CN114031940A - Low-dielectric-constant halogen-free flame-retardant epoxy-cyanate resin and preparation method thereof - Google Patents
Low-dielectric-constant halogen-free flame-retardant epoxy-cyanate resin and preparation method thereof Download PDFInfo
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- 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
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- 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
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- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
Abstract
The invention discloses a low-dielectric-constant halogen-free flame-retardant epoxy-cyanate ester resin and a preparation method thereof, which belong to the field of flame-retardant polymer preparation and thermosetting resin modification, and introduce a phosphorus-nitrogen synergistic reaction type flame retardant containing a nitrile group on the basis of not changing the existing mature epoxy-cyanate ester resin system to develop a low-dielectric-constant flame-retardant resin system, greatly reduce the using amount of a flame retardant, and realize the compatibility of multiple properties such as construction manufacturability, mechanical property, dielectric property, flame retardant property and the like.
Description
Technical Field
The invention relates to a preparation method of low-dielectric-constant halogen-free flame-retardant epoxy-cyanate ester resin, in particular to nitrile group-containing phosphorus-nitrogen synergistic flame-retardant modified epoxy-cyanate ester resin, belonging to the field of flame-retardant polymer preparation and thermosetting resin modification.
Background
Epoxy resin is widely used in various fields such as electronic packaging, high-frequency communication, aerospace, automobile traffic, weaponry and the like due to excellent comprehensive performance, good adhesion, mechanical property, stability and manufacturability. However, the epoxy resin has poor flame retardant property and high dielectric constant and dielectric loss, which limits the application of the epoxy resin in high-end fields, especially in high-frequency and high-speed circuit boards to a certain extent. Therefore, low dielectric and flame retardant modification of epoxy resin is required to meet the demand of high frequency and high speed of modern information communication.
Cyanate modified epoxy resin is one of the methods widely adopted at present, because cyanate resin has excellent dielectric property, good thermal stability, good heat resistance and certain flame retardant property. For example, the li qi team of the university of beijing chemical industry developed a cyanate ester-epoxy hybrid resin, which has both low dielectric constant and high heat resistance (CN 200910081259.2). In addition, chinese patent CN200880020918.5 discloses an epoxy-cyanate resin, which improves heat resistance and mechanical properties, and improves dielectric properties; the cyanate ester-bismaleimide-epoxy resin disclosed in the Chinese patent CN200910071906.1 also has good dielectric properties; the liquid type cyanate ester-epoxy composite resin disclosed in the U.S. Pat. No. 2012/0178853A1 has the characteristics of stable system storage, excellent mechanical property, excellent dielectric property and the like.
However, with the rapid development of electronic technology and the enhancement of awareness of people about environmental safety, cyanate ester and modified epoxy resin thereof are difficult to meet the requirement of flame retardance. Therefore, there is a need for developing epoxy-cyanate ester resin with excellent dielectric properties and good flame retardant properties by a method with simple operation and low cost. There are many methods for flame-retarding polymer materials, and the most widely method is to add flame retardant directly. Although the halogen flame retardant has excellent flame retardant effect, a large amount of gas which is toxic to human bodies is generated during combustion and serious harm is caused to an ecosystem, so the halogen flame retardant is gradually eliminated. In recent years, the phosphorus-nitrogen synergistic flame retardant has excellent performance in the aspects of flame retardant effect and smoke release, and becomes a research hotspot in the current flame retardant industry. The organic phosphorus heterocyclic compound 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) has better flame retardant effect and is a commonly used flame retardant additive at present. Chinese patent CN201610027967.8 adds DOPO in epoxy resin to prepare a flame-retardant cyanate resin; chinese patent CN201310032173.7 discloses a preparation method of a low-dielectric halogen-free flame-retardant glass fiber prepreg, and DOPO and polyphenyl ether are added into a resin system. In addition, DOPO contains active P-H bonds, and is easy to prepare various novel phosphorus-nitrogen synergistic flame retardants through chemical reaction, so that the flame retardant effect is further improved. Chinese patent CN202011509590.2 discloses an additive type crosslinkable flame retardant, which utilizes the reaction of DOPO and 3-aminophenoxy phthalonitrile monomer to prepare a phosphorus-nitrogen synergistic flame retardant containing nitrile group; chinese patent CN202010987990.8 discloses a bisphthalonitrile flame retardant containing DOPO, and the invention utilizes a benzoxazine-containing bisphthalonitrile monomer to react with DOPO to prepare the novel phosphorus-nitrogen synergistic flame retardant of bisphthalonitrile.
The flame retardant is added into an epoxy-cyanate ester system, so that the flame retardant performance of the epoxy-cyanate ester system can be obviously improved, but the content of the additive is required to reach 15-25%. The addition of large amounts of flame retardants also brings about a number of disadvantages: firstly, the use of a large amount of flame retardant increases the cost and increases the viscosity of the resin system, thereby reducing the manufacturability of the resin; secondly, a large amount of flame retardant has dispersion problems in the resin, which can lead to the reduction of the mechanical properties of the resin; finally, a large amount of flame retardant inevitably affects the dielectric properties of the resin, so that the dielectric constant and the dielectric loss of the resin are obviously improved. Therefore, the epoxy-cyanate resin formula with low flame retardant addition is developed, and the preparation has excellent flame retardant property, mechanical property and dielectric property and has great significance.
Disclosure of Invention
In order to solve the problems of cost increase, viscosity increase, construction deterioration, dispersion unevenness, mechanical property reduction, dielectric constant and dielectric loss improvement and the like caused by large addition amount of a flame retardant in the traditional resin formula, the invention aims to introduce nitrile group-containing phosphorus-nitrogen synergistic reaction type flame retardant on the basis of not changing the existing mature epoxy-cyanate ester resin system, develop a low-dielectric constant flame retardant resin system, greatly reduce the consumption of the flame retardant, and realize the compatibility of multiple properties such as construction manufacturability, mechanical property, dielectric property, flame retardant property and the like.
The technical scheme adopted by the invention for realizing the purpose is as follows:
the halogen-free flame retardant epoxy-cyanate resin with the low dielectric constant comprises the following components in parts by weight:
a preparation method of low-dielectric-constant halogen-free flame-retardant epoxy-cyanate ester resin comprises the following steps:
1) mixing 5-50 parts of epoxy resin and 0.5-5 parts of reactive phosphorus-nitrogen synergistic flame retardant containing nitrile groups at one time, and heating and stirring until the epoxy resin and the flame retardant are completely dissolved; or mixing 5-50 parts of epoxy resin with 0.5-5 parts of reactive nitrogen-phosphorus synergistic flame retardant containing nitrile groups, heating and stirring until the mixture is completely dissolved, then adding 3-20 parts of curing agent and 1-10 parts of auxiliary agent, and then adding and mixing the rest 5-50 parts of epoxy resin;
2) adding 10-50 parts of cyanate ester resin and uniformly mixing to obtain epoxy resin-cyanate ester resin containing a polymerization inhibitor;
3) and (3) selecting a curing process according to the addition amount of the phosphorus-nitrogen synergistic flame retardant containing the nitrile group to prepare the low-dielectric-constant halogen-free flame-retardant epoxy-cyanate ester resin composite material.
Further, the structural formula of the phosphorus-nitrogen synergistic flame retardant containing a nitrile group is one or two of formula 1 and formula 2:
furthermore, the temperature of the temperature rise stirring is 110-150 ℃, and preferably 120-130 ℃.
The cyanate ester resin is one or more of bisphenol a cyanate ester resin, bisphenol F cyanate ester resin, bisphenol M cyanate ester resin, bisphenol E cyanate ester resin, and phenol formaldehyde cyanate ester resin.
Further, the epoxy resin is any one or more of bisphenol a type epoxy resin, bisphenol F type epoxy resin, brominated bisphenol a type epoxy resin, phenol aldehyde type epoxy resin, polyfunctional epoxy resin, and alicyclic epoxy resin.
Further, the curing agent is a medium-temperature curing agent or a high-temperature curing agent, and specifically is any one or more of m-phenylenediamine, dicyandiamide, diaminodiphenyl sulfone and diaminodiphenyl methane.
Further, the auxiliary agent is any one or more of substituted urea, imidazole, copper octoate, manganese octoate, copper acetylacetonate, 9920 and 530.
Further, the method for selecting the curing process according to the addition amount of the phosphorus-nitrogen synergistic flame retardant containing the nitrile group comprises the following steps:
if 0.5-2.5 parts of the phosphorus-nitrogen synergistic flame retardant containing the nitrile group is added, selecting a high-temperature curing process;
if 2.5-5 parts of the phosphorus-nitrogen synergistic flame retardant containing the nitrile group is added, selecting a high-temperature curing process or a medium-temperature curing process;
the high-temperature curing process comprises the following steps: selecting one or more temperatures at 90-110 ℃ for 4-8 h, selecting one or more temperatures at 130-190 ℃ for 2-6h, and selecting one or more temperatures at 210-250 ℃ for 2-6h, so as to ensure that the nitrile group in the phosphorus-nitrogen synergistic flame retardant containing the nitrile group is subjected to self-crosslinking reaction;
the medium-temperature curing process comprises the following steps: one or more temperatures are selected at 80-100 ℃ and kept for 2-6h, and one or more temperatures are selected at 110-130 ℃ and kept for 3-8 h.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention introduces the phosphorus-nitrogen synergistic reaction type flame retardant containing nitrile group on the basis of not changing the existing mature epoxy-cyanate resin system, and the addition amount of the flame retardant is very low, even as low as 1 percent, so the operation is simple, the influence on the viscosity of the resin system is very small, and the construction process of the resin is not changed.
(2) The phosphorus-nitrogen synergistic reaction type flame retardant containing the nitrile group can be dissolved in the epoxy resin, and the addition amount is far lower than that of the nitrile resin (such as CN103881309A), so that the flame retardant can be uniformly dispersed without using an additional solvent, the cost and the curing temperature are reduced, the influence on the dielectric property is small, and the flame retardant is more environment-friendly.
(3) The phosphorus-nitrogen synergistic reaction type flame retardant adopted by the invention contains nitrile groups, also contains other active groups (secondary amine/phenolic hydroxyl) capable of reacting with epoxy resin or cyanate ester, does not contain halogen, and can perform chemical reactions such as self-crosslinking reaction of nitrile groups, ring-opening reaction of amino groups and phenolic hydroxyl groups with epoxy groups and the like, so that the mechanical property and the flame retardant property of the resin can be further improved. DOPO contained in flame retardant
And the active hydrogen can realize the improvement of flame retardance and mechanical property under the condition of lower temperature.
(4) The halogen-free flame-retardant epoxy-cyanate ester resin composite material prepared by the invention has low dielectric constant (lower than 4 in general, and can reach 3, even 2.8), and has multiple properties such as construction manufacturability, mechanical property, flame retardant property and the like, so that the requirement of high frequency and high speed of modern information communication can be met, and the application of the halogen-free flame-retardant epoxy-cyanate ester resin composite material in the fields of electronic packaging, high frequency communication, aerospace, automobile traffic, weaponry and the like can be widened.
Drawings
FIG. 1 is a flow chart of the preparation of the halogen-free flame retardant epoxy-cyanate ester resin with low dielectric constant of the present invention.
Detailed Description
In order to make the aforementioned and other features and advantages of the invention more comprehensible, embodiments accompanied with figures are described in detail below.
Example 1
Taking 20 parts of bisphenol A type epoxy resin E51, adding 5 parts of phosphorus-nitrogen synergistic flame retardant (structural formula 1) containing nitrile groups, heating to 110 ℃, stirring for 20 minutes to form uniform liquid, adding 5 parts of dicyandiamide, 3 parts of substituted urea and 1 part of 9920 defoaming agent, stirring uniformly, adding 16 parts of E20 epoxy resin, adding 50 parts of bisphenol A type cyanate (CE01), stirring and mixing uniformly at 90 ℃, pouring into a mold at 100 ℃, vacuumizing for 15 minutes, keeping at 90 ℃ for 4 hours, and keeping at 110 ℃ and 130 ℃ for 3 hours respectively to obtain the low-dielectric-constant halogen-free flame-retardant epoxy-cyanate resin.
Example 2
Taking 20 parts of bisphenol A type epoxy resin E51, adding 3 parts of phosphorus-nitrogen synergistic flame retardant (structural formula 1) containing nitrile groups, adding 2 parts of phosphorus-nitrogen synergistic flame retardant (structural formula 2) containing nitrile groups, heating to 120 ℃, stirring for 20 minutes to form uniform liquid, adding 3 parts of dicyandiamide, 5 parts of substituted urea and 1 part of 9920 defoaming agent, stirring uniformly, adding 16 parts of E20 epoxy resin, adding 50 parts of bisphenol A type cyanate (CE01), stirring and mixing uniformly at 90 ℃, keeping the temperature at 110 ℃ for 4h, 130 ℃, 160 ℃, 190 ℃ for 2h respectively, 210 ℃, 230 ℃ and 250 ℃ for 2h respectively, and obtaining the low-dielectric-constant halogen-free flame-retardant epoxy-cyanate resin.
Example 3
Adding 9 parts of bisphenol A epoxy resin E51, 1 part of phosphorus-nitrogen synergistic flame retardant (structural formula 1) containing nitrile groups, heating to 130 ℃, stirring for 20 minutes to form uniform liquid, adding 4 parts of dicyandiamide, 5 parts of nonylphenol and 1 part of 530 defoaming agent, stirring uniformly, adding 80 parts of bisphenol A cyanate (CE01), stirring and mixing uniformly at 100 ℃, pouring into a mold at 100 ℃, vacuumizing for 15 minutes, keeping at 100 ℃ for 6 hours, respectively keeping at 130 ℃, 160 ℃, 190 ℃ for 2 hours, respectively keeping at 210 ℃, 230 ℃ and 250 ℃ for 2 hours, and obtaining the low-dielectric-constant halogen-free flame-retardant epoxy-cyanate resin.
Example 4
Taking 5 parts of bisphenol A type epoxy resin E51, adding 2 parts of phosphorus-nitrogen synergistic flame retardant (structural formula 2) containing nitrile groups, heating to 150 ℃, stirring for 20 minutes to form uniform liquid, adding 5 parts of dicyandiamide, 6 parts of nonylphenol and 2 parts of 530 defoaming agent, stirring uniformly, adding 50 parts of bisphenol A type cyanate (CE01), adding 30 parts of phenolic type cyanate (CE05), stirring and mixing uniformly at 100 ℃, pouring into a mold at 100 ℃, vacuumizing for 15 minutes, keeping the temperature at 90 ℃, at 130 ℃, at 160 ℃, at 190 ℃ for 2 hours respectively, at 210 ℃, at 230 ℃ and at 250 ℃ for 2 hours respectively, and obtaining the low-dielectric-constant halogen-free flame retardant epoxy-cyanate resin.
Example 5
Taking 50 parts of bisphenol A type epoxy resin E51, adding 5 parts of phosphorus-nitrogen synergistic flame retardant (structural formula 2) containing nitrile groups, heating to 120 ℃, stirring for 20 minutes to form uniform liquid, adding 20 parts of dicyandiamide, 4 parts of substituted urea and 1 part of 9920 defoaming agent, stirring uniformly, adding 20 parts of bisphenol A type cyanate (CE01), stirring and mixing uniformly at 90 ℃, pouring into a mold at 100 ℃, vacuumizing for 15 minutes, keeping at 80 ℃ and 100 ℃ for 3 hours respectively, and keeping at 120 ℃ and 130 ℃ for 1.5 hours respectively to obtain the low-dielectric-constant halogen-free flame-retardant epoxy-cyanate resin.
Example 6
The reaction procedure and conditions were essentially the same as in example 2, except that the high temperature curing process was selected from: the temperature was maintained at 110 ℃ for 4h, 190 ℃ for 2h and 250 ℃ for 2 h.
Example 7
The reaction procedure and conditions were essentially the same as in example 3, except that the high temperature curing process was selected from: the temperature was maintained at 100 ℃ for 6h, 190 ℃ for 4h and 250 ℃ for 4 h.
Example 8
The reaction process and conditions were essentially the same as in example 5, except that the medium temperature curing process was selected from: the temperature was maintained at 100 ℃ for 2 hours and at 110 ℃ and 120 ℃ for 4 hours, respectively.
Comparative example 1
Preparing pure epoxy resin, taking 50 parts of bisphenol A type epoxy resin E51, adding 5 parts of dicyandiamide, 3 parts of substituted urea and 1 part of 9920 defoaming agent, stirring uniformly, adding 41 parts of E20 epoxy resin, stirring and mixing uniformly at 60 ℃, then pouring into a mold at 80 ℃, vacuumizing for 15 minutes, then keeping at 90 ℃ for 4 hours, and keeping at 110 ℃ and 130 ℃ for 3 hours respectively to obtain the epoxy resin.
Comparative example 2
An epoxy-cyanate ester resin containing no flame retardant was prepared and the procedure of example 1 was repeated except that the phosphorus-nitrogen synergistic flame retardant containing nitrile group was not added. Heating 23 parts of bisphenol A type epoxy resin E51 to 120 ℃, stirring for 20 minutes to form uniform liquid, adding 5 parts of dicyandiamide, 3 parts of substituted urea and 1 part of 9920 defoaming agent, stirring uniformly, adding 18 parts of E20 epoxy resin, adding 50 parts of bisphenol A type cyanate (CE01), stirring and mixing uniformly at 90 ℃, pouring into a mold at 100 ℃, vacuumizing for 15 minutes, keeping at 90 ℃ for 4 hours, and keeping at 110 ℃ and 130 ℃ for 3 hours respectively to obtain the corresponding epoxy-cyanate resin.
Comparative example 3
An epoxy-cyanate ester resin containing no flame retardant was prepared and the procedure of example 3 was repeated except that the phosphorus-nitrogen synergistic flame retardant containing nitrile group was not added. Heating 10 parts of bisphenol A type epoxy resin E51 to 120 ℃, stirring for 20 minutes to form uniform liquid, adding 4 parts of dicyandiamide, 5 parts of nonylphenol and 1 part of 530 defoaming agent, stirring uniformly, adding 80 parts of bisphenol A type cyanate (CE01), stirring and mixing uniformly at 100 ℃, pouring into a mold at 100 ℃, vacuumizing for 15 minutes, keeping at 110 ℃ for 4 hours, and keeping at 130 ℃, 160 ℃, 190 ℃, 210 ℃, 230 ℃ and 250 ℃ for 2 hours respectively to obtain the corresponding epoxy-cyanate resin.
TABLE 1 dielectric and flame retardant Properties of different resin systems
| Categories | Dielectric constant | Dielectric loss | Limiting oxygen index (%) | Vertical burning (UL-94) |
| Example 1 | 3.168 | 0.0116 | 29.8 | V-0 |
| Example 2 | 3.078 | 0.0098 | 39.6 | V-0 |
| Example 3 | 2.915 | 0.0093 | 34.2 | V-0 |
| Example 4 | 3.157 | 0.0084 | 38.9 | V-0 |
| Example 5 | 3.357 | 0.0184 | 34.6 | V-0 |
| Example 6 | 3.070 | 0.0096 | 39.2 | V-0 |
| Example 7 | 2.901 | 0.0091 | 33.8 | V-0 |
| Example 8 | 3.342 | 0.0179 | 34.3 | V-0 |
| Comparative example 1 | 4.324 | 0.0311 | 22.6 | Without hierarchy |
| Comparative example 2 | 3.217 | 0.0096 | 26.5 | Without hierarchy |
| Comparative example 3 | 2.946 | 0.0089 | 27.6 | Without hierarchy |
From table 1, it can be seen that the dielectric constant and dielectric loss of the epoxy resin modified without cyanate ester (comparative example 1) are high, and the dielectric property can be effectively improved by adding a certain proportion of cyanate ester. In addition, the epoxy-cyanate ester resin prepared without adding the phosphorus-nitrogen synergistic flame retardant containing nitrile groups on the surface clear in table 1 has poor flame retardant property; 1-5 parts of phosphorus-nitrogen synergistic flame retardant containing nitrile group is added, so that the flame retardant property of the epoxy-cyanate ester resin can be remarkably improved, and the vertical combustion reaches V-0 level. Both comparative example 1 and comparative example 2, and comparative example 3, show that the addition of the phosphorus-nitrogen synergistic flame retardant containing a nitrile group hardly affects the dielectric properties of the epoxy-cyanate ester resin.
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (10)
1. The halogen-free flame retardant epoxy-cyanate resin with the low dielectric constant is characterized by comprising the following components in parts by mass:
2. a preparation method of low-dielectric-constant halogen-free flame-retardant epoxy-cyanate ester resin is characterized by comprising the following steps:
1) mixing 5-50 parts of epoxy resin and 0.5-5 parts of reactive phosphorus-nitrogen synergistic flame retardant containing nitrile groups at one time, and heating and stirring until the epoxy resin and the flame retardant are completely dissolved; or mixing 5-50 parts of epoxy resin with 0.5-5 parts of reactive nitrogen-phosphorus synergistic flame retardant containing nitrile groups, heating and stirring until the mixture is completely dissolved, then adding 3-20 parts of curing agent and 1-10 parts of auxiliary agent, and then adding and mixing the rest 5-50 parts of epoxy resin;
2) adding 10-50 parts of cyanate ester resin and uniformly mixing to obtain epoxy resin-cyanate ester resin containing a polymerization inhibitor;
3) and (3) selecting a curing process according to the addition amount of the phosphorus-nitrogen synergistic flame retardant containing the nitrile group to prepare the low-dielectric-constant halogen-free flame-retardant epoxy-cyanate ester resin composite material.
3. The method of claim 2, wherein the nitrile group-containing phosphorus-nitrogen synergistic flame retardant has a structural formula of one or both of formula 1 and formula 2:
4. the method according to claim 2, wherein the temperature of the temperature-raising stirring is 110 to 150 ℃.
5. The method according to claim 4, wherein the temperature of the temperature-raising stirring is preferably 120 to 130 ℃.
6. The method according to claim 2, wherein the cyanate ester resin is one or more of bisphenol a type cyanate ester resin, bisphenol F type cyanate ester resin, bisphenol M type cyanate ester resin, bisphenol E type cyanate ester resin, and phenol type cyanate ester resin.
7. The method according to claim 2, wherein the epoxy resin is any one or more of bisphenol a type epoxy resin, bisphenol F type epoxy resin, brominated bisphenol a type epoxy resin, phenol novolac type epoxy resin, polyfunctional epoxy resin, and alicyclic epoxy resin.
8. The method of claim 2, wherein the curing agent is a medium-temperature curing agent or a high-temperature curing agent, and is one or more of m-phenylenediamine, dicyandiamide, diaminodiphenyl sulfone, and diaminodiphenyl methane.
9. The method of claim 2, wherein the adjuvant is any one or more of substituted urea, imidazole, copper octoate, manganese octoate, copper acetylacetonate, 9920, 530.
10. The method according to claim 2, wherein the curing process is selected according to the addition amount of the phosphorus-nitrogen synergistic flame retardant containing nitrile groups by:
if 0.5-2.5 parts of the phosphorus-nitrogen synergistic flame retardant containing the nitrile group is added, selecting a high-temperature curing process;
if 2.5-5 parts of the phosphorus-nitrogen synergistic flame retardant containing the nitrile group is added, selecting a high-temperature curing process or a medium-temperature curing process;
the high-temperature curing process comprises the following steps: selecting one or more temperatures at 90-110 ℃ and keeping for 4-8 h, selecting one or more temperatures at 130-190 ℃ and keeping for 2-6h, and selecting one or more temperatures at 210-250 ℃ and keeping for 2-6 h;
the medium-temperature curing process comprises the following steps: one or more temperatures are selected at 80-100 ℃ and kept for 2-6h, and one or more temperatures are selected at 110-130 ℃ and kept for 3-8 h.
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