CN113214605B - Method for preparing epoxy resin composite material from circuit board reclaimed materials - Google Patents
Method for preparing epoxy resin composite material from circuit board reclaimed materials Download PDFInfo
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
The invention discloses a method for preparing an epoxy resin composite material by using a circuit board reclaimed material, which comprises the following raw materials of 20-30 parts of the circuit board reclaimed material, 30-40 parts of an epoxy resin prepolymer and 10-20 parts of a curing agent; the method comprises the steps of A1, crushing the recovered circuit board material into small pieces, boiling the small pieces in sodium hydroxide solution, washing with water, drying, soaking in acid solution, and performing hydrometallurgy to obtain metal compound precipitate from the soaking solution; step A2, putting the metallic compound precipitate and sulfur powder into a flask, adding DMF, stirring until the DMF is dissolved, adding the mixed solution of triethylene tetramine and ethylenediamine and polyvinylpyrrolidone, and carrying out reflux reaction for 5-6 hours at the temperature of 160 ℃ in the nitrogen atmosphere to obtain modified nanocrystals; and A3, heating the epoxy resin prepolymer to a molten state, adding the modified nanocrystal and the curing agent, and curing for 3-4 hours to obtain the epoxy resin composite material.
Description
Technical Field
The invention belongs to the technical field of high polymer material preparation, and relates to a method for preparing an epoxy resin composite material from a circuit board reclaimed material.
Background
The Printed Circuit Board (PCB) is an important component of an electronic component, and not only contains a large amount of valuable metals such as copper, tin, gold, silver and the like; the waste printed circuit board recovery device also contains heavy metals such as lead and cadmium, brominated flame retardants, polyvinyl chloride and other toxic and harmful substances, if the waste printed circuit board is not treated or not treated properly, not only is metal resource waste caused, but also the environment is polluted.
The conductive epoxy resin is a conductive polymer material which is compounded by taking epoxy resin as a matrix material and a conductive filling material. The epoxy resin is a linear polymer, is liquid or solid at normal temperature according to different structures and molecular weights, can be dissolved in various organic solvents, and can be subjected to crosslinking reaction with a curing agent during use to form crosslinked thermosetting plastic, and most of conductive materials are carbon-containing inorganic materials such as carbon black, graphene, carbon nano tubes and the like.
Disclosure of Invention
The invention aims to provide a method for preparing an epoxy resin composite material from a circuit board reclaimed material.
The purpose of the invention can be realized by the following technical scheme:
a method for preparing an epoxy resin composite material from a circuit board reclaimed material comprises the following raw materials in parts by weight:
20-30 parts of circuit board reclaimed materials, 30-40 parts of epoxy resin prepolymers and 10-20 parts of curing agents;
the preparation of the epoxy resin composite material by the circuit board reclaimed material comprises the following steps:
a1, crushing the recovered circuit board material into small pieces, putting the small pieces into a sodium hydroxide solution with the mass fraction of 10% for boiling, washing the small pieces with deionized water for 2-3 times, drying the small pieces at 80-90 ℃ for 3-4 hours, putting the small pieces into an acid solution for soaking for 4-5 hours to prepare a soaking solution, and performing a hydrometallurgy method to prepare a metal compound precipitate from the soaking solution;
step A2, placing the metal compound precipitate and sulfur powder prepared in the step A1 into a flask, adding DMF, controlling the temperature at 80 ℃ and the speed of 250-300rpm to stir for 30-60 minutes until the metal compound precipitate and the sulfur powder are dissolved, adding the mixed solution of triethylene tetramine and ethylenediamine and polyvinylpyrrolidone, stirring uniformly, carrying out reflux reaction at the temperature of 150-160 ℃ in a nitrogen atmosphere for 5-6 hours, after the reaction is finished, centrifuging to obtain the precipitate, washing the precipitate with absolute ethyl alcohol, and drying the precipitate at the temperature of 70-80 ℃ to constant weight to obtain the modified nanocrystal;
step A3, heating the epoxy resin prepolymer to a molten state, pouring the epoxy resin prepolymer into a three-neck flask, adding the modified nanocrystal prepared in the step A2, uniformly stirring, reacting for 1-2 hours, adding a curing agent, and curing at the temperature of 120-130 ℃ for 3-4 hours to obtain the epoxy resin composite material.
Further, the amount of the sodium hydroxide solution in the step A1 is 5-10 times of the mass of the circuit board reclaimed material, the mass fraction of the sodium hydroxide solution is 10-15%, the acid solution is prepared by mixing concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 3:7, the mass fraction of the concentrated sulfuric acid is 98%, and the mass fraction of the concentrated nitric acid is 65%.
Further, the dosage ratio of the metallic compound precipitate, sulfur powder, DMF, mixed solution of triethylene tetramine and ethylene diamine, and polyvinylpyrrolidone in step A2 is 110-130 mg: 240-250 mg: 2-3 mL: 2-3 mL: 4-5mL, and the mixed solution of triethylene tetramine and ethylenediamine is prepared from triethylene tetramine and ethylenediamine according to the volume ratio of 1: 3.
Further, the dosage of the modified nanocrystal in the step A3 is 5-10% of the mass of the epoxy resin prepolymer, and the curing agent is one of maleic anhydride and phthalic anhydride.
Further, the epoxy resin prepolymer is prepared by the following steps:
step S1, adding 3-chlorothiophene and tetrahydrofuran into a three-neck flask, dropwise adding n-butyllithium at-80 ℃ in a nitrogen atmosphere, reacting for 2-3 hours, and adding benzo [1,2-b:4,5-b']Heating dithiophene-4, 8-diketone to 50-55 ℃ for reacting for 1 hour, and then adding SnCl2·2H2Cooling the solution of O and hydrochloric acid to room temperature, and reacting for 30-50 minutes to obtain an intermediate 1;
the reaction process is as follows:
step S2, adding the intermediate 1, potassium carbonate and deionized water into a three-neck flask, uniformly mixing, adding tetraethylammonium bromide, and performing reflux reaction for 2-3 hours at the temperature of 115-120 ℃ to obtain an intermediate 2;
the reaction process is as follows:
step S3, adding the intermediate 2 into a three-neck flask, adding epichlorohydrin, stirring uniformly, reacting for 3-5 hours at a controlled temperature of 70-80 ℃ in a nitrogen atmosphere, cooling to 40-50 ℃, adding a sodium hydroxide solution with a mass fraction of 30%, reacting for 1-2 hours, washing for 2-3 times with deionized water after the reaction is finished, standing for layering, and distilling the organic phase under reduced pressure to obtain the epoxy resin prepolymer.
The reaction process is as follows:
further, in step S1, the raw material includes 3-chlorothiophene, tetrahydrofuran, n-butyllithium, and benzo [1,2-b:4,5-b']Dithiophene-4, 8-diones, SnCl2·2H2The dosage ratio of the O to the hydrochloric acid solution is 2.5-3 g: 15-20 mL: 4-5mL, 0.5-0.8 g: 4-5 g: 15-20mL, and the mass fraction of the hydrochloric acid solution is 10%.
Further, in the step S2, the dosage ratio of the intermediate 1, potassium carbonate, deionized water, and tetraethylammonium bromide is 5-8 g: 0.2-0.4 g: 10-20 g: 0.3-0.6 g.
Further, the mass ratio of the intermediate 2 to the epichlorohydrin in the step S3 is 1:4-5, and the amount of the sodium hydroxide solution is 0.5-1.5 times of the total mass of the intermediate 3 and the epichlorohydrin.
The invention has the beneficial effects that: the method recovers metal compounds including tin oxide, copper sulfate, nickel sulfate and the like from a circuit board by a hydrometallurgy method, the metal compounds are used as raw materials to react with sulfur powder to prepare semiconductor nanocrystals, carriers are generated in the semiconductor nanocrystals through drifting, diffusion and compounding so as to realize the conductive property, in addition, in order to overcome the agglomeration among the nanocrystals, the surface of the semiconductor nanocrystals is coated and modified by polyvinylpyrrolidone serving as a surfactant, so that the interface bonding force is reduced, the oxygen-containing groups grafted on the surface of the nanocrystals improve the interface bonding property of the nanocrystals and an epoxy resin matrix, and the interface bonding strength and compatibility of a composite material are improved, so that the overall performance of the composite material is improved, and the material is endowed with the property of being conductive integrally;
meanwhile, the epoxy resin prepolymer is modified to enable the matrix material of the epoxy resin prepolymer to have conductive capacity, so that the epoxy resin prepolymer cooperates with the semiconductor nanocrystal to promote the smooth flow of electrons, for the epoxy resin prepolymer, 3-chlorothiophene and benzo [1,2-b:4,5-b' ] dithiophene-4, 8-diketone react to generate an intermediate 1, the intermediate 1 is hydrolyzed under alkaline conditions to generate an intermediate 2 containing hydroxyl, the intermediate 2 reacts with epichlorohydrin to generate an epoxy resin prepolymer, the epoxy resin prepolymer and a curing agent undergo a curing reaction, an epoxy group ring is opened and reacts with the curing agent to generate a three-dimensional reticular three-dimensional structure, the elastic property of a high polymer is exerted, meanwhile, the conductive property of the high polymer is increased by the design of the intermediate containing benzodithiophene, a benzodithiophene fragment is introduced to form a large conjugated pi system, and pi electrons are excited by photons, electrons are allowed to jump from the Highest Occupied Molecular Orbital (HOMO) to the Lowest Unoccupied Molecular Orbital (LUMO) with energy to form excitons, and then the dissociation of the excitons is completed depending on the difference in donor and acceptor electrophilicity, after which the different charges are conducted in different directions to generate photogenerated carriers to achieve the conduction function.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A method for preparing an epoxy resin composite material from a circuit board reclaimed material comprises the following raw materials in parts by weight:
20 parts of circuit board reclaimed materials, 30 parts of epoxy resin prepolymers and 10 parts of curing agents;
the preparation of the epoxy resin composite material by the circuit board reclaimed material comprises the following steps:
a1, crushing the recovered circuit board material into small pieces, putting the small pieces into a sodium hydroxide solution with the mass fraction of 10% to boil, washing the small pieces with deionized water for 2 times, drying the small pieces at 80 ℃ for 3 hours, putting the small pieces into an acid solution to soak the small pieces for 4 hours to prepare a soak solution, and performing a hydrometallurgy method to prepare a metal compound precipitate from the soak solution;
step A2, placing the metallic compound precipitate and sulfur powder prepared in the step A1 into a flask, adding DMF, controlling the temperature to be 80 ℃ and the speed of 250rpm, stirring for 30 minutes until the mixture is dissolved, adding the mixed solution of triethylene tetramine and ethylenediamine and polyvinylpyrrolidone, stirring uniformly, carrying out reflux reaction for 5 hours at 150 ℃ in a nitrogen atmosphere, centrifuging to obtain a precipitate after the reaction is finished, washing the precipitate with absolute ethyl alcohol, and drying the precipitate at 70 ℃ to constant weight to obtain modified nanocrystal;
step A3, heating the epoxy resin prepolymer to a molten state, pouring the epoxy resin prepolymer into a three-neck flask, adding the modified nanocrystalline prepared in the step A2, controlling the temperature at 120 ℃ and the stirring speed at 180rpm, reacting for 1 hour, adding a curing agent when the temperature is reduced to 105 ℃, stirring for 15 minutes, and curing for 3 hours at 120 ℃ to obtain the epoxy resin composite material.
The amount of the sodium hydroxide solution in the step A1 is 5 times of the mass of the circuit board reclaimed materials, the acid solution is prepared by mixing concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 3:7, the mass fraction of the concentrated sulfuric acid is 98%, and the mass fraction of the concentrated nitric acid is 65%.
Wherein, the dosage ratio of the metallic compound precipitate, the sulfur powder, the DMF, the mixed solution of the triethylene tetramine and the ethylene diamine and the polyvinylpyrrolidone in the step A2 is 110 mg: 240 mg: 2mL of: 2mL of: 4mL of the mixed solution of triethylene tetramine and ethylenediamine is prepared from triethylene tetramine and ethylenediamine according to the volume ratio of 1: 3.
Wherein, the dosage of the modified nanocrystal in the step A3 is 5% of the mass of the epoxy resin prepolymer, and the curing agent is maleic anhydride.
Wherein the epoxy resin prepolymer is prepared by the following steps:
step S1, adding 3-chlorothiophene and tetrahydrofuran into a three-neck flask, dripping n-butyl lithium into the three-neck flask at the temperature of-80 ℃ in a nitrogen atmosphere, reacting for 2 hours, and adding benzo [1,2-b ]:4,5-b']Heating dithiophene-4, 8-diketone to 50 ℃ for reacting for 1 hour, and then adding SnCl2·2H2Cooling the solution of O and hydrochloric acid to room temperature for reaction for 30 minutes to obtain an intermediate 1;
step S2, adding the intermediate 1, potassium carbonate and deionized water into a three-neck flask, uniformly mixing, adding tetraethylammonium bromide, and carrying out reflux reaction for 2 hours at the temperature of 115 ℃ to obtain an intermediate 2;
step S3, adding the intermediate 2 into a three-neck flask, adding epichlorohydrin, stirring uniformly, reacting for 3 hours at a controlled temperature of 70 ℃ in a nitrogen atmosphere, cooling to 40 ℃, adding a sodium hydroxide solution with the mass fraction of 30%, reacting for 1 hour, washing for 2 times with deionized water after the reaction is finished, standing for layering, and distilling the organic phase under reduced pressure to obtain the epoxy resin prepolymer.
Wherein in step S1, the 3-chlorothiophene, tetrahydrofuran, n-butyllithium and benzo [1,2-b:4,5-b']Dithiophene-4, 8-diones, SnCl2·2H2The dosage ratio of the O to the hydrochloric acid solution is 2.5 g: 15mL of: 4mL:0.5 g: 4 g: 15mL, and the mass fraction of the hydrochloric acid solution is 10%.
Wherein the dosage ratio of the intermediate 1, the potassium carbonate, the deionized water and the tetraethylammonium bromide in the step S2 is 5 g: 0.2 g: 10 g: 0.3 g.
Wherein the mass ratio of the intermediate 2 to the epichlorohydrin in the step S3 is 1:4, and the amount of the sodium hydroxide solution is 0.5 times of the total mass of the intermediate 3 and the epichlorohydrin.
Example 2
A method for preparing an epoxy resin composite material from a circuit board reclaimed material comprises the following raw materials in parts by weight:
25 parts of circuit board reclaimed materials, 35 parts of epoxy resin prepolymers and 15 parts of curing agents;
the preparation of the epoxy resin composite material by the circuit board reclaimed material comprises the following steps:
a1, crushing the recovered circuit board material into small pieces, putting the small pieces into a sodium hydroxide solution with the mass fraction of 10% to boil, washing the small pieces with deionized water for 2 times, drying the small pieces at 85 ℃ for 3 hours, putting the small pieces into an acid solution to soak the small pieces for 4 hours to prepare a soak solution, and performing a hydrometallurgy method to prepare a metal compound precipitate from the soak solution;
step A2, putting the metallic compound precipitate and sulfur powder prepared in the step A1 into a flask, adding DMF, controlling the temperature to be 80 ℃ and the speed of 270rpm, stirring for 40 minutes until the mixture is dissolved, adding the mixed solution of triethylene tetramine and ethylenediamine and polyvinylpyrrolidone, stirring uniformly, carrying out reflux reaction at 155 ℃ for 5.5 hours in a nitrogen atmosphere, centrifuging after the reaction is finished to obtain the precipitate, washing the precipitate with absolute ethyl alcohol, and drying the precipitate at 75 ℃ to constant weight to obtain the modified nanocrystal;
step A3, heating the epoxy resin prepolymer to a molten state, pouring the epoxy resin prepolymer into a three-neck flask, adding the modified nanocrystalline prepared in the step A2, controlling the temperature at 120 ℃ and the stirring speed at 180rpm, reacting for 1 hour, adding a curing agent when the temperature is reduced to 105 ℃, stirring for 20 minutes, and curing for 3 hours at 125 ℃ to obtain the epoxy resin composite material.
The amount of the sodium hydroxide solution in the step A1 is 6 times of the mass of the circuit board reclaimed materials, the acid solution is prepared by mixing concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 3:7, the mass fraction of the concentrated sulfuric acid is 98%, and the mass fraction of the concentrated nitric acid is 65%.
Wherein, the dosage ratio of the metallic compound precipitate, the sulfur powder, the DMF, the mixed solution of the triethylene tetramine and the ethylene diamine and the polyvinylpyrrolidone in the step A2 is 120 mg: 245 mg: 2.5 mL: 2.5 mL: 4.5mL of the mixed solution of triethylene tetramine and ethylenediamine is prepared from triethylene tetramine and ethylenediamine according to the volume ratio of 1: 3.
Wherein, the dosage of the modified nanocrystal in the step A3 is 7% of the mass of the epoxy resin prepolymer, and the curing agent is phthalic anhydride.
Wherein the epoxy resin prepolymer is prepared by the following steps:
step S1, adding 3-chlorothiophene and tetrahydrofuran into a three-neck flask, dropwise adding n-butyllithium at-80 ℃ in a nitrogen atmosphere, reacting for 2 hours, and adding benzo [1,2-b:4,5-b']Heating dithiophene-4, 8-diketone to 52 ℃ for reacting for 1 hour, and then adding SnCl2·2H2O and hydrochloric acid solution, and cooling to room temperature for reaction for 40 minutes to prepare an intermediate 1;
step S2, adding the intermediate 1, potassium carbonate and deionized water into a three-neck flask, uniformly mixing, adding tetraethylammonium bromide, and carrying out reflux reaction for 2 hours at the temperature of 117 ℃ to obtain an intermediate 2;
step S3, adding the intermediate 2 into a three-neck flask, adding epichlorohydrin, stirring uniformly, reacting for 4 hours at a controlled temperature of 75 ℃ in a nitrogen atmosphere, cooling to 45 ℃, adding a sodium hydroxide solution with a mass fraction of 30%, reacting for 1.5 hours, washing for 2 times with deionized water after the reaction is finished, standing for layering, and distilling the organic phase under reduced pressure to obtain the epoxy resin prepolymer.
Wherein in step S1, the 3-chlorothiophene, tetrahydrofuran, n-butyllithium and benzo [1,2-b:4,5-b']Dithiophene-4, 8-diones, SnCl2·2H2The dosage ratio of the O to the hydrochloric acid solution is 3 g: 20mL of: 5mL, 0.8 g: 4.5 g: 17mL, the mass fraction of the hydrochloric acid solution is 10%.
Wherein the dosage ratio of the intermediate 1, the potassium carbonate, the deionized water and the tetraethylammonium bromide in the step S2 is 6 g: 0.3 g: 15 g: 0.5 g.
Wherein the mass ratio of the intermediate 2 to the epichlorohydrin in the step S3 is 1:4, and the amount of the sodium hydroxide solution is 1 time of the total mass of the intermediate 3 and the epichlorohydrin.
Example 3
A method for preparing an epoxy resin composite material from a circuit board reclaimed material comprises the following raw materials in parts by weight:
30 parts of circuit board reclaimed materials, 40 parts of epoxy resin prepolymers and 20 parts of curing agents;
the preparation of the epoxy resin composite material by the circuit board reclaimed material comprises the following steps:
a1, crushing the recovered circuit board material into small pieces, putting the small pieces into a sodium hydroxide solution with the mass fraction of 10% to boil, washing the small pieces with deionized water for 3 times, drying the small pieces at 90 ℃ for 4 hours, putting the small pieces into an acid solution to soak the small pieces for 5 hours to prepare a soak solution, and performing a hydrometallurgy method to prepare a metal compound precipitate from the soak solution;
step A2, placing the metallic compound precipitate and sulfur powder prepared in the step A1 into a flask, adding DMF, controlling the temperature to be 80 ℃ and the speed of 300rpm, stirring for 60 minutes until the mixture is dissolved, adding the mixed solution of triethylene tetramine and ethylenediamine and polyvinylpyrrolidone, stirring uniformly, carrying out reflux reaction at 160 ℃ for 6 hours in a nitrogen atmosphere, after the reaction is finished, centrifuging to obtain a precipitate, washing the precipitate with absolute ethyl alcohol, and drying the precipitate at 80 ℃ to constant weight to obtain modified nanocrystal;
step A3, heating the epoxy resin prepolymer to a molten state, pouring the epoxy resin prepolymer into a three-neck flask, adding the modified nanocrystalline prepared in the step A2, controlling the temperature at 120 ℃ and the stirring speed at 180rpm, reacting for 2 hours, adding a curing agent when the temperature is reduced to 110 ℃, stirring for 30 minutes, and curing for 4 hours at 130 ℃ to obtain the epoxy resin composite material.
The amount of the sodium hydroxide solution in the step A1 is 7 times of the mass of the circuit board reclaimed materials, the acid solution is prepared by mixing concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 3:7, the mass fraction of the concentrated sulfuric acid is 98%, and the mass fraction of the concentrated nitric acid is 65%.
Wherein, the dosage ratio of the metallic compound precipitate, the sulfur powder, the DMF, the mixed solution of the triethylene tetramine and the ethylene diamine and the polyvinylpyrrolidone in the step A2 is 130 mg: 250 mg: 3mL of: 3mL of: 5mL, the mixed solution of triethylene tetramine and ethylenediamine is prepared from triethylene tetramine and ethylenediamine according to the volume ratio of 1: 3.
Wherein, the dosage of the modified nanocrystal in the step A3 is 10% of the mass of the epoxy resin prepolymer, and the curing agent is maleic anhydride.
Wherein the epoxy resin prepolymer is prepared by the following steps:
step S1, adding 3-chlorothiophene and tetrahydrofuran into a three-neck flask, dropwise adding n-butyllithium at-80 ℃ in a nitrogen atmosphere, reacting for 3 hours, and adding benzo [1,2-b:4,5-b']Heating dithiophene-4, 8-diketone to 55 ℃ for reacting for 1 hour, and then adding SnCl2·2H2Cooling the solution of O and hydrochloric acid to room temperature for reaction for 50 minutes to obtain an intermediate 1;
step S2, adding the intermediate 1, potassium carbonate and deionized water into a three-neck flask, uniformly mixing, adding tetraethylammonium bromide, and performing reflux reaction for 3 hours at the temperature of 120 ℃ to obtain an intermediate 2;
and step S3, adding the intermediate 2 into a three-neck flask, adding epoxy chloropropane, uniformly stirring, reacting for 5 hours in a nitrogen atmosphere at a controlled temperature of 80 ℃, cooling to 50 ℃, adding a sodium hydroxide solution with the mass fraction of 30%, reacting for 2 hours, washing for 3 times by using deionized water after the reaction is finished, standing for layering, and distilling an organic phase under reduced pressure to obtain the epoxy resin prepolymer.
Wherein in step S1, the raw materials include 3-chlorothiophene, tetrahydrofuran, n-butyllithium and benzo [1,2-b:4,5-b']Dithiophene-4, 8-diones, SnCl2·2H2The dosage ratio of the O to the hydrochloric acid solution is 3 g: 20mL of: 5mL, 0.8 g: 5 g: 20mL, and the mass fraction of the hydrochloric acid solution is 10%.
Wherein the using amount ratio of the intermediate 1, the potassium carbonate, the deionized water and the tetraethylammonium bromide in the step S2 is 8 g: 0.4 g: 20 g: 0.6 g.
Wherein, the mass ratio of the intermediate 2 to the epichlorohydrin in the step S3 is 1:5, and the using amount of the sodium hydroxide solution is 1.5 times of the total mass of the intermediate 3 and the epichlorohydrin.
Comparative example
Commercially available conductive epoxy resins.
Conductivity tests were conducted on examples 1-3 and comparative examples using a RTS-8 four-probe conductivity tester (four-probe technologies, Inc., Guangzhou) and the test data are shown in Table 1:
TABLE 1
| Example 1 | Example 2 | Example 3 | Comparative example | |
| Conductivity (S/cm) | 1.25×10-3 | 1.32×10-3 | 1.35×10-3 | 0.21×10-3 |
As can be seen from table 1, the epoxy resin composites prepared in examples 1 to 3 have high electrical conductivity and exhibit excellent electrical conductivity.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best understand the invention for and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (4)
1. The method for preparing the epoxy resin composite material from the circuit board reclaimed material is characterized by comprising the following raw materials in parts by weight:
20-30 parts of circuit board reclaimed materials, 30-40 parts of epoxy resin prepolymers and 10-20 parts of curing agents;
a1, crushing the recovered circuit board material into small pieces, boiling the small pieces in a sodium hydroxide solution with the mass fraction of 10%, washing and drying the small pieces with water, soaking the small pieces in an acid solution for 4 to 5 hours to prepare a soaking solution, and performing hydrometallurgy to prepare a metal compound precipitate from the soaking solution;
step A2, putting the metallic compound precipitate and sulfur powder into a flask, adding DMF, stirring until the DMF is dissolved, adding the mixed solution of triethylene tetramine and ethylenediamine and polyvinylpyrrolidone, and carrying out reflux reaction for 5-6 hours at the temperature of 160 ℃ in the nitrogen atmosphere to obtain modified nanocrystals;
step A3, heating the epoxy resin prepolymer to a molten state, pouring the epoxy resin prepolymer into a three-neck flask, adding the modified nanocrystalline prepared in the step A2, wherein the amount of the modified nanocrystalline is 5-10% of the mass of the epoxy resin prepolymer, uniformly stirring, reacting for 1-2 hours, adding a curing agent, and curing at the temperature of 120-130 ℃ for 3-4 hours to obtain the epoxy resin composite material;
the epoxy resin prepolymer is prepared by the following steps:
step S1, adding 3-chlorothiophene and tetrahydrofuran into a three-neck flask, dropwise adding n-butyllithium into the three-neck flask at the temperature of-80 ℃ in a nitrogen atmosphere, reacting for 2 to 3 hours, and adding benzo [1,2-b:4,5-b']Heating dithiophene-4, 8-diketone to 50-55 ℃ for reacting for 1 hour, and then adding SnCl2·2H2Cooling the solution of O and hydrochloric acid to room temperature, and reacting for 30-50 minutes to obtain an intermediate 1;
step S2, adding the intermediate 1, potassium carbonate and deionized water into a three-neck flask, uniformly mixing, adding tetraethylammonium bromide, and carrying out reflux reaction at the temperature of 115 ℃ and 120 ℃ for 2-3 hours to obtain an intermediate 2;
step S3, adding the intermediate 2 into a three-neck flask, adding epoxy chloropropane, introducing nitrogen, reacting at 70-80 ℃ for 3-5 hours, cooling to 40-50 ℃, adding a sodium hydroxide solution with the mass fraction of 30%, reacting for 1-2 hours, washing with water, standing for layering, and distilling the organic phase under reduced pressure to obtain an epoxy resin prepolymer;
3-chlorothiophene, tetrahydrofuran, n-butyllithium, benzo [1,2-b:4,5-b 'in step S1']Dithiophene-4, 8-diones, SnCl2·2H2The dosage ratio of the O to the hydrochloric acid solution is 2.5-3 g: 15-20 mL: 4-5mL, 0.5-0.8 g: 4-5 g: 15-20mL, wherein the mass fraction of the hydrochloric acid solution is 10%;
the dosage ratio of the intermediate 1, the potassium carbonate, the deionized water and the tetraethylammonium bromide in the step S2 is 5-8 g: 0.2-0.4 g: 10-20 g: 0.3-0.6 g;
in the step S3, the mass ratio of the intermediate 2 to the epichlorohydrin is 1:4-5, and the amount of the sodium hydroxide solution is 0.5-1.5 times of the total mass of the intermediate 2 and the epichlorohydrin.
2. The method for preparing the epoxy resin composite material from the circuit board reclaimed material as claimed in claim 1, wherein the method comprises the following steps: the amount of the sodium hydroxide solution in the step A1 is 5-10 times of the mass of the circuit board reclaimed materials, the acid solution is prepared by mixing concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 3:7, the mass fraction of the concentrated sulfuric acid is 98%, and the mass fraction of the concentrated nitric acid is 65%.
3. The method for preparing the epoxy resin composite material from the circuit board reclaimed material according to claim 1, wherein the method comprises the following steps: the dosage ratio of the metallic compound precipitate, the sulfur powder, the DMF, the mixed solution of triethylene tetramine and ethylene diamine and the polyvinylpyrrolidone in the step A2 is 110-130 mg: 240-250 mg: 2-3 mL: 2-3 mL: 4-5mL, and the mixed solution of triethylene tetramine and ethylenediamine is prepared from triethylene tetramine and ethylenediamine according to the volume ratio of 1: 3.
4. The method for preparing the epoxy resin composite material from the circuit board reclaimed material as claimed in claim 1, wherein the method comprises the following steps: the curing agent in the step A3 is one of maleic anhydride and phthalic anhydride.
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