CN113981707B - Cyanate modified bismaleimide-propargyl phenolic resin matrix wave-transparent composite material and preparation method thereof - Google Patents
Cyanate modified bismaleimide-propargyl phenolic resin matrix wave-transparent composite material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a preparation method of a cyanate modified bismaleimide-propargyl phenolic resin matrix wave-transparent composite material, which comprises the following steps: bisphenol type cyanate resin is used as modified resin, and the bismaleimide-propargyl modified phenolic resin is modified to obtain cyanate modified bismaleimide-propargyl phenolic resin; dissolving the cyanate ester modified bismaleimide-propargyl phenolic resin by using a solvent, thereby preparing a glue solution; compounding the glue solution with a fiber reinforcement to prepare a prepreg; and curing the prepreg to obtain the wave-transparent composite material. The invention also provides the wave-transparent composite material prepared by the method. According to the invention, the bismaleimide-propargyl phenolic resin is modified by the cyanate resin, so that better processability is obtained while the temperature resistance is not reduced, the defects of poor interlayer shear strength, high dielectric constant and high dielectric loss of the fiber fabric and the bismaleimide-propargyl phenolic resin composite material are overcome, and the comprehensive excellent high-temperature-resistant wave-transparent composite material is obtained.
Description
Technical Field
The invention belongs to the technical field of wave-transparent composite materials, and particularly relates to a resin-based wave-transparent composite material with high temperature resistance, high strength and low dielectric constant and a preparation method thereof.
Background
With the continuous development of technology, the requirements on the radome are higher and higher, and the radome is not only resistant to high temperature, but also has high mechanical properties, low dielectric constant, loss and the like. The resin matrix of the high temperature resistant wave-transparent material is usually polyimide resin, polybenzimidazole resin, polyarylacetylene (PAA) resin and the like, but the molding process of the resin composite materials is very complex, high temperature and high pressure molding is needed, and the cost and the difficulty are high.
The bismaleimide-propargyl modified phenolic resin developed by the Chinese academy of chemistry has good heat resistance and molding process performance, the thermal decomposition temperature of the resin is higher than 400 ℃, and the short-time use temperature of the composite material is higher than 350 ℃. However, the bismaleimide-propargyl modified phenolic resin has the problems of large curing shrinkage, relatively high dielectric constant and dielectric loss, low interlayer shear strength of the composite material and the like, so that the application of the bismaleimide-propargyl modified phenolic resin as a high-temperature-resistant wave-transparent composite material is limited.
Disclosure of Invention
The following presents a simplified summary of the invention in order to provide a basic understanding of some aspects of the invention. It should be understood that this summary is not an exhaustive overview of the invention. It is not intended to identify key or critical elements of the invention or to delineate the scope of the invention. Its purpose is to present some concepts in a simplified form as a prelude to the more detailed description that is discussed later.
The invention aims to solve the problems that a bismaleimide-propargyl modified phenolic resin material cannot have excellent high-temperature mechanical properties, low dielectric constant and low dielectric loss and cannot meet the use requirement of a high-temperature-resistant wave-transparent composite material in the prior art, and provides a cyanate resin modified bismaleimide-propargyl modified phenolic resin composite material and a preparation method thereof.
The invention provides a preparation method of a resin-based wave-transparent composite material with high temperature resistance, high strength, low dielectric constant and low dielectric loss in a first aspect, which comprises the following steps:
(1) Bisphenol type cyanate resin is used as modified resin, and the bismaleimide-propargyl modified phenolic resin is modified to obtain cyanate modified bismaleimide-propargyl phenolic resin;
(2) Dissolving the cyanate ester modified bismaleimide-propargyl phenolic resin by using a solvent, thereby preparing a glue solution;
(3) Compounding the glue solution with a fiber reinforcement to prepare a prepreg;
(4) And curing the prepreg to obtain the wave-transparent composite material.
In some preferred embodiments, the bisphenol type cyanate resin is selected from at least one or more of bisphenol a type cyanate resin, bisphenol M type cyanate resin, bisphenol S type cyanate resin, bisphenol F type cyanate resin; more preferably, the bisphenol type cyanate resin is a bisphenol a type cyanate resin.
In other preferred embodiments, the fibrous reinforcement is a glass fiber fabric and/or a quartz fiber fabric; more preferably, the fiber reinforcement is a plain quartz fiber fabric.
In other preferred embodiments, the mass ratio of the bismaleimide-propargyl modified phenolic resin to the bisphenol-type cyanate ester resin is 100: (10-40) (e.g., 100:20, 100:30, etc.), more preferably 100: (20-30).
In other preferred embodiments, in step (2), the solvent is an organic solvent, more preferably acetone. It is further preferred that the mass ratio of the solvent to the cyanate ester-modified bismaleic-propargyl phenolic resin is (1-3): 1, a step of; most preferably, the mass ratio of the solvent to the cyanate ester-modified bismaleic-propargyl phenolic resin is (1-1.5): 1.
preferably, in step (1), the modification treatment is performed according to the following method:
(a) Heating the bismaleic-propargyl phenolic resin to 130-150 ℃; more preferably, the heating temperature is 140 ℃;
(b) Adding bisphenol type cyanate ester into the heated bismaleimide-propargyl phenolic resin in the step (a), and stirring until the material is transparent;
(c) And (3) continuously preserving heat for 10-15 minutes at 130-140 ℃, and then pouring out and cooling the materials to obtain the cyanate modified bismaleimide-propargyl phenolic resin.
Preferably, in step (3), the compounding is performed according to the following method: and coating the glue solution on the fiber reinforcement, and drying the coated fiber reinforcement.
Preferably, the mass ratio of the fiber reinforcement to the glue solution is 1: (1.5-3); more preferably, the mass ratio of the fiber reinforcement to the glue solution is 1:2.
preferably, the drying is performed at 80-100 ℃ (e.g., 90 ℃) for 10-30 minutes (e.g., 20 minutes).
Preferably, in the step (4), the prepreg is put into an autoclave for curing under the following conditions: keeping the temperature at 170-180 ℃ for 2-4h, keeping the temperature at 190-200 ℃ for 1.5-2h, keeping the temperature at 220-230 ℃ for 1.5-2h, and keeping the temperature at 240-250 ℃ for 2-4h.
Preferably, during the curing process, after maintaining the temperature at 170-180 ℃ for 1-1.5 hours, the autoclave is pressurized to 0.3-0.5MPa (for example, 0.4 MPa) and then the subsequent curing operation is performed.
In a second aspect, the invention provides a resin-based wave-transparent composite material having high temperature resistance, high strength, low dielectric constant and low dielectric loss, which is prepared by the method according to the first aspect of the invention.
Compared with the prior art, the invention has the following technical advantages: according to the invention, the bismaleimide-propargyl phenolic resin is modified by the cyanate resin, so that better processability is obtained while the temperature resistance is not reduced, the defects of poor interlayer shear strength, high dielectric constant and high dielectric loss of the fiber fabric and the bismaleimide-propargyl phenolic resin composite material are overcome, and the high-temperature-resistant wave-transparent composite material with good mechanical property and excellent dielectric property is obtained.
Detailed Description
Specific embodiments of the present invention are described in detail below. In the following description, for purposes of explanation and not limitation, specific details are set forth in order to provide a thorough understanding of the present invention. It will be apparent, however, to one skilled in the art that the present invention may be practiced in other embodiments that depart from these specific details. Additionally, features that are described and/or illustrated below with respect to one embodiment may be used in the same or similar way in one or more other embodiments and/or in combination with or instead of the features of the other embodiments.
Example 1
200g of bismaleimide-propargyl phenolic resin (purchased from Shandong Santa New Material Co., ltd., the same applies below) was weighed, placed in a three-necked flask, heated to 140 ℃ with an oil bath, 20g of bisphenol A type cyanate resin (purchased from Ningbo Material Co., the same applies below) was added, stirred until the material became a transparent brown glue solution, and after continuing to keep the temperature for 10 minutes, the material was poured out and cooled rapidly to obtain the cyanate modified bismaleimide-propargyl phenolic resin.
200g of the cyanate-modified bismaleic-propargyl phenolic resin prepared above was weighed and added into 200g of acetone, and stirred at normal temperature for 1h, so that the cyanate-modified bismaleic-propargyl phenolic resin was completely dissolved, and the adhesive used in this example was obtained. The glue solution was then uniformly applied to 200g of plain quartz fiber fabric (available from feili Hua Danying glass stock, inc., st., below) and dried at 80℃for 30 minutes to obtain a prepreg.
The prepreg is put into an autoclave for curing, and the curing conditions are as follows: keeping the temperature at 180 ℃ for 3 hours, keeping the temperature at 200 ℃ for 2 hours, keeping the temperature at 230 ℃ for 2 hours, and keeping the temperature at 250 ℃ for 2 hours. Wherein after keeping the temperature at 180 ℃ for 1h, pressurizing the autoclave to 0.3MPa, and then continuing the subsequent curing operation to obtain the wave-transparent composite material.
The wave-transparent composite material obtained after curing is measured, the dielectric constant at normal temperature is 3.32, the loss factor is 0.014, the shear strength is 42.5MPa, the dielectric constant after 10 minutes of heat preservation at 350 ℃ is 3.34, the loss factor is 0.014, and the shear strength is 22.3MPa.
Example 2
200g of bismaleimide-propargyl phenolic resin is weighed, placed into a three-neck flask, heated to 140 ℃ by an oil bath, added with 40g of cyanate ester resin, stirred until the material becomes transparent brown glue solution, continuously kept for 10 minutes, and rapidly poured out and cooled to obtain the cyanate ester modified bismaleimide-propargyl phenolic resin.
200g of the cyanate-modified bismaleic-propargyl phenolic resin prepared above was weighed and added into 200g of acetone, and stirred at normal temperature for 1h, so that the cyanate-modified bismaleic-propargyl phenolic resin was completely dissolved, and the adhesive used in this example was obtained. And then uniformly coating the glue solution on 200g of plain quartz fiber fabric, and drying at 90 ℃ for 20 minutes to obtain the prepreg.
The prepreg is put into an autoclave for curing, and the curing conditions are as follows: keeping the temperature at 180 ℃ for 3 hours, keeping the temperature at 200 ℃ for 2 hours, keeping the temperature at 230 ℃ for 2 hours, and keeping the temperature at 250 ℃ for 2 hours. Wherein after keeping the temperature at 180 ℃ for 1h, pressurizing the autoclave to 0.3MPa, and then continuing the subsequent curing operation to obtain the wave-transparent composite material.
The dielectric constant of the cured wave-transparent composite material is measured to be 3.27, the loss factor is 0.012, the shear strength is 45.7MPa, the dielectric constant after 10 minutes of heat preservation at 350 ℃ is 3.30, the loss factor is 0.013, and the shear strength is 26.4MPa.
Example 3
200g of bismaleimide-propargyl phenolic resin is weighed, placed into a three-neck flask, heated to 140 ℃ by an oil bath, added with 60g of cyanate ester resin, stirred until the material becomes transparent brown glue solution, and immediately poured out and cooled after the heat preservation is continued for 10 minutes, so as to obtain the cyanate ester modified bismaleimide-propargyl phenolic resin.
200g of cyanate-modified bismaleimide-propargyl phenolic resin was weighed and added into 200g of acetone, and stirred at normal temperature for 1h, so that the cyanate-modified bismaleimide-propargyl phenolic resin was completely dissolved, and the adhesive used in this example was obtained. And then uniformly coating the glue solution on 200g of plain quartz fiber fabric, and drying at 100 ℃ for 10 minutes to obtain the prepreg.
The prepreg is put into an autoclave for curing, and the curing conditions are as follows: keeping the temperature at 180 ℃ for 3 hours, keeping the temperature at 200 ℃ for 2 hours, keeping the temperature at 230 ℃ for 2 hours, and keeping the temperature at 250 ℃ for 2 hours. Wherein after keeping the temperature at 180 ℃ for 1h, pressurizing the autoclave to 0.3MPa, and then continuing the subsequent curing operation to obtain the wave-transparent composite material.
The dielectric constant of the cured wave-transparent composite material is measured to be 3.22, the loss factor is 0.010, the shearing strength is 49.4MPa, the dielectric constant after 10 minutes of heat preservation at 350 ℃ is 3.24, the loss factor is 0.012, and the shearing strength is 23.5MPa.
Example 4
200g of bismaleimide-propargyl phenolic resin is weighed, placed into a three-neck flask, heated to 140 ℃ by an oil bath, added with 80g of cyanate ester resin, stirred until the material becomes transparent brown glue solution, continuously kept for 10 minutes, and rapidly poured out and cooled to obtain the cyanate ester modified bismaleimide-propargyl phenolic resin.
200g of the cyanate-modified bismaleic-propargyl phenolic resin prepared above was weighed and added into 200g of acetone, and stirred at normal temperature for 1h, so that the cyanate-modified bismaleic-propargyl phenolic resin was completely dissolved, and the adhesive used in this example was obtained. And then uniformly coating the glue solution on 200g of plain quartz fiber fabric, and drying at 80 ℃ for 20 minutes to obtain the prepreg.
The prepreg is put into an autoclave for curing, and the curing conditions are as follows: keeping the temperature at 180 ℃ for 3 hours, keeping the temperature at 200 ℃ for 2 hours, keeping the temperature at 230 ℃ for 2 hours, and keeping the temperature at 250 ℃ for 2 hours. Wherein after keeping the temperature at 180 ℃ for 1h, pressurizing the autoclave to 0.3MPa, and then continuing the subsequent curing operation to obtain the wave-transparent composite material.
The dielectric constant of the cured wave-transparent composite material is measured to be 3.18, the loss factor is 0.008, the shear strength is 52.0MPa, the dielectric constant after 10 minutes of heat preservation at 350 ℃ is 3.20, the loss factor is 0.010, and the shear strength is 21.7MPa.
Example 5
In the same manner as in example 1 except that bisphenol F type cyanate resin was used instead of bisphenol A type cyanate resin in example 1.
200g of bismaleimide-propargyl phenolic resin is weighed, placed into a three-neck flask, heated to 140 ℃ by an oil bath, added with 20g of bisphenol F type cyanate ester resin (purchased from Ningbo materials, the same applies below), stirred until the materials become transparent brown glue solution, continuously kept for 10 minutes, and rapidly poured out and cooled to obtain the cyanate ester modified bismaleimide-propargyl phenolic resin.
200g of the cyanate-modified bismaleic-propargyl phenolic resin prepared above was weighed and added into 200g of acetone, and stirred at normal temperature for 1h, so that the cyanate-modified bismaleic-propargyl phenolic resin was completely dissolved, and the adhesive used in this example was obtained. And then uniformly coating the glue solution on 200g of plain quartz fiber fabric, and drying at 80 ℃ for 20 minutes to obtain the prepreg.
The prepreg is put into an autoclave for curing, and the curing conditions are as follows: keeping the temperature at 180 ℃ for 3 hours, keeping the temperature at 200 ℃ for 2 hours, keeping the temperature at 230 ℃ for 2 hours, and keeping the temperature at 250 ℃ for 2 hours. Wherein after keeping the temperature at 180 ℃ for 1h, pressurizing the autoclave to 0.3MPa, and then continuing the subsequent curing operation to obtain the wave-transparent composite material.
The dielectric constant of the cured wave-transparent composite material is measured to be 3.33, the loss factor is 0.015, the shearing strength is 41.8MPa, the dielectric constant after 10 minutes of heat preservation at 350 ℃ is 3.35, the loss factor is 0.016, and the shearing strength is 21.9MPa.
Comparative example 1
200g of bismaleic-propargyl phenolic resin was weighed and added into 200g of acetone, and stirred at normal temperature for 1h, so that the bismaleic-propargyl phenolic resin was completely dissolved, and the glue used in this example was obtained. And then uniformly coating the glue solution on 200g of plain quartz fiber fabric, and drying at 80 ℃ for 20 minutes to obtain the prepreg.
The prepreg is put into an autoclave for curing, and the curing conditions are as follows: keeping the temperature at 180 ℃ for 3 hours, keeping the temperature at 200 ℃ for 2 hours, keeping the temperature at 230 ℃ for 2 hours, and keeping the temperature at 250 ℃ for 2 hours. Wherein after keeping the temperature at 180 ℃ for 1h, pressurizing the autoclave to 0.3MPa, and then continuing the subsequent curing operation to obtain the wave-transparent composite material.
The dielectric constant of the wave-transparent composite material obtained after curing is measured to be 3.48, the loss factor is 0.02, the shearing strength is 35.5MPa, the dielectric constant after 10 minutes of heat preservation at 350 ℃ is 3.54, the loss factor is 0.022, and the shearing strength is 16.5MPa.
Table 1 properties of the composite materials prepared and examples
It should be noted that the term "comprises/comprising" when used herein refers to the presence of a feature, integer, step or component, but does not exclude the presence or addition of one or more other features, integers, steps, components or groups thereof.
In addition, the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (14)
1. The preparation method of the cyanate modified bismaleimide-propargyl phenolic resin matrix wave-transparent composite material is characterized by comprising the following steps:
(1) The preparation method comprises the following steps of using bisphenol type cyanate resin as modified resin, and carrying out modification treatment on the bismaleic-propargyl modified phenolic resin to obtain cyanate modified bismaleic-propargyl phenolic resin, wherein the modification treatment comprises the following steps: (a) Heating the bismaleic-propargyl phenolic resin to 130-150 ℃; (b) Adding the bisphenol type cyanate ester into the heated bismaleimide-propargyl phenolic resin in the step (a), and stirring until the material is transparent; (c) Continuously preserving heat for 10-15 minutes at 130-140 ℃, and then pouring out and cooling the materials to obtain the cyanate modified bismaleimide-propargyl phenolic resin;
(2) Dissolving the cyanate ester modified bismaleimide-propargyl phenolic resin by using a solvent, thereby preparing a glue solution;
(3) Compounding the glue solution with a fiber reinforcement to prepare a prepreg, wherein the fiber reinforcement is a glass fiber fabric and/or a quartz fiber fabric;
(4) Solidifying the prepreg to obtain the wave-transparent composite material;
wherein:
the mass ratio of the bismaleimide-propargyl modified phenolic resin to the bisphenol type cyanate resin is 100: (10-40);
the mass ratio of the solvent to the cyanate ester modified bismaleimide-propargyl phenolic resin is (1-3): 1, a step of;
the mass ratio of the fiber reinforcement to the glue solution is 1: (1.5-3).
2. The method of manufacturing according to claim 1, characterized in that:
the bisphenol type cyanate resin is selected from at least one or more of bisphenol A type cyanate resin, bisphenol M type cyanate resin, bisphenol S type cyanate resin and bisphenol F type cyanate resin.
3. The preparation method according to claim 2, characterized in that:
the bisphenol type cyanate resin is bisphenol A type cyanate resin; and/or
The fiber reinforcement is plain quartz fiber fabric.
4. A production method according to any one of claims 1 to 3, wherein the mass ratio of the bismaleimide-propargyl-modified phenolic resin and the bisphenol-type cyanate resin is 100: (20-30).
5. A production method according to any one of claims 1 to 3, wherein in step (2), the solvent is an organic solvent.
6. The method according to claim 5, wherein in the step (2), the solvent is acetone.
7. A production method according to any one of claims 1 to 3, wherein in step (2), the mass ratio of the solvent and the cyanate ester-modified bismaleic-propargyl phenolic resin is (1-1.5): 1.
8. the method of manufacturing according to claim 1, characterized in that:
in step (a), the bismaleimide-propargyl phenolic resin is heated to 140 ℃.
9. A production method according to any one of claims 1 to 3, wherein in step (3), the compounding is performed according to the following method: and coating the glue solution on the fiber reinforcement, and drying the fiber reinforcement.
10. A method according to any one of claims 1 to 3, wherein in step (3), the mass ratio of the fibrous reinforcement and the dope is 1:2.
11. the method according to claim 9, wherein the drying is performed at 80 to 100 ℃ for 10 to 30 minutes.
12. A method according to any one of claims 1 to 3, wherein in step (4) the curing is performed in an autoclave under the following curing conditions: keeping the temperature at 170-180 ℃ for 2-4h, keeping the temperature at 190-200 ℃ for 1.5-2h, keeping the temperature at 220-230 ℃ for 1.5-2h, and keeping the temperature at 240-250 ℃ for 2-4h.
13. The method according to claim 12, wherein the autoclave is pressurized to 0.3 to 0.5MPa after maintaining the temperature at 170 to 180 ℃ for 1 to 1.5 hours during the curing process, and then the subsequent curing operation is performed.
14. A cyanate-modified bismaleimide-propargyl phenolic resin-based wave-transparent composite prepared by the method according to any one of claims 1 to 13.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202110741502.XA CN113981707B (en) | 2021-06-30 | 2021-06-30 | Cyanate modified bismaleimide-propargyl phenolic resin matrix wave-transparent composite material and preparation method thereof |
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| CN103173012A (en) * | 2013-03-01 | 2013-06-26 | 中国科学院深圳先进技术研究院 | Bismaleimide and triazine resin composite material, organic substrate and method for preparing organic substrate |
| CN103724931A (en) * | 2013-12-09 | 2014-04-16 | 航天特种材料及工艺技术研究所 | Improved phenolic resin, wave penetrating composite and preparation methods for both |
| CN106317766A (en) * | 2016-09-08 | 2017-01-11 | 沈阳化工大学 | Preparation method of phenolic resin foam modified by cyanate ester resin |
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| CN103173012A (en) * | 2013-03-01 | 2013-06-26 | 中国科学院深圳先进技术研究院 | Bismaleimide and triazine resin composite material, organic substrate and method for preparing organic substrate |
| CN103724931A (en) * | 2013-12-09 | 2014-04-16 | 航天特种材料及工艺技术研究所 | Improved phenolic resin, wave penetrating composite and preparation methods for both |
| CN106317766A (en) * | 2016-09-08 | 2017-01-11 | 沈阳化工大学 | Preparation method of phenolic resin foam modified by cyanate ester resin |
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