CN113603929A - Recovery method of epoxy resin composite material, obtained glass fiber and application thereof - Google Patents
Recovery method of epoxy resin composite material, obtained glass fiber and application thereof Download PDFInfo
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- CN113603929A CN113603929A CN202111045435.4A CN202111045435A CN113603929A CN 113603929 A CN113603929 A CN 113603929A CN 202111045435 A CN202111045435 A CN 202111045435A CN 113603929 A CN113603929 A CN 113603929A
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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
- C08J11/28—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 compounds containing nitrogen, sulfur or phosphorus
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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
- C08J11/06—Recovery or working-up of waste materials of polymers without chemical reactions
- C08J11/08—Recovery or working-up of waste materials of polymers without chemical reactions using selective solvents for polymer components
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- 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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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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
The invention discloses a method for recovering an epoxy resin composite material, an obtained glass fiber and application thereof, and relates to the field of organic solid material recovery. The method specifically comprises the following steps: s1, mixing the epoxy resin composite material with a composite solvent, placing the mixture in a pressure vessel, controlling the reaction temperature to be 120-150 ℃ and the reaction time to be 3-7 h, and preparing a solid-liquid mixture; s2, filtering the solid-liquid mixture to obtain decomposed filtrate and a solid-phase product, wherein the solid-phase product is glass fiber, and the glass fiber is applied to the fields of waterproof base materials, energy-saving auxiliary reinforcing materials, reinforced cementing materials, building decoration materials and the like. According to the method, the composite solvent is used for degrading the epoxy resin composite material, the experimental process is simple, the reaction condition is mild, the performance of the obtained product is excellent, and the composite solvent is environment-friendly and has economic benefits.
Description
Technical Field
The invention relates to the field of organic solid material recovery, in particular to a method for recovering an epoxy resin composite material, an obtained glass fiber and application thereof.
Background
The epoxy resin is one of three known thermosetting resins, and a molecular chain contains active epoxy groups, so that the epoxy resin and various curing agents can easily perform a cross-linking reaction to form a cured product with a three-dimensional network structure. In recent years, the epoxy resin industry in China has entered a vigorous development period, and the application field of the epoxy resin is increasingly wide. At the same time, the production of ex-service epoxy resins is increasing. In particular, in the composite insulator which is used in the power industry in a large amount, the core rod is formed by compounding an epoxy resin material and a glass fiber material, and is extremely difficult to degrade under natural conditions. With the increase of service life, the composite insulator has already entered the retirement peak period at present; due to the lack of an efficient degradation method, a large amount of retired composite insulators are accumulated, so that a large amount of space resources are occupied, and environmental pollution and resource waste are caused. Research on recycling of epoxy resin waste is still in the research stage, and among them, mechanical method, pyrolysis method, solvent recycling method and supercritical degradation method are the recycling methods which are currently used more.
The mechanical recovery method is to directly use the composite material as a filler to be added into a building material or a recycled composite material by cutting and crushing the composite material through various mechanical means. The method has low production cost, and does not use or generate any toxic substances in the recycling process, but destroys the size of the fiber material. Pyrolysis is a method in which a highly crosslinked network of epoxy resin is destroyed by means of high-temperature heating, so that organic small molecule products are decomposed, the generated heat energy can be recycled, no chemical solvent is used in the recycling process, but high-temperature pyrolysis reduces the tensile strength of the fiber material and releases gases harmful to the environment. The solvent recovery method is a solvent method which can maximally retain the mechanical properties and length of the fiber material in the process of decomposing the epoxy resin composite material by decomposing the polymeric resin into corresponding monomers or oligomers through chemical reaction under the action of some solvents, and meanwhile, resin micromolecule products in the decomposition liquid can be recycled, but the commonly used inorganic acid-base solvents can bring certain harm to the environment. The supercritical fluid has the characteristics of good mass transfer performance, low viscosity and high diffusion coefficient, is an excellent medium for decomposing plastics, can degrade polymers in a green and high-efficiency manner, and comprises supercritical water, supercritical ethanol and supercritical CO2However, the method requires high temperature and high pressure resistant experimental equipment and relatively severe experimental conditions, and is not suitable for large-scale industrial production.
Therefore, research personnel are required to research the epoxy resin waste recovery method which is simple in process, environment-friendly and excellent in surface performance and size index of the recovered product.
Disclosure of Invention
The invention provides a recovery method of an epoxy resin composite material, an obtained glass fiber and application thereof, and aims to solve the technical problems of complex recovery process, severe experimental conditions, environmental pollution and poor surface performance of a recovered product of the epoxy resin composite material.
In order to solve the above technical problem, an embodiment of the present invention provides a method for recycling an epoxy resin composite material, including the following steps:
s1, mixing the epoxy resin composite material with a composite solvent, placing the mixture in a pressure vessel, controlling the reaction temperature to be 120-150 ℃ and the reaction time to be 3-7 h, and preparing a solid-liquid mixture;
s2, filtering the solid-liquid mixture to obtain decomposed filtrate and a solid-phase product;
the composite solvent comprises ionic liquid and polar aprotic solvent, wherein the ionic liquid is imidazole salt or pyridine salt.
By adopting the scheme, the composite solvent is utilized to decompose the epoxy resin composite material, the polar aprotic solvent has a certain dissolving effect on the thermosetting resin base material, has a higher boiling point and is not easy to decompose under the heating condition, the imidazole salt or pyridine salt has a better catalytic degradation effect on the thermosetting resin base material, the epoxy resin is favorably degraded, and the epoxy resin is enabled to generate oligomer or small molecular monomer substances which are easy to separate, in addition, the imidazole salt or pyridine salt ionic liquid is adopted to be matched with the polar aprotic solvent, so that the temperature in the reaction process can be greatly reduced, the reaction condition is mild, the realization is easier compared with pyrolysis, the volatilization of the solvent is reduced by the lower heating temperature, the pressure of the reaction system is lower, the experimental condition and the degradation process are simple, the mechanical property of a solid phase product cannot be damaged, and the surface of the solid phase product is smooth and has uniform size, the composite solvent can be recycled, is environment-friendly and improves the economic benefit; meanwhile, because the saturated vapor pressure of the imidazole salt or pyridine salt ionic liquid is extremely low and the imidazole salt or pyridine salt ionic liquid is not easy to volatilize, the imidazole salt or pyridine salt ionic liquid has better thermal stability and chemical stability, and the operation safety is improved.
Preferably, the polar aprotic solvent comprises one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, and N-methylpyrrolidone.
Preferably, the imidazole salt is one of 1-ethyl-3-methylimidazole acetate, 1-butyl-3-methylimidazole chloride, 1-butyl-3-methylimidazole acetate, 1-butyl-3-methylimidazole tetrafluoroborate, 1-butyl-3-methylimidazole hydroxide and 1-ethyl-3-methylimidazole hydroxide.
Preferably, the pyridinium salt is one of 1-butylpyridinium chloride salt, 1-butylpyridinium bromide salt and 1-hexylpyridinephosphonium bromide salt.
Preferably, in S1, the liquid-solid mass ratio of the composite solvent to the epoxy resin composite material is (15-30): 1.
preferably, the mass ratio of the ionic liquid to the polar aprotic solvent in the composite solvent is (0.11-1): 1.
by adopting the scheme, the polar aprotic solvent has a certain dissolving effect on the thermosetting resin base material, has a high boiling point, and can reduce the viscosity and the operation difficulty of the ionic liquid and improve the dissolving effect of the ionic liquid by adding the polar aprotic solvent with a proper proportion.
Preferably, in S2, the solid phase product is dried after being washed with pure water.
As a preferred scheme, the epoxy resin composite material is a scrapped composite insulator core rod from the power industry and is mainly formed by compounding epoxy resin and glass fiber.
By adopting the scheme, the epoxy resin composite material is prepared by doping and mixing cured epoxy resin and additives such as glass fiber and the like, has the characteristics of light weight and high strength, is greatly superior to traditional products in performance, application and service life attributes, occupies a large market share, is difficult to directly utilize a scrapped rod-shaped composite insulator core rod for the second time, and is difficult to crush due to high strength and high hardness, so that the decommissioned rod-shaped insulator core rod is easy to obtain and low in cost, the recycling rate of organic solid wastes can be improved, and the environment-friendly concept is met.
Preferably, in S1, the pressure vessel is a mechanical stirring reactor, a quartz lining is disposed in the mechanical stirring reactor, and stirring blades and pipelines of the mechanical stirring reactor are made of hastelloy materials.
By adopting the scheme, the stainless steel material of the mechanical stirring reaction kettle is easy to corrode under the high-temperature reaction condition, so that the material contacting with liquid, such as stirring blades and pipelines, is replaced by hastelloy, and the mechanical stirring reaction kettle is more corrosion-resistant; meanwhile, the quartz lining is arranged in the kettle body, compared with Hastelloy, the quartz lining is low in cost, corrosion resistant and fragile, and therefore only the kettle body is adopted, and the stirring rod and the temperature measuring pipeline are made of the Hastelloy.
In order to solve the above technical problems, a second embodiment of the present invention provides a glass fiber obtained by a recycling method of an epoxy resin composite material, including a solid-phase product prepared by the recycling method of the epoxy resin composite material.
In order to solve the above technical problems, a third embodiment of the present invention provides an application of a glass fiber obtained by a recycling method of an epoxy resin composite material, wherein the glass fiber is applied in one of the fields of waterproof substrates, energy-saving auxiliary reinforcing materials, reinforced cementitious materials and building decoration materials.
Compared with the prior art, the embodiment of the invention has the following beneficial effects:
1. the polar aprotic solvent in the scheme has a certain dissolving effect on the thermosetting resin base material, has a high boiling point, is not easy to decompose under a heating condition, has a good catalytic degradation effect on the thermosetting resin base material by adopting imidazolium salts or pyridinium salts, greatly reduces the decomposition temperature, has mild reaction conditions, does not damage the mechanical property and the surface property of a solid-phase product, is simple in experimental conditions and degradation procedures, is environment-friendly, and improves the economic benefit.
2. By adding the polar aprotic solvent in a proper proportion, the viscosity and the operation difficulty of the ionic liquid can be reduced, and the dissolving effect of the ionic liquid is improved.
Drawings
FIG. 1: the picture of the glass fiber solid phase product and the picture of a scanning electron microscope (note: A-picture; B-picture of a scanning electron microscope) prepared by the method for recovering the epoxy resin composite material in the embodiment 1 of the invention;
FIG. 2: the picture of the glass fiber solid phase product and the picture of a scanning electron microscope (note: A-picture; B-picture of a scanning electron microscope) prepared by the method for recovering the epoxy resin composite material in the embodiment 6 of the invention;
FIG. 3: the picture of the glass fiber solid phase product and the picture of a scanning electron microscope (note: A-picture; B-picture of a scanning electron microscope) prepared by the method for recovering the epoxy resin composite material in the embodiment 7 of the invention;
FIG. 4: the scalar quantity of the diameter of the glass fiber solid-phase product prepared by the method for recovering the epoxy resin composite material in the embodiment 1 of the invention is shown.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious 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 one
A method for recycling an epoxy resin composite material comprises the following steps:
s1, cutting the epoxy resin composite material into a sheet sample with a proper size according to the actual demand of the product, wherein the epoxy resin composite material is a composite insulator core rod retired in the power industry, is specifically formed by compounding epoxy resin and glass fiber, and is then placed in a sealing bag for later use;
s2, mixing the ionic liquid and the organic solvent to prepare a composite solvent, wherein the solid-liquid ratio of the composite solvent to the epoxy resin composite material is 15: 1, adding the mixture into a mechanical stirring reaction kettle, wherein the volume of the composite solvent is 1/3-3/4 of the volume of the mechanical stirring reaction kettle, the reaction temperature is controlled to be 150 ℃, the reaction time is controlled to be 3 hours, and the rotating speed of stirring blades of the mechanical stirring reaction kettle is 150rpm to prepare a solid-liquid mixture;
wherein the mass ratio of the ionic liquid to the organic solvent is 1: 1, the ionic liquid is an imidazole salt, in the present embodiment, the imidazole salt is specifically 1-butyl-3-methylimidazole acetate ([ Bmim ] Ac), the organic solvent is a polar aprotic solvent, and in the present embodiment, the polar aprotic solvent is specifically Dimethylsulfoxide (DMSO);
the volume of the mechanical stirring reaction kettle is 100mL, the highest service temperature is 300 ℃, the highest service pressure is 10MPa, a quartz lining is arranged in the mechanical stirring reaction kettle, the stirring blades and the pipelines of the mechanical stirring reaction kettle are made of Hastelloy materials, and the stirring blades and the pipelines are matched for use, so that the corrosion-resistant effect can be achieved, and the strength of the stirring blades is improved.
S3, filtering and separating the solid-liquid mixture to obtain decomposed filtrate and a solid-phase product, wherein the solid-phase product is glass fiber as shown in figure 1, and the fixed product is washed by pure water and dried in an oven at 105 ℃ for 3h, so that the solid-liquid mixture can be applied to the fields of waterproof base materials, energy-saving auxiliary reinforcing materials, reinforced cementing materials, building decoration materials and the like.
Example two
A method for recycling an epoxy resin composite material comprises the following steps:
s1, cutting the epoxy resin composite material into a sheet sample with a proper size according to the actual demand of the product, wherein the epoxy resin composite material is a composite insulator core rod retired in the power industry, is specifically formed by compounding epoxy resin and glass fiber, and is then placed in a sealing bag for later use;
s2, mixing the ionic liquid and the organic solvent to prepare a composite solvent, wherein the solid-liquid ratio of the composite solvent to the epoxy resin composite material is 20: 1, adding the mixture into a mechanical stirring reaction kettle, wherein the volume of the composite solvent is 1/3-3/4 of the volume of the mechanical stirring reaction kettle, the reaction temperature is controlled to be 140 ℃, the reaction time is controlled to be 5 hours, and the rotating speed of stirring blades of the mechanical stirring reaction kettle is 150rpm to prepare a solid-liquid mixture;
wherein the mass ratio of the ionic liquid to the organic solvent is 0.43: the ionic liquid is an imidazolium salt, in this embodiment, the imidazolium salt is specifically 1-butyl-3-methylimidazolium chloride ([ Bmim ] Cl), the organic solvent is a polar aprotic solvent, and in this embodiment, the polar aprotic solvent is specifically N, N-Dimethylformamide (DMF).
The volume of the mechanical stirring reaction kettle is 100mL, the highest service temperature is 300 ℃, the highest service pressure is 10MPa, a quartz lining is arranged in the mechanical stirring reaction kettle, the stirring blades and the pipelines of the mechanical stirring reaction kettle are made of Hastelloy materials, and the stirring blades and the pipelines are matched for use, so that the corrosion-resistant effect can be achieved, and the strength of the stirring blades is improved.
S3, filtering and separating the solid-liquid mixture to obtain decomposed filtrate and a solid-phase product, wherein the solid-phase product is glass fiber, washing the fixed product by pure water, and drying the washed fixed product in an oven at 105 ℃ for 12 hours, so that the product can be applied to the fields of waterproof base materials, energy-saving auxiliary reinforcing materials, reinforced cementing materials, building decoration materials and the like.
EXAMPLE III
A method for recycling an epoxy resin composite material comprises the following steps:
s1, cutting the epoxy resin composite material into a sheet sample with a proper size according to the actual demand of the product, wherein the epoxy resin composite material is a composite insulator core rod retired in the power industry, is mainly formed by compounding epoxy resin and glass fiber, and is then placed in a sealing bag for later use;
s2, mixing the ionic liquid and the organic solvent to prepare a composite solvent, wherein the solid-liquid ratio of the composite solvent to the epoxy resin composite material is 20: 1, adding the mixture into a mechanical stirring reaction kettle, wherein the volume of the composite solvent is 1/3-3/4 of the volume of the mechanical stirring reaction kettle, the reaction temperature is controlled to be 130 ℃, the reaction time is controlled to be 5 hours, and the rotating speed of stirring blades of the mechanical stirring reaction kettle is 500rpm to prepare a solid-liquid mixture;
wherein the mass ratio of the ionic liquid to the organic solvent is 0.11: the ionic liquid is imidazole salt, and in the embodiment, the imidazole salt is specifically 1-butyl-3-methylimidazolium tetrafluoroborate ([ Bmim ]]BF4) The organic solvent being polar aproticThe solvent, in this example embodiment, the polar aprotic solvent is specifically N, N Dimethylacetamide (DMAC).
The volume of the mechanical stirring reaction kettle is 100mL, the highest service temperature is 300 ℃, the highest service pressure is 10MPa, a quartz lining is arranged in the mechanical stirring reaction kettle, the stirring blades and the pipelines of the mechanical stirring reaction kettle are made of Hastelloy materials, and the stirring blades and the pipelines are matched for use, so that the corrosion-resistant effect can be achieved, and the strength of the stirring blades is improved.
S3, filtering and separating the solid-liquid mixture to obtain decomposed filtrate and a solid-phase product, wherein the solid-phase product is glass fiber, washing the fixed product by pure water, and drying the washed fixed product in a drying oven at 105 ℃ for 8 hours, so that the solid-liquid composite material can be applied to the fields of waterproof base materials, energy-saving auxiliary reinforcing materials, reinforced cementing materials, building decoration materials and the like.
Example four
A method for recycling an epoxy resin composite material comprises the following steps:
s1, cutting the epoxy resin composite material into a sheet sample with a proper size according to the actual demand of the product, wherein the epoxy resin composite material is a composite insulator core rod retired in the power industry, is mainly formed by compounding epoxy resin and glass fiber, and is then placed in a sealing bag for later use;
s2, mixing the ionic liquid and the organic solvent to prepare a composite solvent, wherein the solid-liquid ratio of the composite solvent to the epoxy resin composite material is 20: 1, adding the mixture into a mechanical stirring reaction kettle, wherein the volume of the composite solvent is 1/3-3/4 of the volume of the mechanical stirring reaction kettle, the reaction temperature is controlled to be 120 ℃, the reaction time is controlled to be 5 hours, and the rotating speed of stirring blades of the mechanical stirring reaction kettle is 150rpm to prepare a solid-liquid mixture;
wherein the mass ratio of the ionic liquid to the organic solvent is 0.11: the ionic liquid is an imidazole salt, in this embodiment, the imidazole salt is specifically 1-butyl-3-methylimidazole bromide ([ Bmim ] Br), the organic solvent is a polar aprotic solvent, and in this embodiment, the polar aprotic solvent is specifically Dimethylsulfoxide (DMSO).
The volume of the mechanical stirring reaction kettle is 100mL, the highest service temperature is 300 ℃, the highest service pressure is 10MPa, a quartz lining is arranged in the mechanical stirring reaction kettle, the stirring blades and the pipelines of the mechanical stirring reaction kettle are made of Hastelloy materials, and the stirring blades and the pipelines are matched for use, so that the corrosion-resistant effect can be achieved, and the strength of the stirring blades is improved.
S3, filtering and separating the solid-liquid mixture to obtain decomposed filtrate and a solid-phase product, wherein the solid-phase product is glass fiber, washing the fixed product by pure water, and drying the washed fixed product in an oven at 105 ℃ for 6 hours, so that the product can be applied to the fields of waterproof base materials, energy-saving auxiliary reinforcing materials, reinforced cementing materials, building decoration materials and the like.
EXAMPLE five
A method for recycling an epoxy resin composite material comprises the following steps:
s1, cutting the epoxy resin composite material into a sheet sample with a proper size according to the actual demand of the product, wherein the epoxy resin composite material is a composite insulator core rod retired in the power industry, is specifically formed by compounding epoxy resin and glass fiber, and is then placed in a sealing bag for later use;
s2, mixing the ionic liquid and the organic solvent to prepare a composite solvent, wherein the solid-liquid ratio of the composite solvent to the epoxy resin composite material is 30: 1, adding the mixture into a mechanical stirring reaction kettle, wherein the volume of the composite solvent is 1/3-3/4 of the volume of the mechanical stirring reaction kettle, the reaction temperature is controlled to be 120 ℃, the reaction time is controlled to be 7 hours, and the rotating speed of stirring blades of the mechanical stirring reaction kettle is 500rpm to prepare a solid-liquid mixture;
wherein the mass ratio of the ionic liquid to the organic solvent is 0.11: the ionic liquid is an imidazole salt, in this embodiment, the imidazole salt is specifically 1-ethyl-3-methylimidazole acetate ([ Emim ] Ac), the organic solvent is a polar aprotic solvent, and in this embodiment, the polar aprotic solvent is specifically Dimethylsulfoxide (DMSO).
The volume of the mechanical stirring reaction kettle is 100mL, the highest service temperature is 300 ℃, the highest service pressure is 10MPa, a quartz lining is arranged in the mechanical stirring reaction kettle, the stirring blades and the pipelines of the mechanical stirring reaction kettle are made of Hastelloy materials, and the stirring blades and the pipelines are matched for use, so that the corrosion-resistant effect can be achieved, and the strength of the stirring blades is improved.
S3, filtering and separating the solid-liquid mixture to obtain decomposed filtrate and a solid-phase product, wherein the solid-phase product is glass fiber, washing the fixed product by pure water, and drying the washed fixed product in an oven at 105 ℃ for 10 hours, so that the solid-liquid composite material can be applied to the fields of waterproof base materials, energy-saving auxiliary reinforcing materials, reinforced cementing materials, building decoration materials and the like.
EXAMPLE six
A method for recycling an epoxy resin composite material comprises the following steps:
s1, cutting the epoxy resin composite material into a sheet sample with a proper size according to the actual demand of the product, wherein the epoxy resin composite material is a composite insulator core rod retired in the power industry, is specifically formed by compounding epoxy resin and glass fiber, and is then placed in a sealing bag for later use;
s2, mixing the ionic liquid and the organic solvent to prepare a composite solvent, wherein the solid-liquid ratio of the composite solvent to the epoxy resin composite material is 20: 1, adding the mixture into a mechanical stirring reaction kettle, wherein the volume of the composite solvent is 1/3-3/4 of the volume of the mechanical stirring reaction kettle, the reaction temperature is controlled to be 130 ℃, the reaction time is controlled to be 5 hours, and the rotating speed of stirring blades of the mechanical stirring reaction kettle is 150rpm to prepare a solid-liquid mixture;
wherein the mass ratio of the ionic liquid to the organic solvent is 0.11: the ionic liquid is an imidazolium salt, in this embodiment, the imidazolium salt is specifically 1-ethyl-3-methylimidazolium hydroxide ([ Emim ] OH), the organic solvent is a polar aprotic solvent, and in this embodiment, the polar aprotic solvent is specifically N-methylpyrrolidone (NMP).
The volume of the mechanical stirring reaction kettle is 100mL, the highest service temperature is 300 ℃, the highest service pressure is 10MPa, a quartz lining is arranged in the mechanical stirring reaction kettle, the stirring blades and the pipelines of the mechanical stirring reaction kettle are made of Hastelloy materials, and the stirring blades and the pipelines are matched for use, so that the corrosion-resistant effect can be achieved, and the strength of the stirring blades is improved.
S3, filtering and separating the solid-liquid mixture to obtain decomposed filtrate and a solid-phase product, wherein the solid-phase product is glass fiber as shown in figure 2, washing the fixed product by pure water, and drying in an oven at 105 ℃ for 7h, so that the solid-phase product can be applied to the fields of waterproof base materials, energy-saving auxiliary reinforcing materials, reinforced cementing materials, building decoration materials and the like.
EXAMPLE seven
A method for recycling an epoxy resin composite material comprises the following steps:
s1, cutting the epoxy resin composite material into a sheet sample with a proper size according to the actual demand of the product, wherein the epoxy resin composite material is a composite insulator core rod retired in the power industry, is specifically formed by compounding epoxy resin and glass fiber, and is then placed in a sealing bag for later use;
s2, mixing the ionic liquid and the organic solvent to prepare a composite solvent, wherein the solid-liquid ratio of the composite solvent to the epoxy resin composite material is 20: 1, adding the mixture into a mechanical stirring reaction kettle, wherein the volume of the composite solvent is 1/3-3/4 of the volume of the mechanical stirring reaction kettle, the reaction temperature is controlled to be 130 ℃, the reaction time is controlled to be 5 hours, and the rotating speed of stirring blades of the mechanical stirring reaction kettle is 150rpm to prepare a solid-liquid mixture;
wherein the mass ratio of the ionic liquid to the organic solvent is 0.25: the ionic liquid is an imidazole salt, in this embodiment, the imidazole salt is specifically 1-butyl-3-methylimidazole hydroxide ([ Bmim ] OH), the organic solvent is a polar aprotic solvent, and in this embodiment, the polar aprotic solvent is specifically Dimethylsulfoxide (DMSO).
The volume of the mechanical stirring reaction kettle is 100mL, the highest service temperature is 300 ℃, the highest service pressure is 10MPa, a quartz lining is arranged in the mechanical stirring reaction kettle, the stirring blades and the pipelines of the mechanical stirring reaction kettle are made of Hastelloy materials, and the stirring blades and the pipelines are matched for use, so that the corrosion-resistant effect can be achieved, and the strength of the stirring blades is improved.
S3, filtering and separating the solid-liquid mixture to obtain decomposed filtrate and a solid-phase product, wherein the solid-phase product is glass fiber, and the solid-phase product is washed by pure water and dried in an oven at 105 ℃ for 10 hours, so that the solid-liquid separation method can be applied to the fields of waterproof base materials, energy-saving auxiliary reinforcing materials, reinforced cementing materials, building decoration materials and the like.
Example eight
A method for recycling an epoxy resin composite material comprises the following steps:
s1, cutting the epoxy resin composite material into a sheet sample with a proper size according to the actual demand of the product, wherein the epoxy resin composite material is a composite insulator core rod retired in the power industry, is specifically formed by compounding epoxy resin and glass fiber, and is then placed in a sealing bag for later use;
s2, mixing the ionic liquid and the organic solvent to prepare a composite solvent, wherein the solid-liquid ratio of the composite solvent to the epoxy resin composite material is 30: 1, adding the mixture into a mechanical stirring reaction kettle, wherein the volume of the composite solvent is 1/3-3/4 of the volume of the mechanical stirring reaction kettle, the reaction temperature is controlled to be 140 ℃, the reaction time is controlled to be 3 hours, and the rotating speed of stirring blades of the mechanical stirring reaction kettle is 500rpm to prepare a solid-liquid mixture;
wherein the mass ratio of the ionic liquid to the organic solvent is 0.35: 1, the ionic liquid is a pyridinium salt, in the embodiment, the pyridinium salt is specifically 1-butylpyridinium chloride, the organic solvent is a polar aprotic solvent, and in the embodiment, the polar aprotic solvent is specifically Dimethylsulfoxide (DMSO);
the volume of the mechanical stirring reaction kettle is 100mL, the highest service temperature is 300 ℃, the highest service pressure is 10MPa, a quartz lining is arranged in the mechanical stirring reaction kettle, the stirring blades and the pipelines of the mechanical stirring reaction kettle are made of Hastelloy materials, and the stirring blades and the pipelines are matched for use, so that the corrosion-resistant effect can be achieved, and the strength of the stirring blades is improved.
S3, filtering and separating the solid-liquid mixture to obtain decomposed filtrate and a solid-phase product, wherein the solid-phase product is glass fiber, washing the fixed product by pure water, and drying the washed fixed product in a drying oven at 105 ℃ for 8 hours, so that the solid-liquid composite material can be applied to the fields of waterproof base materials, energy-saving auxiliary reinforcing materials, reinforced cementing materials, building decoration materials and the like.
Example nine
A method for recycling an epoxy resin composite material comprises the following steps:
s1, cutting the epoxy resin composite material into a sheet sample with a proper size according to the actual demand of the product, wherein the epoxy resin composite material is a composite insulator core rod retired in the power industry, is specifically formed by compounding epoxy resin and glass fiber, and is then placed in a sealing bag for later use;
s2, mixing the ionic liquid and the organic solvent to prepare a composite solvent, wherein the solid-liquid ratio of the composite solvent to the epoxy resin composite material is 20: 1, adding the mixture into a mechanical stirring reaction kettle, wherein the volume of the composite solvent is 1/3-3/4 of the volume of the mechanical stirring reaction kettle, the reaction temperature is controlled to be 120 ℃, the reaction time is controlled to be 3 hours, and the rotating speed of stirring blades of the mechanical stirring reaction kettle is 500rpm to prepare a solid-liquid mixture;
wherein the mass ratio of the ionic liquid to the organic solvent is 0.65: 1, the ionic liquid is a pyridinium salt, in the embodiment, the pyridinium salt is specifically 1-butylpyridinium bromide, the organic solvent is a polar aprotic solvent, and in the embodiment, the polar aprotic solvent is specifically Dimethylsulfoxide (DMSO);
the volume of the mechanical stirring reaction kettle is 100mL, the highest service temperature is 300 ℃, the highest service pressure is 10MPa, a quartz lining is arranged in the mechanical stirring reaction kettle, the stirring blades and the pipelines of the mechanical stirring reaction kettle are made of Hastelloy materials, and the stirring blades and the pipelines are matched for use, so that the corrosion-resistant effect can be achieved, and the strength of the stirring blades is improved.
S3, filtering and separating the solid-liquid mixture to obtain decomposed filtrate and a solid-phase product, wherein the solid-phase product is glass fiber, washing the fixed product by pure water, and drying in an oven at 105 ℃ for 12h, so that the glass fiber-reinforced composite material can be applied to the fields of waterproof base materials, energy-saving auxiliary reinforcing materials, reinforced cementing materials, building decoration materials and the like.
Example ten
A method for recycling an epoxy resin composite material comprises the following steps:
s1, cutting the epoxy resin composite material into a sheet sample with a proper size according to the actual demand of the product, wherein the epoxy resin composite material is a composite insulator core rod retired in the power industry, is specifically formed by compounding epoxy resin and glass fiber, and is then placed in a sealing bag for later use;
s2, mixing the ionic liquid and the organic solvent to prepare a composite solvent, wherein the solid-liquid ratio of the composite solvent to the epoxy resin composite material is 15: 1, adding the mixture into a mechanical stirring reaction kettle, wherein the volume of the composite solvent is 1/3-3/4 of the volume of the mechanical stirring reaction kettle, the reaction temperature is controlled to be 130 ℃, the reaction time is controlled to be 3 hours, and the rotating speed of stirring blades of the mechanical stirring reaction kettle is 150rpm to prepare a solid-liquid mixture;
wherein the mass ratio of the ionic liquid to the organic solvent is 1: 1, the ionic liquid is a pyridinium salt, in the embodiment, the pyridinium salt is specifically 1-hexylpyridinium bromide, the organic solvent is a polar aprotic solvent, and in the embodiment, the polar aprotic solvent is specifically N-methylpyrrolidone (NMP);
the volume of the mechanical stirring reaction kettle is 100mL, the highest service temperature is 300 ℃, the highest service pressure is 10MPa, a quartz lining is arranged in the mechanical stirring reaction kettle, the stirring blades and the pipelines of the mechanical stirring reaction kettle are made of Hastelloy materials, and the stirring blades and the pipelines are matched for use, so that the corrosion-resistant effect can be achieved, and the strength of the stirring blades is improved.
S3, filtering and separating the solid-liquid mixture to obtain decomposed filtrate and a solid-phase product, wherein the solid-phase product is glass fiber, washing the fixed product by pure water, and drying in an oven at 105 ℃ for 3h, so that the glass fiber-reinforced composite material can be applied to the fields of waterproof base materials, energy-saving auxiliary reinforcing materials, reinforced cementing materials, building decoration materials and the like.
Comparative example 1
A method for recycling an epoxy resin composite material, wherein the steps and reagents and parameters used in the steps are the same as those in example 1, except that: in S2, ethylene glycol phenyl ether was used instead of the ionic liquid and the polar aprotic solvent.
Comparative example 2
A method for recycling an epoxy resin composite material, wherein the steps and reagents and parameters used in the steps are the same as those in example 1, except that: in S2, p-toluic acid is used instead of the polar aprotic solvent.
Performance test
1. The glass fiber solid phase products obtained in examples 1, 6 and 7 were photographed and subjected to a scanning electron microscope, and the detection results are shown in fig. 1-4, which indicates that the glass fiber solid phase products obtained by the present application have the surface effects of fine and smooth surface, integrity, uniform diameter, uniform texture and white and uniform color;
2. decomposition rate of epoxy resin: the initial weight m of the epoxy resin composites used in preparation examples 1 to 10 and comparative examples 1 to 2 was weighed and counted1The solid-phase products m obtained in examples 1 to 10 and comparative examples 1 to 2 were weighed and counted2And the decomposition rate of the epoxy resin is calculated according to the following formula, the detection results of examples 1-10 are shown in table 1, and the detection results of comparative examples 1-2 are shown in table 2, it can be seen that the decomposition rate of the epoxy resin in the scheme of the application is basically more than 90%, the decomposition efficiency is high, and the formula of the decomposition rate of the epoxy resin is specifically as follows:
η＝m1-m2/rm1×100％
wherein: eta-epoxy resin degradation rate,%;
m1-initial weight of epoxy composite sample, g;
m2-mass of solid phase product after reaction, g;
the content of organic components in the r-epoxy resin composite material accounts for percent.
TABLE 1-results of measurement of reagents, parameters and epoxy resin decomposition rates used in the respective steps of examples 1 to 10
Note: [ Bmim ]]Ac (1-butyl-3-methylimidazolium acetate); [ Emim]Ac (1-ethyl-3-methylimidazolium acetate); [ Bmim ]]OH (1-butyl-3-methylimidazolium hydroxide salt); [ Bmim ]]Cl1- (butyl-3-methylimidazolium chloride); [ Bmim ]]BF4(1-butyl-3-methylimidazolium tetrafluoroborate); [ Bmim ]]Br (1-butyl-3-methylimidazole bromide salt); [ Emim]OH (1-ethyl-3-methylimidazolium hydroxide salt); DMSO (dimethyl sulfoxide); NMP (N-methylpyrrolidone).
TABLE 2-results of measurement of reagents, parameters and epoxy resin decomposition rates used in the respective steps of comparative examples 1 to 2
Combining the detection results of the example 1 and the comparative example 1-2 in the tables 1-2, it is known that the epoxy resin composite material is decomposed by using the composite solvent, the catalytic degradation effect of the thermosetting resin base material by using the imidazolium salts or pyridinium salts is better, the degradation efficiency of the epoxy resin is high, and the epoxy resin is made into oligomer or small molecular monomer substances which are easy to separate, and in addition, the temperature in the reaction process can be greatly reduced by using the imidazolium salts or pyridinium salts ionic liquid in combination with the polar aprotic solvent, so that the reaction condition is mild, the implementation is easier compared with pyrolysis, the experimental condition and the degradation process are simple, the mechanical property of the solid phase product cannot be damaged, and as shown in fig. 1-4, the finally obtained solid phase product has a smooth surface, uniform size and excellent performance.
The above-mentioned embodiments are provided to further explain the objects, technical solutions and advantages of the present invention in detail, and it should be understood that the above-mentioned embodiments are only examples of the present invention and are not intended to limit the scope of the present invention. It should be understood that any modifications, equivalents, improvements and the like, which come within the spirit and principle of the invention, may occur to those skilled in the art and are intended to be included within the scope of the invention.
Claims (10)
1. The recycling method of the epoxy resin composite material is characterized by comprising the following steps:
s1, mixing the epoxy resin composite material with a composite solvent, placing the mixture in a pressure vessel, controlling the reaction temperature to be 120-150 ℃ and the reaction time to be 3-7 h, and preparing a solid-liquid mixture;
s2, filtering the solid-liquid mixture to obtain decomposed filtrate and a solid-phase product;
the composite solvent comprises ionic liquid and polar aprotic solvent, wherein the ionic liquid is imidazole salt or pyridine salt.
2. The method of claim 1, wherein the polar aprotic solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, and N-methylpyrrolidone.
3. The method for recycling an epoxy resin composite material as claimed in claim 1 or 2, wherein the imidazolium salt is one of 1-ethyl-3-methylimidazole acetate, 1-butyl-3-methylimidazole chloride salt, 1-butyl-3-methylimidazole acetate, 1-butyl-3-methylimidazole tetrafluoroborate, 1-butyl-3-methylimidazole hydroxide salt and 1-ethyl-3-methylimidazole hydroxide salt.
4. The method for recycling the epoxy resin composite material as claimed in claim 1 or 2, wherein the pyridinium is one of 1-butylpyridinium chloride, 1-butylpyridinium bromide and 1-hexylpyridinephosphonium bromide.
5. The method for recycling an epoxy resin composite material according to claim 1, wherein in the step S1, the liquid-solid mass ratio of the composite solvent to the epoxy resin composite material is (15-30): 1.
6. the method for recycling the epoxy resin composite material as claimed in claim 1, wherein the mass ratio of the ionic liquid to the polar aprotic solvent in the composite solvent is (0.11-1): 1.
7. the recycling method of the epoxy resin composite material as claimed in claim 1, wherein the epoxy resin composite material is a composite insulator core rod which is scrapped from the power industry and mainly formed by compounding epoxy resin and glass fiber.
8. The recycling method of epoxy resin composite material as claimed in claim 1, wherein in the step S1, the pressure vessel is a mechanical stirring reaction kettle, a quartz lining is arranged in the mechanical stirring reaction kettle, and stirring blades and pipelines of the mechanical stirring reaction kettle are made of hastelloy material.
9. A glass fiber obtained by a recycling method of an epoxy resin composite material, wherein the glass fiber is a solid-phase product prepared by the recycling method of the epoxy resin composite material according to any one of claims 1 to 8.
10. The application of the glass fiber obtained by the epoxy resin composite material recycling method is characterized in that the glass fiber obtained by the epoxy resin composite material recycling method of claim 9 is applied to one of the fields of waterproof base materials, energy-saving auxiliary reinforcing materials, reinforced cementing materials and building decoration materials.
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