CN114479363A - High-temperature-resistant epoxy resin-based composite material - Google Patents
High-temperature-resistant epoxy resin-based composite material Download PDFInfo
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- CN114479363A CN114479363A CN202210251102.5A CN202210251102A CN114479363A CN 114479363 A CN114479363 A CN 114479363A CN 202210251102 A CN202210251102 A CN 202210251102A CN 114479363 A CN114479363 A CN 114479363A
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- 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
- C08L63/04—Epoxynovolacs
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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Abstract
The invention discloses a high-temperature-resistant epoxy resin-based composite material which comprises the following raw materials in parts by weight: 40-80 parts of epoxy resin, 20-50 parts of polyamide-imide, 0.5-1 part of curing accelerator and 0-30 parts of filler, and the components are mixed at normal temperature and are subjected to thermosetting at the temperature of 140-180 ℃. The high-temperature-resistant epoxy resin-based composite material has good heat resistance, excellent wear resistance, good fluidity, excellent insulating property and excellent mechanical strength; can be used for a long time under the condition of higher temperature without degradation, deformation and the like; the cured epoxy resin-based composite material has tensile strength of over 150MPa, can be used as an electronic protection element, an electronic device, a large-scale motor and the like to normally work, and can meet the requirements of special industries.
Description
Technical Field
The invention belongs to the technical field of material chemical industry, and particularly relates to a high-temperature-resistant epoxy resin-based composite material.
Background
The epoxy resin is a high molecular polymer and is a generic name of a polymer containing more than two epoxy groups in a molecule. It is a polycondensation product of epichlorohydrin and bisphenol A or a polyol. Because of the chemical activity of the epoxy group, the epoxy group can be opened by a plurality of compounds containing active hydrogen, and the epoxy group is cured and crosslinked to form a network structure, so that the epoxy group is a thermosetting resin. The epoxy resin is used as the polyhydroxy component, combines the advantages of polyurethane and epoxy resin, and has better bonding strength and chemical resistance.
Because of the unique advantages of high insulating property, large structural strength, good sealing property and the like of the epoxy resin, the epoxy resin is widely applied to insulation and packaging of high and low voltage electric appliances, motors and electronic components and is developed quickly. The method is mainly used for: 1. and (4) pouring an insulating packaging part of the electric appliance and the motor. The manufacture of integral fully-sealed insulating package parts of high-voltage and low-voltage electric appliances such as electromagnets, contactor coils, mutual inductors, dry-type transformers and the like. Has been rapidly developed in the electrical industry. The development of atmospheric casting and vacuum casting has progressed to automatic pressure gel molding.
Polyamideimide, PAI for short, is a high molecular polymer containing amide bond and imide ring in its main chain. Because the molecular chain has strong polar amido bond and imide ring with high heat resistance, the polyamide has excellent mechanical property and processability of polyamide, and also has excellent heat resistance, dielectricity, mechanical property, creep resistance and chemical stability of polyimide. In recent years, a polyamide-imide polymer material gradually becomes an engineering plastic with excellent performance, and is more and more widely applied to the fields of aerospace, transportation, chemical equipment and electronic industry, such as enameled wires, integrated optical path materials, nano composite materials, electronic packaging materials and the like.
In some special fields, such as large-scale motors, aerospace materials and the like, the materials are required to have certain mechanical properties and other special properties, such as high temperature resistance, corrosion resistance, aging resistance, radiation resistance and the like. Although the currently sold epoxy resin-based composite material has better mechanical properties such as tensile property, impact property, wear resistance and the like, the heat resistance is slightly insufficient, and the requirement of practical application cannot be met.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a high-temperature-resistant epoxy resin-based composite material.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a high-temperature-resistant epoxy resin-based composite material comprises the following raw materials in parts by mass:
40-80 parts of epoxy resin, 20-50 parts of polyamide-imide, 0.5-1 part of curing accelerator and 0-30 parts of filler, and the epoxy resin, the polyamide-imide and the curing accelerator are mixed at normal temperature and are subjected to thermosetting at the temperature of 140-180 ℃.
Furthermore, the epoxy resin is one or more of bisphenol A type epoxy resin, bisphenol F type epoxy resin or novolac epoxy resin.
Furthermore, the epoxy resin adopts one or more of E-51, E-44, E-20, E-12, novolac epoxy resin F-51 and F-44 resin.
Further, the polyamideimide resin is selected from wholly aromatic or semi-aromatic.
Further, the polyamide-imide resin is synthesized by a diisocyanate method by adopting a substrate A and a substrate B, wherein the substrate A is one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate; the substrate B can be one or more of trimellitic anhydride, pyromellitic anhydride, adipic acid and sebacic acid.
Further, the curing accelerator is DMP-30.
Further, the filler adopts one or two of asbestos and glass fiber.
Furthermore, the raw material proportion of the high-temperature-resistant epoxy resin-based composite material also comprises 0.5-1 part of dispersant, and the dispersant adopts one of Germany BYK-110 and BYK-163.
Furthermore, the raw material proportion of the high-temperature-resistant epoxy resin-based composite material also comprises 0.5-1 part of a flatting agent, and the flatting agent adopts one of Germany BYK-358N and BYK-354.
The invention has the beneficial effects that:
(1) the heat resistance is good: the 5% mass loss temperature of the completely cured composite material is 432 ℃, and the completely cured composite material can be used for a long time under the condition of higher temperature without degradation, deformation and the like;
(2) has excellent wear resistance. The polyamide-imide resin which is one of the used components has better lubricating effect, and the use in special occasions can be met by improving the proportion of the polyamide-imide resin;
(3) the material has good fluidity: the epoxy resin and the polyamide-imide resin have good compatibility, can be uniformly mixed at normal temperature, and can obtain a composite material with good fluidity at normal temperature by using proper epoxy resin, so that the construction is very facilitated;
(4) the insulating material has excellent insulating property: the epoxy resin-based composite material has excellent insulating property, the resistivity of the cured resin is up to 715T omega.mm, and the requirement of a common insulating environment can be completely met;
(5) has excellent mechanical strength: the tensile strength of the cured epoxy resin-based composite material is more than 150 MPa.
Drawings
FIG. 1 is a thermogravimetric comparison curve of an epoxy resin before and after curing in an example of the present invention.
Detailed Description
The invention is illustrated below with reference to specific examples. It will be understood by those skilled in the art that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention in any way.
As shown in the thermogravimetric comparison curve before and after the epoxy resin is cured in FIG. 1, it can be seen that the 5% mass loss temperature of the epoxy resin is increased by 192 ℃ and the 800 ℃ carbon residue rate is increased by 22% after the curing reaction.
Example 1
A high-temperature-resistant epoxy resin-based composite material is obtained by the following steps:
(1) using diphenylmethane diisocyanate and trimellitic anhydride as substrates to synthesize polyamide-imide resin under certain conditions, and removing the solvent by a precipitation method;
(2) taking 40 parts of novolac epoxy resin D431, 40 parts of polyamide-imide resin, 0.5 part of DMP-30 curing accelerator, 0.5 part of BYK-141 dispersant and 0.5 part of BYK-141 flatting agent, and fully and uniformly mixing the components in a sand mill at normal temperature for later use;
(3) and pouring the prepared resin liquid into a mold, and baking the resin liquid in an oven at 160 ℃ for 1 hour to obtain the composite material.
In this example, the Linesis PT 1600 synchronous thermal analyzer was used to determine its heat resistance, and the temperature at which 5% mass loss occurred was 411 ℃. The mechanical strength was measured with a biaxial stretching machine (Shimadzu AGX-V500N) to be 160 MPa. The resistivity was 520.6 T.OMEGA.mm as measured with a four-probe resistivity tester.
Example 2
A high-temperature-resistant epoxy resin-based composite material is obtained by the following steps:
(1) using diphenylmethane diisocyanate and trimellitic anhydride as substrates to synthesize polyamide-imide resin under certain conditions, and removing the solvent by a precipitation method;
(2) taking 60 parts of phenol, namely, aldehyde epoxy resin D431, 20 parts of polyamide-imide resin, 0.5 part of DMP-30 curing accelerator, 0.5 part of BYK-141 dispersant and 0.5 part of BYK-141 flatting agent, and fully and uniformly mixing the components in a sand mill at normal temperature for later use;
(3) and pouring the prepared resin liquid into a mold, and baking the resin liquid in an oven at 160 ℃ for 1 hour to obtain the composite material.
In this example, the Linesis PT 1600 synchronous thermal analyzer was used to determine its heat resistance, and the temperature at which 5% mass loss occurred was 424 ℃. The mechanical strength was measured with a biaxial stretching machine (Shimadzu AGX-V500N) to be 142 MPa. The resistivity was 226.5 T.OMEGA.mm as measured with a four-probe resistivity tester.
While the invention has been described in further detail with reference to specific preferred embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (9)
1. The high-temperature-resistant epoxy resin-based composite material is characterized by comprising the following raw materials in parts by mass:
40-80 parts of epoxy resin, 20-50 parts of polyamide-imide, 0.5-1 part of curing accelerator and 0-30 parts of filler, and the epoxy resin, the polyamide-imide and the curing accelerator are mixed at normal temperature and are subjected to thermosetting at the temperature of 140-180 ℃.
2. The high temperature resistant epoxy resin based composite material as claimed in claim 1, wherein the epoxy resin is one or two of bisphenol A type epoxy resin or novolac epoxy resin.
3. The high temperature resistant epoxy resin based composite material as claimed in claim 1, wherein the epoxy resin is one or more of E-51, E-44, E-20, E-12, novolac epoxy resin F-51, F-44.
4. The high temperature resistant epoxy resin-based composite material as claimed in claim 1, wherein the polyamideimide resin is selected from wholly aromatic or semi-aromatic.
5. The high-temperature-resistant epoxy resin-based composite material as claimed in claim 1, wherein the polyamideimide resin is synthesized by a diisocyanate method by adopting a substrate A and a substrate B, wherein the substrate A is one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate; the substrate B can be one or more of trimellitic anhydride, pyromellitic anhydride, adipic acid and sebacic acid.
6. The high temperature resistant epoxy resin based composite material of claim 1, wherein the curing accelerator is DMP-30.
7. The high temperature resistant epoxy resin based composite material as claimed in claim 1, wherein the filler is one or both of asbestos and glass fiber.
8. The high temperature resistant epoxy resin based composite material as recited in any one of claims 1 to 7, wherein the raw material mixture ratio further comprises 0.5-1 part of dispersant, and the dispersant is one of BYK-110 and BYK-163 in Germany.
9. The high temperature resistant epoxy resin based composite material as recited in any one of claims 1 to 7, wherein the raw material mixture ratio further comprises 0.5-1 parts of a leveling agent, and the leveling agent is one of BYK-358N, BYK-354 in Germany.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210251102.5A CN114479363A (en) | 2022-03-15 | 2022-03-15 | High-temperature-resistant epoxy resin-based composite material |
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| CN202210251102.5A CN114479363A (en) | 2022-03-15 | 2022-03-15 | High-temperature-resistant epoxy resin-based composite material |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102295740A (en) * | 2011-07-11 | 2011-12-28 | 复旦大学 | Polyamideimide cured epoxy resin composite material and preparation method thereof |
| CN106317787A (en) * | 2016-09-13 | 2017-01-11 | 北京市射线应用研究中心 | High-temperature-resistant epoxy resin-based neutron and gamma-ray shielding composite material and preparation method thereof |
| CN107815070A (en) * | 2017-11-09 | 2018-03-20 | 湖北航天化学技术研究所 | A kind of room temperature-curing low-viscosity high strength epoxy resin castable and preparation method |
| CN112680058A (en) * | 2020-12-14 | 2021-04-20 | 无锡中油瑞德防腐科技有限公司 | Polyamide-imide cured epoxy resin water-based paint and preparation method thereof |
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2022
- 2022-03-15 CN CN202210251102.5A patent/CN114479363A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102295740A (en) * | 2011-07-11 | 2011-12-28 | 复旦大学 | Polyamideimide cured epoxy resin composite material and preparation method thereof |
| CN106317787A (en) * | 2016-09-13 | 2017-01-11 | 北京市射线应用研究中心 | High-temperature-resistant epoxy resin-based neutron and gamma-ray shielding composite material and preparation method thereof |
| CN107815070A (en) * | 2017-11-09 | 2018-03-20 | 湖北航天化学技术研究所 | A kind of room temperature-curing low-viscosity high strength epoxy resin castable and preparation method |
| CN112680058A (en) * | 2020-12-14 | 2021-04-20 | 无锡中油瑞德防腐科技有限公司 | Polyamide-imide cured epoxy resin water-based paint and preparation method thereof |
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