phenylenediamine, and the weight ratio of the polyamide: the ratio of m-phenylenediamine is 1: 0.2. The coupling agent is KH 550.
Comparative example 3
This comparative example provides a method for recovering epoxy resin from a waste wiring board, which is different from example 1 in that: in this comparative example, S5: modifying the epoxy resin obtained in the step S4 to obtain a modified epoxy resin, wherein the modification method of the epoxy resin comprises the following steps: mixing 10g of epoxy resin and 1g of boron phenolic resin, heating in a water bath at 85 ℃ for 30min, adding 5g of filler, stirring at 85 ℃ for 2h at the rotating speed of 300r/min, then adding 2g of curing agent, stirring at room temperature at the rotating speed of 200r/min for 10min, and curing at room temperature for 10 h. The filler is a mixture of silicon dioxide and mica powder, and the weight ratio of the silicon dioxide to the mica powder is 1: 3. The curing agent is a mixture of polyamide and m-phenylenediamine, and the weight ratio of the polyamide: the ratio of m-phenylenediamine is 1: 0.2.
Comparative example 4
This comparative example provides a method for recovering epoxy resin from a waste wiring board, which is different from example 1 in that: in this comparative example, the preparation method lacked step S5, i.e., no modification of the epoxy resin was performed.
Detection method
The recovered epoxy resin in this example was weighed and the recovery rate was calculated from the initial epoxy resin content in the waste circuit board, which was 95-97% in this application with a purity of 99 or more.
The shear strength of the epoxy resin is detected according to GB/T7124-2008, and the heat resistance is measured by keeping the epoxy resin in an oven for 1h at a high temperature after the epoxy resin is cured and measuring the shear strength at the high temperature by using an electronic tension and compression testing machine capable of programming temperature rise. The peel strength was determined according to GB/T7122-1996.
TABLE 1 examination results of materials of examples 1 to 8 and comparative examples 1 to 4
Table 1 shows the test results of the materials of the embodiment and the comparative example, and it can be seen that the modified epoxy resin of the embodiment of the invention has a shear strength of 21.25MPa at normal temperature, a shear strength of 5.13MPa at 250 ℃, excellent high temperature resistance, a peel strength of 7.79KN/m, and excellent comprehensive properties. The examples 7 and 8 are better in comprehensive performance by adding the glyceryl monostearate. The comparative example 1 is not subjected to secondary filtration, the comparative example 2 is lack of filler, the comparative example 3 is lack of coupling agent, the comparative example 4 is not used for modifying the epoxy resin, the shear strength and the peel strength of the epoxy resin are obviously reduced, and the performance of the comparative example 4 is the worst, which shows that the formula and the process of the invention have good adaptability and obvious effect.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (7)
1. A method for recovering epoxy resin in a waste circuit board is characterized by comprising the following steps: comprises the following steps:
s1: various components are detached from the surface of the waste circuit board;
s2: crushing the circuit board obtained in the step S1 to obtain fine powder;
s3: sorting the fine powder obtained in the step S2, and removing the metal fine powder to obtain non-metal fine powder; the sorting method is electrostatic sorting, the voltage of an electric sorting machine is 20-25V, the rotating speed of a roller is 50-60r/min, and the distance between a corona electrode and the roller is 5.5-7.5 cm;
s4: adding dilute nitric acid into the nonmetal fine powder obtained in the step S3, heating in a water bath, carrying out primary filtration, collecting filter residue I, washing the filter residue I with ethyl acetate until an organic phase is colorless, combining ethyl acetate solutions, carrying out secondary filtration, removing filter residue II, washing the filter residue II with a sodium carbonate solution until the filter residue is neutral, distilling, and removing ethyl acetate to obtain epoxy resin;
s5: modifying the epoxy resin obtained in the step S4 to obtain modified epoxy resin; the modification method of the epoxy resin comprises the following steps: mixing 10g of epoxy resin and 1-4g of boron phenolic resin, heating in a water bath at 85-90 ℃ for 10-30min, adding 5-6g of filler and 1-2g of coupling agent, stirring at 85-90 ℃ for 1-2h at the rotation speed of 300-400r/min, then adding 2-3g of curing agent, stirring at room temperature at the rotation speed of 200-300r/min for 5-10min, and curing at normal temperature for 10-12 h.
2. The method for recycling epoxy resin from waste circuit boards as claimed in claim 1, wherein the method comprises the steps of: in the step S4, the mass fraction of the dilute nitric acid is 40-50%.
3. The method for recycling epoxy resin from waste circuit boards as claimed in claim 1, wherein the method comprises the steps of: in the step S4, the ratio of the non-metal fine powder to the dilute nitric acid is 10 g: 50-55 ml.
4. The method for recycling epoxy resin from waste circuit boards as claimed in claim 1, wherein the method comprises the steps of: in the step S4, the water bath heating temperature is 80-90 ℃, and the time is 10-15 h; the distillation temperature is 75-80 deg.C, and the distillation time is 12-15 h.
5. The method for recycling epoxy resin from waste circuit boards as claimed in claim 1, wherein the method comprises the steps of: in the step S5, the filler is a mixture of silica and mica powder, and the weight ratio of silica: the ratio of mica powder is 1: 3-5.
6. The method for recycling epoxy resin from waste circuit boards as claimed in claim 1, wherein the method comprises the steps of: in the step S5, the curing agent is a mixture of polyamide and m-phenylenediamine, and the weight ratio of polyamide: the ratio of m-phenylenediamine to m-phenylenediamine is 1: 0.2-0.4.
7. The method for recycling epoxy resin from waste circuit boards as claimed in claim 1, wherein the method comprises the steps of: in step S5, the coupling agent is KH550 or KH 560.
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| CN116410572A (en) * | 2023-04-10 | 2023-07-11 | 湖南映宏新材料股份有限公司 | Composite material based on waste circuit board resin and preparation method thereof |
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| CN101891902A (en) * | 2010-07-23 | 2010-11-24 | 浙江理工大学 | Method for recycling waste epoxy resin |
| CN102583501A (en) * | 2011-01-20 | 2012-07-18 | 常州翔宇资源再生科技有限公司 | Method for recovering copper-contained waster residue generated during copper-clad plate recovery process |
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| US20130274382A1 (en) * | 2010-12-30 | 2013-10-17 | Chaofeng Xiao | Plate synthesized by waste circuit board powder and manufacturing process thereof |
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| CN101891902A (en) * | 2010-07-23 | 2010-11-24 | 浙江理工大学 | Method for recycling waste epoxy resin |
| CN102583501A (en) * | 2011-01-20 | 2012-07-18 | 常州翔宇资源再生科技有限公司 | Method for recovering copper-contained waster residue generated during copper-clad plate recovery process |
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