CN115181079A - Preparation method and application of epoxy resin capable of being cyclically degraded and thermoplastically processed - Google Patents
Preparation method and application of epoxy resin capable of being cyclically degraded and thermoplastically processed Download PDFInfo
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- CN115181079A CN115181079A CN202210291828.1A CN202210291828A CN115181079A CN 115181079 A CN115181079 A CN 115181079A CN 202210291828 A CN202210291828 A CN 202210291828A CN 115181079 A CN115181079 A CN 115181079A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
- C07D303/20—Ethers with hydroxy compounds containing no oxirane rings
- C07D303/22—Ethers with hydroxy compounds containing no oxirane rings with monohydroxy compounds
- C07D303/23—Oxiranylmethyl ethers of compounds having one hydroxy group bound to a six-membered aromatic ring, the oxiranylmethyl radical not being further substituted, i.e.
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
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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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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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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- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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Abstract
The invention relates to an epoxy resin with thermoplasticity processing and cyclic degradation and a preparation method thereof, belonging to the technical field of new material synthesis. The invention comprises the following steps: mixing an epoxy monomer with an aromatic ketone structure with the existing commercial amine curing agent according to the mass part ratio of 1.4-0.7, pouring the mixture into a mold after stirring, heating the mixture step by step, and demolding after complete curing to obtain the thermoplastic processing and cyclic degradation epoxy resin. The cured epoxy resin chips were hot pressed (10 MPa,10 min) at 150-200 ℃ to give a complete sheet. The epoxy resin can be completely degraded circularly in 24 hours at a temperature below 80 ℃ in a mixed solution of an acidic aqueous solution and an organic solvent after being cured, and the degraded product can be recycled for re-curing of the epoxy resin after being recovered. The tensile strength, young modulus and elongation at break of the epoxy resin after the resolidification of the degradation product and repeated hot pressing are equivalent to those of the original epoxy resin. The invention has simple process, and the product has the functions of cyclic degradation and thermoplastic processing, and is expected to be used in the fields of the recovery of reinforced fibers in epoxy composite materials, cyclic degradation or self-repair epoxy coatings, cyclic degradation epoxy adhesives and the like.
Description
Technical Field
The invention relates to an epoxy resin with thermoplasticity processing and cyclic degradation and a preparation method thereof, belonging to the technical field of new material synthesis.
Background
The epoxy resin is widely used in the fields of traffic, aerospace, electronic and electric appliances, coating corrosion prevention and the like, and is a thermosetting resin with the most extensive application at present. The epoxy resin forms a three-dimensional cross-linked network after being cured, so that the cured epoxy resin is not melted and dissolved and is difficult to degrade. The updating and upgrading speed of electronic devices is more and more frequent, so that a large amount of electronic waste is generated, and the environmental protection problem is more and more severe; the carbon fiber/epoxy composite material has large using amount, but the difficult problems of difficult recovery of high-performance and high-added-value carbon fibers in composite material wastes and the like are urgently solved, so that the research and development of the recyclable epoxy material have very important economic and social values.
The cleavable covalent bonds in the existing cyclically degradable epoxy resins are mainly esters of different substituents, such as: sulfonates), sulfites, carbonates, phosphates; acetal structure, etc., and the degradation temperature is generally over 140 ℃, so the carbon fiber recovery energy consumption is high. Since the covalent bonds described above do not have reversible properties, the epoxy thermosetting resins prepared are also not thermoplastically processable. The dynamic covalent bond is a reversible covalent bond, and is introduced into a polymer network to construct Covalent Adaptive Networks (CANs), so that the material has the molecular structure stability of the traditional covalent polymer and the dynamic reversibility of the supermolecule polymer under certain conditions, thereby endowing the material with rich external stimulus responsiveness, and realizing the induced degradation of the thermosetting resin under heat, acid, ultrasound, added micromolecules and the like. Recently, documents report that epoxy monomers and amine curing agents with dynamic covalent bonds such as Diels-Alder dynamic covalent bonds, disulfide bonds and imine dynamic covalent bonds realize the thermoplastic processing and degradation of thermosetting resins.
The epoxy resin with an imine (Schiff base) dynamic covalent bond is prepared in the earlier stage, and the resin is found to be thermoplastically processable and acid degradable, but the degradation product is complex due to uncontrollable cross-linked network structure, so that the degradation product cannot be recycled. In order to realize the recycling of the epoxy resin degradation product, the patent reports for the first time a synthetic route and a preparation method of an epoxy monomer with an aromatic ketone structure, a preparation process of epoxy resin obtained by curing the epoxy monomer with an amine curing agent, and the like. By controlling the curing conditions, the acidic degradation products of the epoxy matrix resin can be recycled. The thermoplastic processing property of the epoxy resin is beneficial to the molding of the composite material. Therefore, the preparation of the epoxy resin with both cyclic degradation and thermoplasticity processing undoubtedly has important application values for the recovery of the reinforcing filler in the epoxy composite material, the reutilization of the epoxy thermosetting resin, the degradable epoxy adhesive, environmental protection and the like.
Disclosure of Invention
The invention aims to solve the technical problems, provides a preparation method of the epoxy resin which can be circularly degraded and can be processed by thermoplasticity, and provides a new idea for preparing the circularly degraded epoxy and recycling the thermosetting resin reinforced fiber.
In order to achieve the above purpose, the invention provides an epoxy monomer and a preparation method thereof.
An epoxy monomer is synthesized by reacting p-hydroxyacetophenone, epichlorohydrin and a phase transfer catalyst at 60-85 ℃ for 1-3 h; adding water and an organic phase extracting agent into the obtained synthetic product mixed solution, separating, collecting, and drying the organic phase solution by using anhydrous sodium sulfate to obtain a pure epoxy resin monomer; the synthesis schematic diagram is shown in figure 1, and the nuclear magnetic spectrum of the monomer is shown in figure 2.
1. A preparation method of an epoxy resin monomer comprises the following steps:
s1, uniformly mixing 1 part of p-hydroxyacetophenone, 3-7 parts of epoxidized monomer and 0.1-0.3 part of phase transfer catalyst, and reacting at 60-85 ℃ for 1-3h to obtain a mixed solution a.
S2, adding 0.1-0.3 part of phase transfer catalyst and 1-2 parts of sodium hydroxide aqueous solution into the mixed solution a obtained in the step S1, and reacting for 0.5-3h at room temperature to obtain a mixed solution b.
And S3, adding 50 parts of water and an organic phase extracting agent into the mixed solution b obtained in the S2, shaking, separating liquid and collecting to obtain an organic phase solution.
S4, adding 30 parts by mass of anhydrous sodium sulfate into the organic phase solution obtained in the step S3 to dry the organic phase solution at 200r/min
S5, rotationally evaporating the dried organic phase solution obtained in the step S4 at the temperature of 80 ℃ to obtain an epoxy resin monomer.
The epoxidation monomer is epoxy chloropropane; phase transfer catalysts include, but are not limited to, existing organic quaternary ammonium salt systems, such as benzyltriethylammonium chloride, and the like; the organic phase extractant is ethyl acetate or dichloromethane.
2. A curing method of epoxy resin monomers comprises the following steps:
s1, uniformly mixing 1 part of epoxy resin monomer and 0.4-0.7 part of curing agent to obtain a mixed solution, pouring the mixed solution into a mold, and heating and reacting at 80 ℃ for 10min to obtain an epoxy resin precursor.
S2, heating the epoxy resin precursor obtained in the step S1 to 180 ℃ for curing for 6h, and obtaining the cured epoxy resin sheet which can be degraded circularly and can be processed by thermoplasticity.
3. A method for degradation and recycling of cured epoxy polymers, the method comprising the steps of:
s1, soaking the cured epoxy resin into a mixed solution of an acidic aqueous solution and an organic solvent I, reacting for 24 hours at the temperature of between room temperature and 80 ℃, and degrading, wherein a degradation product is dissolved in the mixed solution.
And S2, adding equivalent NaOH into the mixed solution obtained in the S1 to neutralize acid, regulating the pH of the degradation solution to be neutral, volatilizing the solvent at room temperature, sequentially adding water with the same volume as the pH of the degradation solution and an organic solvent II to extract degradation products, separating liquid, collecting organic phase solution, and performing rotary evaporation to obtain the degradation products.
Wherein the acidic aqueous solution is 1mol/L hydrochloric acid aqueous solution or 1mol/L sulfuric acid aqueous solution; acidic aqueous solution and organic solvent
The mass fraction ratio is 8; the organic solvent I is methanol or ethanol or tetrahydrofuran; the organic solvent II is dichloromethane or ethyl
And (4) ethyl ester.
The recycled degradation product reacts for 6 hours at 180 ℃, and the cured epoxy resin with the same structure as the initial epoxy resin can be obtained again, so that the cyclic utilization of the degradation product is realized.
4. A thermoplastic processing method of epoxy resin monomer comprises the following steps:
and (3) crushing the cured epoxy resin, placing the crushed epoxy resin into a mold, and placing the mold into a high-temperature flat vulcanizing machine for hot pressing for 10min to obtain the complete epoxy resin sheet.
Wherein the temperature of the plate vulcanizing machine is 150-200 ℃, and the pressure is 10MPa.
By adopting the technical scheme, compared with the prior art, the invention has the following technical effects:
1. the epoxy resin obtained after the epoxy monomer and the amine curing agent are cured can be cyclically degraded in an acidic solution formed by mixing an acidic aqueous solution and an organic solution at 80 ℃ for 24 hours.
2. The epoxy resin obtained by curing the epoxy monomer and the amine curing agent provided by the invention can realize the thermoplastic processing of the thermosetting resin through hot pressing.
3. After the epoxy resin is damaged, the epoxy resin can be self-repaired by hot pressing (10MPa, 10min) at 130-180 ℃, and the tensile strength, modulus and elongation at break of the repaired epoxy resin are equivalent to those of the original resin.
Drawings
FIG. 1 is a route for the preparation of a cyclically degradable and thermoplastically processable epoxy resin monomer;
FIG. 2 is a 1H-NMR chart of an aromatic keto group epoxy monomer.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the examples below. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
It is worth mentioning that: 1) The parts of materials used in the following examples are parts by weight.
Example 1
(1) Synthesis of epoxy resin monomer
S1, uniformly mixing 1 part of p-hydroxyacetophenone, 3.4 parts of epoxidized monomer and 0.17 part of benzyltriethylammonium chloride serving as a catalyst, and reacting at 80 ℃ for 2 hours to obtain a mixed solution a.
S2, adding 0.17 part of benzyltriethylammonium chloride and 1.18 parts of sodium hydroxide aqueous solution into the mixed solution a obtained in the S1, and reacting for 0.5h at room temperature to obtain a mixed solution b.
And S3, adding 50 parts of water and a dichloromethane extracting agent into the mixed solution b obtained in the S2, shaking, separating and collecting liquid to obtain a dichloromethane phase solution.
And S4, adding 30 parts by mass of anhydrous sodium sulfate into the dichloromethane phase solution obtained in the S3, stirring at 200r/min for 30min, standing for 3h, and performing suction filtration and recovery to obtain a dry dichloromethane phase solution.
S5, rotationally evaporating the dried dichloromethane phase solution obtained in the step S4 at the temperature of 80 ℃ to obtain an epoxy resin monomer.
(2) Curing of epoxy resins
S1, uniformly mixing 1 part of epoxy resin monomer and 0.45 part of hexamethylenediamine to obtain a mixed solution, pouring the mixed solution into a mold, placing the mold in an oven, and precuring the mold for 2 hours at 70 ℃ to obtain an epoxy resin precursor.
S2, heating the epoxy resin precursor obtained in the step S1 to 180 ℃ for curing for 6 hours, wherein the cured epoxy resin sheet can be degraded circularly and can be processed thermoplastically.
(3) Degradation and recycling of cured epoxy resin polymers
S1, soaking the cured epoxy resin into a mixed solution of 8 parts of hydrochloric acid aqueous solution (1 mol/L)/2 parts of methanol at the temperature of between room temperature and 80 ℃, and degrading after 24 hours of reaction, wherein a degradation product is dissolved in the mixed solution.
And S2, adding 8 parts of NaOH to the mixed solution obtained in the S1 to neutralize acid, regulating the pH of the degradation solution to be neutral, volatilizing the solvent at room temperature, sequentially adding 5 parts of water and 5 parts of ethyl acetate to extract the degradation product, separating liquid, collecting organic phase solution, and performing rotary evaporation to obtain the degradation product.
The recycled degradation product reacts for 6 hours at 180 ℃, and the cured epoxy resin with the same structure as the initial epoxy resin can be obtained again, so that the cyclic utilization of the degradation product is realized.
(4) And (3) performing thermoplastic processing on the epoxy resin monomer, namely placing the crushed epoxy resin into a mold, and placing the mold into a high-temperature flat vulcanizing machine for hot pressing for 10min to obtain the complete epoxy resin sheet.
Wherein the temperature of the plate vulcanizing machine is 150 ℃, and the pressure is 10MPa.
The sheets obtained by the steps of "(2) curing of epoxy resin", "3) degradation and recycling of cured epoxy resin polymer" and "(4) thermoplastic processing of epoxy resin monomer" were cut and tested according to the national standard GB/T2567-2008 to obtain the curing of the epoxy resin of step "(2), i.e. the young's modulus, tensile strength and elongation at break of the initial resin were 1.4gp,61mpa and 4.0%, respectively; step "(3) degradation and recycling of the cured epoxy resin polymer", that is, the Young modulus, tensile strength and elongation at break of the resin cured again after degradation are 1.4GP,60MPa and 3.8% respectively; and (4) performing thermoplastic processing on the epoxy resin monomer, namely enabling the Young modulus, the tensile strength and the elongation at break of the self-repaired resin to be 1.3GP,60MPa and 4.2 percent respectively.
Claims (2)
1. A thermoplastically processable epoxy resin capable of being cyclically degraded has a structural formula as shown in formula 1:
formula 1 preparation route of epoxy resin monomer capable of cyclic degradation and thermoplastic processing
Commercial amine curing agents, including but not limited to, existing commercial aliphatic and cycloaliphatic amine curing agents.
2. A process for preparing a cyclically degradable and thermoplastically processable epoxy thermosetting resin as claimed in claim 1
The method is characterized by comprising the following steps:
(1) Synthesis of epoxy resin monomer
S1, uniformly mixing 1 part of p-hydroxyacetophenone, 3-7 parts of epoxy monomer and 0.1-0.3 part of phase transfer catalyst, and reacting at 60-85 ℃ for 1-3h to obtain a mixed solution a;
s2, adding 0.1-0.3 part of phase transfer catalyst and 1-2 parts of sodium hydroxide aqueous solution into the mixed solution a obtained in the S1, and reacting for 0.5-3h at room temperature to obtain a mixed solution b;
s3, adding 50 parts of water and an organic phase extracting agent into the mixed solution b obtained in the S2, and separating and collecting liquid after shaking to obtain an organic phase solution;
s4, adding 30 parts by mass of anhydrous sodium sulfate into the organic phase solution obtained in the S3, drying the organic phase solution at a speed of 200r/min, stirring for 30min, standing for 3h, and performing suction filtration and recovery to obtain a dried organic phase solution;
s5, rotationally evaporating the dried organic phase solution obtained in the step S4 at 80 ℃ to obtain an epoxy resin monomer;
the epoxidation monomer is epichlorohydrin; phase transfer catalysts include, but are not limited to, existing organic quaternary ammonium salt systems, such as benzyltriethylammonium chloride, and the like; the organic phase extractant is ethyl acetate or dichloromethane;
(2) Curing of epoxy resin monomers
S1, uniformly mixing 1 part of epoxy resin monomer and 0.4-0.7 part of curing agent to obtain a mixed solution, pouring the mixed solution into a mold, and heating and reacting at 80 ℃ for 10min to obtain an epoxy resin precursor;
s2, heating the epoxy resin precursor obtained in the step S1 to 180 ℃ for curing for 6h, and obtaining the cured epoxy resin sheet which can be degraded circularly and can be processed by thermoplasticity;
(3) Degradation and recycling of cured epoxy resin polymers
S1, soaking the cured epoxy resin into an acidic aqueous solution/organic solvent I mixed solution, reacting for 24 hours at the temperature of between room temperature and 80 ℃, and degrading, wherein degradation products are dissolved in the mixed solution;
s2, adding equivalent NaOH into the mixed solution obtained in the step S1 to neutralize acid, regulating the pH of the degradation solution to be neutral, volatilizing the solvent at room temperature, sequentially adding equivalent water and an organic solvent II to extract degradation products, separating liquid, collecting organic phase solution, and performing rotary evaporation to obtain the product
Degradation products;
wherein the acidic aqueous solution is 1mol/L hydrochloric acid aqueous solution or 1mol/L sulfuric acid aqueous solution; acidic aqueous solution and organic solvent
The mass fraction ratio is 8; the organic solvent I is methanol or ethanol or tetrahydrofuran; the organic solvent II is dichloromethane or ethyl
Ethyl ester acid;
the recycled degradation product reacts for 6 hours at 180 ℃, and the cured epoxy resin with the same structure as the initial epoxy resin can be obtained again, so that the cyclic utilization of the degradation product is realized;
(4) Thermoplastic processing of epoxy monomers
Placing the crushed epoxy resin into a mold, and placing the mold into a high-temperature flat vulcanizing machine for hot pressing for 10min to obtain a complete epoxy resin sheet;
wherein the temperature of the plate vulcanizing machine is 150-200 ℃, and the pressure is 10MPa.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116041753A (en) * | 2023-01-30 | 2023-05-02 | 四川大学 | Method for preparing epoxy resin composite material by upgrading and recycling waste polyamidourea |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116041753A (en) * | 2023-01-30 | 2023-05-02 | 四川大学 | Method for preparing epoxy resin composite material by upgrading and recycling waste polyamidourea |
| CN116041753B (en) * | 2023-01-30 | 2024-05-28 | 四川大学 | Waste polyamidourea upgrading and recycling method |
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