CN113801473A - A kind of absorbing double horse resin, wave absorbing double horse resin composite material and preparation method thereof - Google Patents
A kind of absorbing double horse resin, wave absorbing double horse resin composite material and preparation method thereof Download PDFInfo
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- CN113801473A CN113801473A CN202111226187.3A CN202111226187A CN113801473A CN 113801473 A CN113801473 A CN 113801473A CN 202111226187 A CN202111226187 A CN 202111226187A CN 113801473 A CN113801473 A CN 113801473A
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- 229920005989 resin Polymers 0.000 title claims abstract description 350
- 239000011347 resin Substances 0.000 title claims abstract description 350
- 239000000463 material Substances 0.000 title claims abstract description 48
- 239000000805 composite resin Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 108
- 239000003822 epoxy resin Substances 0.000 claims abstract description 83
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 83
- 239000002250 absorbent Substances 0.000 claims abstract description 38
- 230000002745 absorbent Effects 0.000 claims abstract description 38
- 238000007670 refining Methods 0.000 claims abstract description 37
- 238000003490 calendering Methods 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 25
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical group OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000004952 Polyamide Substances 0.000 claims abstract description 9
- 229920002647 polyamide Polymers 0.000 claims abstract description 9
- 150000004982 aromatic amines Chemical class 0.000 claims abstract description 8
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims abstract description 8
- -1 ether amine Chemical class 0.000 claims abstract description 6
- 229910052797 bismuth Inorganic materials 0.000 claims abstract 13
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract 13
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract 3
- 238000005096 rolling process Methods 0.000 claims description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- 230000001960 triggered effect Effects 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 10
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 8
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 8
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 8
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 5
- 239000004917 carbon fiber Substances 0.000 claims description 5
- 239000002041 carbon nanotube Substances 0.000 claims description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 5
- 229910021389 graphene Inorganic materials 0.000 claims description 5
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 5
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 5
- 229910000859 α-Fe Inorganic materials 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims 1
- 230000009286 beneficial effect Effects 0.000 abstract description 11
- 239000006185 dispersion Substances 0.000 abstract description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 9
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 296
- 229920003192 poly(bis maleimide) Polymers 0.000 description 293
- 238000010521 absorption reaction Methods 0.000 description 13
- 238000002310 reflectometry Methods 0.000 description 12
- 239000002131 composite material Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 230000002349 favourable effect Effects 0.000 description 7
- 239000002313 adhesive film Substances 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- 229960001124 trientine Drugs 0.000 description 6
- 239000004721 Polyphenylene oxide Substances 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 150000008064 anhydrides Chemical class 0.000 description 5
- 150000007860 aryl ester derivatives Chemical class 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 229920000570 polyether Polymers 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 150000001408 amides Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000011358 absorbing material Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910000702 sendust Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08L79/085—Unsaturated polyimide precursors
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
本发明涉及一种吸波双马树脂、吸波双马树脂复材及其制备方法。所述方法包括：将双马树脂、环氧树脂和吸收剂放入密炼机中进行密炼粗混，得到粗混吸波双马树脂；将粗混吸波双马树脂放入开炼机中进行开炼精混，得到精混吸波双马树脂，然后加入固化剂，得到吸波双马树脂固化体系；固化剂选自脂肪胺固化剂、聚酰胺固化剂、芳香胺固化剂、聚醚胺固化剂、双氰胺固化剂、酸酐类固化剂中的一种或多种；将吸波双马树脂固化体系在不同温度阶段触发固化，得到不同粘度的吸波双马树脂。本发明中的吸波双马树脂在不同的工艺过程中具备不同的粘度，有利于吸收剂的分散均匀，有利于压延成型，使吸波双马树脂具有更好的吸波性能稳定性以及工艺特性。
The invention relates to a wave-absorbing double horse resin, a wave-absorbing double horse resin composite material and a preparation method thereof. The method comprises: putting the bismuth resin, the epoxy resin and the absorbent into an internal mixer for internal mixing and rough mixing to obtain the coarsely mixed wave absorbing bismuth resin; putting the coarsely mixed wave absorbing bismuth resin into the open mixer Carry out refining and mixing in the process to obtain a finely mixed absorbing bihorse resin, and then add a curing agent to obtain a curing system of the absorbing bihorse resin; the curing agent is selected from aliphatic amine curing agent, polyamide curing agent, aromatic amine curing agent, polyamide curing agent One or more of ether amine curing agent, dicyandiamide curing agent and acid anhydride curing agent; triggering curing of wave-absorbing bihorse resin curing system at different temperature stages to obtain wave-absorbing bihorse resin of different viscosity. The wave-absorbing double-horse resin in the present invention has different viscosities in different technological processes, which is beneficial to the uniform dispersion of the absorbent and calendering, so that the wave-absorbing double-horse resin has better wave-absorbing performance stability and process characteristic.
Description
Technical Field
The invention belongs to the technical field of wave-absorbing material preparation, and particularly relates to wave-absorbing bismaleimide resin, a wave-absorbing bismaleimide resin composite material and a preparation method thereof.
Background
The wave-absorbing material is a material capable of absorbing and attenuating incident electromagnetic waves, converting electromagnetic energy into heat energy and dissipating the heat energy or enabling the electromagnetic waves to disappear due to interference. With the development of scientific technology, the wave-absorbing material has wide application in various aspects. The method has important significance in the fields of electromagnetic protection, microwave darkroom, mobile communication, military stealth and the like. The resin-based wave-absorbing composite material has the advantages of strong designability, large-area integral forming and the like, and becomes one of the most important application materials in the aerospace stealth field.
The wave-absorbing resin is a raw material for preparing a resin-based wave-absorbing composite material and consists of an electromagnetic wave absorbent and a resin matrix, wherein the electromagnetic wave absorbent determines the wave-absorbing property of the resin-based wave-absorbing composite material, and the resin matrix determines more process characteristics of the resin-based wave-absorbing composite material. The invention realizes that the wave-absorbing resin needs to have different viscosity states in the whole process, for example, when the wave-absorbing resin is mixed, the wave-absorbing resin needs to have lower viscosity, and the low viscosity is favorable for the uniform dispersion of the electromagnetic wave absorbent in the resin matrix. When the wave-absorbing resin is rolled to form a film, the wave-absorbing resin needs to have certain viscosity to endow the adhesive film with film-forming characteristics, and the improvement of plasticity is beneficial to the precise rolling forming of the adhesive film. When the wave-absorbing resin is completely cured and molded, the wave-absorbing resin has the highest viscosity, and the material has good mechanical properties due to complete crosslinking and curing. The wave-absorbing resin has high absorbent content, the viscosity control is particularly important for the performance regulation and control, and the wave-absorbing resin with controllable viscosity can effectively improve the wave-absorbing property and the process property of the resin-based wave-absorbing composite material.
However, the existing wave-absorbing resin generally has the problem of uncontrollable viscosity in the whole process flow. For example, chinese patent application CN111704868A provides a wave-absorbing adhesive film and a method for preparing the same, chinese patent application CN107586436A provides a wave-absorbing prepreg and a method for preparing the same, and chinese patent application CN112029421A discloses a wave-absorbing adhesive film material and a method for preparing the same, but the viscosity of the wave-absorbing resin involved in these methods is not controllable, and is only suitable for a process at a certain stage, or the high or low viscosity is not good for the uniform dispersion and calendering molding of the absorbent, for example, if the viscosity is low, although the resin can be ensured to have good uniformity during mixing, the viscosity is low during calendering, the adhesive film has poor plasticity, the molding precision is not high, and if the viscosity is high, although the resin has high plasticity during calendering, the molding precision is high, but the uniformity during mixing is difficult to ensure.
In summary, it is very necessary to provide a wave-absorbing bismaleimide resin, a wave-absorbing bismaleimide resin composite material and a preparation method thereof.
Disclosure of Invention
The invention provides wave-absorbing bismaleimide resin, a wave-absorbing bismaleimide 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 bismaleimide resin has different viscosities in different technological processes, so that the uniform dispersion of an absorbent is facilitated, and the rolling molding of the wave-absorbing composite intermediate is facilitated, so that the wave-absorbing bismaleimide resin has better wave-absorbing performance (the stability of the wave-absorbing performance is improved) and technological characteristics.
The invention provides a preparation method of wave-absorbing bismaleimide resin in a first aspect, which comprises the following steps:
(1) putting the bismaleimide resin, the epoxy resin and the absorbent into an internal mixer for internal mixing and coarse mixing to obtain coarse mixing wave-absorbing bismaleimide resin;
(2) putting the rough mixed wave-absorbing bismaleimide resin obtained in the step (1) into an open mill for refining and fine mixing to obtain fine mixed wave-absorbing bismaleimide resin, and then adding a curing agent into the fine mixed wave-absorbing bismaleimide resin to obtain a wave-absorbing bismaleimide resin curing system; the curing agent is selected from one or more of aliphatic amine curing agent, polyamide curing agent, aromatic amine curing agent, polyether amine curing agent, dicyandiamide curing agent and anhydride curing agent;
(3) and (3) triggering and curing the wave-absorbing bismaleimide resin curing system obtained in the step (2) at different temperature stages to obtain the wave-absorbing bismaleimide resin with different viscosities.
Preferably, the molar ratio of the bismaleimide 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, triethylene tetramine and tetraethylene pentamine.
Preferably, the bismaleimide resin is one or more of aliphatic bismaleimide resin, ether bismaleimide resin, aryl ester bismaleimide resin, condensed ring bismaleimide resin and amide bismaleimide resin, and preferably, the bismaleimide resin is one or more of diphenylmethane bismaleimide resin, V378-A bismaleimide resin and compound-353 bismaleimide 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 dosage of the absorbent is 5-90% of the sum of the mass of the bismaleimide resin and the mass of the epoxy resin.
Preferably, in the step (1), the temperature of the banburying and rough mixing is 20-300 ℃, the time of the banburying and rough mixing is 10-120 min, and the rotating speed of a rotor of the banburying and rough mixing is 10-250 r/min; in the step (2), the temperature of the refining and mixing is 20-300 ℃, and the roller speed of the refining and mixing is 2-17 m/min; in the step (2), the coarse mixed wave-absorbing bismaleimide resin obtained in the step (1) is placed into an open mill for refining and fine mixing for 10-80 min to obtain fine mixed wave-absorbing bismaleimide resin, then a curing agent is added into the fine mixed wave-absorbing bismaleimide resin, and refining and fine mixing are continuously carried out for 2-10 min to obtain a wave-absorbing bismaleimide resin curing system; and/or in the step (3), triggering the wave-absorbing bismaleimide resin curing system obtained in the step (2) to be cured in a staged manner within the temperature range of 20-300 ℃ to obtain the wave-absorbing bismaleimide resin with different viscosities.
In a second aspect, the invention provides the wave-absorbing bismaleimide resin prepared by the preparation method in the first aspect.
The invention provides a preparation method of a wave-absorbing bismaleimide resin composite material in a third aspect, which comprises the following steps:
(a) putting the bismaleimide resin, the epoxy resin and the absorbent into an internal mixer for internal mixing and coarse mixing to obtain coarse mixing wave-absorbing bismaleimide resin;
(b) putting the rough mixed wave-absorbing bismaleimide resin obtained in the step (a) into an open mill for refining and fine mixing to obtain fine mixed wave-absorbing bismaleimide resin, and then adding a curing agent into the fine mixed wave-absorbing bismaleimide resin to obtain a wave-absorbing bismaleimide resin curing system; the curing agent is selected from one or more of aliphatic amine curing agent, polyamide curing agent, aromatic amine curing agent, polyether amine curing agent, dicyandiamide curing agent and anhydride curing agent;
(c) triggering and curing the wave-absorbing bismaleimide resin curing system obtained in the step (b) at least at one low-temperature stage to obtain a wave-absorbing bismaleimide resin blank, and then putting the wave-absorbing bismaleimide resin blank into a calender for calendering to obtain a wave-absorbing bismaleimide resin film;
(d) and (3) layering a plurality of layers of the wave-absorbing bismaleimide resin films in a laminated manner, and then triggering and curing at least at one high-temperature stage to obtain the wave-absorbing bismaleimide resin composite material.
Preferably, the molar ratio of the bismaleimide resin, the curing agent and the epoxy resin is 1: (0.1-0.5): (0.5 to 0.7); the curing agent is an aliphatic amine curing agent, and preferably, the curing agent is one or more of diethylenetriamine, triethylene tetramine and tetraethylene pentamine.
Preferably, in the step (c), the wave-absorbing bismaleimide resin curing system obtained in the step (b) is triggered and cured at 50-80 ℃ to obtain a wave-absorbing bismaleimide resin blank, and then the wave-absorbing bismaleimide resin blank is placed into a calender for calendering to obtain a wave-absorbing bismaleimide resin film; in the step (d), a plurality of wave-absorbing bismaleimide resin films are laminated and layered, and then triggered and cured at 150-250 ℃ to prepare the wave-absorbing bismaleimide resin composite material.
Preferably, the viscosity of the wave-absorbing bismaleimide resin curing system is 500-20000 cps; and/or the viscosity of the wave-absorbing bismaleimide resin blank is 30000-500000 cps.
In a fourth aspect, the invention provides a wave-absorbing bismaleimide resin composite material prepared by the preparation method in the third aspect.
Compared with the prior art, the invention at least has the following beneficial effects:
(1) the low-viscosity wave-absorbing bismaleimide resin disclosed by the invention is beneficial to uniform dispersion of an absorbent in the processes of banburying, rough mixing and open refining, and the electrical property and the wave-absorbing property stability of the wave-absorbing bismaleimide resin are improved.
(2) The viscosity of the wave-absorbing bismaleimide resin is increased after the curing reaction at a certain temperature is triggered, the plasticity and the film forming property of the wave-absorbing bismaleimide resin are improved, and the precise film forming property is favorable for controlling the wave absorbing performance of the wave-absorbing bismaleimide resin composite material.
(3) The viscosity of the wave-absorbing bismaleimide resin in the mixing stage is in the range of 500-20000 cps, and the surface density Cv values of the wave-absorbing bismaleimide resin composites in different areas can reach 0.02-0.05 in the range; after the first stage curing (low-temperature stage curing), the viscosity is within the viscosity range of 30000-500000 cps, the calendering thickness precision can reach within the thickness range of +/-5%, and the microwave-absorbing bismaleimide resin does not have viscosity after being completely cured.
(4) According to the invention, the low-viscosity wave-absorbing bismaleimide resin is beneficial to the dispersion of an absorbent, the high-viscosity wave-absorbing bismaleimide resin triggered and cured at different temperature stages is beneficial to the thickness precision control, and the reflection rate absorption peak frequency value Cv value can be controlled within 0.1 after the wave-absorbing resin film is rolled into a multi-layer lamination; compared with the wave-absorbing performance of the wave-absorbing bismaleimide resin composite material which is not pre-cured, the wave-absorbing bismaleimide resin composite material obtained by the invention has the advantages that the wave-absorbing performance stability of the wave-absorbing bismaleimide resin composite material is improved; the reflectivity absorption peak frequency value Cv value of the wave-absorbing bismaleimide resin film obtained by the invention can be controlled within 0.1 after the wave-absorbing bismaleimide resin film is laminated in multiple layers, so that the wave-absorbing bismaleimide resin composite material with good wave-absorbing performance can be obtained, and the thickness of the wave-absorbing bismaleimide resin composite material can be accurately controlled within a wider range.
Drawings
FIG. 1 is a process flow chart for preparing wave-absorbing bismaleimide resin.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The invention provides a preparation method of wave-absorbing bismaleimide resin in a first aspect, and fig. 1 is a process flow chart of the preparation method of the wave-absorbing bismaleimide resin, for example, as shown in fig. 1, a wave-absorbing bismaleimide resin curing system is prepared, an absorbent, bismaleimide resin and epoxy resin are firstly banburied and roughly mixed, after being uniformly mixed, the mixture is placed into an open mill for fine mixing, and stage curing reaction is triggered at different temperatures, so that the wave-absorbing bismaleimide resin has different viscosities at different processing stages to adapt to processability; the prepared wave-absorbing bismaleimide resin is triggered and cured at different temperature stages, so that wave-absorbing bismaleimide resin with different viscosities can be obtained, and the viscosity of the wave-absorbing bismaleimide resin is controllable; the wave-absorbing bismaleimide resin with controllable viscosity is beneficial to uniform dispersion of the absorbent and simultaneously beneficial to calendaring formation of the wave-absorbing bismaleimide resin.
In the invention, the preparation method of the wave-absorbing bismaleimide resin comprises the following steps:
(1) putting the bismaleimide resin, the epoxy resin and the absorbent into an internal mixer for internal mixing and coarse mixing to obtain coarse mixing wave-absorbing bismaleimide resin; in the invention, the bismaleimide resin refers to bismaleimide resin;
(2) putting the rough mixed wave-absorbing bismaleimide resin obtained in the step (1) into an open mill for refining and fine mixing to obtain fine mixed wave-absorbing bismaleimide resin, and then adding a curing agent into the fine mixed wave-absorbing bismaleimide resin to obtain a wave-absorbing bismaleimide resin curing system; the curing agent is selected from one or more of aliphatic amine curing agent, polyamide curing agent, aromatic amine curing agent, polyether amine curing agent, dicyandiamide curing agent and anhydride curing agent;
(3) and (3) triggering and curing the wave-absorbing bismaleimide resin curing system obtained in the step (2) at different temperature stages to obtain the wave-absorbing bismaleimide resin with different viscosities.
In the invention, when several curing agents with different curing temperatures are added in the step (2), correspondingly, in the step (3), the curing is triggered at several corresponding curing temperature stages according to a mode that the curing temperatures are sequentially increased to obtain the wave-absorbing bismaleimide resin with different viscosities; in the step (3), the bismaleimide resin is triggered to be cured within the thermal self-polymerization temperature range of the bismaleimide resin to obtain the wave-absorbing bismaleimide resin with different viscosities; in the invention, the curing temperature is strictly controlled, so that the curing at a higher curing temperature stage cannot be initiated at a lower curing temperature stage, and the wave-absorbing bismaleimide resin with different viscosities can be obtained after the curing is triggered at each temperature stage, so that the wave-absorbing bismaleimide resin has different viscosities at different processing stages to adapt to the processability.
According to some preferred embodiments, the molar ratio of the bismaleimide resin, the curing agent and the epoxy resin is 1: (0.1-0.5): (0.5 to 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, triethylene tetramine and tetraethylene pentamine; in the invention, preferably, in the step (2), an aliphatic amine curing agent with a lower curing temperature, for example, an aliphatic amine curing agent with a curing temperature of 50-80 ℃ is added, so that the wave-absorbing bismaleimide resin curing system obtained in the step (2) is triggered to cure in two temperature stages, including the curing in a low-temperature stage of 50-80 ℃ and the curing in a high-temperature bismaleimide resin thermal self-polymerization temperature stage; in the present invention, it is preferable that the molar ratio of the bismaleimide resin to the epoxy resin is 1: (0.5-0.7), in the range of the molar ratio, the microwave-absorbing bismaleimide resin with controllable viscosity can be obtained, on one hand, in the mixing stage of banburying coarse mixing and refining fine mixing, the microwave-absorbing bismaleimide resin curing system with the viscosity of 500-20000 cps can be obtained, the microwave-absorbing bismaleimide resin curing system in the viscosity range is beneficial to uniform dispersion of an absorbent, the density Cv values of the microwave-absorbing bismaleimide resin in different areas can reach 0.02-0.05, and the electrical property and the microwave-absorbing property stability of the microwave-absorbing bismaleimide resin can be improved; on the other hand, after the microwave absorbing bismaleimide resin is cured at the low temperature of 50-80 ℃, the viscosity of the microwave absorbing bismaleimide resin can be within the viscosity range of 30000-500000 cps, the microwave absorbing bismaleimide resin within the viscosity range is favorable for rolling and film forming, the rolling thickness precision can reach the thickness range of +/-5%, the precise film forming characteristic is favorable for controlling the wave absorbing performance of the microwave absorbing bismaleimide resin composite material, the wave absorbing performance and the mechanical performance of the microwave absorbing bismaleimide resin film after being rolled and film formed are favorable for ensuring the wave absorbing performance and the mechanical performance of the microwave absorbing bismaleimide resin film, the Cv value of the reflectivity absorption peak frequency value after the rolled microwave absorbing resin film is laminated in multiple layers can be controlled within 0.1, the stability of the microwave absorbing bismaleimide resin can be effectively improved, if the content of the epoxy resin is higher, the viscosity of the microwave absorbing bismaleimide resin after being cured at the low temperature is increased more, and if the content of the epoxy resin is lower, the viscosity of the microwave absorbing bismaleimide resin after being cured at the low temperature is increased less, the viscosity of the microwave absorbing bismaleimide resin can not be controlled within the range of 30000-500000 cps, this is not beneficial to the calendering molding of the wave-absorbing bismaleimide resin.
According to some preferred embodiments, the bismaleimide resin is one or more of a fatty type bismaleimide resin, an ether type bismaleimide resin, an aryl ester type bismaleimide resin, a condensed ring type bismaleimide resin, and an amide type bismaleimide resin, and preferably, the bismaleimide resin is one or more of a diphenylmethane type bismaleimide resin, a V378-a type bismaleimide resin, and a compound-353 type bismaleimide resin; in the invention, the diphenylmethane bismaleimide resin can be XU292 bismaleimide resin or 6421 bismaleimide resin, for example, and the curing temperature (thermal self-polymerization temperature) is 180-250 ℃; in the invention, the V378-A type bismaleimide resin is diene compound modified bismaleimide resin, and the curing temperature (thermal self-polymerization temperature) is 180 ℃; in the invention, the compound-353 bismaleimide resin is a mixture of aryl ester bismaleimide resin and fatty bismaleimide resin, and the curing temperature (thermal self-polymerization temperature) is 70-130 ℃; in the present invention, the bismaleimide resins employed may be obtained directly from commercial sources.
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, any of these epoxy resins can be used as they are commercially available.
According to some preferred embodiments, the absorbent is one or more of carbonyl iron, sendust, ferrite, conductive carbon black, carbon fiber, graphene, carbon nanotube, and silicon carbide, and preferably, the amount of the absorbent is 5 to 90% (e.g., 5%, 15%, 25%, 40%, 50%, 60%, 70%, 80%, or 90%) and preferably 40 to 85% (e.g., 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, or 85%) of the sum of the masses of the bismaleimide resin and the epoxy resin.
According to some preferred embodiments, in step (1), the temperature of the banburying rough mixing is 20 to 300 ℃ (e.g., 20 ℃, 40 ℃, 60 ℃, 80 ℃, 100 ℃, 120 ℃, 140 ℃, 160 ℃, 180 ℃, 200 ℃, 220 ℃, 240 ℃, 260 ℃, 280 ℃ or 300 ℃), preferably 100 to 300 ℃ (e.g., 100 ℃, 120 ℃, 140 ℃, 160 ℃, 180 ℃, 200 ℃, 220 ℃, 240 ℃, 260 ℃, 280 ℃ or 300 ℃), the time of the banburying rough mixing is 10 to 120min (e.g., 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110 or 120min), preferably 30 to 60min (e.g., 30, 40, 50 or 60min), the rotor speed of the banburying rough mixing is 10 to 250r/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, 120 ℃, 130, 140, 150, 160, 170, 180, 190, 200 ℃, 220 ℃, 180 ℃, 280 ℃ or 300 ℃) 230. 240 or 250r/min), preferably 150 to 250r/min (e.g. 150, 160, 170, 180, 190, 200, 210, 220, 230, 240 or 250 r/min).
In some more preferred embodiments, the temperature of the banburying and rough mixing is 100-300 ℃, the time of the banburying and rough mixing is 30-60 min, and the rotation speed of a rotor of the banburying and rough mixing is 150-250 r/min.
According to some preferred embodiments, in step (2), the temperature of the flash mix is 20 to 300 ℃ (e.g., 20 ℃, 40 ℃, 60 ℃, 80 ℃, 100 ℃, 120 ℃, 140 ℃, 160 ℃, 180 ℃, 200 ℃, 220 ℃, 240 ℃, 260 ℃, 280 ℃, or 300 ℃), preferably 100 to 250 ℃ (e.g., 100 ℃, 120 ℃, 140 ℃, 160 ℃, 180 ℃, 200 ℃, 220 ℃, or 250 ℃), and the roll speed of the flash mix is 2 to 17m/min (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, or 17m/min), preferably 10 to 15m/min (e.g., 10, 11, 12, 13, 14, or 15 m/min); in the present invention, the unit m/min of the roll speed represents meters/minute.
In some more preferred embodiments, the temperature of the refining and mixing is 100-250 ℃, and the roller speed of the refining and mixing is 10-15 m/min.
According to some preferred embodiments, in the step (2), the coarse mixed wave-absorbing bismaleimide resin obtained in the step (1) is placed into an open mill to be refined and mixed for 10 to 80min (for example, 10, 20, 30, 40, 50, 60, 70 or 80min), preferably 30 to 60min (for example, 30, 40, 50 or 60min) to obtain a refined mixed wave-absorbing bismaleimide resin, and then a curing agent is added into the refined mixed wave-absorbing bismaleimide resin and is refined and mixed for 2 to 10min (for example, 2, 5, 8 or 10min) to obtain a wave-absorbing bismaleimide resin curing system, in the present invention, it is preferred that the refined and mixed temperature after the curing agent is added is 40 ℃.
According to some preferred embodiments, in the step (3), the wave-absorbing bismaleimide resin curing system obtained in the step (2) is cured in a triggering stage at the temperature of 20-300 ℃ to obtain wave-absorbing bismaleimide resins with different viscosities.
According to some specific embodiments, the preparation of the wave-absorbing bismaleimide resin comprises the following steps:
(1) putting the bismaleimide resin, the epoxy resin and the absorbent into an internal mixer for internal mixing and coarse mixing to obtain coarse mixing wave-absorbing bismaleimide resin; the molar ratio of the bismaleimide resin to the epoxy resin is 1: (0.5 to 0.7); the bismaleimide resin is one or more of XU292 type bismaleimide resin, 6421 type bismaleimide resin and V378-A type bismaleimide resin;
(2) putting the rough mixed wave-absorbing bismaleimide resin obtained in the step (1) into an open mill for refining and fine mixing to obtain fine mixed wave-absorbing bismaleimide resin, and then adding an aliphatic amine curing agent into the fine mixed wave-absorbing bismaleimide resin to obtain a wave-absorbing bismaleimide resin curing system; the molar ratio of the curing agent to the bismaleimide resin is (0.1-0.5): 1;
(3) and (3) sequentially triggering and curing the wave-absorbing bismaleimide 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 150-250 ℃ (preferably at a high temperature stage of 180-250 ℃) for 1-4 h to obtain the wave-absorbing bismaleimide resin with different viscosities.
According to some more specific embodiments, the preparation of the wave-absorbing bismaleimide resin comprises the following steps:
(1) putting the bismaleimide resin, the epoxy resin and the absorbent into an internal mixer for internal mixing and coarse mixing to obtain coarse mixing wave-absorbing bismaleimide resin; the molar ratio of the bismaleimide 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 bismaleimide resin and the mass of the epoxy resin; the temperature of the banburying and rough mixing is 20-300 ℃, the time of the banburying and rough mixing is 10-120 min, and the rotating speed of a rotor of the banburying and rough mixing is 10-250 r/min; the bismaleimide resin is one or more of fatty bismaleimide resin, ether bismaleimide resin, aryl ester bismaleimide resin, condensed ring bismaleimide resin and amide bismaleimide 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 rough mixed wave-absorbing bismaleimide resin obtained in the step (1) into an open mill, performing open-refining and fine mixing for 10-80 min at the temperature of 20-300 ℃, obtaining fine mixed wave-absorbing bismaleimide resin after uniform mixing, then adding one or more epoxy resin curing agents with different temperatures into the fine mixed wave-absorbing bismaleimide resin, and continuing open-refining and fine mixing for 2-10 min at the temperature of 40 ℃ to obtain a wave-absorbing bismaleimide resin curing system; the molar ratio of the curing agent to the bismaleimide resin is (0.1-0.5): 1; the roll speed of the refining and fine mixing is 2-17 m/min; the epoxy resin curing agent with different temperatures is one or more of aliphatic amine, polyamide, aromatic amine, polyether amine, dicyandiamide and anhydride curing agent.
(3) Triggering the wave-absorbing bismaleimide resin curing system obtained in the step (2) to be cured in a staged manner at different temperatures to obtain wave-absorbing bismaleimide resins with different viscosity states; the range of different curing trigger temperatures is 20-300 ℃.
In a second aspect, the invention provides the wave-absorbing bismaleimide resin prepared by the preparation method in the first aspect.
The invention provides a preparation method of a wave-absorbing bismaleimide resin composite material in a third aspect, which comprises the following steps:
(a) putting the bismaleimide resin, the epoxy resin and the absorbent into an internal mixer for internal mixing and coarse mixing to obtain coarse mixing wave-absorbing bismaleimide resin;
(b) putting the rough mixed wave-absorbing bismaleimide resin obtained in the step (a) into an open mill for refining and fine mixing to obtain fine mixed wave-absorbing bismaleimide resin, and then adding a curing agent into the fine mixed wave-absorbing bismaleimide resin to obtain a wave-absorbing bismaleimide resin curing system; the curing agent is selected from one or more of aliphatic amine curing agent, polyamide curing agent, aromatic amine curing agent, polyether amine curing agent, dicyandiamide curing agent and anhydride curing agent;
(c) triggering and curing the wave-absorbing bismaleimide resin curing system obtained in the step (b) at least at one low-temperature stage to obtain a wave-absorbing bismaleimide resin blank (also called as a wave-absorbing bismaleimide resin composite intermediate), and then putting the wave-absorbing bismaleimide resin blank into a calender for calendering to obtain a wave-absorbing bismaleimide resin film;
(d) and (3) layering (placing) a plurality of wave-absorbing bismaleimide resin films in a laminated manner, and then triggering and curing at least one high-temperature stage to obtain the wave-absorbing bismaleimide resin composite material (also called as a wave-absorbing bismaleimide resin composite material).
The viscosity of the wave-absorbing bismaleimide resin in the mixing stage is in the range of 500-20000 cps, uniform dispersion of an absorbent is facilitated in the range, the surface density Cv value of the wave-absorbing bismaleimide resin composites in different areas can reach 0.02-0.05, and the electrical property and the wave-absorbing property stability of the wave-absorbing bismaleimide resin are improved; after low-temperature stage curing, the viscosity of the wave-absorbing bismaleimide resin is within a viscosity range of 30000-500000 cps, the calendering thickness precision can reach within a thickness range of +/-5%, the precise film-forming property is favorable for controlling the wave-absorbing performance of the wave-absorbing bismaleimide resin composite material, the wave-absorbing performance and the mechanical property of the wave-absorbing bismaleimide resin film after calendering and film-forming are favorable for ensuring the wave-absorbing performance and the mechanical property of the wave-absorbing bismaleimide resin film, so that the reflectivity absorption peak frequency value Cv value of the calendered wave-absorbing bismaleimide resin film after multilayer lamination can be controlled within 0.1; compared with the wave-absorbing performance of the wave-absorbing bismaleimide resin composite material which is not pre-cured, the wave-absorbing bismaleimide resin composite material obtained by the invention is directly rolled into a film, thereby being beneficial to improving the stability of the wave-absorbing performance of the wave-absorbing composite material; the reflectivity absorption peak frequency value Cv value of the wave-absorbing bismaleimide resin film obtained by the invention can be controlled within 0.1 after the wave-absorbing bismaleimide resin film is laminated in multiple layers, so that the wave-absorbing bismaleimide resin composite material with good wave-absorbing performance can be obtained, and the thickness of the wave-absorbing bismaleimide resin composite material can be accurately controlled within a wider range.
According to some preferred embodiments, the molar ratio of the bismaleimide resin, the curing agent and the epoxy resin is 1: (0.1-0.5): (0.5 to 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 an aliphatic amine curing agent, and preferably, the curing agent is one or more of diethylenetriamine, triethylene tetramine and tetraethylene pentamine.
According to some preferred embodiments, in the step (c), the wave-absorbing bismaleimide resin curing system obtained in the step (b) is triggered and cured at 50-80 ℃ to obtain a wave-absorbing bismaleimide resin blank, and then the wave-absorbing bismaleimide resin blank is placed into a calender to be calendered to obtain a wave-absorbing bismaleimide resin film; in the step (d), the wave-absorbing bismaleimide resin composite material is prepared by layering a plurality of layers of wave-absorbing bismaleimide resin films and triggering and curing at 150-250 ℃.
According to some preferred embodiments, the viscosity of the wave-absorbing bismaleimide resin curing system is 500-20000 cps; the viscosity of the wave-absorbing bismaleimide resin blank is 30000-500000 cps.
According to some specific embodiments, the preparation method of the wave-absorbing bismaleimide resin composite material comprises the following steps:
(a) putting the bismaleimide resin, the epoxy resin and the absorbent into an internal mixer for internal mixing and coarse mixing to obtain coarse mixing wave-absorbing bismaleimide resin; the molar ratio of the bismaleimide 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 bismaleimide resin and the mass of the epoxy resin; the temperature of the banburying and rough mixing is 20-300 ℃, the time of the banburying and rough mixing is 10-120 min, and the rotating speed of a rotor of the banburying and rough mixing is 10-250 r/min; the bismaleimide resin is one or more of fatty bismaleimide resin, ether bismaleimide resin, aryl ester bismaleimide resin, condensed ring bismaleimide resin and amide bismaleimide resin, preferably, the bismaleimide resin is one or more of diphenylmethane bismaleimide resin, V378-A bismaleimide resin and compound-353 bismaleimide 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) Putting the rough mixed wave-absorbing bismaleimide resin obtained in the step (a) into an open mill, performing refining and fine mixing for 10-80 min at 20-300 ℃, after uniform mixing, obtaining fine mixed wave-absorbing bismaleimide resin, then adding a curing agent into the fine mixed wave-absorbing bismaleimide resin, and performing refining and fine mixing for 2-10 min at 40 ℃ to obtain a wave-absorbing bismaleimide resin curing system; the molar ratio of the curing agent to the bismaleimide resin is (0.1-0.5): 1; the roll speed of the refining and fine mixing is 2-17 m/min; preferably, the curing agent is one or more of diethylenetriamine, triethylene tetramine and tetraethylene pentamine.
(c) Triggering and curing the wave-absorbing bismaleimide resin curing system obtained in the step (b) at a low temperature stage of 50-80 ℃ to obtain a wave-absorbing bismaleimide resin blank, and then putting the wave-absorbing bismaleimide resin blank into a calender for calendering to obtain a wave-absorbing bismaleimide 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 6m/s), and 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 calendered thickness (calendered thickness) refers to the thickness of each layer of the absorbent bismaleimide resin film.
(d) And (3) layering the multiple layers of wave-absorbing bismaleimide resin films in a laminated manner, and then triggering and curing at a high temperature stage of 150-250 ℃ to obtain the wave-absorbing bismaleimide resin composite material.
In a fourth aspect, the invention provides a wave-absorbing bismaleimide resin composite material prepared by the preparation method in the third aspect.
The invention will be further illustrated by way of example, but the scope of protection is not limited to these examples.
Example 1
(a) Putting bismaleimide resin (XU292 type bismaleimide resin), epoxy resin (E-51 type epoxy resin) and an absorbent (carbonyl iron powder) into an internal mixer for banburying and coarse mixing to obtain coarse mixing wave-absorbing bismaleimide resin; wherein the molar ratio of the XU 292-type bismaleimide 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 XU 292-type bismaleimide resin and the E-51-type epoxy resin; the technological conditions of banburying and coarse mixing are as follows: the temperature of the banburying and rough mixing is 100 ℃, the time of the banburying and rough mixing is 45min, and the rotating speed of a rotor of the banburying and rough mixing is 200 r/min.
(b) Putting the rough mixed wave-absorbing bismaleimide resin obtained in the step (a) into an open mill, performing refining and fine mixing for 45min at the temperature of 100 ℃, after uniform mixing, obtaining fine mixed wave-absorbing bismaleimide resin, then adding a curing agent (triethylene tetramine) into the fine mixed wave-absorbing bismaleimide resin, and continuing refining and fine mixing for 5min at the temperature of 40 ℃ to obtain a wave-absorbing bismaleimide resin curing system; the molar ratio of the curing agent to the XU292 bismaleimide resin is 0.2: 1; the roll speed for the refining and the fine mixing is 12 m/min.
(c) Triggering and curing the wave-absorbing bismaleimide resin curing system obtained in the step (b) for 1h at a low temperature stage of 50 ℃ to obtain a wave-absorbing bismaleimide resin blank, and then putting the wave-absorbing bismaleimide resin blank into a calender for calendering to obtain a wave-absorbing bismaleimide resin film; the process conditions of calendering are as follows: the temperature of the rolling is 100 ℃, the pressure of the rolling is 1000N, the speed of the rolling is 4m/s, and the thickness of the rolling is 1.5 mm.
(d) And (c) placing the wave-absorbing bismaleimide resin films obtained in the four steps in a laminated mode (laminated layer laying), and then triggering and curing for 3 hours at a high temperature stage of 200 ℃ to obtain the wave-absorbing bismaleimide resin composite material.
In this embodiment, the viscosity of the wave-absorbing bismaleimide resin curing system obtained in the step (b) and the viscosity of the wave-absorbing bismaleimide resin blank obtained in the step (c) are tested, and the results are shown in table 1.
The average reflectivity absorption peak value of the wave-absorbing bismaleimide resin composite material prepared in the embodiment at 3GHz is-11.2 dB, the total thickness of the wave-absorbing bismaleimide resin composite material is 6mm, in the embodiment, the film thickness, the surface density and the wave-absorbing performance of the wave-absorbing bismaleimide resin composite material at different positions are uniformly taken, and the Cv (dispersion coefficient) value of typical data is used for representing the process stability, so that the uniform control of the film thickness and the surface density and the stable control of the wave-absorbing performance of the wave-absorbing bismaleimide resin composite material prepared in the embodiment are found, the preparation process stability of the 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 reflectivity absorption peak frequency Cv value are, the better the film thickness and the surface density uniformity of the prepared wave-absorbing bismaleimide resin composite material are, and the wave-absorbing performance stability is better.
Example 2
Example 2 is essentially the same as example 1, except that:
in the step (a), the bismaleimide resin is 6421 type bismaleimide resin, the epoxy resin is E-44 type epoxy resin, and the absorbent is carbonyl iron powder; the molar ratio of the 6421 bismaleimide resin to the E-44 epoxy resin is 1:0.5, and the addition amount of the carbonyl iron powder is 50% of the sum of the 6421 bismaleimide resin and the E-44 epoxy resin.
In step (b), the curing agent is diethylenetriamine; the molar ratio of the curing agent to the 6421 bismaleimide resin was 0.3: 1.
The average reflectivity absorption peak value of the wave-absorbing bismaleimide resin composite material prepared by the embodiment at 3GHz is-9.8 dB.
The same performance test as in example 1 was carried out for this example, and the results are shown in Table 1.
Example 3
Example 3 is essentially the same as example 1, except that:
in the step (a), the bismaleimide resin is V378-A type bismaleimide resin, the epoxy resin is F-44 type epoxy resin, and the absorbent is carbonyl iron powder; the molar ratio of the V378-A bismaleimide resin to the F-44 epoxy resin is 1:0.7, and the adding amount of the carbonyl iron powder is 50% of the sum of the mass of the V378-A bismaleimide resin and the mass of the F-44 epoxy resin.
In step (b), the curing agent is tetraethylenepentamine; the molar ratio of the curing agent to the V378-A bismaleimide resin is 0.4: 1.
The average reflectivity absorption peak value of the wave-absorbing bismaleimide resin composite material prepared by the embodiment at 3GHz is-10.5 dB.
The same performance test as in example 1 was carried out for this example, and the results are shown in Table 1.
Example 4
Example 4 is essentially the same as example 1, except that:
in step (a), the molar ratio of the XU292 bismaleimide resin to the E-51 epoxy resin is 1: 0.2.
The average reflectivity absorption peak value of the wave-absorbing bismaleimide resin composite material prepared by the embodiment at 3GHz is-11 dB.
The same performance test as in example 1 was carried out for this example, and the results are shown in Table 1.
Example 5
Example 5 is essentially the same as example 1, except that:
in step (a), the molar ratio of the XU292 bismaleimide resin to the E-51 epoxy resin is 1: 0.8.
The average reflectivity absorption peak value of the wave-absorbing bismaleimide resin composite material prepared by the embodiment at 3GHz is-10.8 dB.
The same performance test as in example 1 was carried out for this example, and the results are shown in Table 1.
Comparative example 1
(a) Same as in step (a) of example 1.
(b) And (b) putting the rough mixed wave-absorbing bismaleimide resin obtained in the step (a) into an open mill, and performing refining and mixing for 45min at the temperature of 100 ℃, and after uniform mixing, obtaining the refined mixed wave-absorbing bismaleimide resin, wherein the roll speed of the refining and mixing is 12 m/min.
(c) Putting the fine-mixed wave-absorbing bismaleimide resin obtained in the step (b) into a calender for calendering to obtain a wave-absorbing bismaleimide resin film; the process conditions of calendering 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 1.5 mm.
(d) Same as in step (d) of example 1.
The average reflectivity absorption peak value of the wave-absorbing bismaleimide resin composite material prepared by the comparative example at 3GHz is-10.6 dB.
The viscosities of the rough mixed wave-absorbing resin and the fine mixed wave-absorbing bismaleimide resin in the comparative example are equal to 6500 cps.
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
Firstly, putting epoxy resin (E-51 type epoxy resin) and carbonyl iron powder (absorbent) into an internal mixer for banburying and coarse mixing to obtain coarse mixing wave-absorbing resin; wherein the addition amount of the carbonyl iron powder is 50 percent of the mass of the epoxy resin; the technological conditions of banburying and coarse mixing are as follows: the temperature of the banburying and rough mixing is 100 ℃, the time of the banburying and rough mixing is 45min, and the rotating speed of a rotor of the banburying and rough mixing is 200 r/min.
Secondly, putting the rough mixed wave-absorbing resin obtained in the step I into a resin open mill for refining and fine mixing for 45min to obtain fine mixed wave-absorbing resin which is uniformly mixed, and then adding m-xylylenediamine (curing agent) into the fine mixed wave-absorbing resin for continuously refining and fine mixing for 5 min; the technological conditions for refining and mixing are as follows: the temperature of the refining and mixing is 100 ℃, and the roller speed of the refining and mixing is 12 m/min; the curing agent is 1.7 wt% of the amount of the E-51 type epoxy resin.
Thirdly, the fine mixed wave-absorbing resin added with the curing agent obtained in the second step is placed into a precision calender for calendering to obtain a wave-absorbing resin adhesive film (wave-absorbing epoxy resin film); the process conditions of calendering 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 1.5 mm.
Fourthly, the wave-absorbing epoxy resin film obtained in the fourth step is laminated and placed and then cured for 3 hours at the temperature of 200 ℃ to obtain the wave-absorbing epoxy resin composite material.
The average reflectivity absorption peak value of the wave-absorbing epoxy resin composite material prepared by the comparative example at 3GHz is-10.7 dB.
In the comparative example, the viscosity of the rough mixed wave-absorbing resin is equal to that of the fine mixed wave-absorbing resin without the curing agent and is 5800cps, and the viscosity of the fine mixed wave-absorbing resin after the curing agent is added, refined and mixed for 5min is 6300 cps.
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 reference is present.
The invention has not been described in detail and is in part known to those of skill in the art.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present 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 solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114311731A (en) * | 2021-12-29 | 2022-04-12 | 中国航空制造技术研究院 | Segmented curing molding method for high-temperature-resistant bismaleimide resin-based composite material |
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|---|---|---|---|---|
| US4273916A (en) * | 1979-02-14 | 1981-06-16 | Trw Inc. | Curable cycloaliphatic epoxy-polyimide compositions |
| CN112029421A (en) * | 2020-09-11 | 2020-12-04 | 航天特种材料及工艺技术研究所 | Wave-absorbing adhesive film material and preparation method thereof |
| CN112574564A (en) * | 2020-11-23 | 2021-03-30 | 航天特种材料及工艺技术研究所 | High-temperature-resistant modified bismaleimide electromagnetic composite material and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4273916A (en) * | 1979-02-14 | 1981-06-16 | Trw Inc. | Curable cycloaliphatic epoxy-polyimide compositions |
| CN112029421A (en) * | 2020-09-11 | 2020-12-04 | 航天特种材料及工艺技术研究所 | Wave-absorbing adhesive film material and preparation method thereof |
| CN112574564A (en) * | 2020-11-23 | 2021-03-30 | 航天特种材料及工艺技术研究所 | High-temperature-resistant modified bismaleimide electromagnetic composite material and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114311731A (en) * | 2021-12-29 | 2022-04-12 | 中国航空制造技术研究院 | Segmented curing molding method for high-temperature-resistant bismaleimide resin-based composite material |
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