CN111499866B - Preparation method of high-efficiency catalytic curing phenylacetylene-terminated polyimide resin system - Google Patents
Preparation method of high-efficiency catalytic curing phenylacetylene-terminated polyimide resin system Download PDFInfo
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 94
- 239000009719 polyimide resin Substances 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 12
- 238000001723 curing Methods 0.000 claims abstract description 78
- -1 phenylethynyl Chemical group 0.000 claims abstract description 69
- 239000011347 resin Substances 0.000 claims abstract description 45
- 229920005989 resin Polymers 0.000 claims abstract description 45
- 239000003054 catalyst Substances 0.000 claims abstract description 42
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000013035 low temperature curing Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 20
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 claims description 19
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 8
- 239000003292 glue Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 238000005086 pumping Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000004642 Polyimide Substances 0.000 description 16
- 239000002904 solvent Substances 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 5
- 230000004913 activation Effects 0.000 description 4
- 238000005979 thermal decomposition reaction Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 239000012967 coordination catalyst Substances 0.000 description 3
- 239000011953 free-radical catalyst Substances 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
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- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
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- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/022—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polycondensates with side or terminal unsaturations
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C08J3/00—Processes of treating or compounding macromolecular substances
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- C08J2379/00—Characterised by the use 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 C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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Abstract
A preparation method of a phenylacetylene-terminated polyimide resin system with high-efficiency catalytic curing belongs to the field of materials. The method comprises the following steps: preparing a phenylacetylene end-capped polyimide resin solution, adding a novel high-efficiency catalyst into a resin system, carrying out gradient curing on the resin system added with the novel high-efficiency compound catalyst, firstly curing at 120 ℃ for 1h, then curing at 240 ℃ for 2h, and finally curing at 300 ℃ for 3-4 h to obtain the completely cured phenylacetylene end-capped polyimide resin. The invention has the advantages that: the curing temperature of the phenylethynyl terminated polyimide resin prepared by the invention is obviously reduced, and the highest curing temperature is not more than 300 ℃. The phenylethynyl terminated polyimide resin has reliable low-temperature curing process, adopts a novel high-efficiency catalyst to catalyze the curing reaction, ensures uniform reaction, is simple to operate, has stable process, and is suitable for industrial production.
Description
Technical Field
The invention belongs to the field of resin, and particularly relates to a preparation method of a phenylacetylene-terminated polyimide resin system through efficient catalytic curing.
Background
The phenylacetylene-terminated polyimide is a high-performance resin developed in about 90 s of the 20 th century, the molecular structure of the polyimide-terminated polyimide is formed by curing and crosslinking imide oligomers containing active phenylacetylene end groups, and the cured products are mainly aromatic structures. The structure endows the polyimide resin with higher glass transition temperature, and the polyimide resin can be used at high temperature for a long time at the temperature of more than 270 ℃, and the thermal decomposition temperature can reach more than 500 ℃. Meanwhile, the composite material has excellent mechanical properties, low thermal expansion coefficient and good dielectric property, and is widely applied to the high-temperature fields of aviation, aerospace, microelectronics, nano, liquid crystal, separation membranes, laser and the like.
However, due to the conjugation effect and steric hindrance effect of phenylethynyl, phenylethynyl terminated polyimide needs to overcome a large resistance during curing, the activation energy is high, and the curing temperature is above 370 ℃. The high-temperature long-time curing often causes more residual stress in the obtained cured product, which causes poor stability of the service performance of the material, thereby seriously hindering the development and large-scale application of the phenylacetylene-terminated polyimide resin and related materials thereof.
Disclosure of Invention
The invention aims to solve the problem of high curing temperature of phenylacetylene terminated polyimide resin, and provides a preparation method for efficiently catalyzing and curing a phenylacetylene terminated polyimide resin system.
Aiming at the problem of high curing temperature of phenylacetylene-terminated polyimide resin, the invention adds a free radical catalyst to initiate phenylethynyl for crosslinking, and uses a coordination catalyst to directionally regulate and control a polyimide resin crosslinking structure. The free radical catalyst (cumene hydroperoxide) and the coordination catalyst (cobalt naphthenate) are selected to carry out co-catalysis on the polyimide terminated with phenylacetylene, and the synergistic effect of the two catalysts is utilized to enhance the catalytic effect of the curing reaction of the resin, so that the curing temperature of a resin system is reduced, and the purpose of reducing the curing temperature is realized.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a phenylacetylene-terminated polyimide resin system through high-efficiency catalytic curing comprises the following specific steps:
the method comprises the following steps: preparing phenylacetylene end-capped polyimide resin with the mass fraction of 60-80%, adding a novel efficient catalyst into the obtained resin at room temperature, and uniformly mixing, wherein the mass ratio of a resin system to a free radical catalyst to a coordination catalyst is 100: 1-4: 1, putting the resin glue solution mixed system into a vacuum oven for vacuumizing treatment at 60 ℃, wherein the treatment time is 1-2 h;
step two: carrying out gradient curing on the resin system added with the catalyst: firstly curing at the temperature of 120-140 ℃ for 1 hour, then curing at the temperature of 240-250 ℃ for 2-3 hours, and finally curing at the temperature of 300 ℃ for 3-4 hours to obtain the completely cured phenylethynyl terminated polyimide resin.
Further, in the first step, 60 parts of phenylethynyl terminated polyimide resin and 40 parts of 1, 4-dioxane are added; the mass ratio of the resin system to the cumene hydroperoxide and the cobalt naphthenate is 100: 4: 1.
further, in the second step, the gradient curing system is to cure at 120 ℃ for 1h, then at 240 ℃ for 2h, and finally at 300 ℃ for 3 h.
Further, in the first step, 80 parts of phenylethynyl terminated polyimide resin, 20 parts of 1, 4-dioxane and a resin system are mixed, wherein the mass ratio of the resin system to cumene hydroperoxide and cobalt naphthenate is 100: 3: 1.
further, in the second step, the gradient curing system is used for curing at the temperature of 140 ℃ for 1h, then curing at the temperature of 250 ℃ for 2h, and finally curing at the temperature of 300 ℃ for 4 h.
Further, in the first step, 75 parts of phenylethynyl terminated polyimide resin, 25 parts of 1, 4-dioxane and a resin system are mixed, wherein the mass ratio of the resin system to cumene hydroperoxide and cobalt naphthenate is 100: 1: 1.
further, in the second step, the gradient curing system is to cure at 125 ℃ for 1h, then at 245 ℃ for 2h, and finally at 300 ℃ for 3 h.
Further, in the first step, 75 parts of phenylethynyl terminated polyimide resin, 25 parts of 1, 4-dioxane and a resin system are mixed, wherein the mass ratio of the resin system to cumene hydroperoxide and cobalt naphthenate is 100: 4: 1.
further, in the second step, the gradient curing system is used for curing at the temperature of 130 ℃ for 1 hour, then curing at the temperature of 245 ℃ for 2 hours, and finally curing at the temperature of 300 ℃ for 3 hours.
Further, in the first step, the resin glue solution mixed system is placed into a vacuum oven for vacuum pumping treatment at room temperature, and the treatment time is 1.5 h.
Compared with the prior art, the invention has the beneficial effects that:
the curing temperature of the phenylethynyl terminated polyimide resin prepared by the invention is obviously reduced, the highest curing temperature is not more than 300 ℃, and is far lower than 371 ℃ of the phenylethynyl terminated polyimide resin in the prior art; the phenylethynyl terminated polyimide resin still maintains excellent heat resistance (T5 percent is more than or equal to 520 ℃) at the curing temperature of less than or equal to 300 ℃. The phenylethynyl terminated polyimide resin has reliable low-temperature curing process, adopts the novel high-efficiency compound catalyst to catalyze the curing reaction, ensures uniform reaction, is simple to operate, has stable process, and is suitable for industrial production.
Drawings
FIG. 1 is an infrared analysis spectrum of a low-temperature cured phenylethynyl terminated polyimide resin of the present invention; wherein,
in order to obtain the sample one,
is sample two;
FIG. 2 is a TGA analysis of a low temperature cured phenylethynyl terminated polyimide resin of the present invention; wherein,
in order to obtain the sample one,
sample two.
Detailed Description
It will be understood by those of ordinary skill in the art that the foregoing embodiments are specific examples for carrying out the invention, and that various changes in form and details may be made therein without departing from the spirit and scope of the invention in practice.
To make the objects, aspects and advantages of the embodiments of the present invention more apparent, the following detailed description clearly illustrates the spirit of the disclosure, and any person skilled in the art, after understanding the embodiments of the disclosure, may make changes and modifications to the technology taught by the disclosure without departing from the spirit and scope of the disclosure.
The exemplary embodiments of the present invention and the description thereof are provided to explain the present invention and not to limit the present invention.
The invention comprises two parts. The first part is the design of a novel high efficiency catalyst. Because the phenylethynyl terminated polyimide resin has higher curing temperature and large curing reaction resistance, the invention designs a novel efficient compound catalyst which can effectively reduce the curing reaction activation energy, thereby ensuring that the phenylethynyl terminated polyimide resin system can be cured at low temperature and simultaneously maintain excellent heat resistance. According to the invention, through the synergistic effect of cumene hydroperoxide and cobalt naphthenate, the curing reaction activation energy of the phenylethynyl terminated polyimide resin is greatly reduced, and further low-temperature curing is realized. The phenylacetylene-terminated polyimide resin is mainly subjected to free radical polymerization reaction during curing, and cumene hydroperoxide and cobalt naphthenate have certain catalytic reaction on the free radical polymerization reaction, so that the phenylacetylene-terminated polyimide resin is used as a catalyst of a curing system, the reaction activation energy is reduced, and low-temperature curing is realized. The novel efficient compound catalyst is used for catalyzing a phenylethynyl-terminated polyimide resin curing system in the following mechanism: firstly, active hydrogen in cumene hydroperoxide can firstly catalyze phenylacetylene functional groups in the polyimide resin terminated by phenylethynyl groups to carry out trimerization reaction, and a crosslinking network structure with a polyene or multi-ring structure is generated. And then, under the combined action of an active hydrogen cocatalyst, an organic cobalt catalyst and a phenylacetylene functional group form a metal-pi bond intermediate, so that the curing reaction of the phenylethynyl terminated polyimide resin is catalyzed.
The second part is the set-up of the low temperature cure process. The curing temperature of the phenylethynyl terminated polyimide resin is generally higher than 371 ℃, and the properties of the cured product can meet the requirements only when the phenylethynyl terminated polyimide resin is cured at the temperature. When the curing temperature is lower than this temperature, the phenylethynyl terminated polyimide resin is not completely cured and cannot maintain its excellent heat resistance, and in order to maintain excellent properties of the phenylethynyl terminated polyimide resin under the low temperature curing condition, a new curing process needs to be developed. The invention adopts gradient temperature curing to completely cure the phenylethynyl terminated polyimide resin system, can be applied to a plurality of fields requiring low-temperature curing, and keeps the excellent performance of the phenylethynyl terminated polyimide resin.
Example 1:
a preparation method of a phenylacetylene-terminated polyimide resin system through high-efficiency catalytic curing comprises the following specific steps:
A. preparation of Phenylethynyl polyimide resin System
Weighing 60 parts of phenylethynyl terminated polyimide and 40 parts of 1, 4-dioxane, and mixing the phenylethynyl terminated polyimide and the phenylethynyl terminated polyimide to obtain phenylethynyl terminated polyimide resin solution;
B. novel high efficiency catalyst and resin system blends
The novel high-efficiency catalyst is prepared from cumene hydroperoxide and cobalt naphthenate according to the weight ratio of 20: 80 in mass ratio; mixing the novel catalyst and a resin system at room temperature, continuously stirring for 2 hours by using a magnetic stirrer, and ensuring that the catalyst and the resin system are uniformly mixed, wherein the mass ratio of the resin system to cumene hydroperoxide and cobalt naphthenate is 100: 4: 1;
C. establishment of gradient temperature curing process
Keeping the temperature of the mixed resin system and the novel efficient compound catalyst in a vacuum oven at 60 ℃ for 3h, removing most of the solvent in the system, keeping the temperature at 120 ℃ for 1h, completely removing the solvent, curing at 240 ℃ for 2h, and finally curing at 300 ℃ for 3h to obtain the completely cured phenylethynyl terminated polyimide resin; wherein the vacuum oven is a DZF-6000 series vacuum drying oven of Shanghai-Hengshi Co.
The infrared spectrum test of the cured resin obtained in this example is performed, and the test result is shown in fig. 1, where the sample is a cured product of phenylethynyl terminated polyimide without catalyst and completely cured by heat, and the sample is a cured product of phenylethynyl terminated polyimide with catalyst, and it can be known from the spectrogram: the catalyst plays a role in catalyzing the curing process of the resin, so that the phenylethynyl terminated polyimide resin can open carbon-carbon triple bonds for crosslinking and curing at a lower temperature.
According to the infrared spectrum test, the structure in the resin molded body can be preliminarily obtained, and functional groups represented by several infrared spectrum absorption peaks in the figure are shown in Table 1.
TABLE 1 Infrared absorption Peak corresponding functional groups
Example 2:
a preparation method of a phenylacetylene-terminated polyimide resin system through high-efficiency catalytic curing comprises the following specific steps:
A. preparation of composite catalyst and phenylethynyl polyimide resin system
Weighing 70 parts of phenylethynyl terminated polyimide and 30 parts of 1, 4-dioxane, and mixing the phenylethynyl terminated polyimide and the phenylethynyl terminated polyimide to obtain phenylethynyl terminated polyimide resin solution;
B. novel high efficiency catalyst and resin system blends
The novel high-efficiency catalyst is prepared from cumene hydroperoxide and cobalt naphthenate according to the weight ratio of 20: 80 in mass ratio. Mixing the novel catalyst and a resin system at room temperature, continuously stirring for 2 hours by using a magnetic stirrer, and ensuring that the catalyst and the resin system are uniformly mixed, wherein the mass ratio of the resin system to cumene hydroperoxide and cobalt naphthenate is 100: 3: 1;
C. establishment of gradient temperature curing process
And (3) keeping the temperature of the mixed resin system and the novel efficient compound catalyst in a vacuum oven at 60 ℃ for 3h, removing most of the solvent in the system, keeping the temperature at 120 ℃ for 1h, completely removing the solvent, curing at 240 ℃ for 2h, and finally curing at 300 ℃ for 4h to obtain the completely cured phenylethynyl terminated polyimide resin.
Thermogravimetric analysis (TGA) was performed on the cured resin obtained in this example, and the results are shown in fig. 2, wherein the sample is a sample powder obtained by completely thermosetting phenylethynyl terminated polyimide, and the sample is a sample powder obtained by curing phenylethynyl terminated polyimide resin under the operation of this example, and it can be roughly seen from the graph that there is no significant change in the thermal decomposition temperatures of the sample one and the sample two, and the results are calculated as follows: the thermal decomposition temperature of sample one was T5 ═ 557.5 ℃ at 5% and that of sample two was T5 ═ 538.3 ℃. From this, it is understood that the curing system in the operation of the present example does not greatly affect the thermal decomposition temperature of the cured resin.
Example 3:
a preparation method of a phenylacetylene-terminated polyimide resin system through high-efficiency catalytic curing comprises the following specific steps:
A. preparation of composite catalyst and phenylethynyl polyimide resin system
Weighing 80 parts of phenylethynyl terminated polyimide and 20 parts of 1, 4-dioxane, and mixing the phenylethynyl terminated polyimide and the phenylethynyl terminated polyimide to obtain phenylethynyl terminated polyimide resin solution;
B. novel high efficiency catalyst and resin system blends
The novel high-efficiency catalyst is prepared from cumene hydroperoxide and cobalt naphthenate according to the weight ratio of 20: 80 in mass ratio. Mixing the novel catalyst and a resin system at room temperature, continuously stirring for 2 hours by using a magnetic stirrer, and ensuring that the catalyst and the resin system are uniformly mixed, wherein the mass ratio of the resin system to cumene hydroperoxide and cobalt naphthenate is 100: 1: 1;
C. establishment of gradient temperature curing process
And (3) keeping the temperature of the mixed resin system and the novel efficient compound catalyst in a vacuum oven at 60 ℃ for 3h, removing most of the solvent in the system, keeping the temperature at 120 ℃ for 1h, completely removing the solvent, curing at 240 ℃ for 2h, and finally curing at 300 ℃ for 3h to obtain the completely cured phenylethynyl terminated polyimide resin.
Claims (10)
1. A preparation method of a phenylacetylene-terminated polyimide resin system with high-efficiency catalytic curing is characterized by comprising the following steps: the method comprises the following specific steps:
the method comprises the following steps: preparing a compound catalyst and phenylethynyl polyimide resin system:
weighing 60-80 parts of phenylethynyl terminated polyimide resin and 20-40 parts of 1, 4-dioxane, uniformly mixing the phenylethynyl terminated polyimide resin and the phenylethynyl terminated polyimide resin at room temperature to obtain phenylethynyl terminated polyimide resin solution, and adding a compound catalyst into the phenylethynyl terminated polyimide resin solution at room temperature, wherein the compound catalyst is a mixture of cumene hydroperoxide and cobalt naphthenate; the mass ratio of the phenylethynyl terminated polyimide resin solution to the cumene hydroperoxide and the cobalt naphthenate is 100: 1-4: 1; putting the resin glue solution mixed system into a vacuum oven for vacuumizing treatment at room temperature for 1-2 h;
step two: performing gradient curing on the resin glue solution mixed system obtained in the step one: firstly curing at the temperature of 120-140 ℃ for 1h, then curing at the temperature of 240-250 ℃ for 2h, and finally curing at the temperature of 300 ℃ for 3-4 h to obtain the completely cured phenylethynyl terminated polyimide resin.
2. The preparation method of the phenylacetylene capped polyimide resin system with high catalytic curing efficiency according to claim 1, wherein the preparation method comprises the following steps: in the first step, 60 parts of phenylethynyl terminated polyimide resin and 40 parts of 1, 4-dioxane are added; the mass ratio of the resin system to the cumene hydroperoxide and the cobalt naphthenate is 100: 4: 1.
3. the preparation method of the phenylacetylene capped polyimide resin system with high catalytic curing efficiency according to claim 1, wherein the preparation method comprises the following steps: in the second step, the gradient curing system is to cure at 120 ℃ for 1h, then cure at 240 ℃ for 2h, and finally cure at 300 ℃ for 3 h.
4. The preparation method of the low-temperature curing phenylethynyl polyimide resin system catalyzed by the built catalyst according to claim 1 is characterized in that: in the first step, 80 parts of phenylethynyl terminated polyimide resin, 20 parts of 1, 4-dioxane and a resin system, namely cumene hydroperoxide and cobalt naphthenate in a mass ratio of 100: 3: 1.
5. the preparation method of the low-temperature curing phenylethynyl polyimide resin system catalyzed by the built catalyst according to claim 1 is characterized in that: in the second step, the gradient curing system is to cure at 140 ℃ for 1h, then cure at 250 ℃ for 2h, and finally cure at 300 ℃ for 4 h.
6. The preparation method of the low-temperature curing phenylethynyl polyimide resin system catalyzed by the built catalyst according to claim 1 is characterized in that: in the first step, 75 parts of phenylethynyl terminated polyimide resin, 25 parts of 1, 4-dioxane and a resin system, namely cumene hydroperoxide and cobalt naphthenate in a mass ratio of 100: 1: 1.
7. the preparation method of the low-temperature curing phenylethynyl polyimide resin system catalyzed by the built catalyst according to claim 1 is characterized in that: in the second step, the gradient curing system is to cure at 125 ℃ for 1h, then cure at 245 ℃ for 2h, and finally cure at 300 ℃ for 3 h.
8. The preparation method of the low-temperature curing phenylethynyl polyimide resin system catalyzed by the built catalyst according to claim 1 is characterized in that: in the first step, 75 parts of phenylethynyl terminated polyimide resin, 25 parts of 1, 4-dioxane and a resin system, namely cumene hydroperoxide and cobalt naphthenate in a mass ratio of 100: 4: 1.
9. the preparation method of the low-temperature curing phenylethynyl polyimide resin system catalyzed by the built catalyst according to claim 1 is characterized in that: in the second step, the gradient curing system is to cure for 1 hour at the temperature of 130 ℃, then cure for 2 hours at the temperature of 245 ℃, and finally cure for 3 hours at the temperature of 300 ℃.
10. The preparation method of the low-temperature curing phenylethynyl polyimide resin system catalyzed by the built catalyst according to claim 1 is characterized in that: in the first step, the resin glue solution mixed system is placed into a vacuum oven for vacuum pumping treatment at room temperature, and the treatment time is 1.5 h.
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| US4876153A (en) * | 1987-04-09 | 1989-10-24 | Basf Corporation | Process for the preparation of cyanate resin-based prepregs and films which maintain their tack |
| US5231147A (en) * | 1989-04-10 | 1993-07-27 | Rheox, Inc. | Thermosetting polyurethane structural adhesive compositions and processes for producing the same |
| CN1844237A (en) * | 2005-04-06 | 2006-10-11 | 中国科学院化学研究所 | Solvent-free impregnating resin and its preparation process and use |
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| CN109423010A (en) * | 2017-08-21 | 2019-03-05 | 味之素株式会社 | Resin combination |
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