CN113698762A - Low-density high-toughness bismaleimide foam material and preparation method thereof - Google Patents
Low-density high-toughness bismaleimide foam material and preparation method thereof Download PDFInfo
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- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
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Abstract
The invention provides a bismaleimide foam material, wherein the density of the bismaleimide foam material is 70-300 kg/m3(ii) a The aperture of the bismaleimide foam material is 0.2-1 mm. The invention realizes the synergistic effect of the foaming reaction of the bismaleimide resin and the resin curing molding by controlling the selection of the physical foaming agent and the chemical foaming agent, further realizes the maximization of the foaming capacity by controlling the formula proportion of the physical foaming agent and the chemical foaming agent, avoids the phenomena of high density of the physical foaming agent, core burning, implosion and the like of the chemical foaming agent, and realizes the additionAfter the thermoplastic toughening agent is added, the high-toughness bismaleimide resin foam with lower density can be obtained. The bismaleimide foam provided by the invention has the characteristics of high heat resistance, mechanical property, low density and high toughness, and the preparation process is simple and easy to control, and is beneficial to realizing industrial continuous production.
Description
Technical Field
The invention belongs to the technical field of bismaleimide foam materials, relates to a bismaleimide foam material and a preparation method thereof, and particularly relates to a low-density high-toughness bismaleimide foam material and a preparation method thereof.
Background
With the rapid development of special fields such as aerospace, aviation and the like, the performance requirements of the foamed plastics are continuously improved, and the traditional foamed plastics cannot meet the requirements of the fields on material strength, rigidity, heat resistance, corrosion resistance and the like. Therefore, the high performance has become a new trend target for the research of the foam plastics. High-performance foam plastics have been used abroad as load-bearing structural core materials in the fields of aviation, aerospace, transportation and the like, such as frameworks of satellite solar cells, rocket front end fairings, unmanned aircraft empennages, missile empennages, large-scale radomes and the like.
Bismaleimide (BMI) is a polymer with double-bond active end groups, and the Tg of the modified bismaleimide resin can reach about 320 ℃ after being cured, and can reach about 260-270 ℃ after being used for a long time. The composite material is widely applied to the industries of aerospace, military industry, high-end carbon fiber composite materials and the like. The high-performance bismaleimide foam is prepared by adding a foaming agent and other auxiliary agents into a polymer and controlling the gel speed and the foaming speed of the BMI resin through a formula and process conditions, wherein the foaming agent and the auxiliary agents are in the range of ultrahigh temperature resistance and mechanical properties of the resin. However, bismaleimide foams have been studied in the early stages and no commercial BMI foam is available on the market. The BMI resin is heated by the chemical foaming agent of the invention patent CN101343413A, and other auxiliary agents are not added to prepare BMI foam, the BMI foam is prepared by the invention patent CN106009666A by using carbon fiber felt as a carrier, impregnating bismaleimide resin containing foaming microspheres, and then carrying out mould pressing foaming to obtain the bismaleimide foam composite material which is added with carbon fibers and is not a foam plastic body.
Therefore, how to design and prepare the bismaleimide foam with more excellent comprehensive performance, further widening the application depth and the application width of the bismaleimide foam material, having important scientific and engineering values, is also one of the focuses of great research and development type enterprises and first-line researchers in the field.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a bismaleimide foam material and a preparation method thereof, and particularly to a low-density high-toughness bismaleimide foam material. And the preparation process is simple and easy to control, and is favorable for realizing industrial continuous production.
The invention provides a bismaleimide foam material, wherein the density of the bismaleimide foam material is 70-300 kg/m3；
The aperture of the bismaleimide foam material is 0.2-1 mm.
Preferably, the bismaleimide foam material is obtained by co-foaming a physical foaming material and a chemical foaming agent;
the bismaleimide foam material has uniform cell distribution;
the bismaleimide foam material contains a thermoplastic toughening agent;
the core of the bismaleimide foam does not have a yellow appearance resulting from internal coring and/or implosion.
Preferably, the physically foamable material comprises expandable microspheres;
the chemical blowing agent comprises an organic blowing agent;
the organic foaming agent comprises an azo chemical foaming agent and/or a sulfonyl hydrazine chemical foaming agent;
the cells are of a closed cell structure;
the bismaleimide foam material comprises a bismaleimide rigid foam material.
Preferably, the chemical blowing agent comprises one or more of azoisobutyryl cyano formamide, azodicarbonamide, azodiisobutyronitrile and 2, 4-xylene disulfonyl hydrazide;
the mass ratio of the physical foaming material to the chemical foaming agent is (2-10): (0.1-2);
the bismaleimide foam material is low-density high-toughness bismaleimide foam;
the bismaleimide foam material is a thermosetting foam material;
the compression strength of the bismaleimide foam material is 1.5-8 Mpa.
The invention provides a bismaleimide foam material which comprises the following raw materials in parts by weight
Preferably, the bismaleimide resin comprises one or more of N, N '- (4, 4-methylenediphenyl) bismaleimide, 2' -bis [4- (4-maleinimidphenoxy) phenyl ] propane, and bis (3-ethyl-5-methyl-4-maleimidophenyl) methane;
the allylate is one or more of allyl bisphenol A, diallyl ether, diallylamine and diallyl disulfide;
the physically foamable material comprises expandable microspheres;
the chemical foaming agent comprises one or more of 4,4' -oxo-bis-benzenesulfonyl hydrazide, azodicarbonamide, 2, 4-xylene disulfonyl hydrazide and N, N-dinitrosopentamethylenetetramine;
the thermoplastic toughening agent comprises one or more of polyaryletherketone, polyetherimide, polyphenylene sulfide and polybenzimidazole.
Preferably, the physical foaming material comprises one or more of 920DU40, 920DU80, F230D, F190D, EHM401 and EM 304;
the thixotropic agent comprises one or more of fumed silica, organic bentonite, polyamide wax and kaolin;
the surfactant comprises AK-8877, AK-8890, B-8123, B-8002, B-2470, B-8110, L-580, L-7608 or L-627;
the inorganic filler comprises one or more of expandable graphite, expandable perlite powder and expandable vermiculite powder.
The invention also provides a preparation method of the bismaleimide foam material in any one of the technical schemes, which comprises the following steps:
(1) reacting bismaleimide with an allyl compound to obtain a prepolymer;
(2) and mixing the prepolymer obtained in the step, a physical foaming material, a chemical foaming agent, a thermoplastic toughening agent, a thixotropic agent, a surfactant and an inorganic filler, foaming and curing in a mold, and post-curing to obtain the bismaleimide foam material.
Preferably, the reaction temperature is 130-150 ℃;
the reaction time is 1-3 hours;
the mixing mode comprises high-speed stirring;
the mixing speed is 500-2000 r/min;
the foaming and curing temperature is 130-150 ℃;
the foaming and curing time is 1-2 hours;
the mold comprises an aluminum mold.
Preferably, the post-curing comprises a three-stage step-temperature post-curing process;
the temperature of the first stage of post-curing is 160-180 ℃;
the time of the first stage of post-curing is 1-2 hours;
the temperature of the second stage of post-curing is 180-200 ℃;
the time of the second stage of post-curing is 1-2 hours;
the temperature of the third stage of post-curing is 230-250 ℃;
the time of the third stage of post-curing is 2-3 hours.
The invention provides a bismaleimide foam material, which is prepared from bismaleimideThe density of the bismaleimide foam material is 70-300 kg/m3(ii) a The aperture of the bismaleimide foam material is 0.2-1 mm. Compared with the prior art, the preparation process of the bismaleimide foam is researched, the foaming process is particularly selected in a targeted manner, and the chemical foaming agent is considered to be decomposed and foamed at a certain temperature, and heat is released and accumulated along with the progress of a crosslinking reaction, so that the internal core burning, implosion and comprehensive performance are reduced; the method of simply using a physical foaming agent or filling hollow microspheres has the defect of inherent foaming materials, so that the obtained foam has higher density and is difficult to solve. Thus, the present invention specifically uses a combination of chemical blowing agents and physical blowing agents, where the physical blowing agents need to absorb heat for expansion and can absorb the heat build up caused by the foam, while chemical blowing agents can solve the problem of excessive density. According to the invention, the chemical foaming agent and the physical foaming agent are combined for use, and then the specific additive is combined, especially the high-temperature-resistant thermoplastic powder material is added, so that the toughening effect and the thickening effect are achieved, the foaming effect is facilitated, the high-toughness bismaleimide foam with low density is obtained, and the high-temperature resistance and the high mechanical performance can be kept at a high level.
According to the invention, the synergistic effect of the foaming reaction of the bismaleimide resin and the resin curing molding is realized by controlling the selection of the physical foaming agent and the chemical foaming agent, the foaming capacity is maximized by further controlling the formula proportion of the physical foaming agent and the chemical foaming agent, the phenomena of high density of the physical foaming agent, core burning, implosion and the like of the chemical foaming agent are avoided, and the high-toughness bismaleimide resin foam with lower density can be obtained after the thermoplastic toughening agent is added. The bismaleimide foam provided by the invention has the characteristics of high heat resistance, mechanical property, low density and high toughness, and the preparation process is simple and easy to control, and is beneficial to realizing industrial continuous production.
Experimental results show that the bismaleimide foam prepared by combining the physical foaming agent and the chemical foaming agent has the density of 70-300 kg/m3The compression strength at normal temperature is 4-6 Mpa, and the glass transition temperature isThe temperature reaches 220-260 ℃ and the 5 percent thermal weight loss temperature reaches over 380 ℃, the reaction heat can be well controlled, the phenomenon of core explosion and core burning of the core part of the foam material is avoided, and the strong guarantee is provided for obtaining high performance of the bismaleimide foam.
Drawings
FIG. 1 is a photograph of a core of a bismaleimide foam prepared by a conventional chemical foaming process;
FIG. 2 is a photograph of the core of a bismaleimide foam made according to the present invention.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
All of the starting materials of the present invention are not particularly limited in their purity, and the present invention preferably employs purity requirements that are conventional in the art of analytically pure or polybismaleimide foam preparation.
All the raw materials, the marks and the acronyms thereof belong to the conventional marks and acronyms in the field, each mark and acronym is clear and definite in the field of related application, and the raw materials can be purchased from the market or prepared by a conventional method by the technical staff in the field according to the marks, the acronyms and the corresponding application.
The invention provides a bismaleimide foam material, wherein the density of the bismaleimide foam material is 70-300 kg/m3；
The aperture of the bismaleimide foam material is 0.2-1 mm.
In the invention, the density of the bismaleimide foam material is 70-300 kg/m3Preferably 120 to 250kg/m3More preferably 170 to 200kg/m3。
In the invention, the aperture of the bismaleimide foam material is 0.2-1 mm, preferably 0.3-0.9 mm, more preferably 0.4-0.8 mm, and more preferably 0.5-0.7 mm.
In the present invention, the bismaleimide foam is preferably obtained by co-foaming a physical foaming material and a chemical foaming agent.
In the present invention, the physically foaming material preferably comprises expandable microspheres.
In the present invention, the chemical foaming agent preferably includes an organic foaming agent, and more specifically, the organic foaming agent preferably includes an azo-based chemical foaming agent and/or a sulfonyl hydrazide-based chemical foaming agent, and more preferably, an azo-based chemical foaming agent or a sulfonyl hydrazide-based chemical foaming agent.
In the present invention, the chemical blowing agent preferably includes one or more of azoisobutyrylcyanamide, azodicarbonamide, azobisisobutyronitrile, and 2, 4-xylene disulfonylhydrazide, and more preferably, azoisobutyrylcyanamide, azodicarbonamide, azobisisobutyronitrile, or 2, 4-xylene disulfonylhydrazide.
In the invention, the mass ratio of the physical foaming material to the chemical foaming agent is preferably (2-10): (0.1-2), more preferably (3-9): (0.1-2), more preferably (4-8): (0.1-2), more preferably (5-7): (0.1-2), more preferably (2-10): (0.5 to 1.6), more preferably (2 to 10): (0.9-1.2).
In the present invention, the bismaleimide foam preferably has a uniform cell distribution, and more particularly, the cells are preferably of a closed cell structure.
In the present invention, the bismaleimide foam preferably contains a thermoplastic toughening agent.
In the present invention, the bismaleimide foam is preferably a bismaleimide rigid foam, and particularly, the bismaleimide foam is preferably a thermosetting foam.
In the invention, the compression strength of the bismaleimide foam material is preferably 1.5-8 Mpa, more preferably 2.5-7 Mpa, more preferably 3.5-6 Mpa, and more preferably 4.5-5 Mpa.
In the present invention, the bismaleimide foam material is preferably a low-density high-toughness bismaleimide foam.
In the present invention, the core of the bismaleimide foam preferably does not have an internal core burn and/or yellow appearance resulting from implosion, and more preferably does not have an internal core burn and yellow appearance resulting from implosion.
The invention provides a bismaleimide foam material which comprises the following raw materials in parts by weight
The amount of the bismaleimide added is 40-60 parts by weight, preferably 44-66 parts by weight, more preferably 48-62 parts by weight, and more preferably 52-58 parts by weight.
In the present invention, the bismaleimide resin preferably includes one or more of N, N '- (4, 4-methylenediphenyl) bismaleimide, 2' -bis [4- (4-maleimidophenoxy) phenyl ] propane and bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, and more preferably N, N '- (4, 4-methylenediphenyl) bismaleimide, 2' -bis [4- (4-maleimidophenoxy) phenyl ] propane or bis (3-ethyl-5-methyl-4-maleimidophenyl) methane.
The addition amount of the allyl compound is 20-30 parts by weight, preferably 22-28 parts by weight, and more preferably 24-26 parts by weight.
In the present invention, the allylate is preferably one or more of allyl bisphenol a, diallyl ether, diallylamine and diallyl disulfide, and more preferably allyl bisphenol a, diallyl ether, diallyl amine or diallyl disulfide.
The addition amount of the physical foaming material is 2-10 parts by weight, preferably 3-9 parts by weight, more preferably 4-8 parts by weight, and more preferably 5-7 parts by weight.
In the present invention, the physical foaming material preferably comprises expandable microspheres, and specifically, the physical foaming material preferably comprises one or more of 920DU40, 920DU80, F230D, F190D, EHM401 and EM304, more preferably 920DU40, 920DU80, F230D, F190D, EHM401 or EM 304.
The addition amount of the chemical foaming agent is 0.1-2 parts by weight, preferably 0.5-1.6 parts by weight, and more preferably 0.9-1.2 parts by weight.
In the present invention, the chemical blowing agent preferably includes one or more of 4,4 '-oxybis-benzenesulfonyl hydrazide, azodicarbonamide, 2, 4-xylene-disulfonyl hydrazide and N, N-dinitroso-pentamethyl tetramine, and more preferably 4,4' -oxybis-benzenesulfonyl hydrazide, azodicarbonamide, 2, 4-xylene-disulfonyl hydrazide or N, N-dinitroso-pentamethyl tetramine.
The addition amount of the thermoplastic toughening agent is 5-20 parts by weight, preferably 8-17 parts by weight, and more preferably 11-14 parts by weight.
In the present invention, the thermoplastic toughening agent preferably includes a thermoplastic resin toughening agent (thermoplastic polymer toughening agent), more preferably includes a high temperature resistant thermoplastic polymer toughening agent, more preferably includes one or more of polyaryletherketone, polyetherimide, polyphenylene sulfide and polybenzimidazole, more preferably polyaryletherketone, polyetherimide, polyphenylene sulfide or polybenzimidazole.
The addition amount of the thixotropic agent is 1-10 parts by weight, preferably 3-8 parts by weight, and more preferably 5-6 parts by weight.
In the present invention, the thixotropic agent preferably includes one or more of fumed silica, organobentonite, polyamide wax and kaolin, more preferably fumed silica, organobentonite, polyamide wax or kaolin.
The addition amount of the surfactant is 1 to 5 parts by weight, preferably 1.5 to 4.5 parts by weight, more preferably 2 to 4 parts by weight, and still more preferably 2.5 to 3.5 parts by weight.
In the present invention, the surfactant preferably comprises AK-8877, AK-8890, B-8123, B-8002, B-2470, B-8110, L-580, L-7608 or L-627.
The inorganic filler is added in an amount of 2 to 10 parts by weight, preferably 3 to 9 parts by weight, more preferably 4 to 8 parts by weight, and still more preferably 5 to 7 parts by weight.
In the present invention, the inorganic filler preferably includes one or more of expandable graphite, expandable perlite powder and expandable vermiculite powder, more preferably expandable graphite, expandable perlite powder or expandable vermiculite powder.
The invention also provides a preparation method of the bismaleimide foam material, which comprises the following steps:
(1) reacting bismaleimide with an allyl compound to obtain a prepolymer;
(2) and mixing the prepolymer obtained in the step, a physical foaming material, a chemical foaming agent, a thermoplastic toughening agent, a thixotropic agent, a surfactant and an inorganic filler, foaming and curing in a mold, and post-curing to obtain the bismaleimide foam material.
Firstly, bismaleimide and an allyl compound are reacted to obtain a prepolymer.
In the invention, the reaction temperature is preferably 130-150 ℃, more preferably 134-146 ℃, and more preferably 138-142 ℃.
In the present invention, the reaction time is preferably 1 to 3 hours, more preferably 1.4 to 2.6 hours, and still more preferably 1.8 to 2.2 hours.
The invention then mixes the prepolymer obtained in the above steps, a physical foaming material, a chemical foaming agent, a thermoplastic toughening agent, a thixotropic agent, a surfactant and an inorganic filler, foams and solidifies in a mold, and then post-solidifies to obtain the bismaleimide foam material.
In the present invention, the mixing means preferably includes high-speed stirring.
In the invention, the rotation speed of the mixing is preferably 500-2000 r/min, more preferably 800-1700 r/min, and more preferably 1100-1400 r/min.
In the present invention, the mold preferably comprises an aluminum mold.
In the invention, the foaming and curing temperature is preferably 130-150 ℃, more preferably 134-146 ℃, and more preferably 138-142 ℃.
In the invention, the time for foaming and curing is preferably 1 to 2 hours, more preferably 1.2 to 1.8 hours, and still more preferably 1.4 to 1.6 hours.
In the present invention, the post-curing preferably includes a gradient post-curing process, more preferably includes a gradient temperature-rise post-curing process, and specifically may be a three-stage step temperature-rise post-curing process.
In the invention, the temperature of the first stage of post-curing is preferably 160-180 ℃, more preferably 164-176 ℃, and more preferably 168-172 ℃.
In the present invention, the time of the first stage of post-curing is preferably 1 to 2 hours, more preferably 1.2 to 1.8 hours, and still more preferably 1.4 to 1.6 hours.
In the invention, the temperature of the second stage of post-curing is preferably 180-200 ℃, more preferably 184-196 ℃, and more preferably 188-192 ℃.
In the present invention, the time of the second stage of the post-curing is preferably 1 to 2 hours, more preferably 1.2 to 1.8 hours, and still more preferably 1.4 to 1.6 hours.
In the invention, the temperature of the third stage of post-curing is preferably 230-250 ℃, more preferably 234-246 ℃, and more preferably 238-242 ℃.
In the present invention, the time of the third stage of the post-curing is preferably 2 to 3 hours, more preferably 2.2 to 2.8 hours, and more preferably 2.4 to 2.6 hours.
The invention is a complete and refined integral technical scheme, better ensures the structure and the appearance of the bismaleimide foam material, does not have the conditions of internal core burning and implosion, and further improves the comprehensive performance of the bismaleimide foam material, and the specific formula and the preparation process of the bismaleimide foam material can be as follows:
the bismaleimide foam is prepared by combining a chemical foaming agent and a physical foaming agent. The material comprises the following components in percentage by weight: 40-60% of BMI resin, 20-30% of allyl compound, 2-10% of expandable microspheres, 0.1-2% of chemical foaming agent, 5-20% of toughening agent, 1-10% of thixotropic agent, 1-5% of surfactant and 2-10% of inorganic filler.
The preparation method comprises the following steps: respectively weighing BMI resin and an allyl compound according to the mass ratio, and reacting at 130-150 ℃ for 1-3 hours to obtain a prepolymer;
adding expandable microspheres, a chemical foaming agent, a toughening agent, a thixotropic agent, a surfactant and an inorganic filler into the prepolymer, stirring at a high speed, uniformly mixing, placing in an aluminum die, heating at 130-150 ℃ for 1-2 hours, and foaming and curing in the process;
post-curing, heating the foaming body to 160-180 ℃, post-curing for 1-2 hours, heating to 180-200 ℃, post-curing for 1-2 hours, and finally heating to 230-250 ℃ and post-curing for 2-3 hours. Taking out and cooling to room temperature to obtain the foam.
The steps of the invention provide a low-density high-toughness bismaleimide foam material, and particularly a chemical foaming agent and a physical foaming agent are combined for use, the physical foaming agent needs to absorb heat when expanding and can absorb the problem of heat accumulation caused by foam, and the chemical foaming agent can solve the problem of overlarge density. According to the invention, the chemical foaming agent and the physical foaming agent are combined for use, and then the specific additive is combined, especially the high-temperature-resistant thermoplastic powder material is added, so that the toughening effect and the thickening effect are achieved, the foaming effect is facilitated, the high-toughness bismaleimide foam with low density is obtained, and the high-temperature resistance and the high mechanical performance can be kept at a high level.
According to the invention, the synergistic effect of the foaming reaction of the bismaleimide resin and the resin curing molding is realized by controlling the selection of the types of the physical foaming agent and the chemical foaming agent, the maximization of the foaming capacity is realized by further controlling the formula proportion of the physical foaming agent and the chemical foaming agent, the phenomena of high density of the physical foaming agent, core burning, implosion and the like of the chemical foaming agent are avoided, and the high-toughness bismaleimide resin foam with lower density can be obtained after the thermoplastic toughening agent is added. The bismaleimide foam provided by the invention has the characteristics of high heat resistance, mechanical property, low density and high toughness, and the preparation process is simple and easy to control, and is beneficial to realizing industrial continuous production.
Experimental results show that the bismaleimide foam prepared by combining the physical foaming agent and the chemical foaming agent has the density of 70-300 kg/m3The compression strength at normal temperature is 4-6 Mpa, the glass transition temperature reaches 220-260 ℃, and the 5% thermal weight loss temperature reaches over 380 ℃, and the reaction heat can be well controlled, so that the phenomenon of core explosion and core burning of the core part of the foam material is avoided, and a powerful guarantee is provided for obtaining high-performance of the bismaleimide foam.
For further illustration of the present invention, a bismaleimide foam and a preparation method thereof provided by the present invention are described in detail below with reference to examples, but it should be understood that the examples are implemented on the premise of the technical scheme of the present invention, and detailed embodiments and specific procedures are given, only for further illustration of the features and advantages of the present invention, not for limitation of the claims of the present invention, and the scope of protection of the present invention is not limited to the following examples.
Example 1
Reacting N, N' - (4, 4-methylene diphenyl) bismaleimide resin 40% and allyl bisphenol A24% at 140 ℃ for 2 hours, adding F230D 10%, azodicarbonamide 1%, polyether imide 10%, gas phase silicon dioxide 2%, AK-88903% and expandable graphite 10% into the prepolymer, stirring uniformly, and placing in an aluminum mould. Heating at 150 deg.C for 2 hr, foaming and curing in the process, further heating to 180 deg.C for curing for 2 hr, heating to 200 deg.C for curing for 2 hr, and finally heating to 250 deg.C for curing for 2 hr. Taking out and cooling to room temperature to obtain the bismaleimide foam.
Example 2
Reacting 50% of bis (3-ethyl-5-methyl-4-maleimide phenyl) methane resin and 30% of diallylamine at 130 ℃ for 2 hours, adding 920DU 408%, N-dinitrosopentamethylenetetramine 1%, polyaryletherketone 10%, fumed silica 2%, B-80023% and expandable graphite 10% into the prepolymer, uniformly stirring, and placing the mixture in an aluminum die. Heating at 140 deg.C for 2 hr, foaming and curing in the process, further heating to 160 deg.C for curing for 2 hr, heating to 180 deg.C for curing for 2 hr, and finally heating to 230 deg.C for curing for 2 hr. Taking out and cooling to room temperature to obtain the bismaleimide foam.
Example 3
Reacting N, N' - (4, 4-methylene diphenyl) bismaleimide resin 50% and allyl bisphenol A25% at 140 ℃ for 2 hours, adding EHM401, azodicarbonamide 2%, polybenzimidazole 10%, fumed silica 2%, L-7608, and expandable vermiculite powder 5%, stirring uniformly, and placing in an aluminum mold. Heating at 150 deg.C for 2 hr, foaming and curing in the process, further heating to 170 deg.C for curing for 2 hr, heating to 200 deg.C for curing for 2 hr, and finally heating to 240 deg.C for curing for 2 hr. Taking out and cooling to room temperature to obtain the bismaleimide foam.
The low-density high-toughness bismaleimide foam material prepared by the embodiment of the invention is subjected to performance detection.
Referring to table 1, table 1 shows the comparison of the properties of bismaleimide foams and polymethacrylimide foams prepared according to the present invention.
TABLE 1
It can be seen from table 1 that the bismaleimide foam provided by the present invention has high temperature resistance and excellent mechanical properties. The use requirement of the structural core material for high-temperature bearing can be met.
The low-density conductive wave-absorbing bismaleimide foam material prepared by the embodiment of the invention is compared with the bismaleimide foam material core prepared by the existing chemical foaming in characterization.
Referring to fig. 1, fig. 1 is a photograph of a core of a bismaleimide foam prepared by a conventional chemical foaming process.
Referring to fig. 2, fig. 2 is a photograph of a core of bismaleimide foam made according to the present invention.
As is clear from FIGS. 1 and 2, the bismaleimide foam material prepared by the present invention has no burnt core, implosion and the like in the core part, and has the advantages of generated burnt yellow appearance and strength cracks, uniform pore diameter and good uniformity.
While the present invention has been described in detail with respect to a low density, high toughness bismaleimide foam material and method of making the same, the principles and embodiments of the present invention are described herein using specific examples, which are set forth only to facilitate an understanding of the methods of the present invention and their core concepts, including the best mode, and to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
Claims (10)
1. The bismaleimide foam material is characterized in that the density of the bismaleimide foam material is 70-300 kg/m3；
The aperture of the bismaleimide foam material is 0.2-1 mm.
2. The bismaleimide foam according to claim 1, wherein the bismaleimide foam is obtained by co-foaming a physical foaming material and a chemical foaming agent;
the bismaleimide foam material has uniform cell distribution;
the bismaleimide foam material contains a thermoplastic toughening agent;
the core of the bismaleimide foam does not have a yellow appearance resulting from internal coring and/or implosion.
3. The bismaleimide foam of claim 2 wherein the physical foaming material comprises expandable microspheres;
the chemical blowing agent comprises an organic blowing agent;
the organic foaming agent comprises an azo chemical foaming agent and/or a sulfonyl hydrazine chemical foaming agent;
the cells are of a closed cell structure;
the bismaleimide foam material comprises a bismaleimide rigid foam material.
4. The bismaleimide foam of claim 2, wherein the chemical blowing agent comprises one or more of azoisobutyronitrile formamide, azodicarbonamide, azodiisobutyronitrile, and 2, 4-xylene disulfonyl hydrazide;
the mass ratio of the physical foaming material to the chemical foaming agent is (2-10): (0.1-2);
the bismaleimide foam material is low-density high-toughness bismaleimide foam;
the bismaleimide foam material is a thermosetting foam material;
the compression strength of the bismaleimide foam material is 1.5-8 Mpa.
5. The bismaleimide foam material is characterized by comprising the following raw materials in parts by weight
6. The bismaleimide foam according to claim 5 wherein the bismaleimide resin comprises one or more of N, N '- (4, 4-methylenediphenyl) bismaleimide, 2' -bis [4- (4-maleimidophenoxy) phenyl ] propane, and bis (3-ethyl-5-methyl-4-maleimidophenyl) methane;
the allylate is one or more of allyl bisphenol A, diallyl ether, diallylamine and diallyl disulfide;
the physically foamable material comprises expandable microspheres;
the chemical foaming agent comprises one or more of 4,4' -oxo-bis-benzenesulfonyl hydrazide, azodicarbonamide, 2, 4-xylene disulfonyl hydrazide and N, N-dinitrosopentamethylenetetramine;
the thermoplastic toughening agent comprises one or more of polyaryletherketone, polyetherimide, polyphenylene sulfide and polybenzimidazole.
7. The bismaleimide foam of claim 4, wherein the physical foam comprises one or more of 920DU40, 920DU80, F230D, F190D, EHM401, and EM 304;
the thixotropic agent comprises one or more of fumed silica, organic bentonite, polyamide wax and kaolin;
the surfactant comprises AK-8877, AK-8890, B-8123, B-8002, B-2470, B-8110, L-580, L-7608 or L-627;
the inorganic filler comprises one or more of expandable graphite, expandable perlite powder and expandable vermiculite powder.
8. A method for preparing bismaleimide foam material according to any one of claims 1 to 7, comprising the steps of:
(1) reacting bismaleimide with an allyl compound to obtain a prepolymer;
(2) and mixing the prepolymer obtained in the step, a physical foaming material, a chemical foaming agent, a thermoplastic toughening agent, a thixotropic agent, a surfactant and an inorganic filler, foaming and curing in a mold, and post-curing to obtain the bismaleimide foam material.
9. The preparation method according to claim 8, wherein the reaction temperature is 130-150 ℃;
the reaction time is 1-3 hours;
the mixing mode comprises high-speed stirring;
the mixing speed is 500-2000 r/min;
the foaming and curing temperature is 130-150 ℃;
the foaming and curing time is 1-2 hours;
the mold comprises an aluminum mold.
10. The method of claim 9, wherein the post-curing comprises a three-stage step-temperature post-curing process;
the temperature of the first stage of post-curing is 160-180 ℃;
the time of the first stage of post-curing is 1-2 hours;
the temperature of the second stage of post-curing is 180-200 ℃;
the time of the second stage of post-curing is 1-2 hours;
the temperature of the third stage of post-curing is 230-250 ℃;
the time of the third stage of post-curing is 2-3 hours.
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