CN112829123B - Method for preparing high-activity filler by using waste epoxy resin based on solid-phase shearing and milling technology - Google Patents
Method for preparing high-activity filler by using waste epoxy resin based on solid-phase shearing and milling technology Download PDFInfo
- Publication number
- CN112829123B CN112829123B CN202011455078.4A CN202011455078A CN112829123B CN 112829123 B CN112829123 B CN 112829123B CN 202011455078 A CN202011455078 A CN 202011455078A CN 112829123 B CN112829123 B CN 112829123B
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- waste
- grinding
- waste epoxy
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
- B29B17/04—Disintegrating plastics, e.g. by milling
- B29B17/0404—Disintegrating plastics, e.g. by milling to powder
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
- B29B17/04—Disintegrating plastics, e.g. by milling
- B29B2017/0424—Specific disintegrating techniques; devices therefor
- B29B2017/0484—Grinding tools, roller mills or disc mills
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2063/00—Use of EP, i.e. epoxy resins or derivatives thereof, as moulding material
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/52—Mechanical processing of waste for the recovery of materials, e.g. crushing, shredding, separation or disassembly
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention provides a method for preparing high-activity filler by utilizing waste epoxy resin based on a solid-phase shearing and grinding technology, which comprises the steps of pretreating and grinding a waste epoxy resin material or a product, adding the pretreated and ground waste epoxy resin material or product into a grinding disc type solid-phase mechanochemical reactor for grinding and grinding, and collecting waste epoxy resin superfine powder after grinding is finished. The method has the advantages that the technological parameters of the millstone type solid-phase mechanochemical reactor are strictly limited, the cross-linking bond in the epoxy resin is destroyed by the mechanochemical action, the cross-linking density of the waste epoxy resin can be effectively reduced, the waste epoxy resin is endowed with the characteristic of re-crosslinking, the waste epoxy resin is used as a high-activity filler, and the mechanical property of a regenerated product can be greatly improved by re-crosslinking.
Description
Technical Field
The invention belongs to the technical field of epoxy resin recycling, and particularly relates to a method for preparing a high-activity filler from waste epoxy resin based on a solid-phase shearing and grinding technology, in particular to a method for treating the waste epoxy resin by using a mechanochemical reactor disclosed in China granted invention patent ZL95111258.9 as the high-activity filler.
Background
The epoxy resin has excellent mechanical and electrical properties, flexible use process, outstanding adhesion, weather resistance, dimensional stability and corrosion resistance, is widely applied to various fields as coating, adhesive, plastic packaging material, composite material and the like, becomes one of thermosetting resins with the largest use amount, has the epoxy resin yield of 230 ten thousand tons in 2017 in China, and is increased at a high speed every year (Zhang and modesty, Wang and Cuo, Bi Zhi Gong. elastomer, 2019,29(1): 76-80). A large amount of waste materials and leftover materials are generated in the processing and production processes of epoxy resin related products such as wind power blades, electronic products and the like, and the waste amount of the products is increased rapidly in addition to the scrapping of the products (Hall WJ, Williams PT. resources, maintenance and Recycling,2007,51(3):691 + 709).
Because epoxy resin has a three-dimensional cross-linked network structure, is insoluble and infusible, is extremely difficult to recycle, is mainly buried and incinerated at present, seriously pollutes the environment and greatly wastes resources (Jeffrey Morris. journal of Hazardous Materials,1996,47 (1)).
The recovery methods reported so far include chemical recovery methods and physical mechanical recovery methods, in which chemical recovery uses a large amount of solvent and faces problems of complicated process, high recovery cost, secondary pollution of solvent, and the like (Wenzhe Song, Ahmed large, Diyang Li, Koon-Yang lee. journal of Environmental Management,2020,269). Physical mechanical recycling has the advantages of simple operation process, low cost, no generation of toxic and harmful substances in the recycling process and the like, and has become a research hotspot (S.J. Pickering. composites Part A,2005,37 (8)). However, the traditional physical mechanical recovery method is difficult to realize the decrosslinking of the thermosetting resin, the obtained powder has low surface activity, the mechanical property of the regenerated product is poor, and the practical application is difficult.
In the past literature, a solid phase grinding apparatus "mechanochemical reactor" (ZL95111258.9) owned by the university of sichuan, which has been used as a technique for recycling waste crosslinked polyethylene, has been used, in which the crosslinking bonds of the waste crosslinked polyethylene are broken by the strong shear stress of the solid phase mechanochemical reactor, and the waste crosslinked polyethylene after grinding is imparted with thermoplastic processability again. ("a waste crosslinked polyethylene recovery material and recovery method", CN201410526660.3)
However, since the waste epoxy resin is a thermosetting resin, most of the currently reported methods for decrosslinking are a chemical solvent method and a high-temperature pyrolysis method, and a document for realizing decrosslinking by a physical method is rarely reported. The inventor of the present invention has found that when grinding treatment of waste epoxy resin is attempted by using a solid-phase mechanochemical reactor, when grinding treatment is performed according to the process parameters of decrosslinking other polymers by using the solid-phase mechanochemical reactor, the particle size of the obtained recovered powder is large and the crosslink density is high because the degree of crosslinking of thermosetting resin is high and the crosslink bonds are very firm, and thus it is difficult to obtain the decrosslinked waste epoxy resin ultrafine powder. If a high-value and high-efficiency recycling technology for the waste epoxy resin is provided, the recycling of the waste epoxy resin is greatly promoted.
Disclosure of Invention
The invention aims to solve the problems in the background art and provide a method for preparing a high-activity filler by using waste epoxy resin based on a solid-phase shearing and grinding technology, which can effectively reduce the crosslinking density of the waste epoxy resin by strictly limiting the technological parameters of a grinding disc type solid-phase mechanochemical reactor and destroying the crosslinking bonds in the epoxy resin by utilizing mechanochemical action, thereby endowing the waste epoxy resin with the characteristic of re-crosslinking, and the mechanical property of a regenerated product can be greatly improved by using the waste epoxy resin as the high-activity filler through the re-crosslinking.
In order to achieve the purpose, the invention adopts the technical scheme formed by the following technical measures.
A method for preparing a high-activity filler by using waste epoxy resin based on a solid-phase shearing and grinding technology comprises the following steps:
(1) selecting waste epoxy resin materials or products with the epoxy resin content of not less than 90%, carrying out pretreatment including cleaning, and then treating and crushing the waste epoxy resin materials or products into waste epoxy resin powder with the average particle size of not more than 8 mm;
(2) adding the waste epoxy resin powder into a millstone type solid-phase mechanochemical reactor for grinding and crushing, and collecting the waste epoxy resin superfine powder after grinding is finished; wherein, the technological parameters of the millstone type solid-phase mechanochemical reactor are as follows: the grinding pressure is 5-8 MPa, the temperature of the disc surface of the grinding disc is controlled to be-16 to-14 ℃ by introducing circulating cooling liquid, the grinding disc is circularly ground for 10-20 times, and the rotating speed of the grinding disc is 45-50 revolutions per minute.
Epoxy resin is one of thermosetting resins with the largest consumption, and an industrialized crosslinking-releasing technology is rarely reported, molecular chains of the epoxy resin form a three-dimensional network crosslinking structure after heating and curing, and the molecular chains of the epoxy resin do not have enough energy to destroy chemical bonds at low temperature, and generally realize crosslinking-releasing by swelling with a chemical solvent and then carrying out treatment with high temperature or ultrasonic waves and the like to destroy the molecular chains.
The inventor of the invention accidentally discovers that the crosslinking density of the waste epoxy resin superfine powder after solid phase grinding is obviously reduced by 18-21% in a low-temperature environment, particularly under the condition that the temperature of the disc surface of a grinding disc is-16 to-14 ℃, because the molecular motion and chain segment motion are reduced at low temperature, the free volume is reduced, the chain flexibility of a molecular chain is reduced, and the disentanglement effect of the molecular chain is better when the grinding disc is subjected to strong shearing stress.
According to the technological parameters of the solid-phase mechanochemical reactor for carrying out decrosslinking on other polymers, particularly when the temperature of the disc surface of a grinding disc is normal temperature, the particle size of the obtained recovered powder is large and the crosslinking density is high due to the high crosslinking degree and the firm crosslinking bond of the thermosetting resin, so that the decrosslinked waste epoxy resin superfine powder is difficult to obtain. When the temperature of the disc surface of the grinding disc is controlled to be-14-0 ℃, and other process conditions are the same, the reduction range of the cross-linking density of the waste epoxy resin superfine powder after grinding and crushing is only 5-10%; and if the temperature of the disc surface of the grinding disc is further controlled to be lower than-16 ℃, the required recovery cost is higher, the requirement on cooling liquid is higher, and the principles of low recovery cost, green and no pollution in the invention are not met. Therefore, the temperature of the disc surface of the grinding disc is limited to be controlled to be-16 to-14 ℃ due to the attitude of practical experience and the control of industrial cost.
Wherein, the waste epoxy resin material or product with the epoxy resin content of not less than 90% in the step (1) is specifically the material or product with the main component of bisphenol A type epoxy resin, and generally speaking, when the epoxy resin content of not less than 90%, the waste epoxy resin material or product can be selected as the raw material of the invention.
Generally speaking, the waste epoxy resin material or product includes waste wind power blade leftover and defective products, waste materials generated in the preparation of glass fiber reinforced plastics, waste materials generated in the manufacturing of electronic components and the like, and industrial waste with large waste amount, and a person skilled in the art can inquire the specification of the waste epoxy resin material or product to determine whether the waste epoxy resin material or product meets the requirement of selecting the waste epoxy resin material or product as the raw material of the invention.
Wherein, the step (1) includes a cleaning pretreatment, which is mainly to remove impurities on the surface of the waste epoxy resin material or product, and if necessary, to remove non-epoxy resin parts, and those skilled in the art can perform specific treatment according to the prior art according to the actual condition of the waste epoxy resin material or product which needs to be recycled.
Generally, the waste epoxy resin powder pulverized to have a mean particle size of not more than 8mm by the treatment described in step (1) may be treated by existing conventional pulverizing equipment such as a jaw crusher, a planetary ball mill, a refrigerated ball mill, etc.
Wherein, the millstone type solid-phase mechanochemical reactor in the step (2) is the mechanochemical reactor disclosed in a patent ZL95111258.9 previously issued by the applicant of the present invention.
Generally, the above-mentioned cyclic grinding process is carried out by grinding the mixed material in a millstone type mechanochemical reactor, collecting the discharge end product and placing the product in the millstone type mechanochemical reactor again for grinding, and the above-mentioned process is regarded as cyclic grinding 1 time.
Wherein, in the step (2), the temperature of the disc surface of the grinding disc is controlled to be-16 to-14 ℃ by introducing circulating cooling liquid, and the cooling liquid is any one of glycol, glycerol and ethanol.
It is worth further explaining that according to the working principle of the millstone type solid-phase mechanochemical reactor, the millstone surface generates heat during milling, thereby influencing the actual temperature of the millstone surface. Because the invention strictly limits the temperature of the disc surface of the grinding disc to be lower than 0 ℃, the heat generated by the grinding disc in the grinding process has certain influence on the de-crosslinking degree of the waste epoxy resin. In order to reduce the influence of heat generated in the grinding process as much as possible, through multiple comparison experiments of the invention, the rotation speed of the grinding disc is controlled to be 45-50 r/min, and the de-crosslinking degree of the waste epoxy resin superfine powder obtained by grinding is optimal.
In order to further reduce the influence of heat generation in the grinding process, the temperature of the disc surface of the grinding disc in the step (2) is controlled by introducing circulating cooling liquid with the temperature of-25 to-20 ℃, and the circulating exchange rate of the cooling liquid is 6 to 9L/min.
Generally, the above-mentioned circulation exchange of the circulating cooling liquid is performed by a low-temperature cooling liquid circulation pump, and those skilled in the art can select an appropriate circulating liquid exchange device according to actual conditions.
The waste epoxy resin superfine powder finally obtained by the technical scheme provided by the invention has the volume average particle size of 17.1-37.6 mu m and the crosslinking density of (27.0-28.7) x 10-4mol/ml。
The prepared waste epoxy resin ultrafine powder contains a large amount of functional groups on the surface, has the characteristic of re-crosslinking, can be used as a high-activity filler, can be generally applied to preparing a regenerated product by using epoxy resin or phenolic resin as a matrix, and can remarkably improve the mechanical property of the regenerated product by uniformly dispersing the epoxy resin or phenolic resin in the matrix and firmly bonding the re-crosslinked interface with the matrix resin.
In order to better illustrate the invention and provide an application mode, the obtained waste epoxy resin ultrafine powder is added into epoxy resin to prepare a high-performance regenerated product, and the method comprises the following steps in parts by weight:
preparing materials: 100 parts of epoxy resin, 10-30 parts of waste epoxy resin superfine powder, 15-25 parts of diluent, 25-50 parts of curing agent and 0.5-10 parts of curing accelerator;
(II) crosslinking and curing: and (2) uniformly mixing the prepared materials in the step (1), precuring for 2-4 h at the temperature of 80-110 ℃, and curing for 2-4 h at the temperature of 120-150 ℃ to obtain the high-performance regenerated product.
Wherein, the epoxy resin in the step (one) is a commercial epoxy resin raw material or an epoxy resin raw material prepared according to the prior art, such as E-128, E-54, E-51 or E-44 epoxy resin.
Wherein, the diluent in the step (one) is selected from common diluents in the prior art for crosslinking and curing epoxy resin, and comprises one or more of ethylene glycol diglycidyl ether, styrene oxide and dibutyl phthalate.
Wherein, the curing agent in the step (one) is selected from common curing agents in the prior art for epoxy resin crosslinking curing, and comprises one or more of 4, 4-diaminodiphenylmethane, diaminodiphenyl sulfone, m-phenylenediamine, isophorone diamine and diethylenetriamine; imidazole or anhydride curing agents are also generally selected and may be added in amounts consistent with the prior art.
Wherein, the curing accelerator in the step (one) is selected from curing accelerators commonly used in the prior art for crosslinking and curing the epoxy resin, and comprises one or more of 2-ethyl-4-methylimidazole, DMP-30, pyridine, BDMA, boron trifluoride complex and phenol.
Generally speaking, those skilled in the art can determine appropriate process conditions according to the prior art of epoxy resin crosslinking and curing, and the selected epoxy resin, diluent, curing agent and curing accelerator, and the selected combinations and the adapted process conditions recorded in the prior art are also applicable to the application of the waste epoxy resin ultrafine powder as the high-activity filler.
The invention has the following beneficial effects:
1. the invention provides a method for preparing a high-activity filler by utilizing waste epoxy resin based on a solid-phase shearing and grinding technology, which is characterized in that the technological parameters of a grinding disc type solid-phase mechanochemical reactor are strictly limited, the cross-linking bond in the epoxy resin is destroyed by utilizing the mechanochemical action, and the cross-linking density of the waste epoxy resin can be effectively reduced, so that the waste epoxy resin is endowed with the characteristic of re-crosslinking, and the mechanical property of a regenerated product can be greatly improved by re-crosslinking when the waste epoxy resin is used as the high-activity filler.
2. Through further exploring the process parameters of the millstone type solid-phase mechanochemical reactor, the invention discovers that the method has practical value of industrial application aiming at the de-crosslinking effect of the thermosetting epoxy resin on the basis of strictly limiting the temperature of the surface of the millstone, and provides guidance for further solving the recycling of the waste epoxy resin in the future.
3. The waste epoxy resin superfine powder prepared by the method is used as a high-activity filler, so that the interface crosslinking of the waste epoxy resin superfine powder and matrix resin is realized, the waste epoxy resin superfine powder is uniformly dispersed in the matrix, the interface compatibility is good after the crosslinking, and the mechanical property of a regenerated product is greatly improved.
4. The process provided by the invention is simple and convenient, is easy for large-scale production, does not need high temperature and chemical solvent, has no secondary pollution, and is a new way for recycling the waste epoxy resin.
Drawings
FIG. 1 is a photograph showing the appearance and morphology of the waste epoxy resin ultrafine powder prepared in example 1 of the present invention.
FIG. 2 is a DSC cure curve comparing the high performance recycled article made in example 1 of the present invention with the untreated article made in comparative example 1. It can be seen that the waste epoxy resin superfine powder prepared by the solid-phase mechanochemical technology has higher reaction activity, and the curing process of the regenerated product is obviously promoted.
FIG. 3 is a photograph showing the appearance and appearance of a test piece of a high-performance recycled product prepared in application example 1 of the present invention.
FIG. 4 is a photograph showing a tensile test conducted on a test specimen of a high-performance recycled article prepared in application example 1 of the present invention.
FIG. 5 is a photograph showing a test piece of a high-performance recycled article prepared in application example 1 of the present invention when an impact test is performed.
FIG. 6 is a scanning electron micrograph of a brittle fracture surface of a test specimen of a high performance recycled article produced in application example 1 of the present invention magnified 1000 times. Obviously, the waste epoxy resin superfine powder is uniformly dispersed in the matrix phase, and the interface bonding strength with the matrix is higher, so that the high performance of the regenerated product is ensured.
FIG. 7 is a graph comparing the mechanical property curves of the high performance recycled article prepared in application example 1 of the present invention and the untreated article prepared in comparative example 1.
Detailed Description
The invention is further illustrated by the following examples in conjunction with the accompanying drawings. It should be noted that the examples given are not to be construed as limiting the scope of the invention, and that those skilled in the art, on the basis of the teachings of the present invention, will be able to make numerous insubstantial modifications and adaptations of the invention without departing from its scope.
The tensile properties of the application examples and the comparative examples of the invention are tested according to GB/T2567-; the bending property is tested according to ISO-178-2010; the impact properties were tested according to GB/T1043.1-2008.
Example 1
The method for preparing the high-activity filler by using the waste epoxy resin based on the solid-phase shearing and grinding technology comprises the following steps of:
(1) selecting waste wind power blade leftover materials of which the main component is bisphenol A epoxy resin and the proportion is 95%, and treating and crushing the waste wind power blade leftover materials into waste epoxy resin powder with the average particle size of 6mm after the pretreatment including cleaning;
(2) adding the waste epoxy resin powder into a millstone type solid-phase mechanochemical reactor for grinding and crushing, and collecting the waste epoxy resin superfine powder after grinding is finished; wherein, the technological parameters of the millstone type solid-phase mechanochemical reactor are as follows: the grinding pressure is 8MPa, the temperature of the disc surface of the grinding disc is controlled to be-15 ℃ by introducing circulating cooling liquid, the grinding disc is circularly ground for 20 times, and the rotating speed of the grinding disc is 50 revolutions per minute;
the temperature of the disc surface of the grinding disc is controlled by introducing circulating cooling liquid with the temperature of-20 ℃, the cooling liquid is ethylene glycol, and the circulating exchange rate of the cooling liquid is 8L/min.
The waste epoxy resin ultrafine powder prepared in this example has a volume average particle size of 17.1 μm and a cross-linking density of 27.0X 10-4mol/ml。
Example 2
The method for preparing the high-activity filler by using the waste epoxy resin based on the solid-phase shearing and grinding technology comprises the following steps of:
(1) selecting waste wind power blade leftover materials of which the main component is bisphenol A epoxy resin and the proportion is 95%, and treating and crushing the waste wind power blade leftover materials into waste epoxy resin powder with the average particle size of 6mm after the pretreatment including cleaning;
(2) adding the waste epoxy resin powder into a millstone type solid-phase mechanochemical reactor for grinding and crushing, and collecting the waste epoxy resin superfine powder after grinding is finished; wherein, the technological parameters of the millstone type solid-phase mechanochemical reactor are as follows: the grinding pressure is 8MPa, the temperature of the disc surface of the grinding disc is controlled to be-15 ℃ by introducing circulating cooling liquid, the grinding is carried out for 10 times in a circulating way, and the rotating speed of the grinding disc is 50 revolutions per minute;
the temperature of the disc surface of the grinding disc is controlled by introducing circulating cooling liquid with the temperature of-20 ℃, the cooling liquid is ethylene glycol, and the circulating exchange rate of the cooling liquid is 8L/min.
The waste epoxy resin ultrafine powder prepared in the example has a volume average particle size of 37.6 μm and a crosslinking density of 28.7X 10-4mol/ml。
Example 3
The method for preparing the high-activity filler by using the waste epoxy resin based on the solid-phase shearing and grinding technology comprises the following steps of:
(1) selecting waste wind power blade leftover materials of which the main component is bisphenol A epoxy resin and the proportion is 95%, and treating and crushing the waste wind power blade leftover materials into waste epoxy resin powder with the average particle size of 6mm after the waste wind power blade leftover materials are subjected to cleaning pretreatment;
(2) adding the waste epoxy resin powder into a millstone type solid-phase mechanochemical reactor for grinding and crushing, and collecting the waste epoxy resin superfine powder after grinding is finished; wherein, the technological parameters of the millstone type solid-phase mechanochemical reactor are as follows: the grinding pressure is 8MPa, the temperature of the disc surface of the grinding disc is controlled to be-15 ℃ by introducing circulating cooling liquid, the grinding disc is circularly ground for 15 times, and the rotating speed of the grinding disc is 50 revolutions per minute;
the temperature of the disc surface of the grinding disc is controlled by introducing circulating cooling liquid with the temperature of minus 25 ℃, the cooling liquid is glycol, and the circulating exchange rate of the cooling liquid is 6L/min.
The waste epoxy resin ultrafine powder prepared in this example has a volume average particle size of 23.0 μm and a cross-linking density of 27.7X 10-4mol/ml。
Example 4
The method for preparing the high-activity filler by using the waste epoxy resin based on the solid-phase shearing and grinding technology comprises the following steps of:
(1) selecting electronic component shell waste with the main component of bisphenol A epoxy resin and the proportion of the electronic component shell waste being 98%, carrying out pretreatment including cleaning, and then processing and crushing the electronic component shell waste into waste epoxy resin powder with the average particle size of 8 mm;
(2) adding the waste epoxy resin powder into a millstone type solid-phase mechanochemical reactor for grinding and crushing, and collecting the waste epoxy resin superfine powder after grinding is finished; wherein, the technological parameters of the millstone type solid-phase mechanochemical reactor are as follows: the grinding pressure is 8MPa, the temperature of the disc surface of the grinding disc is controlled to be-14 ℃ by introducing circulating cooling liquid, the grinding disc is circularly ground for 20 times, and the rotating speed of the grinding disc is 50 revolutions per minute;
the temperature of the disc surface of the grinding disc is controlled by introducing circulating cooling liquid with the temperature of-20 ℃, the cooling liquid is glycerin, and the circulating exchange rate of the cooling liquid is 7L/min.
Example 5
The method for preparing the high-activity filler by using the waste epoxy resin based on the solid-phase shearing and grinding technology comprises the following steps of:
(1) selecting electronic component shell waste with bisphenol A epoxy resin as a main component and 90% of the bisphenol A epoxy resin, carrying out pretreatment including cleaning, and then treating and crushing the electronic component shell waste into waste epoxy resin powder with the average particle size of 2 mm;
(2) adding the waste epoxy resin powder into a millstone type solid-phase mechanochemical reactor for grinding and crushing, and collecting the waste epoxy resin superfine powder after grinding is finished; wherein, the technological parameters of the millstone type solid-phase mechanochemical reactor are as follows: the grinding pressure is 5MPa, the temperature of the disc surface of the grinding disc is controlled to be-16 ℃ by introducing circulating cooling liquid, the grinding disc is circularly ground for 10 times, and the rotating speed of the grinding disc is 45 revolutions per minute;
the temperature of the disc surface of the grinding disc is controlled by introducing circulating cooling liquid with the temperature of-20 ℃, the cooling liquid is ethanol, and the circulating exchange rate of the cooling liquid is 9L/min.
Application example 1
The waste epoxy resin superfine powder prepared in the embodiment 1 is added into epoxy resin to prepare a high-performance regenerated product, and the method comprises the following steps in parts by weight:
preparing materials: 100 parts of E-128 epoxy resin, 25 parts of waste epoxy resin superfine powder, 20 parts of ethylene glycol diglycidyl ether, 26 parts of 4, 4-diaminodiphenylmethane and 0.5 part of 2-ethyl-4-methylimidazole;
(II) crosslinking and curing: and (2) uniformly mixing the prepared materials in the step (1), placing the materials in an oven for precuring for 2 hours at the temperature of 80 ℃, and curing for 2 hours at the temperature of 120 ℃ to obtain the high-performance regenerated product.
Compared with the comparative example 1, the high-performance regenerated product prepared by the application example has the advantages that the tensile strength is improved by 62%, the elongation at break is improved by 181%, the bending strength is improved by 40%, and the impact strength is improved by 109%.
Application example 2
The waste epoxy resin superfine powder prepared in the embodiment 2 is added into epoxy resin to prepare a high-performance regenerated product, and the method comprises the following steps in parts by weight:
preparing materials: 100 parts of E-128 epoxy resin, 25 parts of waste epoxy resin superfine powder, 20 parts of ethylene glycol diglycidyl ether, 26 parts of 4, 4-diaminodiphenylmethane and 0.5 part of 2-ethyl-4-methylimidazole;
(II) crosslinking and curing: and (2) uniformly mixing the prepared materials in the step (1), placing the materials in an oven for precuring for 2 hours at the temperature of 80 ℃, and curing for 2 hours at the temperature of 120 ℃ to obtain the high-performance regenerated product.
Application example 3
The waste epoxy resin superfine powder prepared in the embodiment 3 is added into epoxy resin to prepare a high-performance regenerated product, and the method comprises the following steps in parts by weight:
preparing materials: 100 parts of E-128 epoxy resin, 25 parts of waste epoxy resin superfine powder, 20 parts of ethylene glycol diglycidyl ether, 26 parts of 4, 4-diaminodiphenylmethane and 0.5 part of 2-ethyl-4-methylimidazole;
(II) crosslinking and curing: and (2) uniformly mixing the prepared materials in the step (1), placing the materials in an oven for precuring for 2 hours at the temperature of 80 ℃, and curing for 2 hours at the temperature of 120 ℃ to obtain the high-performance regenerated product.
Application example 4
The waste epoxy resin superfine powder prepared in the embodiment 1 is added into epoxy resin to prepare a high-performance regenerated product, and the method comprises the following steps in parts by weight:
preparing materials: 100 parts of E-128 epoxy resin, 25 parts of waste epoxy resin superfine powder, 20 parts of ethylene glycol diglycidyl ether, 75 parts of methyltetrahydrophthalic anhydride and 1 part of BDMA;
(II) crosslinking and curing: and (2) uniformly mixing the prepared materials in the step (1), placing the materials in an oven for precuring for 2 hours at the temperature of 100 ℃, and curing for 5 hours at the temperature of 150 ℃ to obtain the high-performance regenerated product.
Compared with the product prepared by the technical scheme without adding the waste epoxy resin ultrafine powder, the high-performance regenerated product prepared by the application example has the advantages that the tensile strength is improved by 57%, the elongation at break is improved by 169%, the bending strength is improved by 42%, and the impact strength is improved by 114%.
Application example 5
The waste epoxy resin superfine powder prepared in the embodiment 1 is added into epoxy resin to prepare a high-performance regenerated product, and the method comprises the following steps in parts by weight:
preparing materials: 100 parts of E-128 epoxy resin, 11 parts of waste epoxy resin superfine powder, 20 parts of ethylene glycol diglycidyl ether, 26 parts of 4, 4-diaminodiphenylmethane and 0.5 part of 2-ethyl-4-methylimidazole;
(II) crosslinking and curing: and (2) uniformly mixing the prepared materials in the step (1), placing the materials in an oven for precuring for 2 hours at the temperature of 80 ℃, and curing for 2 hours at the temperature of 120 ℃ to obtain the high-performance regenerated product.
Compared with the product prepared by the technical scheme without adding the waste epoxy resin ultrafine powder, the high-performance regenerated product prepared by the application example has the advantages that the tensile strength is improved by 59 percent, the elongation at break is improved by 113 percent, the bending strength is improved by 39 percent, and the impact strength is improved by 91 percent.
Application example 6
The waste epoxy resin superfine powder prepared in the embodiment 1 is added into epoxy resin to prepare a high-performance regenerated product, and the method comprises the following steps in parts by weight:
preparing materials: 100 parts of E-54 epoxy resin, 30 parts of waste epoxy resin superfine powder, 25 parts of diglycidyl ether, 50 parts of diaminodiphenyl sulfone and DMP-3010 parts;
(II) crosslinking and curing: and (2) uniformly mixing the prepared materials in the step (1), placing the materials in an oven to be pre-cured for 4 hours at the temperature of 110 ℃, and then curing for 4 hours at the temperature of 150 ℃ to obtain a high-performance regenerated product.
Application example 7
The waste epoxy resin superfine powder prepared in the embodiment 1 is added into epoxy resin to prepare a high-performance regenerated product, and the method comprises the following steps in parts by weight:
preparing materials: 100 parts of E-44 epoxy resin, 10 parts of waste epoxy resin superfine powder, 15 parts of styrene oxide, 25 parts of m-phenylenediamine and 0.5 part of boron trifluoride complex;
(II) crosslinking and curing: and (2) uniformly mixing the prepared materials in the step (1), placing the materials in an oven for precuring for 2 hours at the temperature of 80 ℃, and curing for 2 hours at the temperature of 120 ℃ to obtain the high-performance regenerated product.
Comparative example 1
The comparative example is a product prepared by adding waste epoxy resin superfine powder which is not milled by a solid-phase mechanochemical reactor and has similar particle size, and comprises the following steps in parts by weight:
preparing materials: 100 parts of E-128 epoxy resin, 25 parts of waste epoxy resin superfine powder without grinding treatment, 20 parts of ethylene glycol diglycidyl ether, 26 parts of 4, 4-diaminodiphenylmethane and 0.5 part of 2-ethyl-4-methylimidazole;
(II) crosslinking and curing: uniformly mixing the prepared materials in the step (1), placing the materials in an oven for precuring for 2 hours at the temperature of 80 ℃, and curing for 2 hours at the temperature of 120 ℃ to obtain a product;
wherein the waste epoxy resin superfine powder without grinding treatment is prepared by grinding the waste epoxy resin superfine powder without solid-phase mechanochemical reaction, and crushing the waste epoxy resin superfine powder into powder with the volume average particle size of 30.5 mu m and the crosslinking density of 33.8 multiplied by 10 by a planetary ball mill-4mol/ml。
The article prepared in this comparative example had a tensile strength of 26.1MPa, an elongation at break of 2.7%, a flexural strength of 52.1MPa, and an impact strength of 4.2 MPa.
Comparative example 2
The method for preparing the high-activity filler by using the waste epoxy resin based on the solid-phase shearing and grinding technology is carried out at normal temperature, and comprises the following steps:
(1) selecting waste wind power blade leftover materials of which the main component is bisphenol A epoxy resin and the proportion is 95%, and treating and crushing the waste wind power blade leftover materials into waste epoxy resin powder with the average particle size of 6mm after the waste wind power blade leftover materials are subjected to cleaning pretreatment;
(2) adding the waste epoxy resin powder into a millstone type solid-phase mechanochemical reactor for grinding and crushing, and collecting the waste epoxy resin superfine powder after grinding is finished; wherein, the technological parameters of the millstone type solid-phase mechanochemical reactor are as follows: the grinding pressure is 8MPa, the grinding is carried out for 20 times in a circulating way under the normal temperature condition, and the grinding disc rotating speed is 50 r/min.
The waste epoxy resin ultrafine powder prepared by the comparative example has the volume average particle size of 23.1 mu m and the crosslinking density of 30.4 multiplied by 10-4mol/ml。
The method for preparing the regenerated product by adding the waste epoxy resin superfine powder prepared in the comparative example into the epoxy resin comprises the following steps in parts by weight:
preparing materials: 100 parts of E-128 epoxy resin, 25 parts of waste epoxy resin superfine powder, 20 parts of ethylene glycol diglycidyl ether, 26 parts of 4, 4-diaminodiphenylmethane and 0.5 part of 2-ethyl-4-methylimidazole;
(II) crosslinking and curing: and (2) uniformly mixing the prepared materials in the step (1), placing the materials in an oven for precuring for 2h at the temperature of 80 ℃, and curing for 2h at the temperature of 120 ℃ to obtain a regenerated product.
Compared with the regenerated product prepared by the application example 1, the tensile strength is reduced by 23%, the elongation at break is reduced by 79%, the bending strength is reduced by 27%, and the impact strength is reduced by 46%.
Comparative example 3
The method for preparing the high-activity filler by using the waste epoxy resin based on the solid-phase shearing and grinding technology in the comparative example controls the temperature of the disc surface of the grinding disc to be 0 ℃, and comprises the following steps:
(1) selecting waste wind power blade leftover materials of which the main component is bisphenol A epoxy resin and the proportion is 95%, and treating and crushing the waste wind power blade leftover materials into waste epoxy resin powder with the average particle size of 6mm after the waste wind power blade leftover materials are subjected to cleaning pretreatment;
(2) adding the waste epoxy resin powder into a millstone type solid-phase mechanochemical reactor for grinding and crushing, and collecting the waste epoxy resin superfine powder after grinding is finished; wherein, the technological parameters of the millstone type solid-phase mechanochemical reactor are as follows: the grinding pressure is 8MPa, the temperature of the disc surface of the grinding disc is controlled to be 0 ℃ by introducing circulating cooling liquid, the grinding disc is circularly ground for 20 times, and the rotating speed of the grinding disc is 50 revolutions per minute;
the temperature of the disc surface of the grinding disc is controlled by introducing circulating cooling liquid with the temperature of-20 ℃, the cooling liquid is ethylene glycol, and the circulating exchange rate of the cooling liquid is 3L/min.
The waste epoxy resin superfine powder prepared by the comparative example has the volume average particle size of 19.2 mu m and the crosslinking density of 29.1 multiplied by 10-4mol/ml。
The method for preparing the regenerated product by adding the waste epoxy resin superfine powder prepared in the comparative example into the epoxy resin comprises the following steps in parts by weight:
preparing materials: 100 parts of E-128 epoxy resin, 25 parts of waste epoxy resin superfine powder, 20 parts of ethylene glycol diglycidyl ether, 26 parts of 4, 4-diaminodiphenylmethane and 0.5 part of 2-ethyl-4-methylimidazole;
(II) crosslinking and curing: and (2) uniformly mixing the prepared materials in the step (1), placing the materials in an oven for precuring for 2h at the temperature of 80 ℃, and curing for 2h at the temperature of 120 ℃ to obtain a regenerated product.
Compared with the application example 1, the regenerated product prepared by the comparative example has the advantages that the tensile strength is reduced by 15%, the elongation at break is reduced by 36%, the bending strength is reduced by 18%, and the impact strength is reduced by 29%.
Claims (10)
1. A method for preparing a high-activity filler by using waste epoxy resin based on a solid-phase shearing and grinding technology is characterized by comprising the following steps:
(1) selecting waste epoxy resin materials or products with the epoxy resin content of not less than 90%, carrying out pretreatment including cleaning, and then treating and crushing the waste epoxy resin materials or products into waste epoxy resin powder with the average particle size of not more than 8 mm;
(2) adding the waste epoxy resin powder into a millstone type solid-phase mechanochemical reactor for grinding and crushing, and collecting the waste epoxy resin superfine powder after grinding is finished; wherein, the technological parameters of the millstone type solid-phase mechanochemical reactor are as follows: the grinding pressure is 5-8 MPa, the temperature of the disc surface of the grinding disc is controlled to be-16 to-14 ℃ by introducing circulating cooling liquid, the grinding disc is circularly ground for 10-20 times, and the rotating speed of the grinding disc is 45-50 revolutions per minute;
the temperature of the disc surface of the grinding disc is controlled by introducing circulating cooling liquid with the temperature of minus 25 to minus 20 ℃.
2. The method of claim 1, further comprising: and (3) in the step (2), the temperature of the disc surface of the grinding disc is controlled to be-16 to-14 ℃ by introducing circulating cooling liquid, and the cooling liquid is any one of glycol, glycerol and ethanol.
3. The method of claim 1, further comprising: and (3) in the step (2), the disc surface temperature of the grinding disc is controlled by introducing circulating cooling liquid with the temperature of-25 to-20 ℃, and the circulating exchange rate of the cooling liquid is 6 to 9L/min.
4. The waste epoxy resin ultrafine powder prepared by the method according to any one of claims 1 to 3.
5. The use of the waste epoxy resin ultrafine powder of claim 4 as a high-activity filler.
6. A method for preparing a high-performance regenerated product by adding the waste epoxy resin ultrafine powder as defined in claim 4 into epoxy resin is characterized by comprising the following steps in parts by weight:
preparing materials: 100 parts of epoxy resin, 10-30 parts of waste epoxy resin superfine powder, 15-25 parts of diluent, 25-50 parts of curing agent and 0.5-10 parts of curing accelerator;
(II) crosslinking and curing: and (2) uniformly mixing the prepared materials in the step (1), precuring for 2-4 h at the temperature of 80-110 ℃, and curing for 2-4 h at the temperature of 120-150 ℃ to obtain the high-performance regenerated product.
7. The method of claim 6, further comprising: the epoxy resin in the step (one) is E-128, E-54, E-51 or E-44 epoxy resin.
8. The method of claim 6, wherein: in the step (I), the diluent is one or more of ethylene glycol diglycidyl ether, styrene oxide and dibutyl phthalate.
9. The method of claim 6, further comprising: in the step (one), the curing agent is one or more of 4, 4-diaminodiphenylmethane, diaminodiphenyl sulfone, m-phenylenediamine, isophoronediamine and diethylenetriamine.
10. The method of claim 6, further comprising: in the step (one), the curing accelerator is one or more of 2-ethyl-4-methylimidazole, DMP-30, pyridine, BDMA, boron trifluoride complex and phenol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011455078.4A CN112829123B (en) | 2020-12-10 | 2020-12-10 | Method for preparing high-activity filler by using waste epoxy resin based on solid-phase shearing and milling technology |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011455078.4A CN112829123B (en) | 2020-12-10 | 2020-12-10 | Method for preparing high-activity filler by using waste epoxy resin based on solid-phase shearing and milling technology |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112829123A CN112829123A (en) | 2021-05-25 |
| CN112829123B true CN112829123B (en) | 2022-05-24 |
Family
ID=75923540
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011455078.4A Active CN112829123B (en) | 2020-12-10 | 2020-12-10 | Method for preparing high-activity filler by using waste epoxy resin based on solid-phase shearing and milling technology |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112829123B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115042345A (en) * | 2022-06-30 | 2022-09-13 | 上杭鑫昌龙实业有限公司 | Regenerated product containing crosslinked polyethylene regenerated material and preparation method thereof |
| CN117816254B (en) * | 2023-12-12 | 2024-06-11 | 华能国际电力股份有限公司德州电厂 | Invalid heavy metal adsorption resin-based catalyst and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6313182B1 (en) * | 1999-05-04 | 2001-11-06 | Air Products And Chemicals, Inc. | Acetylenic diol ethylene oxide/propylene oxide adducts and processes for their manufacture |
| US6425540B1 (en) * | 2000-02-29 | 2002-07-30 | Charles D. Morris | Method and apparatus for grinding rubber |
| CN103642064A (en) * | 2013-11-29 | 2014-03-19 | 江门市奇德工程塑料科技有限公司 | Regeneration technique of urea-formaldehyde resin and composite material containing regenerated urea-formaldehyde resin |
| CN106832905A (en) * | 2017-02-28 | 2017-06-13 | 四川大学 | Polymer matrix micro-/ nano composite material powder and preparation method thereof |
| CN111205597A (en) * | 2020-02-28 | 2020-05-29 | 厦门市宜帆达新材料有限公司 | High-performance epoxy resin and preparation method thereof |
| CN111662521A (en) * | 2020-06-09 | 2020-09-15 | 四川大学 | Method for toughening and modifying polyvinyl chloride by using waste NBR/PVC rubber-plastic heat-insulating material |
-
2020
- 2020-12-10 CN CN202011455078.4A patent/CN112829123B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6313182B1 (en) * | 1999-05-04 | 2001-11-06 | Air Products And Chemicals, Inc. | Acetylenic diol ethylene oxide/propylene oxide adducts and processes for their manufacture |
| US6425540B1 (en) * | 2000-02-29 | 2002-07-30 | Charles D. Morris | Method and apparatus for grinding rubber |
| CN103642064A (en) * | 2013-11-29 | 2014-03-19 | 江门市奇德工程塑料科技有限公司 | Regeneration technique of urea-formaldehyde resin and composite material containing regenerated urea-formaldehyde resin |
| CN106832905A (en) * | 2017-02-28 | 2017-06-13 | 四川大学 | Polymer matrix micro-/ nano composite material powder and preparation method thereof |
| CN111205597A (en) * | 2020-02-28 | 2020-05-29 | 厦门市宜帆达新材料有限公司 | High-performance epoxy resin and preparation method thereof |
| CN111662521A (en) * | 2020-06-09 | 2020-09-15 | 四川大学 | Method for toughening and modifying polyvinyl chloride by using waste NBR/PVC rubber-plastic heat-insulating material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112829123A (en) | 2021-05-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112829123B (en) | Method for preparing high-activity filler by using waste epoxy resin based on solid-phase shearing and milling technology | |
| CN102226023B (en) | Composite board based on mixed waste polymers and preparation method thereof | |
| CN109320918B (en) | Recyclable carbon fiber reinforced epoxy resin composite material, and preparation method and application thereof | |
| CN105670223B (en) | Epoxy resin composition for wind turbine blade and composite material | |
| Kang et al. | Novel application of mechanochemistry in waste epoxy recycling via solid-state shear milling | |
| CN100395386C (en) | Method of improving surface cohesion performance of relative molecular weight polyethylene | |
| CN104327374A (en) | Waste circuit board non-metal ultra-fine powder, waste circuit board non-metal ultra-fine powder and polyolefin composite material, and preparation methods of the powder and the composite material | |
| CN110951158A (en) | Thermoplastic composite material prepared from regenerated waste plastics and preparation method thereof | |
| CN111171513B (en) | Method for toughening thermosetting resin by using collagen fibers and modified thermosetting resin | |
| Zhao et al. | Environment-friendly recycling of CFRP composites via gentle solvent system at atmospheric pressure | |
| CN101525439A (en) | Modified epoxide resin for structural adhesive of wind generating blades and preparation method thereof | |
| CN101109113B (en) | Method of preparing polythene fibre with high surface adhesion ultra-high relative molecular mass | |
| CN1213084C (en) | Preparation method and application of modified double maleimide resin | |
| CN102002188A (en) | Method for preparing dynamic curing epoxy resin, inorganic filler and polyolefin composite | |
| CN105754174A (en) | Rubber antiager prepared by utilizing petroleum coke | |
| CN105111689A (en) | Self-repaired conducting polymer nanomaterial and preparation method thereof | |
| CN114106517B (en) | High-strength high-toughness flame-retardant epoxy resin and preparation method thereof | |
| CN115678204A (en) | Epoxy fiber composite material for wind power blade and preparation method thereof | |
| CN113136015B (en) | Thermosetting phenolic resin and preparation method, regeneration method and recovery method thereof | |
| WO2023103081A1 (en) | Carbon fiber-reinforced polypropylene composite material and preparation method therefor | |
| CN115703892A (en) | High-performance degradable epoxy resin-carbon fiber composite material and preparation method thereof | |
| CN111393582B (en) | Method for recycling and reusing waste thermosetting polyurethane | |
| CN118063854A (en) | Glass fiber reinforced plastic regenerated product using waste wind power blade as raw material and preparation method thereof | |
| CN114410065B (en) | Epoxy resin composition, carbon fiber prepreg and carbon fiber composite material | |
| CN116178900A (en) | Rapid preparation method of high-toughness solid epoxy resin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |