CN111793185B - Preparation, remodeling and recovery method of printed circuit board substrate based on phenolic resin - Google Patents
Preparation, remodeling and recovery method of printed circuit board substrate based on phenolic resin Download PDFInfo
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- CN111793185B CN111793185B CN202010693390.0A CN202010693390A CN111793185B CN 111793185 B CN111793185 B CN 111793185B CN 202010693390 A CN202010693390 A CN 202010693390A CN 111793185 B CN111793185 B CN 111793185B
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/54—Polycondensates of aldehydes
- C08G18/542—Polycondensates of aldehydes with phenols
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/003—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor characterised by the choice of material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/02—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/02—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
- B29C43/20—Making multilayered or multicoloured articles
- B29C43/203—Making multilayered articles
- B29C43/206—Making multilayered articles by pressing the material between two preformed layers, e.g. deformable layers
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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
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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
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
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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
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/16—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with inorganic material
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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
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
- C08J11/22—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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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
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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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
Abstract
A preparation, remodeling and recovery method of a printed circuit board substrate based on phenolic resin belongs to the technical field of substrate preparation on printed circuit boards. The preparation method comprises the following steps: uniformly mixing phenolic resin, divinyl ether, diisocyanate and an organic solvent, adding an organic metal catalyst and an inorganic filler, heating to volatilize the solvent, heating to 70-100 ℃ for 30-60 min, transferring to a hot press, carrying out hot pressing at 120-150 ℃ for 20-50 min to obtain a pre-cured dynamic network structure, then continuously heating to 160-180 ℃, carrying out hot pressing for 1-3 h, and curing to obtain the printed circuit board substrate. The substrate of the invention has excellent cycle hot processing performance, and the mechanical performance can still keep good after multiple cycles. The substrate in the completely failed circuit board can be degraded under heating and acidic conditions to recover phenolic resin, reinforcing materials and the like, and can be used for reproducing the circuit board substrate, so that resources are saved and environmental pollution is reduced.
Description
Technical Field
The invention belongs to the technical field of preparation of substrates on printed circuit boards, and particularly relates to a preparation, remodeling and recovery method of a printed circuit board substrate based on phenolic resin.
Background
The thermosetting resin is an insoluble, infusible and chemically cross-linked three-dimensional network polymer formed by irreversible curing reaction (including heating, radiation or other modes) of liquid, soft solid or viscous chemical substances, has higher modulus, strength, thermal stability, dimensional stability and chemical solvent resistance, and can be widely applied to the fields of high-performance coatings, adhesives, composite materials, packaging materials of light-emitting diodes and solar cells and the like. Thermoset resins produced worldwide during 2010-2015 exceed 6500 million tons/year, thermoset plastics are currently and in the future an attractive material for high temperature electronics or automotive applications, currently accounting for 15% -20% of global plastic production. The products prepared by the thermosetting resin are inevitably unqualified products in the production process and are discarded as waste products after the products reach the service life, and the thermosetting resin is difficult to recycle and degrade due to the special properties of the thermosetting resin, so that not only is the resource waste caused, but also the environment is polluted. The popularity of mobile devices, as well as computer devices, has now dramatically increased the demand for thermosetting resins, such as Printed Circuit Boards (PCBs), which are providers of electrical connections for electronic components.
Generally, a circuit board connects various electronic components to a substrate by using a soldering technique to form a conductive path. The main material of the circuit board is a copper-clad plate, and the copper-clad plate is composed of a substrate, an adhesive, a copper foil, solder resist ink (green oil layer) and the like. The substrate is an insulating laminate composed of polymer synthetic resin and a reinforcing material; the binder is typically a thermosetting resin that can be cured to form a crosslinked network. However, such printed circuit boards using thermosetting resin adhesives require removal of the electronic components from the substrate after the device fails, but the presence of the crosslinked thermosetting resin adhesive does not ensure removal or replacement of new electronic components without compromising the integrity of the assembly. And the recovered non-damaged and failed components can be reused in a circuit board of a new semiconductor device. Resin and reinforcing materials which are difficult to reprocess, remold and recycle are mostly adopted for substrate materials, for example, phenolic resin, epoxy resin, polytetrafluoroethylene and the like are mostly used for the resin. The resin has high recovery cost, large energy consumption and poor performance of recovering and preparing samples, and can not realize the regeneration of resources and the recycling economy after being generally discarded after one-time use.
Therefore, resin design in substrates is required to have good thermal stability and impact resistance, while having reworkable remolding properties, degradable recycling and recycling properties. When the electronic components on the circuit board are slightly damaged, the components can be replaced through reprocessing and remodeling treatment; when the serious damage is not solved through replacement, the substrate can be degraded, and the degraded product can be recycled, so that the monomer-polymer-monomer closed cycle process is realized, the resource use is effectively saved, and the environmental pollution is reduced.
Disclosure of Invention
The invention aims to realize the reprocessing, the degradation and the recovery of the substrate in the circuit board, and provides a preparation, the remodeling and the recovery method of the substrate of the printed circuit board based on the phenolic resin; when the circuit board is seriously damaged, the circuit board can be degraded and recycled, and can be used for preparing a substrate again.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a printed circuit board substrate based on phenolic resin comprises the following steps:
uniformly mixing phenolic resin, divinyl ether, diisocyanate and an organic solvent, adding an organic metal catalyst and an inorganic filler, heating to volatilize the solvent, heating to 70-100 ℃ for 30-60 min, transferring to a hot press, carrying out hot pressing at 120-150 ℃ for 20-50 min to obtain a pre-cured dynamic network structure, then continuously heating to 160-180 ℃, carrying out hot pressing for 1-3 h, and curing to obtain the printed circuit board substrate.
The method for remodeling the substrate of the printed circuit board based on the phenolic resin comprises the following steps: and putting the damaged substrate between steel plates covered with two layers of polyimide films or polytetrafluoroethylene films, hot-pressing at 150-200 ℃ for 20-40 min under the pressure of 5-10 MPa, and cooling to obtain the reprocessed substrate.
The method for recovering the prepared printed circuit board substrate based on the phenolic resin comprises the following steps: immersing a substrate to be recycled into a mixed solution of acid, an organic solvent and water at 25-100 ℃ for degradation; and transferring the residue which cannot be completely dissolved into a vacuum oven for drying for 5-10 hours, and recovering.
Compared with the prior art, the invention has the beneficial effects that: the substrate resin applied to the circuit board has excellent cyclic hot processing performance, and the mechanical performance can still keep good after multiple cycles of processing. In addition, the substrate in the completely failed circuit board can be degraded under heating and acidic conditions to recover phenolic resin, reinforcing materials and the like, and can be used for preparing the substrate of the circuit board again. Realizes the regeneration of raw materials and reduces the pollution of the waste circuit board to the environment.
Drawings
Fig. 1 is a schematic diagram of reworking a remodelable printed circuit board substrate made with a phenolic resin.
Detailed Description
The technical solution of the present invention is further described below with reference to the drawings and the embodiments, but the present invention is not limited thereto, and modifications or equivalent substitutions may be made to the technical solution of the present invention without departing from the spirit of the technical solution of the present invention, and the technical solution of the present invention is covered by the protection scope of the present invention.
The invention prepares phenolic resin containing two dynamic covalent bond acetal bonds, two vinyl ethers and diisocyanate through phenolic resin novolac, and utilizes inorganic filler to enhance the mechanical property of matrix resin, the dynamic non-covalent bond hydrogen bond is easy to be destroyed under heating condition, and the two dynamic covalent bonds are subjected to bond exchange or bond fracture recombination at higher temperature, so that the matrix resin has the function of remodeling. Since acetal linkages can be degraded into hydroxyl-containing compounds and acetaldehyde, the urethane linkages are cleaved by heating to release isocyanate groups. When the material reaches the service life, the material can be degraded under the heating acidic condition, and the product is recovered to obtain the renewable linear phenolic resin and the reinforced inorganic filler, which can be used for reproduction, thereby realizing the reutilization of resources.
The first embodiment is as follows: the embodiment describes a method for preparing a printed circuit board substrate based on phenolic resin, which specifically comprises the following steps:
uniformly mixing phenolic resin, divinyl ether, diisocyanate and an organic solvent, adding an organic metal catalyst and an inorganic filler, heating to 70-100 ℃ for 30-60 min after heating to volatilize the solvent, transferring to a hot press, carrying out hot pressing at 120-150 ℃ for 20-50 min to obtain a pre-cured dynamic network structure, then continuously heating to 160-180 ℃, carrying out hot pressing for 1-3 h, and curing to obtain a laminated product which can be used as a printed circuit board substrate in radio equipment.
The second embodiment is as follows: in the first embodiment, the method for preparing a substrate of a printed circuit board based on a phenolic resin comprises the following steps: double bond in bisvinylethers: the molar ratio of isocyanate groups is 1: 0.1-1: 0.1 to 1.
The third concrete implementation mode: detailed description of the preferred embodimentsa method for preparing a phenolic resin-based printed circuit board substrate, the divinyl ether is one or more of divinyl ether, tri (ethylene glycol) divinyl ether, di (ethylene glycol) divinyl ether, tetra (ethylene glycol) divinyl ether, 1, 4-dicyclohexyl dimethyl divinyl ether, 1, 4-cyclohexanedimethanol divinyl ether, 1, 4-butanediol vinyl ether, or 1, 6-hexanediol divinyl ether; the diisocyanate is one or more of 1, 4-cyclohexane diisocyanate, methyl-2, 4-diisocyanate, 1, 5-naphthalene diisocyanate, m-xylylene diisocyanate, isophorone diisocyanate, dimethylene diisocyanate, methylene diisocyanate or ethyl (yl) benzene diisocyanate; the organic solvent is acetone or dichloromethane.
The fourth concrete implementation mode: in a first specific embodiment of the method for preparing a printed circuit board substrate based on a phenolic resin, the organic metal catalyst is one or more of dibutyltin dilaurate, tetrabutyl titanate or organic metal palladium nickel platinum, and the addition amount is 0.1% to 0.4% of the total mass of the resin.
The fifth concrete implementation mode: in a specific embodiment, the inorganic filler is SiO, and the phenolic resin is used as a binder for the phenolic resin-based printed circuit board substrate2、TiO2、ZrO2One or more of silicon carbide, aluminum oxide, zinc oxide or boron nitride, and the addition amount is 1-80% of the total mass of the resin.
The sixth specific implementation mode: a method for reshaping a phenolic resin-based printed circuit board substrate prepared according to any one of embodiments one to five, the method comprising: and (3) putting the damaged substrate between steel plates covered with two layers of polyimide films or polytetrafluoroethylene films, hot-pressing at 150-200 ℃ for 20-40 min under the pressure of 5-10 MPa, cooling to obtain a reprocessed substrate, and repeating the operation to obtain reprocessed and remolded samples which are circulated for different times. Due to the phenolic resin containing dynamic covalent bond acetal bond, urethane bond and dynamic non-covalent bond hydrogen bond, the substrate can be reshaped and reprocessed by heating to destroy the hydrogen bond and exchange or break and recombine the dynamic covalent bond.
The seventh embodiment: a method for recycling a substrate of a printed circuit board based on phenolic resin, which is prepared according to any one of the first to fifth embodiments, the method comprises the following steps: immersing a substrate to be recycled into a mixed solution of acid, an organic solvent and water at 25-100 ℃ for degradation; and transferring the residue which cannot be completely dissolved into a vacuum oven for drying for 5-10 hours, and recovering. The mixing ratio of the organic solvent to the water is 10: 0. 1: 9. 2: 8. 3: 7. 4: 6. 1: 1. 6: 4. 7: 3. 8: 2. 9: 1 and 0: 10. since acetal linkages can be degraded into hydroxyl-containing compounds and acetaldehyde, the urethane linkages are cleaved by heating to release isocyanate groups. The recycled linear phenolic resin and the reinforced material can be used for synthesizing new remodelable degradable phenolic resin subsequently, thereby realizing the regeneration of the monomer, forming a monomer-polymer-monomer circulation closed circuit and effectively saving natural resources. The degradation process is influenced by various factors such as degradation time, degradation temperature, types and concentrations of acids and the like.
The specific implementation mode is eight: in the method for recycling a substrate of a printed circuit board based on phenolic resin according to the seventh embodiment, the acid is one or more of HCl, acetic acid, sulfuric acid, nitric acid, or phosphoric acid, and the concentration is 0.01 to 1.0 mol/L.
The specific implementation method nine: seventh embodiment a method for recycling a printed circuit board substrate based on phenolic resin, wherein the organic solvent is one or more of acetone, THF, ethanol, methanol, DMF or DMSO.
Example 1:
a preparation method of a printed circuit board substrate based on phenolic resin comprises the following steps:
uniformly mixing phenolic resin, tri (ethylene glycol) divinyl ether, 1, 5-naphthalene diisocyanate and organic solvent acetone, adding an organic metal catalyst dibutyltin dilaurate and inorganic filler silicon carbide, heating to 70-100 ℃ for 30-60 min after heating to volatilize the solvent, transferring to a hot press, carrying out hot pressing at 120-150 ℃ for 20-50 min to obtain a pre-cured dynamic network structure, then continuously heating to 160-180 ℃ for hot pressing for 1-3 h, and curing to obtain a laminated product which can be used as a printed circuit board substrate in radio equipment. Hydroxyl group in phenolic resin: double bond in bisvinylethers: the molar ratio of isocyanate groups is 1: 0.5: 0.5. the amount of the organometallic catalyst added was 0.3% of the total mass of the resin. The addition amount of the inorganic filler is 50% of the total mass of the resin.
Example 2:
a remodeling method of a printed circuit board substrate based on phenolic resin comprises the following steps:
and (3) putting the damaged substrate between steel plates covered with two layers of polyimide films or polytetrafluoroethylene films, hot-pressing at 200 ℃ for 20min under the pressure of 7MPa, cooling to obtain a reprocessed substrate, and repeating the operation to obtain reprocessed and remolded samples which are circulated for different times. Due to the phenolic resin containing dynamic covalent bond acetal bond, urethane bond and dynamic non-covalent bond hydrogen bond, the substrate can be reshaped and reprocessed by heating to destroy the hydrogen bond and exchange or break and recombine the dynamic covalent bond.
Example 3:
a method for recovering a substrate of a printed circuit board based on phenolic resin comprises the following steps:
immersing a substrate to be recovered into a mixed solution of HCl, acetone and water at 80 ℃ for degradation; and transferring the residue which cannot be completely dissolved into a vacuum oven for drying for 5-10 hours, and recovering. The mixing volume ratio of the acetone to the water is 1: 1. since acetal linkages can be degraded into hydroxyl-containing compounds and acetaldehyde, the urethane linkages are cleaved by heating to release isocyanate groups. The recycled linear phenolic resin and the reinforced material can be used for synthesizing new remodelable degradable phenolic resin subsequently, thereby realizing the regeneration of the monomer, forming a monomer-polymer-monomer circulation closed circuit and effectively saving natural resources. The degradation process is influenced by various factors such as degradation time, degradation temperature, types and concentrations of acids and the like.
Claims (8)
1. A preparation method of a printed circuit board substrate based on phenolic resin is characterized by comprising the following steps: the method specifically comprises the following steps:
uniformly mixing phenolic resin, divinyl ether, diisocyanate and an organic solvent, adding an organic metal catalyst and an inorganic filler, heating to volatilize the solvent, heating to 70-100 ℃ for 30-60 min, transferring to a hot press, carrying out hot pressing at 120-150 ℃ for 20-50 min to obtain a pre-cured dynamic network structure, continuously heating to 160-180 ℃, carrying out hot pressing for 1-3 h, and curing to obtain a printed circuit board substrate; hydroxyl group in phenolic resin: double bond in bisvinylethers: the molar ratio of isocyanate groups is 1: 0.1-1: 0.1 to 1.
2. The method for preparing the printed circuit board substrate based on the phenolic resin according to claim 1, is characterized in that: the divinyl ether is one or more of divinyl ether, tri (ethylene glycol) divinyl ether, di (ethylene glycol) divinyl ether, tetra (ethylene glycol) divinyl ether, 1, 4-dicyclohexyl dimethyl divinyl ether, 1, 4-cyclohexanedimethanol divinyl ether, 1, 4-butanediol vinyl ether or 1, 6-hexanediol divinyl ether; the diisocyanate is one or more of 1, 4-cyclohexane diisocyanate, methyl-2, 4-diisocyanate, 1, 5-naphthalene diisocyanate, m-xylylene diisocyanate, isophorone diisocyanate, dimethylene diisocyanate, methylene diisocyanate or ethyl (yl) benzene diisocyanate; the organic solvent is acetone or dichloromethane.
3. The method for preparing the printed circuit board substrate based on the phenolic resin according to claim 1, is characterized in that: the organic metal catalyst is one or more of dibutyltin dilaurate, tetrabutyl titanate or organic metal palladium nickel platinum, and the addition amount of the organic metal catalyst is 0.1-0.4% of the total mass of the resin.
4. A phenol-based composition according to claim 1The preparation method of the printed circuit board substrate of the aldehyde resin is characterized by comprising the following steps of: the inorganic filler is SiO2、TiO2、ZrO2One or more of silicon carbide, aluminum oxide, zinc oxide or boron nitride, and the addition amount is 1-80% of the total mass of the resin.
5. A method for reshaping a printed circuit board substrate based on phenolic resin prepared according to any one of claims 1 to 4, which is characterized in that: the method specifically comprises the following steps: and putting the damaged substrate between steel plates covered with two layers of polyimide films or polytetrafluoroethylene films, hot-pressing at 150-200 ℃ for 20-40 min under the pressure of 5-10 MPa, and cooling to obtain the reprocessed substrate.
6. A method for recycling a printed circuit board substrate based on phenolic resin prepared according to any one of claims 1 to 4, characterized in that: the method specifically comprises the following steps: immersing a substrate to be recycled into a mixed solution of acid, an organic solvent and water at 25-100 ℃ for degradation; and transferring the residue which cannot be completely dissolved into a vacuum oven for drying for 5-10 hours, and recovering.
7. The method of claim 6 for recycling a phenolic resin-based printed circuit board substrate, wherein the method comprises the steps of: the acid is one or more of HCl, acetic acid, sulfuric acid, nitric acid or phosphoric acid, and the concentration is 0.01-1.0 mol/L.
8. The method of claim 6 for recycling a phenolic resin-based printed circuit board substrate, wherein the method comprises the steps of: the organic solvent is one or more of acetone, THF, ethanol, methanol, DMF or DMSO.
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