CN114686004A - Toughening cyanate and preparation method thereof - Google Patents
Toughening cyanate and preparation method thereof Download PDFInfo
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- CN114686004A CN114686004A CN202011636803.8A CN202011636803A CN114686004A CN 114686004 A CN114686004 A CN 114686004A CN 202011636803 A CN202011636803 A CN 202011636803A CN 114686004 A CN114686004 A CN 114686004A
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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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
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Abstract
The invention provides a toughened cyanate ester and a preparation method thereof. The preparation method of the toughened cyanate ester comprises the following steps: blending the end group functional group nano rubber, the epoxy resin and the coupling agent to obtain a blend; and carrying out polymerization reaction on the blend and the cyanate ester molten liquid to obtain the toughened cyanate ester. The toughening cyanate prepared by the method has better toughness and processability and lower cost; meanwhile, the prepolymer has a good prepreg/composite material processing technology, the requirements of the prepreg on the use shelf life are met, and the elongation at break of the prepreg is greatly improved.
Description
Technical Field
The invention relates to the field of preparation of cyanate resin, and particularly relates to toughened cyanate ester and a preparation method thereof.
Background
The cyanate ester resin has good temperature resistance, excellent mechanical property and excellent dielectric property, so that the cyanate ester resin is more and more applied to the fields of electronic information, aerospace, military and the like, in particular to the aspects of radar antenna covers, high-performance circuit boards, wave-transmitting materials and the like.
The cyanate resin contains two-OCN functional groups, can be trimerized into a ring under the condition of heating or catalysis to form a three-dimensional network crosslinking structure, and a large amount of rigid triazine ring structures generated by the cyanate resin cause a cured product of the cyanate resin to have large brittleness and poor toughness. In order to expand the application range of the cyanate ester, the cyanate ester needs to be toughened and modified. However, the toughness of the existing modified cyanate can not meet the application requirements. Therefore, it is required to develop a new cyanate ester having more excellent toughness.
Disclosure of Invention
The invention mainly aims to provide a toughening cyanate and a preparation method thereof, and aims to solve the problem that the application range of the existing cyanate resin or modified cyanate resin is limited by the toughness range of the existing cyanate resin or modified cyanate resin.
In order to achieve the above object, one aspect of the present invention provides a method for preparing a toughened cyanate ester, the method comprising: blending the end group functional group nano rubber, the epoxy resin and the coupling agent to obtain a blend; and carrying out polymerization reaction on the blend and the cyanate ester molten liquid to obtain the toughened cyanate ester.
Further, in the blending step, the weight ratio of the coupling agent to the end group functional group nano rubber is (0.1-2): 100, and the weight ratio of the end group functional group nano rubber to the epoxy resin is (1-50): 100; preferably, in the blending step, the weight ratio of the coupling agent to the terminal functional group nano rubber is (0.5-1): 100, and the weight ratio of the terminal functional group nano rubber to the epoxy resin is (10-20): 100.
Further, the terminal functional group nanometer rubber is selected from one or more of the group consisting of fully vulcanized carboxyl nitrile rubber, terminal vinyl nitrile rubber and terminal carboxyl isoprene rubber; the coupling agent is one or more selected from the group consisting of silane coupling agent, aminopropyltriethoxysilane, r- (2, 3-epoxypropane) propyltrimethoxysilane, vinyltrimethoxysilane and polyethylene glycol; the epoxy resin is one or more of E51 type epoxy resin, 4, 5-epoxy hexane-1, 2-dicarboxylic acid diglycidyl ester, 4-diaminodiphenylmethane epoxy resin, aminophenol trifunctional epoxy resin and aminophenol trifunctional epoxy resin.
Further, the polymerization reaction comprises: and melting cyanate to prepare cyanate molten liquid, and then adding the blend into the cyanate molten liquid for reaction to obtain the toughened cyanate.
Further, the temperature of the polymerization reaction is 90-150 ℃, and the reaction time is 0.5-10 h; preferably, the temperature of the polymerization reaction is 120-140 ℃, and the copolymerization time is 2-5 h.
Further, the polymerization reaction further comprises: detecting the viscosity of the polymerization reaction system, and finishing the polymerization reaction when the viscosity of the polymerization reaction system is 1000-20000 mPa & s at 100 ℃; preferably, the polymerization reaction is terminated when the viscosity of the polymerization reaction system is 2000 to 10000 mPas at 100 ℃.
Further, in the polymerization reaction, the mass ratio of the epoxy resin to the cyanate ester in the blend is (10-50): 50; preferably, the mole number of the epoxy group and the cyanate group in the blend in the polymerization reaction is (15-25): 50.
Further, the cyanate is selected from one or more of the group consisting of bisphenol A cyanate monomer, bisphenol F cyanate, phenolic cyanate and dicyclopentadiene bisphenol cyanate.
Furthermore, the particle size of the end group functional group nano rubber is 20-100 nm.
The other aspect of the application also provides toughened cyanate ester, and the toughened cyanate ester is prepared by the preparation method provided by the application.
By applying the technical scheme of the invention, the epoxy resin has better heat resistance, flexibility, dielectric property and the like. The epoxy resin and cyanate ester are subjected to polymerization reaction to generate oxazoline ketone and the like, so that the cross-linking density of the triazine ring can be reduced, and the toughness of a cured product can be improved. The epoxy resin and the cyanate ester are subjected to polymerization reaction, no additional catalyst is required, the polymerization reaction is relatively mild and easy to control, and the prepared prepolymer or prepreg has a longer shelf life. In addition, the addition of the epoxy resin improves the processing manufacturability of the cyanate ester prepolymer to a greater extent. The addition of the silane coupling agent increases the compatibility of the end group functional group nano rubber particles and the epoxy resin, the viscosity of the glue solution is gradually increased while the epoxy resin and the cyanate ester are gradually polymerized, and the end group functional group nano rubber particles are uniformly dispersed in the epoxy/cyanate ester prepolymer under the physical stirring action. Compared with micron rubber particles, the nano rubber particles with the end group functional groups are smaller, are blended with epoxy/cyanate ester, are dispersed more uniformly, do not increase the viscosity of the epoxy/cyanate ester, and have better processing manufacturability. After being cured with the epoxy/cyanate ester prepolymer, when the epoxy/cyanate ester prepolymer is subjected to static force, the uniformly distributed end group functional group nano rubber particles can resist more crack growth through plastic stretching, shear deformation, tearing, debonding, crack deflection and the like, and the expiration date of the composite material is prolonged. When dynamic force is applied, the cavities of the nano particles grow, so that the surrounding matrix is caused to be plastically expanded, the shear band is deformed, and the fracture absorption energy is effectively increased. On the basis, the toughening cyanate prepared by the method has better toughness and processability and lower cost; meanwhile, the prepolymer has a good prepreg/composite material processing technology, the requirements of the prepreg on the use shelf life are met, and the elongation at break of the prepreg is greatly improved.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As described in the background, the range of toughness of the existing cyanate resins or modified cyanate resins limits the range of applications. In order to solve the above technical problems, the present application provides a preparation method of a toughened cyanate ester, including: blending the end group functional group nano rubber, the epoxy resin and the coupling agent to obtain a blend; and carrying out polymerization reaction on the blend and the cyanate ester molten liquid to obtain the toughened cyanate ester.
In the preparation method, the blend is prepared by treating the end group functional group nano rubber particles and the epoxy resin with a silane coupling agent, and then the treated blend and the cyanate are subjected to copolymerization modification to obtain the modified prepolymer. And curing the cyanate ester prepolymer to obtain the required toughened cyanate ester.
The epoxy resin has excellent heat resistance, flexibility, dielectric property and the like. Epoxy resin and cyanate ester are polymerized to generate oxazoline ketone, which can reduce the cross-linking density of triazine ring and improve the toughness of the cured product. The epoxy resin and the cyanate ester are subjected to polymerization reaction, no additional catalyst is required, the polymerization reaction is relatively mild and easy to control, and the prepared prepolymer or prepreg has a longer shelf life. In addition, the addition of the epoxy resin improves the processing manufacturability of the cyanate ester prepolymer to a greater extent. The addition of the silane coupling agent increases the compatibility of the end group functional group nano rubber particles and the epoxy resin, the viscosity of the glue solution is gradually increased while the epoxy resin and the cyanate ester are gradually polymerized, and the end group functional group nano rubber particles are uniformly dispersed in the epoxy/cyanate ester prepolymer under the physical stirring action. Compared with micron rubber particles, the nano rubber particles with the end group functional groups are smaller, are blended with epoxy/cyanate ester, are dispersed more uniformly, do not increase the viscosity of the epoxy/cyanate ester, and have better processing manufacturability. After being cured with the epoxy/cyanate ester prepolymer, when the epoxy/cyanate ester prepolymer is subjected to static force, the uniformly distributed end group functional group nano rubber particles can resist more crack growth through plastic stretching, shear deformation, tearing, debonding, crack deflection and the like, and the expiration date of the composite material is prolonged. When dynamic force is applied, the cavities of the nano particles grow, so that the surrounding matrix is plastically expanded, the shear band is deformed, and the fracture absorption energy is effectively increased. On the basis, the toughening cyanate prepared by the method has better toughness and processability and lower cost; meanwhile, the prepolymer has a good prepreg/composite material processing technology, the requirements of the prepreg on the use shelf life are met, and the elongation at break of the prepreg is greatly improved.
The addition of the coupling agent is used for improving the compatibility of the end group functional group nano rubber and the epoxy resin and simultaneously improving the dispersibility of the end group functional group nano rubber in the toughening type cyanate. In a preferred embodiment, in the blending step, the weight ratio of the coupling agent to the terminal functional group nano rubber is (0.1-2): 100, and the weight ratio of the terminal functional group nano rubber to the epoxy resin is (1-50): 100. The weight ratio of the terminal functional group nano rubber to the epoxy resin and the coupling agent includes, but is not limited to, the above range, and the weight ratio is limited to the above range, which is beneficial to further improving the toughness and mechanical properties of the toughening type cyanate ester. More preferably, in the blending step, the weight ratio of the coupling agent to the terminal functional group nano rubber is (0.5-1): 100, and the weight ratio of the terminal functional group nano rubber to the epoxy resin is (10-20): 100.
In the preparation method, the terminal functional group nano rubber can be selected from the types commonly used in the field. In a preferred embodiment, the terminal functional nano-rubber includes, but is not limited to, one or more of the group consisting of fully vulcanized carboxylated nitrile rubber, vinyl terminated nitrile rubber, carboxyl terminated nitrile rubber, hydroxyl terminated polybutadiene acrylonitrile rubber, and hydroxyl terminated polybutadiene rubber. The rubbers have better heat resistance, water resistance, wear resistance and aging resistance, so that the service life, performance stability and the like of the toughened cyanate ester are favorably prolonged by selecting the rubbers as the raw materials for preparing the toughened cyanate ester.
In the above preparation method, the coupling agent may be selected from those commonly used in the art. Preferably, the coupling agent includes, but is not limited to, one or more of the group consisting of silane coupling agent, aminopropyltriethoxysilane (KH550), r- (2, 3-epoxypropane) propyltrimethoxysilane (KH560), vinyltrimethoxysilane (a171), and polyethylene glycol.
In a preferred embodiment, the epoxy resin includes, but is not limited to, one or more of the group consisting of epoxy resin type E51, diglycidyl 4, 5-epoxyhexane-1, 2-dicarboxylate (TDE-85), 4-diaminodiphenylmethane epoxy resin (AG80), aminophenol trifunctional epoxy resin, and aminophenol trifunctional epoxy resin (AFG 90).
In a preferred embodiment, the polymerization reaction comprises: and melting cyanate to prepare cyanate molten liquid, and then adding the blend into the cyanate molten liquid for reaction to obtain the toughened cyanate.
In a preferred embodiment, the polymerization temperature is 90-150 ℃ and the reaction time is 0.5-10 h. The temperature and time of the polymerization reaction include, but are not limited to, the above ranges, and are limited to the above ranges, the epoxy resin and the cyanate ester are in a molten state, so that the epoxy resin and the cyanate ester can be mixed more uniformly, the polymerization reaction is more sufficient, and the comprehensive performance of the toughened cyanate ester can be further improved. More preferably, the temperature of the polymerization reaction is 120-140 ℃, and the copolymerization time is 2-5 h.
As the polymerization proceeds, the viscosity of the polymerization system gradually increases. In a preferred embodiment, the polymerization reaction further comprises: the viscosity of the polymerization reaction system is detected, and the polymerization reaction is terminated when the viscosity of the polymerization reaction system is 1000 to 20000 mPas at 100 ℃. Limiting the viscosity of the polymerization system within the above range is advantageous for better processability of the toughened cyanate ester. More preferably, the polymerization reaction is terminated when the viscosity of the polymerization reaction system is 2000 to 10000 mPas at 100 ℃.
In order to further improve the polymerization degree of the epoxy resin and the cyanate ester, the mass ratio of the epoxy resin to the cyanate ester in the blend in the polymerization reaction is preferably (10-50): 50. More preferably, in the polymerization reaction, the mass ratio of the epoxy resin to the cyanate ester in the blend is (15-25): 50.
In the above preparation method, cyanate ester may be selected from those commonly used in the art. Preferably, the cyanate ester includes, but is not limited to, one or more of the group consisting of CY-1 monomer (bisphenol a type cyanate ester), bisphenol F type cyanate ester, phenolic cyanate ester, and dicyclopentadiene bisphenol cyanate ester.
In a preferred embodiment, the particle size of the terminal functional group nano rubber is 20-100 nm.
The other aspect of the application also provides toughened cyanate ester, which is prepared by the preparation method provided by the application.
The epoxy resin has excellent heat resistance, flexibility, dielectric property and the like. Epoxy resin and cyanate ester are polymerized to generate oxazoline ketone, which can reduce the cross-linking density of triazine ring and improve the toughness of the cured product. The epoxy resin and the cyanate ester are used for polymerization reaction, no additional catalyst is needed, the polymerization reaction is relatively smooth, the copolymerization process is easier to control, and the processed prepolymer or prepreg has a longer shelf life. In addition, the addition of the epoxy resin improves the processing manufacturability of the cyanate ester prepolymer to a greater extent. The addition of the silane coupling agent increases the compatibility of the end group functional group nano rubber particles and the epoxy resin, the viscosity of the glue solution is gradually increased while the epoxy resin and the cyanate ester are gradually polymerized, and the end group functional group nano rubber particles are uniformly dispersed in the epoxy/cyanate ester prepolymer under the physical stirring action. Compared with micron rubber particles, the nano rubber particles with the end group functional groups are smaller, are blended with epoxy/cyanate ester, are dispersed more uniformly, do not increase the viscosity of the epoxy/cyanate ester, and have better processing manufacturability. After being cured with the epoxy/cyanate ester prepolymer, when the epoxy/cyanate ester prepolymer is subjected to static force, the uniformly distributed end group functional group nano rubber particles can resist more crack growth and prolong the expiration date of the composite material through plastic stretching, shearing deformation, tearing, debonding, crack deflection and the like. When dynamic force is applied, the cavities of the nano particles grow, so that the surrounding matrix is plastically expanded, the shear band is deformed, and the fracture absorption energy is effectively increased. On the basis, the toughening cyanate prepared by the method has better toughness and processability and lower cost; meanwhile, the prepolymer has a better prepreg/composite material processing technology, and the requirements of the prepreg on the use shelf life are met.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
Example 1
(1) Preparing a blend of the end group functional group nano rubber and the epoxy resin modified by a silane coupling agent.
Taking a proper amount of epoxy resin in a beaker, placing the beaker in a drying oven at 100 ℃ for dehydration and bubble removal, observing no bubble, and keeping the temperature at 60 ℃ for later use. Weighing a proper amount of silane coupling agent and the end group functional group nano rubber, pouring the silane coupling agent and the end group functional group nano rubber into a beaker of epoxy resin in sequence, placing the beaker into a stirrer, and uniformly dispersing the end group functional group nano rubber in the epoxy resin by utilizing physical stirring. After dispersion, the blend is placed into a 60 ℃ oven for heat preservation for later use. The weight ratio of the silane coupling agent to the end group functional group nano rubber in the blend is 1:100, and the weight ratio of the end group functional group nano rubber particles to the epoxy resin is 20: 100. The end group functional group nano rubber is fully vulcanized carboxyl nitrile rubber, the silane coupling agent is KH560, and the epoxy resin is E51.
(2) And (3) preparing a modified cyanate ester prepolymer.
Taking a proper amount of cyanate ester, placing the cyanate ester into a reactor, and placing the reactor into an oil bath pan at 140 ℃ for heating. After the resin is melted, the melt is continuously stirred by a stirrer. And (c) after the temperature is constant, pouring a proper amount of the blend obtained in the step a into the cyanate ester molten liquid, and carrying out polymerization reaction for 4 hours. And in the reaction process, a cone-plate viscometer is used for sampling and testing in real time, and the copolymer is poured out and cooled at the temperature of 100 ℃ when the viscosity is 1000-20000 mPa s, so that the cyanate ester prepolymer suitable for the composite material is obtained. The weight ratio of the blend obtained in the step a to the cyanate ester is 10: 50.
Compared with the prior art, the invention utilizes the copolymer of the end group functional group nano rubber and the epoxy resin which are modified by the silane coupling agent to carry out copolymerization toughening modification with the cyanate, thus obtaining the modified cyanate prepolymer.
And (4) performance testing: the modified cyanate ester has a better prepreg/composite material processing technology, the elongation at break of the obtained resin cured product is up to 4.5% according to a GB/T2567 test, and the elongation at break of the commercially available cyanate resin (Yangzhou Tianqi New Material Co., Ltd., CY-1) is 1.42%.
Example 2
The differences from example 1 are: the weight ratio of the coupling agent to the terminal functional group nano rubber is 0.5:100, and the weight ratio of the terminal functional group nano rubber to the epoxy resin is 15: 100.
The elongation at break of the resulting cured resin was 4.2%.
Example 3
The differences from example 1 are: the weight ratio of the coupling agent to the terminal functional group nano rubber is 2:100, and the weight ratio of the terminal functional group nano rubber to the epoxy resin is 50: 100.
The elongation at break of the resulting cured resin was 4.1%.
Example 4
The differences from example 1 are: the weight ratio of the coupling agent to the terminal functional group nano rubber is 5:100, and the weight ratio of the terminal functional group nano rubber to the epoxy resin is 80: 100.
The elongation at break of the resulting cured resin was 3.5%.
Example 5
The differences from example 1 are: the polymerization temperature was 100 ℃ and the copolymerization time was 10 h.
The elongation at break of the resulting cured resin was 3.4%.
Example 6
The differences from example 1 are: the polymerization temperature was 150 ℃ and the copolymerization time was 0.5 h.
The elongation at break of the resulting cured resin was 2.8%.
Example 7
The differences from example 1 are: the polymerization temperature was 80 ℃ and the copolymerization time was 2 h.
The elongation at break of the resulting cured resin was 2.8%.
Example 8
The differences from example 1 are: the weight ratio of epoxy resin to cyanate in the blend was 15: 50.
The elongation at break of the resulting cured resin was 4.0%.
Example 9
The differences from example 1 are: the weight ratio of epoxy resin to cyanate in the blend was 25: 50.
The elongation at break of the resulting cured resin was 4.2%.
Example 10
The differences from example 1 are: the ratio of the moles of epoxy groups in the blend to the moles of cyanate groups in the cyanate ester is 2: 50.
The elongation at break of the resulting cured resin was 2.9%.
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
it can be seen from comparison of examples 1 to 4 that limiting the weight ratio of the coupling agent to the terminal functional group nano rubber and to the epoxy resin within the preferred range of the present application is advantageous for improving the toughness of the toughened cyanate ester.
It is understood from comparative examples 1 and 5 to 7 that limiting the reaction temperature and time of the polymerization reaction to the preferred ranges of the present application is advantageous for improving the toughness of the toughening type cyanate ester.
Comparing examples 1 and 8 to 10, it can be seen that limiting the weight percentage of the cyanate group in the cyanate ester to the epoxy group in the blend is advantageous for improving the toughness of the toughened cyanate ester.
It is noted that the terms first, second and the like in the description and in the claims of the present application are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the terms so used are interchangeable under appropriate circumstances such that the embodiments of the application described herein are, for example, capable of operation in sequences other than those described or illustrated herein.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the toughened cyanate ester is characterized by comprising the following steps of:
blending the end group functional group nano rubber, the epoxy resin and the coupling agent to obtain a blend; and
and carrying out polymerization reaction on the blend and cyanate ester molten liquid to obtain the toughened cyanate ester.
2. The preparation method of the toughened cyanate ester according to claim 1, wherein in the blending step, the weight ratio of the coupling agent to the terminal functional group nano rubber is (0.1-2): 100, and the weight ratio of the terminal functional group nano rubber to the epoxy resin is (1-50): 100;
preferably, in the blending step, the weight ratio of the coupling agent to the terminal functional group nano rubber is (0.5-1): 100, and the weight ratio of the terminal functional group nano rubber to the epoxy resin is (10-20): 100.
3. The preparation method of the toughened cyanate ester according to claim 1 or 2, wherein the terminal functional group nano rubber is one or more selected from the group consisting of fully vulcanized carboxylated nitrile rubber, vinyl terminated nitrile rubber and carboxyl terminated isoprene rubber;
the coupling agent is selected from one or more of silane coupling agent, aminopropyltriethoxysilane, r- (2, 3-epoxypropane) propyltrimethoxysilane, vinyl trimethoxysilane and polyethylene glycol;
the epoxy resin is one or more selected from the group consisting of E51 type epoxy resin, 4, 5-epoxyhexane-1, 2-dicarboxylic acid diglycidyl ester, 4-diaminodiphenylmethane epoxy resin, aminophenol trifunctional epoxy resin and aminophenol trifunctional epoxy resin.
4. The method for preparing the toughening cyanate ester according to any one of claims 1 to 3, wherein the polymerization reaction comprises:
and melting cyanate to prepare the cyanate molten liquid, and then adding the blend into the cyanate molten liquid for reaction to obtain the toughened cyanate.
5. The preparation method of the toughened cyanate ester according to claim 4, wherein the temperature of the polymerization reaction is 90-150 ℃ and the reaction time is 0.5-10 h;
preferably, the temperature of the polymerization reaction is 120-140 ℃, and the copolymerization time is 2-5 h.
6. The method for preparing the toughened cyanate according to claim 5, wherein the polymerization reaction further comprises: detecting the viscosity of the polymerization reaction system, and finishing the polymerization reaction when the viscosity of the polymerization reaction system is 1000-20000 mPa & s at 100 ℃;
preferably, the polymerization reaction is terminated when the viscosity of the polymerization reaction system is 2000 to 10000 mPas at 100 ℃.
7. The preparation method of the toughened cyanate ester according to claim 1, wherein in the polymerization reaction, the mass ratio of the epoxy resin to the cyanate ester in the blend is (10-50): 50;
preferably, in the polymerization reaction, the mole number of the epoxy group in the blend and the cyanate group in the cyanate ester is (15-25): 50.
8. The method for preparing the toughened cyanate according to claim 1, wherein the cyanate is one or more selected from the group consisting of bisphenol a cyanate monomer, bisphenol F cyanate, phenolic cyanate, and dicyclopentadiene bisphenol cyanate.
9. The preparation method of the toughened cyanate ester according to claim 1, wherein the particle size of the end group functional group nano rubber is 20 to 100 nm.
10. Toughened cyanate ester, characterized in that it is prepared by the process of any one of claims 1 to 9.
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| EP0301361A2 (en) * | 1987-07-30 | 1989-02-01 | The Dow Chemical Company | Rubber-modified cyanate ester resins, their preparation and polytriazines derived therefrom |
| CN103131181A (en) * | 2013-03-20 | 2013-06-05 | 中国科学院长春应用化学研究所 | Toughened cyanate resin and preparation method thereof |
| CN105038223A (en) * | 2015-06-02 | 2015-11-11 | 长春长光宇航复合材料有限公司 | Cyanate resin for hot-melt prepregs and preparation method thereof |
| CN106751819A (en) * | 2016-11-23 | 2017-05-31 | 江苏恒神股份有限公司 | A kind of RTM techniques cyanate resin composition and preparation method |
| CN108276597A (en) * | 2018-01-10 | 2018-07-13 | 亚天顿（廊坊）复合材料科技有限公司 | A kind of production method of the high wave transparent Epoxies Resins Modified Cyanater system prepreg of intermediate temperature setting |
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2020
- 2020-12-31 CN CN202011636803.8A patent/CN114686004A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0301361A2 (en) * | 1987-07-30 | 1989-02-01 | The Dow Chemical Company | Rubber-modified cyanate ester resins, their preparation and polytriazines derived therefrom |
| CN103131181A (en) * | 2013-03-20 | 2013-06-05 | 中国科学院长春应用化学研究所 | Toughened cyanate resin and preparation method thereof |
| CN105038223A (en) * | 2015-06-02 | 2015-11-11 | 长春长光宇航复合材料有限公司 | Cyanate resin for hot-melt prepregs and preparation method thereof |
| CN106751819A (en) * | 2016-11-23 | 2017-05-31 | 江苏恒神股份有限公司 | A kind of RTM techniques cyanate resin composition and preparation method |
| CN108276597A (en) * | 2018-01-10 | 2018-07-13 | 亚天顿（廊坊）复合材料科技有限公司 | A kind of production method of the high wave transparent Epoxies Resins Modified Cyanater system prepreg of intermediate temperature setting |
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