CN113755013B - Wave-absorbing cyanate resin, wave-absorbing cyanate resin composite material and preparation method thereof - Google Patents
Wave-absorbing cyanate resin, wave-absorbing cyanate resin composite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a wave-absorbing cyanate resin, a wave-absorbing cyanate resin composite material and a preparation method thereof. The method comprises the following steps: mixing the cyanate resin, the epoxy resin and the absorbent in a banburying way to obtain a coarse mixed wave-absorbing cyanate resin; carrying out open mill fine mixing on the coarse mixed wave-absorbing cyanate resin to obtain fine mixed wave-absorbing cyanate resin, and then adding a curing agent to obtain a wave-absorbing cyanate resin curing system; the curing agent is one or more selected from fatty amine curing agent, polyamide curing agent, aromatic amine curing agent, polyether amine curing agent, dicyandiamide curing agent and anhydride curing agent; triggering and curing the wave-absorbing cyanate resin curing system at different temperature stages to obtain the wave-absorbing cyanate resin with different viscosities. The wave-absorbing cyanate resin has different viscosities in different technological processes, is favorable for uniform dispersion of the absorbent, is favorable for calendaring and molding, and has better wave-absorbing performance stability and technological characteristics.
Description
Technical Field
The invention belongs to the technical field of preparation of wave-absorbing materials, and particularly relates to wave-absorbing cyanate resin, a wave-absorbing cyanate resin composite material and a preparation method thereof.
Background
The wave absorbing material is a material capable of absorbing and attenuating incident electromagnetic waves, and converting the electromagnetic energy into heat energy to be dissipated or to enable the electromagnetic waves to disappear due to interference. With the development of science and technology, the wave-absorbing material has been widely used in various aspects. Such as electromagnetic protection, microwave darkroom, mobile communication, military stealth, etc. The resin-based wave-absorbing composite material has the advantages of strong designability, large-area integral molding and the like, and is one of the most important application materials in the field of aerospace stealth.
The wave-absorbing resin is a raw material for preparing the resin-based wave-absorbing composite material and consists of an electromagnetic wave absorber and a resin matrix, wherein the electromagnetic wave absorber determines the wave-absorbing characteristic of the resin matrix, and the resin matrix determines the technological characteristic of the resin matrix more. The present invention recognizes that the wave-absorbing resin needs to have different viscosity states throughout the process, for example, when the wave-absorbing resin is mixed, the wave-absorbing resin needs to have a low viscosity, which is advantageous for uniform dispersion of the electromagnetic wave-absorbing agent in the resin matrix. When the film is formed by calendering, the wave-absorbing resin needs to have certain viscosity, so that the film forming property of the adhesive film is endowed, and the improvement of the plasticity is beneficial to the precise calendering and forming of the adhesive film. In the process of complete curing and forming, the viscosity of the wave-absorbing resin is highest, and the complete crosslinking and curing endows the material with good mechanical properties. The wave-absorbing resin has high absorbent content, the viscosity control is particularly important to the performance regulation and control of the wave-absorbing resin, and the wave-absorbing resin with controllable viscosity can effectively improve the wave-absorbing characteristic and the technological characteristic of the resin-based wave-absorbing composite material.
However, the existing wave-absorbing resin generally has the problem that the viscosity is not controllable in the whole process flow. For example, chinese patent application CN111704868A provides a wave-absorbing adhesive film and a preparation method thereof, chinese patent application CN107586436a provides a wave-absorbing prepreg and a preparation method thereof, chinese patent application CN112029421a discloses a wave-absorbing adhesive film material and a preparation method thereof, but the viscosity of wave-absorbing resin involved in the preparation methods is not controllable, and is only suitable for a certain stage of process, or the viscosity of high or low is unfavorable for uniform dispersion of absorbent and calendaring, for example, if the viscosity is low, although the resin can be ensured to have better uniformity during mixing, the viscosity is low during calendaring, the plastic of the adhesive film is poor, the molding precision is not high, and if the viscosity is high, the molding precision is high during calendaring, but the uniformity during mixing is difficult to be ensured.
In view of the foregoing, it is highly desirable to provide a wave-absorbing cyanate resin, a wave-absorbing cyanate resin composite material, and a method for preparing the same.
Disclosure of Invention
The invention provides a wave-absorbing cyanate resin, a wave-absorbing cyanate resin composite material and a preparation method thereof, aiming at solving the technical problem that the viscosity of the existing wave-absorbing resin is uncontrollable in the whole process flow. The wave-absorbing cyanate resin has different viscosities in different technological processes, is favorable for uniform dispersion of the absorbent, and is subjected to calendaring molding of the wave-absorbing composite intermediate, so that the wave-absorbing cyanate resin has better wave-absorbing performance (stability of wave-absorbing performance is improved) and technological characteristics.
The present invention provides in a first aspect a method for producing a wave-absorbing cyanate resin, the method comprising the steps of:
(1) Placing cyanate resin, epoxy resin and absorbent into an internal mixer for internal mixing to obtain coarse mixed wave-absorbing cyanate resin;
(2) Placing the coarse mixed wave-absorbing cyanate resin obtained in the step (1) into an open mill for open mill fine mixing to obtain fine mixed wave-absorbing cyanate resin, and then adding a curing agent into the fine mixed wave-absorbing cyanate resin to obtain a wave-absorbing cyanate resin curing system; the curing agent is one or more selected from fatty amine curing agents, polyamide curing agents, aromatic amine curing agents, polyether amine curing agents, dicyandiamide curing agents and anhydride curing agents;
(3) Triggering and curing the wave-absorbing cyanate resin curing system obtained in the step (2) at different temperature stages to obtain the wave-absorbing cyanate resin with different viscosities.
Preferably, the molar ratio of the cyanate resin, the curing agent and the epoxy resin is 1: (0.1-0.5): (0.5 to 0.7); and/or the curing agent is an aliphatic amine curing agent, preferably, the curing agent is one or more of diethylenetriamine, triethylenetetramine and tetraethylenepentamine.
Preferably, the cyanate resin is one or more of bisphenol A type cyanate resin, tetramethyl bisphenol F type cyanate resin, bisphenol M type cyanate resin, bisphenol E type cyanate resin and multifunctional cyanate resin; the epoxy resin is one or more of E-51 type epoxy resin, E-44 type epoxy resin, E-20 type epoxy resin, F-44 type epoxy resin and F-51 type epoxy resin; and/or the absorbent is one or more of carbonyl iron, iron-silicon-aluminum, ferrite, conductive carbon black, carbon fiber, graphene, carbon nano tube and silicon carbide, and preferably, the amount of the absorbent is 5-90% of the sum of the mass of the cyanate resin and the mass of the epoxy resin.
Preferably, in the step (1), the temperature of the internal mixing and coarse mixing is 20-300 ℃, the time of the internal mixing and coarse mixing is 10-120 min, and the rotating speed of a rotor of the internal mixing and coarse mixing is 10-250 r/min; in the step (2), the temperature of the open mill refined mixing is 20-300 ℃, and the roll speed of the open mill refined mixing is 2-17 m/min; in the step (2), the coarse mixed wave-absorbing cyanate resin obtained in the step (1) is put into an open mill for open mill fine mixing for 10-80 min to obtain fine mixed wave-absorbing cyanate resin, and then a curing agent is added into the fine mixed wave-absorbing cyanate resin and the open mill fine mixing is continued for 2-10 min to obtain a wave-absorbing cyanate resin curing system; and/or in the step (3), triggering the stage curing of the wave-absorbing cyanate resin curing system obtained in the step (2) within the range of 20-300 ℃ to obtain the wave-absorbing cyanate resin with different viscosities.
The present invention provides in a second aspect a wave-absorbing cyanate resin prepared by the preparation method of the present invention described in the first aspect.
The invention provides a preparation method of a wave-absorbing cyanate resin composite material in a third aspect, which comprises the following steps:
(a) Placing cyanate resin, epoxy resin and absorbent into an internal mixer for internal mixing to obtain coarse mixed wave-absorbing cyanate resin;
(b) Placing the coarse mixed wave-absorbing cyanate resin obtained in the step (a) into an open mill for open mill fine mixing to obtain fine mixed wave-absorbing cyanate resin, and then adding a curing agent into the fine mixed wave-absorbing cyanate resin to obtain a wave-absorbing cyanate resin curing system; the curing agent is one or more selected from fatty amine curing agents, polyamide curing agents, aromatic amine curing agents, polyether amine curing agents, dicyandiamide curing agents and anhydride curing agents;
(c) Triggering and curing the wave-absorbing cyanate resin curing system obtained in the step (b) at least at a low temperature stage to obtain a wave-absorbing cyanate resin blank, and then placing the wave-absorbing cyanate resin blank into a calender for calendering to obtain a wave-absorbing cyanate resin film;
(d) And (3) layering a plurality of layers of the wave-absorbing cyanate resin film, and triggering and curing at least at one high-temperature stage to prepare the wave-absorbing cyanate resin composite material.
Preferably, the molar ratio of the cyanate resin, the curing agent and the epoxy resin is 1: (0.1-0.5): (0.5 to 0.7); the curing agent is a fatty amine curing agent, preferably one or more of diethylenetriamine, triethylenetetramine and tetraethylenepentamine.
Preferably, in the step (c), triggering and curing the wave-absorbing cyanate ester resin curing system obtained in the step (b) at 50-80 ℃ to obtain a wave-absorbing cyanate ester resin blank, and then placing the wave-absorbing cyanate ester resin blank into a calender for calendering to obtain a wave-absorbing cyanate ester resin film; in the step (d), a plurality of layers of the wave-absorbing cyanate resin film are laminated, and then trigger curing is carried out at 180-250 ℃ to prepare the wave-absorbing cyanate resin composite material.
Preferably, the viscosity of the wave-absorbing cyanate resin curing system is 500-20000 cps; and/or the viscosity of the blank of the wave-absorbing cyanate ester resin is 30000-500000 cps.
The present invention provides in a fourth aspect a wave-absorbing cyanate ester resin composite material prepared by the preparation method of the present invention described in the third aspect.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) The low-viscosity wave-absorbing cyanate resin is favorable for uniform dispersion of the absorbent in the course of internal mixing and open mixing, and improves the electrical property and the stability of wave-absorbing property of the wave-absorbing cyanate resin.
(2) The viscosity of the wave-absorbing cyanate resin is increased after the curing reaction at a certain temperature is triggered, so that the plasticity and film forming property of the wave-absorbing cyanate resin are improved, and the precise film forming property is favorable for controlling the wave-absorbing property of the wave-absorbing cyanate resin composite material.
(3) The viscosity of the wave-absorbing cyanate resin in the mixing stage is in the range of 500-20000 cps, and the surface density Cv value of the wave-absorbing cyanate resin composite material in different areas can reach 0.02-0.05 in the range; after the first-stage curing (low-temperature curing), the viscosity is within the viscosity range of 30000-500000 cps, the thickness precision of calendaring can reach +/-5% thickness range, and the wave-absorbing cyanate resin is completely cured and has no viscosity.
(4) In the invention, the low-viscosity wave-absorbing cyanate resin is favorable for dispersing the absorbent, the high-viscosity wave-absorbing cyanate resin which is triggered to be solidified in different temperature stages is favorable for thickness precision control, and the reflectance absorption peak frequency value Cv value after being rolled into the wave-absorbing resin film multilayer lamination can be controlled within 0.1; compared with the wave absorbing performance of the wave absorbing cyanate resin composite material obtained by the invention, the wave absorbing performance of the wave absorbing cyanate resin composite material obtained by the invention is beneficial to the improvement of the wave absorbing performance stability of the wave absorbing composite material by directly calendering the wave absorbing resin system which is not cured in advance into a film; the reflectance absorption peak frequency Cv value after the multi-layer lamination of the wave-absorbing cyanate resin film is controlled within 0.1, thereby being beneficial to obtaining the wave-absorbing cyanate resin composite material with good wave-absorbing performance and being capable of accurately controlling the thickness precision of the wave-absorbing cyanate resin composite material in a wider range.
Drawings
FIG. 1 is a flow chart of the process for preparing the wave-absorbing cyanate ester resin according to the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In a first aspect, fig. 1 is a process flow diagram of the preparation of the wave-absorbing cyanate resin according to the invention, for example, as shown in fig. 1, a wave-absorbing cyanate resin curing system is prepared, firstly, an absorbent is mixed with cyanate resin and epoxy resin in a banburying way, after the absorbent is mixed uniformly, the mixture is put into an open mill for fine mixing, and curing reaction is triggered at different temperatures for curing reaction at different stages, so that the wave-absorbing cyanate resin has different viscosities at different processing stages to adapt to the processability; the wave-absorbing cyanate resin prepared by the method is triggered and cured at different temperature stages, so that the wave-absorbing cyanate resin with different viscosities can be obtained, and the wave-absorbing cyanate resin is the wave-absorbing cyanate resin with controllable viscosity; the wave-absorbing cyanate resin with controllable viscosity is beneficial to uniform dispersion of the absorbent and calendaring molding of the wave-absorbing cyanate resin.
In the invention, the preparation method of the wave-absorbing cyanate resin comprises the following steps:
(1) Placing cyanate resin, epoxy resin and absorbent into an internal mixer for internal mixing to obtain coarse mixed wave-absorbing cyanate resin; the invention is not particularly limited in the kind and source of the cyanate resin and the epoxy resin, and the cyanate resin which can be directly purchased or synthesized by the existing method can be adopted.
(2) Placing the coarse mixed wave-absorbing cyanate resin obtained in the step (1) into an open mill for open mill fine mixing to obtain fine mixed wave-absorbing cyanate resin, and then adding a curing agent into the fine mixed wave-absorbing cyanate resin to obtain a wave-absorbing cyanate resin curing system; the curing agent is one or more selected from fatty amine curing agents, polyamide curing agents, aromatic amine curing agents, polyether amine curing agents, dicyandiamide curing agents and anhydride curing agents;
(3) Triggering and curing the wave-absorbing cyanate resin curing system obtained in the step (2) at different temperature stages to obtain the wave-absorbing cyanate resin with different viscosities.
In the invention, when the curing agent with different curing temperatures is added in the step (2), correspondingly, in the step (3), the curing is triggered and performed in a mode of sequentially increasing the curing temperature under a plurality of corresponding curing temperature stages to obtain the isocyanate resin with different viscosities; in the step (3), the cyanate resin is finally required to be triggered to be cured in a thermal self-polymerization temperature range of the cyanate resin (the cyanate thermal self-polymerization temperature is generally above 177 ℃), so that the wave-absorbing cyanate resin with different viscosities is obtained; according to the invention, the curing temperature is strictly controlled, so that the curing in the higher curing temperature stage cannot be initiated in the lower curing temperature stage, and therefore, after the curing is triggered in each temperature stage, the wave-absorbing cyanate resin with different viscosities can be obtained, and the wave-absorbing cyanate resin has different viscosities in different processing stages so as to adapt to the processing property.
According to some preferred embodiments, the molar ratio of the cyanate resin, the curing agent, and the epoxy resin is 1: (0.1-0.5): (0.5-0.7) (e.g., 1:0.1:0.5, 1:0.1:0.6, 1:0.1:0.7, 1:0.2:0.5, 1:0.2:0.6, 1:0.2:0.7, 1:0.3:0.5, 1:0.3:0.6, 1:0.3:0.7, 1:0.4:0.5, 1:0.4:0.6, 1:0.4:0.7, 1:0.5:0.5, 1:0.5:0.6, or 1:0.5:0.7); and/or the curing agent is an aliphatic amine curing agent, preferably, the curing agent is one or more of diethylenetriamine, triethylenetetramine and tetraethylenepentamine; in the invention, preferably, in the step (2), a fatty amine curing agent with lower curing temperature, for example, a fatty amine curing agent with the curing temperature of 50-80 ℃ is added, so that the wave-absorbing cyanate resin curing system obtained in the step (2) triggers curing in two temperature stages, including curing in a low-temperature 50-80 ℃ stage and curing in a high-temperature cyanate resin thermal self-polymerization temperature stage; in the present invention, it is preferable that the molar ratio of the cyanate resin to the epoxy resin is 1: (0.5-0.7), in the molar ratio range, the method is favorable for obtaining the wave-absorbing cyanate resin with controllable viscosity, on one hand, in the mixing stage of banburying coarse mixing and open mixing, the wave-absorbing cyanate resin curing system with the viscosity in the range of 500-20000 cps is favorable for obtaining the wave-absorbing cyanate resin curing system with the viscosity in the range of 500-20000 cps, the wave-absorbing cyanate resin curing system with the viscosity in the range of 500-20000 cps is favorable for uniformly dispersing the absorbent, and the density Cv value of the wave-absorbing cyanate resin in different areas can reach 0.02-0.05, so that the electric property and the wave-absorbing property stability of the wave-absorbing cyanate resin are favorable for being improved; on the other hand, after the curing at the low temperature of 50-80 ℃, the viscosity of the wave-absorbing cyanate resin can be controlled within the viscosity range of 30000-500000 cps, the wave-absorbing cyanate resin within the viscosity range is favorable for calendaring and film forming, the precision of the calendaring thickness can reach +/-5% of the thickness range, the precision film forming characteristic is favorable for controlling the wave-absorbing property of the wave-absorbing cyanate resin composite material, the wave-absorbing property and the mechanical property of the wave-absorbing cyanate resin film after calendaring and film forming are favorable for ensuring, the refractive index absorption peak frequency Cv value of the rolled wave-absorbing resin film after multi-layer lamination can be controlled within 0.1, the stability of the wave-absorbing property of the wave-absorbing cyanate resin is effectively improved, the viscosity of the wave-absorbing cyanate resin after curing at the low temperature is more if the epoxy resin content is higher, and the viscosity of the wave-absorbing cyanate resin after curing at the low temperature is less if the epoxy resin content is lower, the viscosity of the wave-absorbing cyanate resin cannot be controlled within the range of 30000-500000 cps, and the wave-absorbing cyanate resin cannot be calendared and formed.
According to some preferred embodiments, the cyanate ester resin is one or more of bisphenol a type cyanate ester resin, tetramethyl bisphenol F type cyanate ester resin, bisphenol M type cyanate ester resin, bisphenol E type cyanate ester resin, polyfunctional type cyanate ester resin; in the present invention, the cyanate ester resins used may be obtained directly from the market or synthesized by the existing methods.
According to some preferred embodiments, the epoxy resin is one or more of an E-51 type epoxy resin, an E-44 type epoxy resin, an E-20 type epoxy resin, an F-44 type epoxy resin, an F-51 type epoxy resin; in the present invention, these epoxy resins are used as they are, and are commercially available.
According to some preferred embodiments, the absorbent is one or more of carbonyl iron, iron-silicon-aluminum, ferrite, conductive carbon black, carbon fiber, graphene, carbon nanotube, silicon carbide, preferably, the absorbent is used in an amount of 5 to 90% (e.g. 5%, 15%, 25%, 40%, 50%, 60%, 70%, 80% or 90%), preferably 40 to 85% (e.g. 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80% or 85%) of the sum of the mass of the cyanate resin and the epoxy resin.
According to some preferred embodiments, in step (1), the temperature of the banburying coarse mix is 20-300 ℃ (e.g. 20 ℃, 40 ℃, 60 ℃, 80 ℃, 100 ℃, 120 ℃, 140 ℃, 160 ℃, 180 ℃, 200 ℃, 220 ℃, 240 ℃, 260 ℃, 280 ℃ or 300 ℃), preferably 80-300 ℃ (e.g. 80 ℃, 100 ℃, 120 ℃, 140 ℃, 160 ℃, 180 ℃, 200 ℃, 220 ℃, 240 ℃, 260 ℃, 280 ℃ or 300 ℃), the time of the banburying coarse mix is 10-120 min (e.g. 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110 or 120 min), preferably 30-60 min (e.g. 30, 40, 50 or 60 min), and the rotor speed of the banburying coarse mix is 10-250 r/min (e.g. 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240 or 250 r/min), preferably 150-250 r/min (e.g. 10, 20, 30, 40, 100, 180, 240 or 250 r/min).
In some more preferred embodiments, the temperature of the internal rough mixing is 80-300 ℃, the time of the internal rough mixing is 30-60 min, and the rotor speed of the internal rough mixing is 150-250 r/min.
According to some preferred embodiments, in step (2), the temperature of the mill finish is 20-300 ℃ (e.g. 20 ℃, 40 ℃, 60 ℃, 80 ℃, 100 ℃, 120 ℃, 140 ℃, 160 ℃, 180 ℃, 200 ℃, 220 ℃, 240 ℃, 260 ℃, 280 ℃ or 300 ℃), preferably 80-250 ℃ (e.g. 80 ℃, 100 ℃, 120 ℃, 140 ℃, 160 ℃, 180 ℃, 200 ℃, 220 ℃ or 250 ℃), the roll speed of the mill finish is 2-17 m/min (e.g. 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16 or 17 m/min), preferably 10-15 m/min (e.g. 10, 11, 12, 13, 14 or 15 m/min); in the present invention, the unit of the roll speed m/min means meter/min.
In some more preferred embodiments, the temperature of the open mill finish mix is 80 to 250 ℃, and the roll speed of the open mill finish mix is 10 to 15m/min.
According to some preferred embodiments, in step (2), the coarse mixed isocyanate resin obtained in step (1) is put into an open mill and subjected to open mill fine mixing for 10 to 80 minutes (for example, 10, 20, 30, 40, 50, 60, 70 or 80 minutes), preferably 30 to 60 minutes (for example, 30, 40, 50 or 60 minutes), to obtain a fine mixed isocyanate resin, and then a curing agent is added to the fine mixed isocyanate resin and further open mill fine mixing is performed for 2 to 10 minutes (for example, 2, 5, 8 or 10 minutes), to obtain an isocyanate resin curing system, and in the present invention, it is preferred that the temperature of the open mill fine mixing after the curing agent is added is 40 ℃.
According to some preferred embodiments, in step (3), the isocyanate resin curing system obtained in step (2) is cured in a trigger stage within a temperature range of 20 to 300 ℃ to obtain isocyanate resins with different viscosities.
According to some specific embodiments, the preparation of the wave-absorbing cyanate ester resin comprises the steps of:
(1) Placing cyanate resin, epoxy resin and absorbent into an internal mixer for internal mixing to obtain coarse mixed wave-absorbing cyanate resin; the molar ratio of the cyanate resin to the epoxy resin is 1: (0.5 to 0.7); the cyanate resin is one or more of bisphenol A type cyanate resin, tetramethyl bisphenol F type cyanate resin, bisphenol M type cyanate resin, bisphenol E type cyanate resin and multifunctional type cyanate resin;
(2) Placing the coarse mixed wave-absorbing cyanate resin obtained in the step (1) into an open mill for open mill fine mixing to obtain fine mixed wave-absorbing cyanate resin, and then adding an aliphatic amine curing agent into the fine mixed wave-absorbing cyanate resin to obtain a wave-absorbing cyanate resin curing system; the molar ratio of the curing agent to the cyanate resin is (0.1-0.5): 1, a step of;
(3) And (3) triggering and curing the wave-absorbing cyanate resin curing system obtained in the step (2) at a low temperature stage of 50-80 ℃ for 0.5-2 h and at a high temperature stage of 180-250 ℃ for 1-4 h in sequence to obtain the wave-absorbing cyanate resin with different viscosities.
According to some more specific embodiments, the preparation of the wave-absorbing cyanate ester resin comprises the steps of:
(1) Placing cyanate resin, epoxy resin and absorbent into an internal mixer for internal mixing to obtain coarse mixed wave-absorbing cyanate resin; the molar ratio of the cyanate resin to the epoxy resin is 1: (0.5 to 0.7); the dosage of the absorbent is 5-90% of the sum of the mass of the cyanate resin and the mass of the epoxy resin; the temperature of the banburying coarse mixing is 20-300 ℃, the time of the banburying coarse mixing is 10-120 min, and the rotating speed of a rotor of the banburying coarse mixing is 10-250 r/min; the cyanate resin is one or more of bisphenol A type cyanate resin, tetramethyl bisphenol F type cyanate resin, bisphenol M type cyanate resin, bisphenol E type cyanate resin and multifunctional type cyanate resin; the epoxy resin is one or more of E-51 type epoxy resin, E-44 type epoxy resin, E-20 type epoxy resin, F-44 type epoxy resin and F-51 type epoxy resin; the absorbent is one or more of carbonyl iron, iron-silicon-aluminum, ferrite, conductive carbon black, carbon fiber, graphene, carbon nano tube and silicon carbide.
(2) Placing the crude mixed wave-absorbing cyanate resin obtained in the step (1) into an open mill, carrying out open mill fine mixing for 10-80 min at the temperature of 20-300 ℃, obtaining fine mixed wave-absorbing cyanate resin after uniform mixing, adding one or more epoxy resin curing agents with different temperatures into the fine mixed wave-absorbing cyanate resin, and continuously carrying out open mill fine mixing for 2-10 min at the temperature of 40 ℃ to obtain a wave-absorbing cyanate resin curing system; the molar ratio of the curing agent to the cyanate resin is (0.1-0.5): 1, a step of; the roll speed of the open mill fine mixing is 2-17 m/min; the epoxy resin curing agent with different temperatures is one or more of fatty amine, polyamide, aromatic amine, polyether amine, dicyandiamide and anhydride curing agents.
(3) Triggering the wave-absorbing cyanate resin curing system obtained in the step (2) to be cured in stages at different temperatures to obtain wave-absorbing cyanate resins in different viscosity states; the different curing trigger temperature ranges from 20 to 300 ℃.
The present invention provides in a second aspect a wave-absorbing cyanate resin prepared by the preparation method of the present invention described in the first aspect.
The invention provides a preparation method of a wave-absorbing cyanate resin composite material in a third aspect, which comprises the following steps:
(a) Placing cyanate resin, epoxy resin and absorbent into an internal mixer for internal mixing to obtain coarse mixed wave-absorbing cyanate resin;
(b) Placing the coarse mixed wave-absorbing cyanate resin obtained in the step (a) into an open mill for open mill fine mixing to obtain fine mixed wave-absorbing cyanate resin, and then adding a curing agent into the fine mixed wave-absorbing cyanate resin to obtain a wave-absorbing cyanate resin curing system; the curing agent is one or more selected from fatty amine curing agents, polyamide curing agents, aromatic amine curing agents, polyether amine curing agents, dicyandiamide curing agents and anhydride curing agents;
(c) Triggering and curing the wave-absorbing cyanate resin curing system obtained in the step (b) at least at a low temperature stage to obtain a wave-absorbing cyanate resin blank (also called as a wave-absorbing cyanate resin composite intermediate), and then placing the wave-absorbing cyanate resin blank into a calender for calendering to obtain a wave-absorbing cyanate resin film;
(d) The wave-absorbing cyanate resin composite material (also called as wave-absorbing cyanate resin composite material) is prepared by layering (laying) a plurality of wave-absorbing cyanate resin film layers, and triggering and curing at least at one high temperature stage.
The viscosity of the wave-absorbing cyanate resin in the mixing stage is in the range of 500-20000 cps, in this range, the uniform dispersion of the absorbent is facilitated, the surface density Cv value of the wave-absorbing cyanate resin composite material in different areas can reach 0.02-0.05, and the improvement of the electrical property and the wave-absorbing property stability of the wave-absorbing cyanate resin is facilitated; through low-temperature stage curing, the viscosity of the wave-absorbing cyanate resin is within the viscosity range of 30000-500000 cps, the rolling thickness precision can reach +/-5% thickness range, the precise film forming characteristic is beneficial to controlling the wave-absorbing performance of the wave-absorbing cyanate resin composite material, the wave-absorbing performance and the mechanical property of the wave-absorbing cyanate resin film after rolling film forming are beneficial to ensuring, and the reflectance absorption peak frequency Cv value of the rolled wave-absorbing resin film after multi-layer lamination can be controlled within 0.1; compared with the wave absorbing performance of the wave absorbing cyanate resin composite material obtained by the invention, the wave absorbing performance of the wave absorbing cyanate resin composite material obtained by the invention is beneficial to the improvement of the wave absorbing performance stability of the wave absorbing composite material by directly calendering the wave absorbing resin which is not pre-cured into a film; the peak frequency Cv of the reflectivity absorption after the multi-layer lamination of the wave-absorbing cyanate resin film can be controlled within 0.1, which is favorable for the wave-absorbing cyanate resin composite material with good wave-absorbing performance and can accurately control the thickness of the wave-absorbing cyanate resin composite material in a wider range.
According to some preferred embodiments, the molar ratio of the cyanate resin, the curing agent, and the epoxy resin is 1: (0.1-0.5): (0.5-0.7) (e.g., 1:0.1:0.5, 1:0.1:0.6, 1:0.1:0.7, 1:0.2:0.5, 1:0.2:0.6, 1:0.2:0.7, 1:0.3:0.5, 1:0.3:0.6, 1:0.3:0.7, 1:0.4:0.5, 1:0.4:0.6, 1:0.4:0.7, 1:0.5:0.5, 1:0.5:0.6, or 1:0.5:0.7); the curing agent is a fatty amine curing agent, preferably one or more of diethylenetriamine, triethylenetetramine and tetraethylenepentamine.
According to some preferred embodiments, in step (c), the curing system of the isocyanate resin obtained in step (b) is triggered and cured at 50-80 ℃ to obtain an isocyanate resin blank, and then the isocyanate resin blank is put into a calender to be calendered to obtain an isocyanate resin film; in the step (d), a plurality of layers of the wave-absorbing cyanate resin film are laminated and then triggered and cured at 180-250 ℃ to prepare the wave-absorbing cyanate resin composite material.
According to some preferred embodiments, the viscosity of the isocyanate resin curing system is 500 to 20000cps; the viscosity of the wave-absorbing cyanate ester resin blank is 30000-500000 cps.
According to some specific embodiments, the method for preparing the wave-absorbing cyanate resin composite material comprises the following steps:
(a) Placing cyanate resin, epoxy resin and absorbent into an internal mixer for internal mixing to obtain coarse mixed wave-absorbing cyanate resin; the molar ratio of the cyanate resin to the epoxy resin is 1: (0.5 to 0.7); the dosage of the absorbent is 5-90% of the sum of the mass of the cyanate resin and the mass of the epoxy resin; the temperature of the banburying coarse mixing is 20-300 ℃, the time of the banburying coarse mixing is 10-120 min, and the rotating speed of a rotor of the banburying coarse mixing is 10-250 r/min; the cyanate resin is one or more of bisphenol A type cyanate resin, tetramethyl bisphenol F type cyanate resin, bisphenol M type cyanate resin, bisphenol E type cyanate resin and multifunctional type cyanate resin; the epoxy resin is one or more of E-51 type epoxy resin, E-44 type epoxy resin, E-20 type epoxy resin, F-44 type epoxy resin and F-51 type epoxy resin; the absorbent is one or more of carbonyl iron, iron-silicon-aluminum, ferrite, conductive carbon black, carbon fiber, graphene, carbon nano tube and silicon carbide.
(b) Placing the crude mixed wave-absorbing cyanate resin obtained in the step (a) into an open mill, carrying out open mill fine mixing for 10-80 min at 20-300 ℃, obtaining fine mixed wave-absorbing cyanate resin after uniform mixing, adding a curing agent into the fine mixed wave-absorbing cyanate resin, and continuously carrying out open mill fine mixing for 2-10 min at 40 ℃ to obtain a wave-absorbing cyanate resin curing system; the molar ratio of the curing agent to the cyanate resin is (0.1-0.5): 1, a step of; the roll speed of the open mill fine mixing is 2-17 m/min; preferably, the curing agent is one or more of diethylenetriamine, triethylenetetramine and tetraethylenepentamine.
(c) Triggering and curing the wave-absorbing cyanate resin curing system obtained in the step (b) at a low temperature of 50-80 ℃ to obtain a wave-absorbing cyanate resin blank, and then putting the wave-absorbing cyanate resin blank into a calender for calendering to obtain a wave-absorbing cyanate resin film; the temperature of the rolling is 100-200 ℃ (e.g. 100 ℃, 120 ℃, 140 ℃, 160 ℃, 180 ℃ or 200 ℃), the pressure of the rolling is 500-1500N (e.g. 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400 or 1500N), the speed of the rolling is 3-6 m/s (e.g. 3, 4, 5 or 6 m/s), the thickness of the rolling is 0.1-5 mm, preferably 1-2 mm (e.g. 1, 1.5 or 2 mm); in the present invention, the thickness of the rolling (rolling thickness) means the thickness of each layer of the wave-absorbing cyanate resin film.
(d) And (3) layering the multi-layer wave-absorbing cyanate resin film, and triggering and curing at a high temperature of 180-250 ℃ to prepare the wave-absorbing cyanate resin composite material.
The present invention provides in a fourth aspect a wave-absorbing cyanate ester resin composite material prepared by the preparation method of the present invention described in the third aspect.
The invention will be further illustrated by way of example, but the scope of the invention is not limited to these examples.
Example 1
(a) Placing cyanate resin (bisphenol A type cyanate resin), epoxy resin (E-51 type epoxy resin) and absorbent (carbonyl iron powder) into an internal mixer for internal mixing to obtain coarse mixed wave-absorbing cyanate resin; wherein the mol ratio of the bisphenol A type cyanate resin to the E-51 type epoxy resin is 1:0.6, and the addition amount of the carbonyl iron powder is 50% of the sum of the masses of the bisphenol A type cyanate resin and the E-51 type epoxy resin; the technological conditions of banburying and coarse mixing are as follows: the temperature of the banburying coarse mixing is 120 ℃, the time of the banburying coarse mixing is 45min, and the rotating speed of a rotor of the banburying coarse mixing is 200r/min.
(b) Placing the crude mixed wave-absorbing cyanate resin obtained in the step (a) into an open mill, carrying out open mill fine mixing at the temperature of 120 ℃ for 45min, obtaining fine mixed wave-absorbing cyanate resin after uniform mixing, adding a curing agent (triethylene tetramine) into the fine mixed wave-absorbing cyanate resin, and continuously carrying out open mill fine mixing at the temperature of 40 ℃ for 5min to obtain a wave-absorbing cyanate resin curing system; the molar ratio of the curing agent to the bisphenol A type cyanate resin is 0.2:1; the roll speed of the open mill fine mixing is 12m/min.
(c) Triggering and curing the wave-absorbing cyanate resin curing system obtained in the step (b) at a low temperature of 50 ℃ for 1h to obtain a wave-absorbing cyanate resin blank, and then placing the wave-absorbing cyanate resin blank into a calender for calendering to obtain a wave-absorbing cyanate resin film; the technological conditions of calendaring are as follows: the temperature of the rolling is 150 ℃, the pressure of the rolling is 1000N, the speed of the rolling is 4m/s, and the thickness of the rolling is 1.5mm.
(d) And (3) placing four layers of the wave-absorbing cyanate resin film obtained in the step (c) in a lamination manner (laminated layer), and then triggering and curing for 3 hours at a high temperature of 200 ℃ to obtain the wave-absorbing cyanate resin composite material.
In this example, the viscosities of the isocyanate resin cured system obtained in step (b) and the isocyanate resin blank obtained in step (c) were measured, and the results are shown in table 1.
The average reflectance absorption peak value of the wave-absorbing cyanate resin composite material prepared in the embodiment is-10.6 dB at 3GHz, and the total thickness of the wave-absorbing cyanate resin composite material is 6mm.
In this embodiment, the adhesive film thickness, the surface density and the wave absorbing performance of the adhesive film at different positions of the uniform point of the composite material of the wave absorbing cyanate ester are tested, and the typical Cv (discrete coefficient) value of data is used to characterize the process stability, so that the adhesive film thickness, the surface density control uniformity and the wave absorbing performance control stability of the composite material of the wave absorbing cyanate ester prepared in this embodiment are found, the preparation process stability of this embodiment is quite good, and the results are shown in table 1.
In the invention, the smaller the film thickness Cv value, the surface density Cv value and the reflectance absorption peak frequency Cv value, the better the uniformity of the film thickness and the surface density of the prepared wave-absorbing cyanate resin composite material, and the better the stability of wave-absorbing performance.
Example 2
Example 2 is substantially the same as example 1 except that:
in the step (a), the cyanate resin is tetramethyl bisphenol F type cyanate resin, the epoxy resin is E-44 type epoxy resin, and the absorbent is carbonyl iron powder; the molar ratio of the tetramethyl bisphenol F type cyanate resin to the E-44 type epoxy resin is 1:0.5, and the addition amount of the carbonyl iron powder is 50% of the sum of the masses of the tetramethyl bisphenol F type cyanate resin and the E-44 type epoxy resin.
In step (b), the curing agent is diethylenetriamine; the molar ratio of the curing agent to the tetramethyl bisphenol F-type cyanate resin is 0.3:1.
The average reflectance absorption peak value of the wave-absorbing cyanate resin composite material prepared in the embodiment is-10.0 dB at 3 GHz.
The same performance test was performed as in example 1, and the results are shown in table 1.
Example 3
Example 3 is substantially the same as example 1 except that:
in the step (a), the cyanate resin is bisphenol E type cyanate resin, the epoxy resin is F-44 type epoxy resin, and the absorbent is carbonyl iron powder; the molar ratio of the bisphenol E type cyanate resin to the F-44 type epoxy resin is 1:0.7, and the addition amount of the carbonyl iron powder is 50% of the sum of the mass of the bisphenol E type cyanate resin and the mass of the F-44 type epoxy resin.
In step (b), the curing agent is tetraethylenepentamine; the molar ratio of the curing agent to the bisphenol E type cyanate ester resin is 0.4:1.
The average reflectance absorption peak value of the wave-absorbing cyanate resin composite material prepared in the embodiment is-10.4 dB at 3 GHz.
The same performance test was performed as in example 1, and the results are shown in table 1.
Example 4
Example 4 is substantially the same as example 1 except that:
in step (a), the molar ratio of bisphenol A type cyanate resin to E-51 type epoxy resin is 1:0.2.
The average reflectivity absorption peak value of the wave-absorbing cyanate resin composite material prepared in the embodiment is-10.5 dB at 3 GHz.
The same performance test was performed as in example 1, and the results are shown in table 1.
Example 5
Example 5 is substantially the same as example 1 except that:
in step (a), the molar ratio of bisphenol A type cyanate resin to E-51 type epoxy resin is 1:0.8.
The average reflectance absorption peak value of the wave-absorbing cyanate resin composite material prepared in the embodiment is-11.0 dB at 3 GHz.
The same performance test was performed as in example 1, and the results are shown in table 1.
Comparative example 1
(a) The procedure is as in step (a) of example 1.
(b) And (c) placing the crude mixed wave-absorbing cyanate resin obtained in the step (a) into an open mill, carrying out open mill fine mixing for 45min at the temperature of 120 ℃, and obtaining the fine mixed wave-absorbing cyanate resin after uniform mixing, wherein the roll speed of the open mill fine mixing is 12m/min.
(c) Placing the fine mixed wave-absorbing cyanate resin obtained in the step (b) into a calender for calendering to obtain a wave-absorbing cyanate resin film; the technological conditions of calendaring are as follows: the temperature of the rolling is 150 ℃, the pressure of the rolling is 1000N, the speed of the rolling is 4m/s, and the thickness of the rolling is 1.5mm.
(d) The same as in step (d) of example 1.
The average reflectance absorption peak value of the wave-absorbing cyanate resin composite material prepared in the comparative example at 3GHz is-9.9 dB.
The viscosities of the coarse and fine wave-absorbing resins in this comparative example were equal to each other and were 7100cps.
The comparative example was subjected to the same performance test as in example 1, and the results are shown in table 1.
Comparative example 2
(1) Placing epoxy resin (E-51 type epoxy resin) and carbonyl iron powder (absorbent) into an internal mixer for banburying and coarse mixing to obtain coarse mixed wave-absorbing resin; wherein the addition amount of carbonyl iron powder is 50% of the mass of the epoxy resin; the technological conditions of banburying and coarse mixing are as follows: the temperature of the banburying coarse mixing is 100 ℃, the time of the banburying coarse mixing is 45min, and the rotating speed of a rotor of the banburying coarse mixing is 200r/min.
(2) Placing the coarse mixed wave-absorbing resin obtained in the step (1) into a resin open mill for open mill fine mixing for 45min to obtain a uniformly mixed fine mixed wave-absorbing resin, and then adding m-xylylenediamine (curing agent) into the fine mixed wave-absorbing resin for continuous open mill fine mixing for 5min; the technological conditions of the open mill fine mixing are as follows: the temperature of the open mill refined mixing is 100 ℃, and the roll speed of the open mill refined mixing is 12m/min; the curing agent is 1.7wt% of the E-51 type epoxy resin.
(3) Placing the fine mixed wave-absorbing resin added with the curing agent obtained in the step (2) into a precise calender for calendering, and obtaining a wave-absorbing resin adhesive film (wave-absorbing epoxy resin film) after calendering; the technological conditions of calendaring are as follows: the temperature of the rolling is 150 ℃, the pressure of the rolling is 1000N, the speed of the rolling is 4m/s, and the thickness of the rolling is 1.5mm.
(4) And (3) placing the four layers of the wave-absorbing epoxy resin film obtained in the step (3) in a lamination manner, and then curing at 200 ℃ for 3 hours to obtain the wave-absorbing epoxy resin composite material.
The average reflectivity absorption peak value of the wave-absorbing epoxy resin composite material prepared in the comparative example is-10.7 dB at 3 GHz.
The viscosity of the crude mixed wave-absorbing resin in this comparative example was 5800cps, and the viscosity of the fine mixed wave-absorbing resin after 5min of fine mixing with the curing agent was 6300cps.
The comparative example was subjected to the same performance test as in example 1, and the results are shown in table 1.
In particular, the symbol "/" in table 1 indicates that no corresponding index exists.
The invention is not described in detail in a manner known to those skilled in the art.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; 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 (5)
1. The preparation method of the wave-absorbing cyanate resin composite material is characterized by comprising the following steps of:
(a) Placing cyanate resin, epoxy resin and absorbent into an internal mixer for internal mixing to obtain coarse mixed wave-absorbing cyanate resin;
(b) Placing the coarse mixed wave-absorbing cyanate resin obtained in the step (a) into an open mill for open mill fine mixing to obtain fine mixed wave-absorbing cyanate resin, and then adding a curing agent into the fine mixed wave-absorbing cyanate resin to obtain a wave-absorbing cyanate resin curing system; the curing agent is one or more of diethylenetriamine, triethylenetetramine and tetraethylenepentamine; the molar ratio of the cyanate resin, the curing agent and the epoxy resin is 1: (0.1-0.5): (0.5 to 0.7); the viscosity of the wave-absorbing cyanate resin curing system is 500-20000 cps;
(c) Triggering and curing the wave-absorbing cyanate resin curing system obtained in the step (b) at 50-80 ℃ to obtain a wave-absorbing cyanate resin blank, and then placing the wave-absorbing cyanate resin blank into a calender for calendering to obtain a wave-absorbing cyanate resin film; the viscosity of the wave-absorbing cyanate ester resin blank is 30000-500000 cps;
(d) And (3) layering a plurality of layers of the wave-absorbing cyanate resin film, and triggering and curing at 180-250 ℃ to prepare the wave-absorbing cyanate resin composite material.
2. The method of manufacturing according to claim 1, characterized in that:
the cyanate resin is one or more of bisphenol A type cyanate resin, tetramethyl bisphenol F type cyanate resin, bisphenol M type cyanate resin, bisphenol E type cyanate resin and multifunctional type cyanate resin;
the epoxy resin is one or more of E-51 type epoxy resin, E-44 type epoxy resin, E-20 type epoxy resin, F-44 type epoxy resin and F-51 type epoxy resin; and/or
The absorbent is one or more of carbonyl iron, iron-silicon-aluminum, ferrite, conductive carbon black, carbon fiber, graphene, carbon nano tube and silicon carbide.
3. The preparation method according to claim 2, characterized in that:
the amount of the absorbent is 5 to 90% of the sum of the mass of the cyanate resin and the mass of the epoxy resin.
4. The method of manufacturing according to claim 1, characterized in that:
in the step (a), the temperature of the internal mixing and coarse mixing is 20-300 ℃, the time of the internal mixing and coarse mixing is 10-120 min, and the rotating speed of a rotor of the internal mixing and coarse mixing is 10-250 r/min;
in the step (b), the temperature of the open mill refined mixing is 20-300 ℃, and the roll speed of the open mill refined mixing is 2-17 m/min;
in the step (b), the coarse mixed wave-absorbing cyanate resin obtained in the step (a) is put into an open mill for open mill fine mixing for 10-80 min to obtain fine mixed wave-absorbing cyanate resin, and then a curing agent is added into the fine mixed wave-absorbing cyanate resin and the open mill fine mixing is continued for 2-10 min to obtain a wave-absorbing cyanate resin curing system.
5. A wave-absorbing cyanate resin composite material prepared by the preparation method of any one of claims 1 to 4.
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