CN107399928B - Glass fiber ball bundle and preparation method thereof - Google Patents
Glass fiber ball bundle and preparation method thereof Download PDFInfo
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- CN107399928B CN107399928B CN201710725455.3A CN201710725455A CN107399928B CN 107399928 B CN107399928 B CN 107399928B CN 201710725455 A CN201710725455 A CN 201710725455A CN 107399928 B CN107399928 B CN 107399928B
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/10—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B26/14—Polyepoxides
Abstract
The invention discloses a glass fiber ball bundle and a preparation method thereof, wherein the glass fiber ball bundle comprises the following components: step 1, crushing and sorting the waste printed circuit board to obtain nonmetal powder; step 2, adding the non-metal powder into inorganic acid, and reacting for 8-40 h at 50-95 ℃; step 3, filtering, and respectively collecting glass fiber powder solid and filtrate; step 4, extracting the filtrate by using an extracting agent to obtain recycled epoxy resin; step 5, mixing the glass fiber powder and the recycled epoxy resin according to the ratio of 100: 0.1-10, adding the mixture into an organic amine solution under stirring, reacting for 0.5-30 h at 40-80 ℃, and filtering to obtain the glass fiber ball bundle. The method of the invention not only avoids the harm of the recycled glass fiber and the glass fiber dust to human bodies in the processes of treatment and recycling, but also can be used as a carrier of catalysts, nano materials and other materials for the recycled glass fiber ball bundles, can be used for directly preparing composite materials, avoids the performance reduction caused by high temperature in the process of extrusion granulation, and has good application prospect.
Description
Technical Field
The invention relates to recovery of glass fibers in waste printed circuit board nonmetal powder, in particular to a glass fiber ball bundle and a preparation method thereof.
Background
Printed Circuit Boards (PCBs for short) are the most basic components of electronic products, and are the basis for connecting the components in the electronic products. Household appliances commonly seen in our daily life are mainly televisions, washing machines, refrigerators, air conditioners and computers. In recent years, these household appliances have entered peak periods of elimination and scrapping. These appliances contain a large number of printed wiring boards. As the number of waste home appliances is continuously increased, the amount of waste PCBs is also increased year by year.
In addition to being derived from electronic waste, one source of waste PCBs is scrap and rejects produced during PCB production. Leftover materials and unqualified products account for about 10-20% of the total production amount of the PCB. China is a large producing country of printed circuit boards, so that a large amount of leftover materials and unqualified products are produced every year.
The waste PCBs contain a large amount of metals, and many enterprises are engaged in recycling the metals from the waste PCBs. Through the steps of disassembling, crushing, sorting and the like, most of metals can be recycled, and the remaining non-metal powder becomes secondary pollutants and is accumulated in a certain corner in a large amount.
Landfilling and incineration are conventional methods for large-scale disposal of these thermosetting epoxy resin wastes. Landfill not only occupies precious land resources, but also pollutes the environment. Some thermosetting epoxy resin wastes contain heavy metals and brominated flame retardants (such as waste printed circuit board nonmetal powder), which are leached by rainwater to pollute soil, underground water, and the like. Incineration generates a large amount of slag, and wastes containing brominated flame retardants (such as waste PCB non-metal powder) generate a large amount of toxic substances, particularly polybrominated dibenzodioxin and polybrominated dibenzofuran, when incinerated.
These non-metallic powders contain a large amount of glass fibers, which accounts for about 70% by weight. Patent CN101407596B discloses a method for recovering glass fiber from waste printed circuit board nonmetal powder by chemical method. The glass fiber recovered by the method is white powder, and the glass fiber powder is easy to generate dust when being processed and used, enters respiratory tracts and eyes, is especially easy to prick into skin, causes harm to human bodies and causes discomfort. In order to improve the harm of the glass fiber powder, the invention discloses a preparation method of glass fiber ball bundles, which gathers the glass fiber powder into the ball bundles to avoid the harm of the glass fiber powder.
Disclosure of Invention
The invention aims to provide a method for preparing glass fiber ball bundles by taking waste printed circuit boards as raw materials, which not only recycles glass fibers in non-metal powder of the waste printed circuit boards to be recycled, but also avoids the harm of the recycled glass fibers and glass fiber dust to human bodies in the processes of treatment and recycling.
In order to achieve the above object, the present invention provides a method for preparing glass fiber ball bundles, comprising:
step 1, crushing and sorting the waste printed circuit board to obtain nonmetal powder;
step 2, adding the nonmetal powder prepared in the step 1 into inorganic acid, heating to 50-95 ℃, and reacting for 8-40 hours; wherein, the weight of the non-metal powder is as follows: volume of inorganic acid 1 g: 3-10 mL of inorganic acid, wherein the concentration of the inorganic acid is 3-8 mol/L;
step 3, filtering, and respectively collecting glass fiber powder solid and filtrate;
step 4, extracting the filtrate by using an extracting agent, and removing the extracting agent to obtain recovered epoxy resin;
and 5, mixing the glass fiber powder collected in the step 3 and the recycled epoxy resin prepared in the step 4 according to a ratio of 100: (0.1-10), adding the mixture into an organic amine solution under stirring, reacting for 0.5-30 hours at the temperature of 40-80 ℃, and filtering to obtain glass fiber ball bundles; the organic amine has the function of enabling the glass fiber powder to form a ball bundle, and one or two of ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, diethylaminopropylamine and dipropylenetriamine is selected.
Preferably, the inorganic acid in step 2 is one or a mixture of two of sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid. The inorganic acid is used as a decomposer to decompose the thermosetting epoxy resin coated on the surface of the glass fiber, so that the glass fiber is dissociated.
Preferably, the extractant in step 4 is selected from one or more of ethyl ether, butyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol butyl ether, methyl acetate, ethyl acetate, propyl acetate and butyl acetate.
Preferably, step 3 further comprises: and (3) washing the glass fiber powder solid by using a detergent.
Preferably, the detergent is selected from one or more of ethyl ether, butyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol butyl ether, methyl acetate, ethyl acetate, propyl acetate and butyl acetate.
Preferably, in step 5, the total weight of the glass fiber powder and the recycled epoxy resin is as follows: the volume of the organic amine solution was 1 g: 3-30 mL.
Preferably, the concentration of the organic amine solution is 1-30% by weight.
Preferably, the solvent of the organic amine solution is one or more of ethyl acetate, propyl acetate, butyl acetate, methyl acetate, ethanol, methanol, propanol, isopropanol and acetone.
Preferably, step 5 further comprises a step of cleaning the glass fiber ball bundle with a cleaning agent to remove the resin remaining on the surface of the glass fiber ball bundle: adding the glass fiber ball bundles into a cleaning agent, stirring for 1-20 hours at 35-90 ℃, filtering, and collecting the glass fiber ball bundles, wherein the weight-volume ratio of the glass fiber ball bundles to the cleaning agent is 1: (3-8) g/mL, wherein the cleaning agent is one or a combination of more of water, sulfuric acid, nitric acid, phosphoric acid, hydrochloric acid, ethanol, methanol, propanol, ethyl acetate and methyl acetate-propyl acetate.
The invention also provides the glass fiber ball bundle obtained by the preparation method of the glass fiber ball bundle, and the glass fiber ball bundle can be used for preparing composite materials and can be used as a carrier of catalysts, nano materials and other materials.
Compared with the prior art, the invention has the following advantages:
① the method of the invention can avoid the pollution of the environment and the harm to the human health caused by the glass fiber dust generated in the process of recovery, treatment and reuse of the glass fiber.
② the glass fiber ball bundle prepared by the invention has a certain surface area as the ball bundle, and is easy to adsorb some nanometer or polar materials, such as graphene oxide, etc., thus the glass fiber ball bundle can be used as a carrier of catalyst, nanometer material and other materials, and the application of recovering glass fiber powder is expanded.
③ the glass fiber ball bundle prepared by the invention can be directly injected with polymer material to form product, which saves the extrusion granulation process, avoids the impact of extrusion granulation process on the product performance, and saves the cost.
④ the inorganic acid used in the invention can be recycled without causing secondary pollution.
Drawings
FIG. 1 is a view showing the appearance of a glass fiber ball bundle of the present invention.
Detailed Description
The technical solution of the present invention is further described below with reference to the accompanying drawings and examples.
Example 1
And crushing and sorting the waste printed circuit board, and collecting the nonmetal powder. Adding 100g of nonmetal powder into 300mL of 6mol/L nitric acid solution, heating at 85 ℃ for 20 hours, filtering, extracting the filtrate with ethylene glycol ether, and washing the solid with ethylene glycol ether to obtain glass fiber powder; and combining the ethylene glycol ethyl ether extract and the washing liquid, and evaporating the ethylene glycol ethyl ether by using a rotary evaporator to obtain the recovered epoxy resin.
Taking 50g of glass fiber powder, recovering 1g of epoxy resin, adding the glass fiber powder into 200mL of ethanol solution of 6 percent (by weight percentage) of diethylenetriamine, heating the mixture at 50 ℃ for 7 hours, filtering the mixture to obtain glass fiber ball bundles, then adding the glass fiber ball bundles into 150mL of ethanol, heating the mixture at 40 ℃ for 5 hours, filtering and drying the mixture to obtain the glass fiber ball bundles shown in the figure 1.
Example 2
And crushing and sorting the waste printed circuit board, and collecting the nonmetal powder. Adding 130g of nonmetal powder into 910mL of 8mol/L nitric acid and phosphoric acid solution (volume is 3: 1), heating at 80 ℃ for 10 hours, filtering, extracting filtrate with ethyl acetate, and washing solids with ethyl acetate to obtain glass fiber powder; and combining the ethyl acetate extract and the washing liquid, and evaporating ethyl acetate by using a rotary evaporator to obtain the recovered epoxy resin.
50g of glass fiber powder is taken, 3g of epoxy resin is recovered, the glass fiber powder is added into 230mL of 9 percent (by weight percentage) propanol solution of hexamethylene diamine, the mixture is heated for 6 hours at the temperature of 60 ℃, the mixture is filtered to obtain glass fiber ball bundles, then the glass fiber ball bundles are added into 150mL of 4M nitric acid, the mixture is heated for 3 hours at the temperature of 50 ℃, and the mixture is filtered and dried.
Example 3
And crushing and sorting the waste printed circuit board, and collecting the nonmetal powder. Adding 120g of nonmetal powder into 720mL of 6mol/L nitric acid and sulfuric acid solution (according to the volume of 4: 1), heating at 83 ℃ for 12 hours, filtering, extracting filtrate by using butyl acetate, and washing solids by using butyl acetate to obtain glass fiber powder; and (3) combining the butyl acetate extract and the washing liquid, and evaporating butyl acetate by using a rotary evaporator to obtain the recovered epoxy resin.
50g of glass fiber powder is taken, 0.5g of epoxy resin is recovered, the glass fiber powder is added into 200mL of a 15 percent (by weight percentage) methanol solution of ethylenediamine, the mixture is heated for 6 hours at the temperature of 60 ℃, the mixture is filtered to obtain glass fiber ball bundles, then the glass fiber ball bundles are added into 150mL of a 4M nitric acid and phosphoric acid solution (according to the volume ratio of 3: 1), the mixture is heated for 10 hours at the temperature of 60 ℃, and the mixture is filtered and dried.
In summary, the invention is characterized in that the waste printed circuit board is crushed and sorted, the residual nonmetal powder is heated in inorganic acid for a certain time and then filtered to obtain glass fiber powder, and the epoxy resin is recovered from the filtrate by an extraction method; adding the glass fiber powder and the recycled epoxy resin into an organic amine solution, stirring, heating and filtering to obtain a glass fiber ball bundle; and finally, adding the glass fiber ball beam into a proper amount of cleaning agent for heating, removing the residual resin on the surface of the glass fiber ball beam, and drying to obtain the glass fiber ball beam. The glass fiber ball bundle can be used for preparing composite materials, and can also be used as a carrier of catalysts, nano materials and other materials.
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. Various modifications and alterations to this invention will become apparent to those skilled in the art upon reading the foregoing description. Accordingly, the scope of the invention should be determined from the following claims.
Claims (10)
1. A method for preparing glass fiber ball bundles, the method comprising:
step 1, crushing and sorting the waste printed circuit board to obtain nonmetal powder;
step 2, adding the nonmetal powder prepared in the step 1 into inorganic acid, heating to 50-95 ℃, and reacting for 8-40 hours; wherein, the weight of the non-metal powder is as follows: volume of inorganic acid 1 g: 3-10 mL of inorganic acid, wherein the concentration of the inorganic acid is 3-8 mol/L;
step 3, filtering, and respectively collecting glass fiber powder solid and filtrate;
step 4, extracting the filtrate by using an extracting agent, and removing the extracting agent to obtain recovered epoxy resin;
and 5, mixing the glass fiber powder collected in the step 3 and the recycled epoxy resin prepared in the step 4 according to a ratio of 100: 0.1-10, adding the mixture into an organic amine solution under stirring, reacting for 0.5-30 hours at 40-80 ℃, and filtering to obtain glass fiber ball bundles; the organic amine is one or two of ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylene tetramine, diethylaminopropylamine and dipropylenetriamine.
2. The method for preparing glass fiber bundles according to claim 1, wherein the inorganic acid in step 2 is one or a mixture of two of sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid.
3. The method for preparing glass fiber bundles according to claim 1, wherein the extractant in step 4 is selected from one or more of ethyl ether, butyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol butyl ether, methyl acetate, ethyl acetate, propyl acetate, and butyl acetate.
4. The method of preparing glass fiber strands according to claim 1, wherein step 3 further comprises: and (3) washing the glass fiber powder solid by using a detergent.
5. The method for preparing glass fiber bundles according to claim 4, wherein the detergent is selected from one or more of ethyl ether, butyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol butyl ether, methyl acetate, ethyl acetate, propyl acetate, and butyl acetate.
6. The method for preparing glass fiber bundles according to claim 1, wherein in the step 5, the total weight of the glass fiber powder and the recycled epoxy resin is as follows: the volume of the organic amine solution was 1 g: 3-30 mL.
7. The method for producing glass fiber bundles according to claim 6, wherein the concentration of the organic amine solution is 1 to 30% by weight.
8. The method for preparing glass fiber bundles according to claim 7, wherein the solvent of the organic amine solution is one or more of ethyl acetate, propyl acetate, butyl acetate, methyl acetate, ethanol, methanol, propanol, isopropanol and acetone.
9. The method for preparing glass fiber ball bundles according to claim 1, wherein the step 5 further comprises the step of cleaning the glass fiber ball bundles with a cleaning agent: adding the glass fiber ball bundles into a cleaning agent, stirring for 1-20 hours at 35-90 ℃, filtering, and collecting the glass fiber ball bundles, wherein the weight of the glass fiber ball bundles is as follows: the volume of the cleaning agent is 1 g: 3-8 mL, wherein the cleaning agent is one or a combination of more of water, sulfuric acid, nitric acid, phosphoric acid, hydrochloric acid, ethanol, methanol, propanol, ethyl acetate, methyl acetate and propyl acetate.
10. A glass fiber strand obtained by the method for producing glass fiber strands according to any one of claims 1 to 9.
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| CN201710725455.3A CN107399928B (en) | 2017-08-22 | 2017-08-22 | Glass fiber ball bundle and preparation method thereof |
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| CN201710725455.3A CN107399928B (en) | 2017-08-22 | 2017-08-22 | Glass fiber ball bundle and preparation method thereof |
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| CN107399928A CN107399928A (en) | 2017-11-28 |
| CN107399928B true CN107399928B (en) | 2020-03-17 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112138645A (en) * | 2020-11-02 | 2020-12-29 | 上海第二工业大学 | Glass fiber ball beam supported GO/TiO2Photocatalyst and preparation method thereof |
| CN112808240A (en) * | 2021-02-08 | 2021-05-18 | 上海第二工业大学 | Glass fiber ball bundle GO/ZIF-8 loaded composite material and preparation method thereof |
| CN114377706B (en) * | 2022-01-04 | 2024-03-12 | 上海第二工业大学 | Glass fiber ball bundle loaded MXene/TiO 2 Aerogel composite material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101407596A (en) * | 2008-09-25 | 2009-04-15 | 上海第二工业大学 | Method for recycling epoxy resins and glass fibre from non-metal powder of waste printed circuit board |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101407596A (en) * | 2008-09-25 | 2009-04-15 | 上海第二工业大学 | Method for recycling epoxy resins and glass fibre from non-metal powder of waste printed circuit board |
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