CN111484704B - Method for reprocessing thermosetting high polymer material - Google Patents
Method for reprocessing thermosetting high polymer material Download PDFInfo
- Publication number
- CN111484704B CN111484704B CN201910074470.5A CN201910074470A CN111484704B CN 111484704 B CN111484704 B CN 111484704B CN 201910074470 A CN201910074470 A CN 201910074470A CN 111484704 B CN111484704 B CN 111484704B
- Authority
- CN
- China
- Prior art keywords
- thermosetting
- epoxy resin
- polymer material
- diglycidyl ether
- acid
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/08—Polyurethanes from polyethers
Abstract
The invention provides a novel method for reprocessing thermosetting high polymer materials, in particular to a simple method for reprocessing thermosetting epoxy resin materials. The thermosetting epoxy resin used in the method does not contain a catalyst and comprises common epoxy resin and liquid crystal epoxy resin containing liquid crystal elements. The reprocessing method has the advantages of no need of a catalyst, simple steps, high material stability, strong universality and the like, and realizes direct recycling of a large amount of the conventional epoxy resin.
Description
Technical Field
The invention relates to the field of processing of high polymer materials, in particular to a reprocessing method of a thermosetting epoxy resin material.
Background
Epoxy resin is an important thermosetting resin, and is one of the most widely applied materials in common polymer composite materials. The cured epoxy resin has excellent electrical insulating property, high adhesion, dimensional stability, corrosion resistance and other properties, is used as a coating, an adhesive, an electronic and electrical material and the like, and is widely applied to the fields of mechanical aviation, chemical engineering, construction automobiles and the like. As an important thermosetting material, epoxy resin is insoluble and infusible, so that the epoxy resin cannot be processed again after being formed, and the epoxy resin material is difficult to recycle after being discarded, aged and damaged, thereby causing resource waste and solid waste pollution.
In recent years, a researcher introduces dynamic covalent bonds into a cross-linked network of epoxy resin, and the performance of re-processing a thermosetting polymer material after processing and molding is realized for the first time. Leibler introduces dynamic ester bond and catalyst for accelerating ester exchange reaction into epoxy resin, utilizes ester bond to make quick ester exchange reaction (ester bond breaking-recombination) at high temperature, and makes the epoxy resin undergo the process of moulding treatment again. The catalyst plays an important role in the process, but the addition of the catalyst undoubtedly has a significant influence on the preparation and use of the material. On one hand, the addition of the catalyst increases the preparation cost, and formula research, process optimization, use temperature range adjustment and the like are required; on the other hand, since the catalyst is always present inside the material, the new shape obtained by rework is unstable at high temperature (stress relaxation is liable to occur by external force), and is unstable even after being left or used at low temperature for a long time because the transesterification reaction proceeds slowly at low temperature, but according to the principle of time-temperature equivalence, a phenomenon of stress relaxation occurs when the epoxy resin is used at low temperature or left for a long time.
Furthermore, the existing large amount of epoxy resins are applied to the crosslinked network of finished products or waste products without catalysts, and they can be stably stored or used at room temperature or low temperature, but cannot be reprocessed and recycled at high temperature. Therefore, if a large amount of epoxy resin application finished products or waste products can be stably stored or used at room temperature or low temperature, and can be reprocessed and recycled at high temperature without a catalyst, the environmental pollution caused by epoxy resin waste is reduced, resources are fully utilized, the processing process of the epoxy resin is simplified, and the service life of the epoxy resin is prolonged. Therefore, there is an urgent need to develop a catalyst-free method for directly reworking a large amount of thermosetting epoxy resin materials available.
In addition, besides epoxy resin, exchange reaction exists inside the cross-linked network of many other thermosetting materials (such as transcarbamylation reaction exists inside polyurethane), and the method for reprocessing and recycling the epoxy resin is very expected to be used for recycling other thermosetting materials.
Disclosure of Invention
The present invention has been made to solve the above-mentioned problems occurring in the prior art, and an object of the present invention is to provide a method for directly reworking a large amount of thermosetting polymer materials, particularly epoxy resin materials, without using a catalyst.
A method of reprocessing a thermoset polymeric material comprising:
providing a thermosetting high polymer material to be treated, wherein the thermosetting high polymer material can perform exchange reaction and is provided with a part to be treated; using external force to deform the part to be processed, then keeping the new shape and heating at high temperature to make the material generate exchange reaction to permanently fix the new shape; thereby realizing the direct deformation processing of the thermosetting polymer material and obtaining the thermosetting polymer material which can be hot-formed and utilized again.
Specifically, the heating temperature is not lower than 100 ℃, and the heating time is 0.5 to 8 hours.
Specifically, the above-mentioned exchange reaction is a transesterification reaction, or a transamination reaction.
Specifically, the thermosetting polymer material includes, but is not limited to, thermosetting epoxy resin, polyurethane, and the like.
More specifically, the thermosetting epoxy resin material includes a general epoxy resin and a liquid crystal epoxy resin containing mesogen.
More specifically, the thermosetting epoxy resin materials include, but are not limited to, diglycidyl ethers and aliphatic diacids, or diglycidyl ethers and anhydrides.
Further, the diglycidyl ether may include one of bisphenol a diglycidyl ether, 1, 4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, and 1, 4-dihydroxybiphenyl diglycidyl ether; the aliphatic diacid can comprise one of adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecyl diacid, hexadecyl diacid, octadecyl diacid and hexadecyl diacid; the acid anhydride may include one of glutaric anhydride, adipic anhydride, and succinic anhydride.
More specifically, in the high-temperature rework step in the process of the present invention, the time required for heating is relatively shorter as the temperature to be employed is higher. When the thermosetting polymer material is a thermosetting epoxy resin, it is preferable that the heating time is 8 hours when the temperature is 100 ℃,4 hours when the temperature is 150 ℃, 2 hours when the temperature is 180 ℃, 1 hour when the temperature is 200 ℃ and 0.5 hour when the temperature is 220 ℃. When the thermosetting polymer material is polyurethane, it is preferable that the heating time is 3 hours at a temperature of 100 ℃, 2 hours at a temperature of 120 ℃ and 1 hour at a temperature of 140 ℃.
Specifically, the deformation process includes, but is not limited to, mechanical stretching, reshaping, welding, and pressing.
The invention also protects the thermosetting polymer material with the reprocessing characteristic obtained by the reprocessing method.
The method for reprocessing the thermosetting polymer material can ensure that the thermosetting polymer material has the characteristic of reprocessing after molding without a catalyst. Specifically, in the processing method of the invention, the exchange reaction of the thermosetting polymer material is excited at high temperature, and after the exchange reaction is carried out for a long enough time, the cross-linked network of the material is changed under the condition of unchanged cross-linked density, thereby realizing the direct deformation processing and the direct recycling of the thermosetting polymer material.
The method of the invention is very simple, because the material has no catalyst, the performance of the thermosetting polymer material after being remolded is very stable, thus the service life of the thermosetting polymer material can be prolonged, and the reprocessing cost of the method of the invention is very low.
Drawings
FIG. 1 is a flow chart of the high temperature processing of an epoxy material for reshaping according to an embodiment of the present invention.
FIG. 2 is a flow chart of high temperature recycling of epoxy chips according to an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more clearly understood, the following method for processing thermosetting polymer materials according to the present invention is further described in detail with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The method for reprocessing the thermosetting polymer material provided by the invention is used for carrying out deformation treatment on the thermosetting polymer material to be treated by using external force, then carrying out high-temperature heating to enable the material to have exchange reaction, wherein the high temperature is not lower than 100 ℃, and then keeping the new shape at the temperature for not less than 0.5 hour, thereby realizing the direct deformation processing on the thermosetting polymer material and obtaining the thermosetting polymer material which can be subjected to hot forming and utilization again.
The thermosetting polymer material in the present invention includes, but is not limited to, thermosetting epoxy resin, polyurethane, and the like.
Example 1:
the epoxy resin used in this example is a material in which an ester exchange reaction can occur, and is cured by bisphenol a diglycidyl ether and adipic acid.
The specific reshaping processing method for the epoxy resin of this example is as follows:
referring to fig. 1, the strip-shaped epoxy resin material is heated to 180 ℃, deformed into a spiral shape by an external force, kept at 180 ℃ for 2 hours, and then cooled to room temperature, and the spiral shape is a permanent stable shape. Repeating the above steps to obtain another permanent stable spiral shape.
Example 2:
the specific recycling processing method for the epoxy resin of example 1 of the present invention is as follows:
referring to fig. 2, the epoxy resin fragments are heated to 180 ℃, and then are heated and pressed for 2 hours by external force and then cooled to room temperature, so that the epoxy resin fragments are hot-pressed again to form a new material for reuse.
Example 3:
the polyurethane used in this embodiment is a material in which transcarbamylation reaction can occur, and is specifically formed by curing diisocyanate, polyethylene glycol and a crosslinking agent.
The specific reshaping procedure for the polyurethane of this example was as follows:
heating the strip-shaped polyurethane material to 120 ℃, deforming and stretching the polyurethane material by 50 percent by using external force, keeping the stretched state, placing the polyurethane material at 120 ℃ for 2 hours, and then cooling the polyurethane material to room temperature, wherein the stretched state is the permanent stable shape.
The above examples are described by taking the relatively common thermosetting polymer material as an example, but it should be understood that the invention is not limited to the above materials, and the thermosetting polymer material capable of undergoing exchange reaction can be directly recycled by the method of the invention.
The above-mentioned embodiments only express one embodiment of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (6)
1. A method of reworking a thermoset polymeric material, comprising:
providing a thermosetting high polymer material to be treated, wherein an exchange reaction can occur in the thermosetting high polymer material and is provided with a part to be treated, and the exchange reaction is an ester exchange reaction or a transcarbamoyl reaction;
the part to be treated is deformed by external force without using a catalyst, and then the new shape is kept to be heated at high temperature, so that the material is subjected to exchange reaction and is permanently fixed;
thereby realizing the direct deformation processing of the thermosetting polymer material and obtaining the thermosetting polymer material which can be hot-formed and utilized again;
the heating temperature is not lower than 100 ℃, and the heating time is 0.5-8 hours;
the thermosetting polymer material comprises one of thermosetting epoxy resin and polyurethane.
2. A method of reworking a thermosetting polymeric material according to claim 1, wherein said thermosetting epoxy material comprises a conventional epoxy resin and a liquid crystal epoxy resin containing mesogens.
3. The method of reworking a thermoset polymeric material according to claim 1, wherein the thermoset epoxy material comprises a diglycidyl ether and an aliphatic diacid, or comprises a diglycidyl ether and an anhydride.
4. The method of reworking a thermoset polymeric material according to claim 3, wherein the diglycidyl ether comprises one of bisphenol A diglycidyl ether, 1, 4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, and 1, 4-dihydroxybiphenyl diglycidyl ether.
5. A method of reworking a thermosetting polymeric material according to claim 3, wherein said aliphatic diacid comprises one of adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, hexadecanedioic acid, octadecanedioic acid.
6. The method of reprocessing a thermoset polymeric material according to claim 3, wherein said anhydride comprises one of glutaric anhydride, adipic anhydride, and succinic anhydride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910074470.5A CN111484704B (en) | 2019-01-25 | 2019-01-25 | Method for reprocessing thermosetting high polymer material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910074470.5A CN111484704B (en) | 2019-01-25 | 2019-01-25 | Method for reprocessing thermosetting high polymer material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111484704A CN111484704A (en) | 2020-08-04 |
| CN111484704B true CN111484704B (en) | 2021-07-16 |
Family
ID=71791244
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910074470.5A Active CN111484704B (en) | 2019-01-25 | 2019-01-25 | Method for reprocessing thermosetting high polymer material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111484704B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110319524A1 (en) * | 2010-05-31 | 2011-12-29 | Centre National De La Recherche Scientifique | Epoxy Acid Thermoset Resins and Composites that Can Be Hot-Fashioned and Recycled |
| CN107828051A (en) * | 2017-10-18 | 2018-03-23 | 清华大学 | The processing method and sweep-out method of thermosetting resin |
| CN108219111A (en) * | 2018-01-03 | 2018-06-29 | 中国工程物理研究院化工材料研究所 | Selfreparing, the thermosets that can be reprocessed and can be recycled and its processing method under a kind of temperate condition |
-
2019
- 2019-01-25 CN CN201910074470.5A patent/CN111484704B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110319524A1 (en) * | 2010-05-31 | 2011-12-29 | Centre National De La Recherche Scientifique | Epoxy Acid Thermoset Resins and Composites that Can Be Hot-Fashioned and Recycled |
| CN107828051A (en) * | 2017-10-18 | 2018-03-23 | 清华大学 | The processing method and sweep-out method of thermosetting resin |
| CN108219111A (en) * | 2018-01-03 | 2018-06-29 | 中国工程物理研究院化工材料研究所 | Selfreparing, the thermosets that can be reprocessed and can be recycled and its processing method under a kind of temperate condition |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111484704A (en) | 2020-08-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3275923B1 (en) | Fiber-reinforced plastic molding material, method for producing same, and molded article | |
| CN110627998B (en) | Method for regulating and controlling stress relaxation and reprocessing molding temperature of glass-like polymer material through dynamic bond content | |
| CN112979925B (en) | Medium-low temperature curing type epoxy glass polymer | |
| WO2015067569A1 (en) | Self-healing thermally conductive polymer materials | |
| CN104231994A (en) | Adhesive material | |
| CN109762139A (en) | It can weld the preparation method that can repair and can reprocess molding thermosetting polymer under a kind of moderate temperature | |
| Li et al. | An investigation on the performance of epoxy vitrimers based on disulfide bond | |
| CN111484704B (en) | Method for reprocessing thermosetting high polymer material | |
| CN109575334A (en) | A kind of shape memory epoxy resin prepreg and preparation method thereof | |
| CN110054795B (en) | Thermosetting polymer material processing, healing and welding method | |
| CN114907548A (en) | Epoxy resin batch for pultrusion of composite material and preparation method thereof | |
| CN110564109A (en) | Preparation method of high-strength solvent-resistant epoxy fiber composite material capable of being rapidly disassembled and recycled | |
| CN114806166A (en) | Triple shape memory cyanate and preparation method thereof | |
| CN106977875A (en) | A kind of low-temperature catalyzed solidification aldol resin system and preparation method thereof | |
| CN112608452A (en) | High-performance recyclable and easily-repaired epoxy resin and preparation method thereof | |
| KR20210071285A (en) | Recyclable self-healing epoxy vitrimer and method for manufacturing the same | |
| CN115109385A (en) | Epoxy resin composition for prepreg and preparation method thereof | |
| CN113980305A (en) | Preparation method of degradable high-performance fiber-reinforced epoxy resin-based composite material | |
| CN101092504A (en) | Solvent free resin applied to technique of vacuum pressure for dipping electrical motor in high voltage | |
| CN104592870A (en) | Preparation process of impregnating varnish with high storage stability for transformer | |
| CN115353610B (en) | Water-based epoxy resin degraded in water and preparation method thereof | |
| CN117143319A (en) | Reversible covalent bond curing agent, self-repairing epoxy resin and preparation method thereof | |
| CN111051379A (en) | Resin composition and material comprising the same | |
| CN117209837A (en) | Hot-pressing recovery method of retired epoxy insulating material of dry-type transformer | |
| CN107958764A (en) | A kind of computer CPU radiator fan ultra-thin Agglutinate neodymium-iron-boron magnet and preparation method thereof |
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 |