CN109232970A - The recovery method of epoxy resin in a kind of discarded circuit board - Google Patents
The recovery method of epoxy resin in a kind of discarded circuit board Download PDFInfo
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- CN109232970A CN109232970A CN201811262793.9A CN201811262793A CN109232970A CN 109232970 A CN109232970 A CN 109232970A CN 201811262793 A CN201811262793 A CN 201811262793A CN 109232970 A CN109232970 A CN 109232970A
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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
-
- 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
-
- 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
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Mechanical Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
The present invention provides a kind of recovery methods of epoxy resin in discarded circuit board, belong to electronic material recovery technology field comprising the steps of: S1: various components are removed from discarded circuit board surface；S2: the resulting wiring board of step S1 is crushed, fine powder is obtained；S3: the obtained fine powder of step S2 is sorted, and is removed lemel, is obtained nonmetallic fine powder；S4: dust technology will be added in nonmetallic fine powder that step S3 is obtained, after heating water bath, it is once filtered, collecting filter residue I and being washed with ethyl acetate to organic phase is colourless, combined ethyl acetate solution, carry out secondary filter, filter residue II is removed, is washed with sodium carbonate liquor to neutrality, is distilled, ethyl acetate is removed, epoxy resin is obtained；S5: the obtained epoxy resin of step S4 is modified, modified epoxy is obtained.The rate of recovery of epoxy resin of the present invention is high, and is modified to epoxy resin, excellent combination property.
Description
Technical field
The present invention relates to electronic material recovery technology fields, and in particular to the recycling of epoxy resin in a kind of discarded circuit board
Method.
Background technique
Electronics and information industry is the most fast industry of Developing, and electronic product is even more ubiquitous, with new and high technology
It continues to develop and the raising of people's level of consumption, the frequency that electronic product updates constantly is accelerated, the life cycle of electronic product
Shorter and shorter, to produce the waste and old electric electric equipment products being largely eliminated, these waste and old electric electric equipment products are referred to as
Electron wastes or electronic waste.The quantity of discarded circuit board is very big.It is even more all kinds of since wiring board is the basis of electronics industry
The important composition component of electronic product, is widely used in computer, communication apparatus, control and measuring instrument and household electrical appliance produce
Where product, therefore, where is it electronic product just have wiring board, and where where is it electron wastes just have discarded circuit board.Separately
Outside, wiring board can generate a large amount of leftover pieces and waste product in the fabrication process, while assist side industry high speed development, it will produce
Raw a large amount of wiring board leftover bits.
Discarded circuit board is one of the component that recovery processing is most difficult in electron wastes.Wiring board is by high molecular polymer
The complex that (resin), reinforcing material and metal (copper foil) are constituted, the building form of material are more complicated, it is not easy to realize
A variety of materials efficiently separate；In addition, also have the substance of serious harm containing some pairs of environment in wiring board, as heavy metal lead,
Brominated flame retardant etc. will generate serious harm to environment if dealt with improperly.
Recycling about discarded circuit board non-metal powder attracts wide public concern.Contain first in these powder
The glass fibre of dissociation, a small amount of resin agglomerate, but most of powder is that thermosetting epoxy resin is wrapped in glass fiber granules, very
It is easy to mention in the same breath with fillers such as sawdust, talcum powder, calcium carbonate, thus a large amount of research uses these non-metal powders to increase as filler
Heat-flash plastic resin prepares construction material and composite material.Due to non-metal powder and high-molecular organic material and inorganic polymer material
The compatibility of material is poor, thus the compatibility for needing to spend biggish cost to improve the two, can sacrifice composite material in this way
Cost advantage.
The patent document of Publication No. CN102181127A discloses a kind of circuit board recycling powder modified glass-fiber increasing
The preparation method of strong epoxy resin composite material.Glass fibre is passed through coupling agent modified processing by the invention, obtains surface-active
Glass fiber reinforcements；Dry circuit board recycling powder surface is subjected to active processing, then is mixed with epoxy resin, is obtained
Circuit board recycles the modified epoxy resin-base of powder packed；Finally by coupling agent modified glass fiber reinforcement derived above
The epoxy resin-matrix bluk recombination that body and circuit board recycling powder packed are modified obtains the modified glass fibre of circuit board recycling powder
Reinforced epoxy composite material.But the inventive step is complicated, severe reaction conditions are at high cost, in circuit board in reclaimed materials
The utilization rate of epoxy resin is low.
The patent document of Publication No. CN106947109A discloses a kind of side from discarded circuit board recycling epoxy resin
Discarded circuit board surface electronic element is removed, discarded circuit board is then cut into wiring board small pieces by method；Later by line
Road plate small pieces are put into closed reactor, and the mixed liquor of polyethylene glycol 400 and polypropylene glycol 500 is added, and solid-to-liquid ratio control exists
1:10~1:12g/mL, and polyethylene glycol 400 and polypropylene glycol 500 are added by the mass ratio of 2:1~6:1；Then hydrogen-oxygen is added
Change potassium, additive amount is 1~5g/L；It is then switched off closed reactor, temperature is risen into 120~180 degree and is reacted, the reaction time
It is 1~2 hour；After reaction, closed reactor is opened, liquid product is separated, in last rectifying reclaim liquid phase product
Polyethylene glycol 400 and polypropylene glycol 500, then the remaining residue of rectifying is the epoxy resin being recovered to.But it is verified,
The rate of recovery of epoxy resin is low in this method, and more containing metal impurities, and purity is low, the epoxy resin discomfort zygonema of recycling
The reproduction of road plate.
Summary of the invention
In view of this, epoxy resin returns the present invention provides a kind of recovery method of epoxy resin in discarded circuit board
High income, and epoxy resin is modified, excellent combination property.
In order to solve the above technical problems, the technical solution used in the present invention is:
The recovery method of epoxy resin in a kind of discarded circuit board comprising the steps of:
S1: various components are removed from discarded circuit board surface；
S2: the resulting wiring board of step S1 is crushed, fine powder is obtained；
S3: the obtained fine powder of step S2 is sorted, and is removed lemel, is obtained nonmetallic fine powder；
S4: will be added dust technology in nonmetallic fine powder that step S3 is obtained, after heating water bath, once filtered, collect filter residue I
Being washed with ethyl acetate to organic phase is colourless, combined ethyl acetate solution, carries out secondary filter, removes filter residue II, use carbonic acid
Sodium solution is washed to neutrality, and distillation removes ethyl acetate, obtains epoxy resin；
S5: the obtained epoxy resin of step S4 is modified, modified epoxy is obtained.
Preferably, in the step S3, the method for sorting is electrostatic separation, and the voltage of electrostatic separator is 20-25V, and roller turns
Speed is 50-60r/min, and the distance between corona electrode and roller are 5.5-7.5cm.
Preferably, in the step S4, the mass fraction of dust technology is 40-50%.
Preferably, in the step S4, the ratio of nonmetallic fine powder and dust technology addition is 10g:50-55ml.
Preferably, in the step S4, the time of heating water bath is 80-90 DEG C, time 10-15h；Vapo(u)rizing temperature is
75-80 DEG C, time 12-15h.
Preferably, in the step S5, the method for modifying of epoxy resin are as follows: by epoxy resin 10g, boron bakelite resin 1-4g
Mixing after being placed in 85-90 DEG C of heating water bath 10-30min, is added filler 5-6g, coupling agent 1-2g, 85-90 DEG C of stirring 1-2h, turns
Speed is 300-400r/min, and curing agent 2-3g is then added, at room temperature, after stirring 5-10min with the revolving speed of 200-300r/min,
Normal temperature cure 10-12h.
Preferably, in the step S5, filler is the mixture of silica, mica powder, weight ratio silica: mica
Powder is 1:3-5.
Preferably, in the step S5, curing agent is the mixture of polyamide, m-phenylene diamine (MPD), weight ratio polyamide: isophthalic
Diamines is 1:0.2-0.4.
Preferably, in the step S5, coupling agent is KH550 or KH560.
The beneficial effects of the present invention are:
Various components are removed from discarded circuit board surface, convenient for the recovery processing of wiring board, while by after component disassembling,
It is reusable on other products through the qualified component of detection, it increases operation rate.The resulting wiring board of step S1 is crushed,
Fine powder is obtained, convenient for carrying out metal and nonmetallic sorting to fine powder, common wiring board crushing plant mainly has shredding machine, rotation broken
Broken machine, beating crusher, hammer-mill etc., powder particle size are 50-200 mesh.
The obtained fine powder of step S2 is sorted, lemel is removed, obtains nonmetallic fine powder；The method of sorting is quiet
Electricity sorting, the voltage of electrostatic separator are 20-25V, and roller revolving speed is 50-60r/min, and the distance between corona electrode and roller are
5.5-7.5cm.It is different according to the speed of metallic particles in high voltage electric field and the non-metallic particle velocity of discharge, thus by metal and non-
Lemel separates.In the present invention, the nonmetallic rate of recovery reaches 96%-98%, and purity is 99 or more.
It will be added dust technology in nonmetallic fine powder that step S3 is obtained, after heating water bath, once filtered, collect filter residue
I with ethyl acetate wash to organic phase be colourless, combined ethyl acetate solution, carry out secondary filter, remove filter residue II, use carbonic acid
Sodium solution is washed to neutrality, and distillation removes ethyl acetate, obtains epoxy resin；The mass fraction of dust technology is 40-50%.It is non-
Lemel and the ratio of dust technology addition are 10g:50-55ml.The time of heating water bath is 80-90 DEG C, time 10-15h；
Vapo(u)rizing temperature is 75-80 DEG C, time 12-15h.
Dust technology removes oxidation of impurities in nonmetallic fine powder, and filter residue I is used containing ingredients such as epoxy resin, glass fibres
Ethyl acetate washing, epoxy resin therein is extracted, is separated with glass fibre.Secondary filter, be filled into containing solid it is miscellaneous
Matter improves purity.
Resulting epoxy resin is modified, comprehensive performance more preferably modified epoxy is made.Boron bakelite resin energy
The impact strength for enough effectively improving epoxy resin improves the toughness of epoxy resin, improves flame retardant property and peel strength.Filler two
Silica improves the high temperature resistance of epoxy resin, and mica powder has high electrical insulating property, antiacid caustic corrosion, elasticity, toughness
And sliding property, improve the electrical insulation capability and mechanical performance of epoxy resin.Coupling agent KH550, KH560 and boron bakelite resin are filled out
Material organically combines, and enhances adhesive property.Curing agent polyamide and m-phenylene diamine (MPD) improve curing degree, at the same with the organic knot of silica
It closes, improves the high temperature resistance of epoxy resin.
The present invention first wiring board is crushed after with electrostatic separation, obtain nonmetallic fine powder, then with dust technology acidification impurity removal, second
After acetoacetic ester washing, distillation obtains epoxy resin, and the rate of recovery reaches 95-97%, and purity is 99 or more, and by resulting asphalt mixtures modified by epoxy resin
Rouge is modified, and is improved mechanical performance, high temperature resistance, electrical insulation capability etc., is obtained excellent combination property, and wiring board is suitable for
The modified epoxy of reproduction reduces the waste and pollution of resource, improves the utilization rate of material, energy conservation and environmental protection.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below to the skill of the embodiment of the present invention
Art scheme is clearly and completely described.Obviously, described embodiment is a part of the embodiments of the present invention, rather than complete
The embodiment in portion.Based on described the embodiment of the present invention, those of ordinary skill in the art's every other implementation obtained
Example, shall fall within the protection scope of the present invention.
Embodiment 1
The present embodiment provides a kind of recovery methods of epoxy resin in discarded circuit board comprising the steps of:
S1: various components are removed from discarded circuit board surface；
S2: the resulting wiring board of step S1 is crushed with the beating crusher that power is 110Kw, obtains 50-200 mesh fine powder；
S3: the obtained fine powder of step S2 is sorted, and removes lemel, obtains nonmetallic fine powder, and the method for sorting is quiet
Electricity sorting, the voltage of electrostatic separator are 20V, and roller revolving speed is 60r/min, and the distance between corona electrode and roller are 5.5cm；
S4: the dust technology that mass fraction is 40%, nonmetallic fine powder and dust technology are added in the nonmetallic fine powder that step S3 is obtained
The ratio of addition is 10g:55ml, after 80 DEG C of heating 15h of water-bath, is once filtered, collection filter residue I with ethyl acetate wash to
Organic phase is colourless, combined ethyl acetate solution, carries out secondary filter, removes filter residue II, is washed with sodium carbonate liquor to neutrality
Afterwards, it distills, vapo(u)rizing temperature is 75 DEG C, time 15h, removes ethyl acetate, obtains epoxy resin；
S5: the obtained epoxy resin of step S4 is modified, and obtains modified epoxy, the method for modifying of epoxy resin are as follows:
Epoxy resin 10g, boron bakelite resin 1g are mixed, after being placed in 85 DEG C of heating water bath 30min, are added filler 5g, coupling agent 1g, 85
DEG C stirring 2h, revolving speed 300r/min, are then added curing agent 2g, at room temperature, after stirring 10min with the revolving speed of 200r/min,
Normal temperature cure 10h.Filler is the mixture of silica, mica powder, weight ratio silica, mica powder 1:3.Curing agent is
The mixture of polyamide, m-phenylene diamine (MPD), weight ratio polyamide: m-phenylene diamine (MPD) 1:0.2.Coupling agent is KH550.
Embodiment 2
The present embodiment provides a kind of recovery methods of epoxy resin in discarded circuit board comprising the steps of:
S1: various components are removed from discarded circuit board surface；
S2: the resulting wiring board of step S1 is crushed with the beating crusher that power is 110Kw, obtains 50-200 mesh fine powder；
S3: the obtained fine powder of step S2 is sorted, and removes lemel, obtains nonmetallic fine powder, and the method for sorting is quiet
Electricity sorting, the voltage of electrostatic separator are 21V, and roller revolving speed is 58r/min, and the distance between corona electrode and roller are 6cm；
S4: the dust technology that mass fraction is 42%, nonmetallic fine powder and dust technology are added in the nonmetallic fine powder that step S3 is obtained
The ratio of addition is 10g:54ml, after 82 DEG C of heating 14h of water-bath, is once filtered, collection filter residue I with ethyl acetate wash to
Organic phase is colourless, combined ethyl acetate solution, carries out secondary filter, removes filter residue II, is washed with sodium carbonate liquor to neutrality
Afterwards, it distills, vapo(u)rizing temperature is 76 DEG C, time 14h, removes ethyl acetate, obtains epoxy resin；
S5: the obtained epoxy resin of step S4 is modified, and obtains modified epoxy, the method for modifying of epoxy resin are as follows:
Epoxy resin 10g, boron bakelite resin 2g are mixed, after being placed in 86 DEG C of heating water bath 28min, are added filler 5g, coupling agent 1g, 86
DEG C stirring 2h, revolving speed 300r/min, are then added curing agent 2g, at room temperature, after stirring 10min with the revolving speed of 200r/min,
Normal temperature cure 10h.Filler is the mixture of silica, mica powder, weight ratio silica, mica powder 1:3.Curing agent is
The mixture of polyamide, m-phenylene diamine (MPD), weight ratio polyamide: m-phenylene diamine (MPD) 1:0.2.Coupling agent is KH560.
Embodiment 3
The present embodiment provides a kind of recovery methods of epoxy resin in discarded circuit board comprising the steps of:
S1: various components are removed from discarded circuit board surface；
S2: the resulting wiring board of step S1 is crushed with the beating crusher that power is 110Kw, obtains 50-200 mesh fine powder；
S3: the obtained fine powder of step S2 is sorted, and removes lemel, obtains nonmetallic fine powder, and the method for sorting is quiet
Electricity sorting, the voltage of electrostatic separator are 22V, and roller revolving speed is 55r/min, and the distance between corona electrode and roller are 6.5cm；
S4: the dust technology that mass fraction is 45%, nonmetallic fine powder and dust technology are added in the nonmetallic fine powder that step S3 is obtained
The ratio of addition is 10g:53ml, after 85 DEG C of heating 13h of water-bath, is once filtered, collection filter residue I with ethyl acetate wash to
Organic phase is colourless, combined ethyl acetate solution, carries out secondary filter, removes filter residue II, is washed with sodium carbonate liquor to neutrality
Afterwards, it distills, vapo(u)rizing temperature is 78 DEG C, time 14h, removes ethyl acetate, obtains epoxy resin；
S5: the obtained epoxy resin of step S4 is modified, and obtains modified epoxy, the method for modifying of epoxy resin are as follows:
Epoxy resin 10g, boron bakelite resin 2g are mixed, after being placed in 87 DEG C of heating water bath 20min, are added filler 5g, coupling agent 1g, 87
DEG C stirring 1.5h, revolving speed 350r/min, are then added curing agent 2g, at room temperature, after stirring 8min with the revolving speed of 250r/min,
Normal temperature cure 11h.Filler is the mixture of silica, mica powder, weight ratio silica, mica powder 1:3.Curing agent is
The mixture of polyamide, m-phenylene diamine (MPD), weight ratio polyamide: m-phenylene diamine (MPD) 1:0.2.Coupling agent is KH550.
Embodiment 4
The present embodiment provides a kind of recovery methods of epoxy resin in discarded circuit board comprising the steps of:
S1: various components are removed from discarded circuit board surface；
S2: the resulting wiring board of step S1 is crushed with the beating crusher that power is 110Kw, obtains 50-200 mesh fine powder；
S3: the obtained fine powder of step S2 is sorted, and removes lemel, obtains nonmetallic fine powder, and the method for sorting is quiet
Electricity sorting, the voltage of electrostatic separator are 23V, and roller revolving speed is 58r/min, and the distance between corona electrode and roller are 7cm；
S4: the dust technology that mass fraction is 48%, nonmetallic fine powder and dust technology are added in the nonmetallic fine powder that step S3 is obtained
The ratio of addition is 10g:52ml, after 88 DEG C of heating 12h of water-bath, is once filtered, collection filter residue I with ethyl acetate wash to
Organic phase is colourless, combined ethyl acetate solution, carries out secondary filter, removes filter residue II, is washed with sodium carbonate liquor to neutrality
Afterwards, it distills, vapo(u)rizing temperature is 78 DEG C, time 14h, removes ethyl acetate, obtains epoxy resin；
S5: the obtained epoxy resin of step S4 is modified, and obtains modified epoxy, the method for modifying of epoxy resin are as follows:
Epoxy resin 10g, boron bakelite resin 3g are mixed, after being placed in 88 DEG C of heating water bath 15min, are added filler 5g, coupling agent 1g, 88
DEG C stirring 1.5h, revolving speed 350r/min, are then added curing agent 2g, at room temperature, after stirring 8min with the revolving speed of 250r/min,
Normal temperature cure 11h.Filler is the mixture of silica, mica powder, weight ratio silica, mica powder 1:3.Curing agent is
The mixture of polyamide, m-phenylene diamine (MPD), weight ratio polyamide: m-phenylene diamine (MPD) 1:0.2.Coupling agent is KH560.
Embodiment 5
The present embodiment provides a kind of recovery methods of epoxy resin in discarded circuit board comprising the steps of:
S1: various components are removed from discarded circuit board surface；
S2: the resulting wiring board of step S1 is crushed with the beating crusher that power is 110Kw, obtains 50-200 mesh fine powder；
S3: the obtained fine powder of step S2 is sorted, and removes lemel, obtains nonmetallic fine powder, and the method for sorting is quiet
Electricity sorting, the voltage of electrostatic separator are 25V, and roller revolving speed is 50r/min, and the distance between corona electrode and roller are 7.5cm；
S4: the dust technology that mass fraction is 50%, nonmetallic fine powder and dust technology are added in the nonmetallic fine powder that step S3 is obtained
The ratio of addition is 10g:50ml, after 90 DEG C of heating 10h of water-bath, is once filtered, collection filter residue I with ethyl acetate wash to
Organic phase is colourless, combined ethyl acetate solution, carries out secondary filter, removes filter residue II, is washed with sodium carbonate liquor to neutrality
Afterwards, it distills, vapo(u)rizing temperature is 80 DEG C, time 12h, removes ethyl acetate, obtains epoxy resin；
S5: the obtained epoxy resin of step S4 is modified, and obtains modified epoxy, the method for modifying of epoxy resin are as follows:
Epoxy resin 10g, boron bakelite resin 4g are mixed, after being placed in 90 DEG C of heating water bath 10min, are added filler 6g, coupling agent 2g, 90
DEG C stirring 1h, revolving speed 400r/min, are then added curing agent 3g, at room temperature, after stirring 5min with the revolving speed of 300r/min, often
Temperature solidification 12h.Filler is the mixture of silica, mica powder, weight ratio silica, mica powder 1:5.Curing agent is poly-
The mixture of amide, m-phenylene diamine (MPD), weight ratio polyamide: m-phenylene diamine (MPD) 1:0.4.Coupling agent is KH550.
Embodiment 6
The present embodiment provides a kind of recovery method of epoxy resin in discarded circuit board, same embodiment 4 is comprised the steps of, but with
Unlike embodiment 4, in the present embodiment, in step S5, filler is the mixture of silica, mica powder, weight ratio dioxy
SiClx, mica powder 1:4.Curing agent be polyamide, m-phenylene diamine (MPD) mixture, weight ratio polyamide: m-phenylene diamine (MPD) 1:
0.3.Coupling agent is KH550.
Embodiment 7
The present embodiment provides a kind of recovery method of epoxy resin in discarded circuit board, same embodiment 6 is comprised the steps of, but with
Unlike embodiment 6, in the present embodiment, in step S4, the filtrate I being once obtained by filtration is extracted with ethyl acetate rear remaining
Spent acid is Ke Xunhuanliyong, is not discharged into environment.
S5: the obtained epoxy resin of step S4 is modified, and obtains modified epoxy, the method for modifying of epoxy resin
Are as follows: epoxy resin 10g, boron bakelite resin 3g are mixed, after being placed in 88 DEG C of heating water bath 15min, filler 5g, coupling agent is added
Then curing agent 2g is added in 1g, glycerin monostearate 1g, 88 DEG C of stirrings 1.5h, revolving speed 350r/min, at room temperature, with
After the revolving speed stirring 8min of 250r/min, normal temperature cure 11h.Filler is the mixture of silica, mica powder, weight ratio dioxy
SiClx, mica powder 1:3.Curing agent be polyamide, m-phenylene diamine (MPD) mixture, weight ratio polyamide: m-phenylene diamine (MPD) 1:
0.2.Coupling agent is KH560.
Embodiment 8
The present embodiment provides a kind of recovery method of epoxy resin in discarded circuit board, same embodiment 6 is comprised the steps of, but with
Unlike embodiment 6, in the present embodiment, in step S4, the filtrate I being once obtained by filtration is extracted with ethyl acetate rear remaining
Spent acid is Ke Xunhuanliyong, is not discharged into environment.
S5: the obtained epoxy resin of step S4 is modified, and obtains modified epoxy, the method for modifying of epoxy resin
Are as follows: epoxy resin 10g, boron bakelite resin 3g are mixed, after being placed in 88 DEG C of heating water bath 15min, filler 5g, coupling agent is added
Then curing agent 2g is added in 1g, glycerin monostearate 1.5g, 88 DEG C of stirrings 1.5h, revolving speed 350r/min, at room temperature, with
After the revolving speed stirring 8min of 250r/min, normal temperature cure 11h.Filler is the mixture of silica, mica powder, weight ratio dioxy
SiClx, mica powder 1:3.Curing agent be polyamide, m-phenylene diamine (MPD) mixture, weight ratio polyamide: m-phenylene diamine (MPD) 1:
0.2.Coupling agent is KH560.
Comparative example 1
This comparative example provides a kind of recovery method of epoxy resin in discarded circuit board, the difference from embodiment 1 is that: this comparison
In example, the dust technology that mass fraction is 40%, nonmetallic fine powder and dilute nitre S4: are added in the nonmetallic fine powder that step S3 is obtained
The ratio of acid addition is 10g:55ml, after 80 DEG C of heating 15h of water-bath, is once filtered, and collection filter residue I is washed with ethyl acetate
To organic phase be it is colourless, combined ethyl acetate solution is washed with sodium carbonate liquor to neutrality, distillation, vapo(u)rizing temperature be 75 DEG C,
Time is 15h, removes ethyl acetate, obtains epoxy resin.
Comparative example 2
This comparative example provides a kind of recovery method of epoxy resin in discarded circuit board, the difference from embodiment 1 is that: this comparison
In example, S5: the obtained epoxy resin of step S4 is modified, and obtains modified epoxy, the method for modifying of epoxy resin are as follows:
Epoxy resin 10g, boron bakelite resin 1g are mixed, after being placed in 85 DEG C of heating water bath 30min, coupling agent 1g, 85 DEG C of stirrings are added
Then curing agent 2g is added in 2h, revolving speed 300r/min, at room temperature, after stirring 10min with the revolving speed of 200r/min, room temperature is solid
Change 10h.Curing agent is the mixture of polyamide, m-phenylene diamine (MPD), weight ratio polyamide: m-phenylene diamine (MPD) 1:0.2.Coupling agent is
KH550。
Comparative example 3
This comparative example provides a kind of recovery method of epoxy resin in discarded circuit board, the difference from embodiment 1 is that: this comparison
In example, S5: the obtained epoxy resin of step S4 is modified, and obtains modified epoxy, the method for modifying of epoxy resin are as follows:
Epoxy resin 10g, boron bakelite resin 1g are mixed, after being placed in 85 DEG C of heating water bath 30min, filler 5g, 85 DEG C of stirring 2h are added,
Revolving speed is 300r/min, and curing agent 2g is then added, at room temperature, after stirring 10min with the revolving speed of 200r/min, normal temperature cure
10h.Filler is the mixture of silica, mica powder, weight ratio silica, mica powder 1:3.Curing agent be polyamide,
The mixture of m-phenylene diamine (MPD), weight ratio polyamide: m-phenylene diamine (MPD) 1:0.2.
Comparative example 4
This comparative example provides a kind of recovery method of epoxy resin in discarded circuit board, the difference from embodiment 1 is that: this comparison
In example, preparation method lacks step S5, i.e., is not modified to epoxy resin.
Detection method
By the epoxy resin weighing of the present embodiment recycling and the rate of recovery is calculated according to initial epoxy resin content in discarded circuit board,
For the application epoxy resin rate of recovery between 95-97%, purity is 99 or more.
The shear strength detection of epoxy resin is referring to GB/T7124-2008, after the measurement of heat resistance is epoxy resin cure
High temperature keeps 1h, and the shear strength measured at high temperature with the electronics tensile and compression testing machine that programmable heats up in an oven.Stripping
Measurement from intensity is executed according to GB/T7122-1996.
1 embodiment 1-8 of table and comparative example 1-4 material tests result
Table 1 gives the test result of the material of the embodiment of the present invention and comparative example, it can be seen that the modification of the embodiment of the present invention
Shear strength can reach 21.25MPa under epoxy resin room temperature, under the conditions of 250 DEG C, reach 5.13MPa, high temperature resistance is excellent
Different, peel strength reaches 7.79KN/m, excellent combination property.Embodiment 7 and 8 adds glycerin monostearate, and comprehensive performance is more
It is excellent.Comparative example 1 does not carry out secondary filter, and comparative example 2 lacks filler, and comparative example 3 lacks coupling agent, and comparative example 4 is not to asphalt mixtures modified by epoxy resin
Rouge is modified, and shear strength, the peel strength of epoxy resin are decreased obviously, and the performance of comparative example 4 is worst, illustrates that the present invention matches
Side and technique suitability are good, significant effect.
The above is a preferred embodiment of the present invention, it is noted that for those skilled in the art
For, without departing from the principles of the present invention, it can also make several improvements and retouch, these improvements and modifications
It should be regarded as protection scope of the present invention.
Claims (9)
1. the recovery method of epoxy resin in a kind of discarded circuit board, it is characterised in that: comprise the steps of:
S1: various components are removed from discarded circuit board surface；
S2: the resulting wiring board of step S1 is crushed, fine powder is obtained；
S3: the obtained fine powder of step S2 is sorted, and is removed lemel, is obtained nonmetallic fine powder；
S4: will be added dust technology in nonmetallic fine powder that step S3 is obtained, after heating water bath, once filtered, collect filter residue I
Being washed with ethyl acetate to organic phase is colourless, combined ethyl acetate solution, carries out secondary filter, removes filter residue II, use carbonic acid
Sodium solution is washed to neutrality, and distillation removes ethyl acetate, obtains epoxy resin；
S5: the obtained epoxy resin of step S4 is modified, modified epoxy is obtained.
2. the recovery method of epoxy resin in a kind of discarded circuit board according to claim 1, it is characterised in that: the step
In rapid S3, the method for sorting is electrostatic separation, and the voltage of electrostatic separator is 20-25V, and roller revolving speed is 50-60r/min, corona electricity
The distance between pole and roller are 5.5-7.5cm.
3. the recovery method of epoxy resin in a kind of discarded circuit board according to claim 1, it is characterised in that: the step
In rapid S4, the mass fraction of dust technology is 40-50%.
4. the recovery method of epoxy resin in a kind of discarded circuit board according to claim 1, it is characterised in that: the step
In rapid S4, the ratio of nonmetallic fine powder and dust technology addition is 10g:50-55ml.
5. the recovery method of epoxy resin in a kind of discarded circuit board according to claim 1, it is characterised in that: the step
In rapid S4, the time of heating water bath is 80-90 DEG C, time 10-15h；Vapo(u)rizing temperature is 75-80 DEG C, time 12-15h.
6. the recovery method of epoxy resin in a kind of discarded circuit board according to claim 1, it is characterised in that: the step
In rapid S5, the method for modifying of epoxy resin are as follows: epoxy resin 10g, boron bakelite resin 1-4g are mixed, 85-90 DEG C of water-bath is placed in
After heating 10-30min, filler 5-6g, coupling agent 1-2g, 85-90 DEG C of stirring 1-2h, revolving speed 300-400r/min is added, so
Curing agent 2-3g is added afterwards, at room temperature, after stirring 5-10min with the revolving speed of 200-300r/min, normal temperature cure 10-12h.
7. the recovery method of epoxy resin in a kind of discarded circuit board according to claim 6, it is characterised in that: the step
In rapid S5, filler is the mixture of silica, mica powder, weight ratio silica: mica powder 1:3-5.
8. the recovery method of epoxy resin in a kind of discarded circuit board according to claim 6, it is characterised in that: the step
In rapid S5, curing agent is the mixture of polyamide, m-phenylene diamine (MPD), weight ratio polyamide: m-phenylene diamine (MPD) 1:0.2-0.4.
9. the recovery method of epoxy resin in a kind of discarded circuit board according to claim 6, it is characterised in that: the step
In rapid S5, coupling agent is KH550 or KH560.
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| CN201811262793.9A CN109232970B (en) | 2018-10-27 | 2018-10-27 | Method for recovering epoxy resin in waste circuit board |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111823447A (en) * | 2020-07-29 | 2020-10-27 | 湖北珍正峰新材料有限公司 | Recovery device for high-temperature-resistant epoxy resin |
| 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 |
| 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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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891902A (en) * | 2010-07-23 | 2010-11-24 | 浙江理工大学 | Method for recycling waste epoxy resin |
| US20130274382A1 (en) * | 2010-12-30 | 2013-10-17 | Chaofeng Xiao | Plate synthesized by waste circuit board powder and manufacturing process thereof |
| 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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111823447A (en) * | 2020-07-29 | 2020-10-27 | 湖北珍正峰新材料有限公司 | Recovery device for high-temperature-resistant epoxy resin |
| 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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| CN109232970B (en) | 2021-06-22 |
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