CN101130632A - Polyimide froth in situ filling honeycomb composite material - Google Patents
Polyimide froth in situ filling honeycomb composite material Download PDFInfo
- Publication number
- CN101130632A CN101130632A CNA2007101200467A CN200710120046A CN101130632A CN 101130632 A CN101130632 A CN 101130632A CN A2007101200467 A CNA2007101200467 A CN A2007101200467A CN 200710120046 A CN200710120046 A CN 200710120046A CN 101130632 A CN101130632 A CN 101130632A
- Authority
- CN
- China
- Prior art keywords
- composite material
- polyimide
- honeycomb
- foam
- polyimide foam
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The invention discloses a medlin foam original position filling honeycomb composite material, which is characterized by the following: comprising (1) foaming medlin forerunner body powder or micro sphere, (2) functional filling, (3) coupling agent or surface active agent and (4) honeycomb; making up 5% wt-89% wt of the total weight of the composite material with the (1); counting 0. 01% wt-70% wt of the total weight of the composite material with the (2); making up 1% wt-3% wt of the total weight of the composite material with the (3); counting 10% wt-94% wt of the total weight of the composite material with the (4). The material possesses good fire resistant, low temperature resistance and mechanics property.
Description
Technical field
The present invention relates to a kind of polyimide foam filling honeycomb composite material, specifically, relate to the polyimide froth in situ filling honeycomb composite material that a kind of functional stuffing disperses modification.
Background technology
Polyimide is a class excellent combination property, the exsertile macromolecular material of thermotolerance, all is widely used in fields such as Aeronautics and Astronautics, microelectronics, electric, liquid crystal, separatory membrane, laser.Polyimide-type materials goods kind is numerous, mainly comprises: moulding resin/part, film, fiber, prepreg/matrix material, coating, tackiness agent and soft, foam etc.
Polyimide foam has excellent flame-retardant performance, and anti-naked light is not fuming, and does not produce obnoxious flavour; Light weight; Flexibility and rebound resilience preferably; Be easy to install, safeguard; High-and low-temperature resistance; Environmental friendliness, not halogen-containing and consume advantage such as ozone material, therefore obtained using widely.
The polyimide foam preparation methods is more, U.S. Pat 3249561, US3483144, US4305796, US4439381, US4822537, US4900761, US507183, US5122546, US5298531, European patent EP 0376592, Chinese patent CN1528808A etc. have reported that some prepare the method for polyimide foam material, comprise solution foaming method, foam melt method, microwave foaming, presoma microballoon foaming.
Commercial polyimide foam product is less, and has only a few countries to have the ability of producing polyimide foam.Be mainly the Solimide that U.S. Ethyl company produces
The Sordal that polyimide foam, NASA authorize
The TEEK of Rexfoam series product, U.S. NASA exploitation
TMThe series polyimide foam, this foam mainly uses for NASA.In addition, the Rohacell polymethacrylimide foam that also has German R hm company to produce.Wherein, the life-time service temperature is flexibility or semi-rigid foam material greater than 200 ℃ polyimide foam, can't directly use as structured material, [PolymerComposite such as Yudin, 1999,20 (3): 337] reported and utilize fibrefelt to strengthen polyimide foam, foam compression intensity can be improved nearly 50 times, but density has also increased by tens times.
U.S. Pat 5011551 has been reported a kind of by adding the method for inorganic particulate raising foam flame retardant properties, this method is that the polyimide foam with perforate is immersed in the suspension liquid or gel of inorganic particulate, make foamy soak full liquid in the air, remove unnecessary gel then, the oven dry foam, inorganic particulate is stayed in the foamy hole, thereby improved its flame retardant properties.But this method only is suitable for the bulk polyimide foam of perforate, is not suitable for the polyimide foam filling honeycomb composite material.
For solving the insufficient problem of polyimide foam mechanical strength, European patent EP 0514623A2 has reported a kind of method of polyimide foam filled honeycomb, be about to the polyimide foam precursor powder and be filled in the honeycomb, foamable forms foam-filled honeycomb sheet material then.This method is a polyimide foam precursor powder filled honeycomb.U.S. Pat 5188879 has been reported a kind of polyimide foam filled honeycomb structure, with the Procuring of polyimide foam precursor powder, become a kind of easy to handle rigid state, then honeycomb is pressed into wherein, reheat solidify to form foam-filled honeycomb sheet material.This method has been improved the manufacturing process of polyimide foam filled honeycomb material to a certain extent.These two patented methods only are filled into simple polyimide foam in the honeycomb, fire-retardant, heat insulation, damping, noise reduction and performance such as stealthy often can not satisfy many application request, therefore, the present invention develops a kind of polyimide foam filling honeycomb composite material that has good mechanical properties and have good function (inhaling ripple, fire-retardant, noise reduction etc.) simultaneously.
Summary of the invention
The purpose of this invention is to provide the polyimide froth in situ filling honeycomb composite material that a kind of functional stuffing disperses modification, promptly by filling the difference in functionality particle, cooperate with the cellular material of different size and material, the collaborative mechanical property that improves the polyimide foam filling honeycomb composite material, and give that it is fire-retardant, heat insulation, damping, noise reduction and inhale function such as ripple.Therefore, great advantage of the present invention is and can by selecting difference in functionality particle and mass content, cellular composite material be designed, thereby give various function of cellular composite material and mechanical property according to using needs.Specific as follows:
The polyimide foam filling honeycomb composite material is usually used in various weaponrys, and modern war requires various weaponrys to have good radar invisible performance, therefore gives the stealthy performance that its wave-sucking performance helps to improve weaponry.In addition, the polyimide foam filling honeycomb composite material also can be used for inhaling the ripple darkroom.Therefore, the present invention cooperates metal beehive, ceramic honeycomb and glass or fibre reinforced resin honeycomb with polyimide foam, and by in polyimide foam, adding wave absorbing agent, as the cenosphere and the various composite wave-absorbing agent of carbon black, carbon nanotube, carbon fiber, silicon carbide fiber, silicon carbide/carbon fiber, polycrystalline iron fiber, metal oxide, surface metalation, give the matrix material absorbing property.
Polyimide foam itself has heat-proof quality preferably, can be used as light heat insulation layer, but also needs further raising in some its flame retardant propertiess of special application scenario.Therefore, the present invention cooperates ceramic honeycomb and glass-fibre reinforced resin honeycomb with polyimide foam, and by in polyimide foam, adding not halogen-containing fire retardant, as aluminium hydroxide, magnesium hydroxide, antimonous oxide, wollastonite, polynite, kaolin, mica, porous mineral dust (float stone, expanded vermiculite, perlite etc.), silicon-dioxide, quartz sand, lime carbonate, talcum powder and composition thereof, prepare matrix material with good flame-retardance energy.
In addition, the polyimide foam filling honeycomb composite material also can be used for building, equipment room, tank cabin, the sound insulation of Naval Vessels Cabin, damping, noise reduction layer.The present invention if you would take off soil, kaolin, mica, terra alba, glass microballon etc. by add flaky inorganic filler and tiny balloon in polyimide foam, further improves the damping performance of matrix material.
Modified polyimides foam original position filling honeycomb composite material provided by the invention is formed and is comprised:
(1) foamable polyimide precursor powder or microballoon;
(2) functional stuffing;
(3) coupling agent or tensio-active agent;
(4) cellular material.
The porous material that cellular material is meant the successive wallboard that is formed by materials such as metal, pottery, fiber-reinforced resins and the cross section is triangular in shape, the hole of tetragon, pentagon, hexagon, circle and irregular polygon is formed, its apparent density is 0.02～0.2g/cm
3
Wherein, (1) foamable polyimide precursor powder or microballoon account for the 5%wt～89%wt of matrix material total mass, are preferably 15%wt～70%wt, more preferably 30%wt～60%wt; (2) functional stuffing accounts for the 0.01%wt～70%wt of matrix material total mass, is preferably 0.3%wt～50%wt, more preferably 1%wt～30%wt; (3) coupling agent accounts for the 3%wt of matrix material total mass at most; (4) honeycomb accounts for the 10%wt～94%wt of matrix material total mass, is preferably 25%wt～80%wt, more preferably 30%wt～60%wt.
Described foamable polyimide precursor powder or microballoon are meant the material of the formation polyimide foam that can foam or bond under certain condition, generally prepare by aromatic series dianhydride or derivatives thereof A, aromatic diamine B and end-capping reagent C, the mol ratio of A, B and C comprises 1: (0.5～2): (0～2.0), be preferably 1: (0.75～1.5): (0～1.0), more preferably 1: (0.9～1.1): (0～0.2);
Wherein, the A component comprises: 3,3 ', 4,4 '-phenyl ether tetracarboxylic dianhydride (ODPA), 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (s-BTDA), 2,3 ', 3,4 '-benzophenone tetracarboxylic dianhydride (a-BTDA), bisphenol A-type phenyl ether dianhydride (BPADA), 3,3 ', 4,4 '-BPDA (s-BPDA), 2,3 ', 3,4 '-BPDA (a-BPDA), 1,2,4,5-pyromellitic acid dianhydride (PMDA), 3,3 ', 4,4 '-phenyl ether tetracid, 3,3 ', 4,4 '-phenyl ether, two acid diesters, 3,3 ', 4,4 '-benzophenone tetracid, 3,3 ', 4,4 '-benzophenone, two acid diesters, 2,3 ', 3,4 '-benzophenone tetracid, 2,3 ', 3,4 '-benzophenone, two acid diesters, bisphenol A-type phenyl ether tetracid, bisphenol A-type phenyl ether two acid diesters, 3,3 ', 4,4 '-biphenyl tetracid, 3,3 ', 4,4 '-biphenyl acid diester, 2,3 ', 3,4 '-biphenyl tetracid, 2,3 ', 3,4 '-biphenyl acid diester, 1,2,4, the 5-pyromellitic acid, 1,2,4, the equal phthalic acid diester of 5-or its mixture.
The B component comprises: 3,4 '-diaminodiphenyl oxide (3,4 '-ODA), 4,4 '-diaminodiphenyl oxide (4,4 '-ODA), 4,4 '-diaminobenzophenone (4,4 '-DABP), 3,4 '-diaminobenzophenone (3,4 '-DABP), 3,3 '-diaminobenzophenone (3,3 '-DABP), dihydroxyphenyl propane phenyl ether diamines (BAPP) or its mixture.
The C component comprises: adjacent benzene tetracarboxylic acid acid anhydride, 4-ethynyl phthalic anhydride, phenylacetylene phthalic anhydride, aniline, 3-ethynyl aniline, 4-ethynyl aniline, phenylacetylene aniline, N-(β-aminoethyl)-γ-aminopropyl methyl dimethoxysilane, N-(β-aminoethyl)-γ-An Bingjisanyiyangjiguiwan, N-(β-aminoethyl)-γ-An Bingjisanjiayangjiguiwan, γ-An Bingjisanyiyangjiguiwan, γ-An Bingjisanjiayangjiguiwan or γ-aminopropyl methyl dimethoxysilane or its mixture.
Described functional stuffing comprises: inhale in the cenosphere etc. that the ripple filler is selected from carbon black, carbon nanotube, carbon fiber, silicon carbide fiber, silicon carbide/carbon fiber (conjugated fibre of silicon carbide and carbon), polycrystalline iron fiber, metal oxide, surface metalation one or more; Fire-retardant filler is selected from one or more in aluminium hydroxide, magnesium hydroxide, antimonous oxide, wollastonite, polynite, kaolin, mica, porous mineral dust (float stone, expanded vermiculite, perlite etc.), silicon-dioxide, quartz sand, lime carbonate, the talcum powder etc.; The noise reduction filler is selected from one or more in polynite, kaolin, mica, terra alba, the glass microballon etc.
Described functional stuffing, its surface are through one or more modifications in the titanate coupling agent, silane coupling agent, acrylic acid or the like coupling agent, polymethyl siloxane, polydimethylsiloxane, polyether-modified polysiloxane, vinyl polysiloxane etc.
Described cellular material comprises: metal beehive, ceramic honeycomb, spin the honeycomb of wheel honeycomb, phenolic aldehyde honeycomb, quartzy honeycomb and various fiber-reinforced resins; The honeycomb hole shape comprises: hexagon, circle, trilateral, tetragon and irregular polygon; The honeycomb hole area of section is 10mm
3～5000mm
3
Modified polyimides foam original position filling honeycomb composite material provided by the invention can be by being prepared as follows step:
(1) aromatic series dianhydride or derivatives thereof or the mixture of the two, aromatic diamine and end-capping reagent reacted in appropriate solvent 2 hours～24 hours, prepare the polyimide foam precursor solution, described solvent is selected from tetrahydrofuran (THF), methyl alcohol, ethanol, n-propyl alcohol, Virahol and composition thereof;
(2) functional stuffing is evenly spread in the described polyimide foam precursor solution;
(3) polyimide precursor solution with modification heats (35 ℃～100 ℃), remove most of small molecules volatile matter, obtain precursor powder, because of still containing a small amount of solvent in the precursor powder with hydrogen bonded, when heating once more, small molecules and bonded solvent are emitted in presoma generation ring-closure reaction, thereby cause the presoma foaming;
(4) described precursor powder is heated at 100 ℃～180 ℃, pre-frothing obtains polyimide foam presoma microballoon;
(5) polyimide precursor powder or microballoon evenly are filled in the hole of cellular material, form rigid particles modified polyimides foam original position filled honeycomb material at 250 ℃～400 ℃ imidizations.
Described functional stuffing makes by described coupling agent surface modification.
Advantage of the present invention has:
1) polyimide foam presoma preparation technology is simple.
2) foam foam in place in honeycomb hole combines well with honeycomb.
3) functional stuffing kind and content can be controlled flexibly, can design cellular composite material as required, thereby give the foam-filled honeycomb matrix material different functions.
4) cellular material lightweight, compressive property are given prominence to, under the prerequisite that does not improve the matrix material global density, can effectively improve the intensity of matrix material, also can improve the structural integrity and the non-deformability of foam materials, thereby realize the incorporate target of 26S Proteasome Structure and Function of matrix material; The kind and the matrix material of honeycomb mate mutually, in having the matrix material of inhaling wave energy, cellular material itself just can be with the material preparation with absorbing property, and in having the matrix material of anti-flaming function, cellular material itself just can be with the material preparation with absorbing property.
Filling honeycomb composite material of the present invention can be used in aircraft, aircraft, weaponry, submarine, naval vessel, automobile, radar, building, microwave unreflected chamber or the senior sports goods.For example: the heat insulation noise reduction layer of the corridor of aircraft, luggage carrier, top ceiling etc., the fireproof and explosion suppression layer of fuel tanker, the nose cone of launch vehicle, space shuttle surface low-temperature district thermal insulation layer, the housing of heat insulation on naval vessel, the submarine, noise reduction, heat insulation, noise reduction matrix material on panzer, the bullet train, and high-grade physical culture is with heat insulation, the noise reduction of the helmet, shakeproof layer etc.
Embodiment
Present invention is described by the following examples; and only be applicable to and further specify of the present invention; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can do some nonessential improvement and adjustment to the present invention according to the invention described above content.
Embodiment 1
In being furnished with three neck round-bottomed flasks of agitator, add 400 grams 4,4 '-ODA, in the mixed solvent of 2400 gram tetrahydrofuran (THF)s and 800 gram methyl alcohol, stirring is all dissolved solid, adds 620 gram ODPA then, 30 ℃ were stirred 12 hours, add 20 gram carbon nanotubes again, continue to stir 3～5 hours, this solution is pulverized after 18 hours 70 ℃ of oven dry is the polyimide foam precursor powder.
Utilize 80 order stainless steel meshs that 300 these powder of gram evenly are filled into a hexagonal side length and be 10mm, be of a size of in the hole of quartzy honeycomb of 500mm * 500mm * 10mm, the honeycomb bottom is lined with a graphite flat board, at honeycomb loam cake lastblock graphite flat board, put into high temperature oven then, heat 1 hour, 300 ℃ heating of 1 hour, 250 ℃ heating 1 hour down at 140 ℃, cooling promptly gets carbon nano-tube modification polyimide foam filling honeycomb composite material afterwards.
Embodiment 2
Earlier polyimide foam precursor powder 300 grams that obtain among the embodiment 1 are become microballoon 140 ℃ of pre-frothing, then microballoon evenly is filled up in the quartzy honeycomb identical with embodiment 1, the honeycomb bottom is lined with a graphite flat board, at honeycomb loam cake lastblock graphite flat board, put into high temperature oven then, heat 1 hour, 300 ℃ heating 1 hour down at 250 ℃, cooling promptly gets carbon nano-tube modification polyimide foam filling honeycomb composite material afterwards.
Embodiment 3
In being furnished with three neck round-bottomed flasks of agitator, add 200 grams 4,4 '-ODA, in the mixed solvent of 1200 gram tetrahydrofuran (THF)s and 400 gram methyl alcohol, stirring is all dissolved solid, adds 310 gram ODPA then, 30 ℃ were stirred 12 hours, this solution is pulverized after 18 hours 70 ℃ of oven dry, with 10 gram carbon nanotubes and the precursor powder thorough mixing that obtains, obtain the polyimide foam precursor powder again.All the other are with embodiment 1.
Embodiment 4
Spin the wheel honeycomb with what the quartzy honeycomb among the embodiment 1 changed same size into, other is with embodiment 1.
Embodiment 5
Change the 20g carbon nanotube among the embodiment 1 into the 100g polycrystalline iron fiber, other is with embodiment 1.
Embodiment 6
Change the 20g carbon nanotube among the embodiment 1 into the 200g polycrystalline iron fiber, other is with embodiment 1.
Embodiment 7
In being furnished with three neck round-bottomed flasks of agitator, add 400 grams 4,4 '-ODA, in the mixed solvent of 2400 gram tetrahydrofuran (THF)s and 800 gram methyl alcohol, stirring is all dissolved solid, add 620 gram ODPA then, 30 ℃ were stirred 12 hours, added 2 gram KH550 coupling agents again, added 98 gram magnesium hydroxides after stirring again, continue to stir 3 hours～5 hours, this solution is pulverized after 18 hours 70 ℃ of oven dry is the polyimide foam precursor powder.
Other is with embodiment 1.
Embodiment 8
Change the magnesium hydroxide among the embodiment 5 into organo montmorillonite, other is with embodiment 7.
Embodiment 9
In being furnished with three neck round-bottomed flasks of agitator, add 200 grams 3,4 '-ODA, in the mixed solvent of 1200 gram tetrahydrofuran (THF)s and 400 gram methyl alcohol, stirring is all dissolved solid, adds 310 gram ODPA then, 30 ℃ were stirred 12 hours, add 20 gram carbon nanotubes again, continue to stir 3 hours～5 hours, this solution is pulverized after 18 hours 70 ℃ of oven dry is the polyimide foam precursor powder.
Polyimide foam precursor powder 300 grams that obtain are become microballoon 140 ℃ of pre-frothing, then microballoon evenly is filled up in the identical aluminium honeycomb of a size and embodiment 1, the honeycomb bottom is lined with a graphite flat board, at honeycomb loam cake lastblock graphite flat board, put into high temperature oven then, heat 1 hour, 300 ℃ heating 1 hour down at 250 ℃, cooling promptly gets carbon nano-tube modification polyimide foam filling honeycomb composite material afterwards.
Embodiment 10
In being furnished with three neck round-bottomed flasks of agitator, add 200 grams 3,4 '-ODA, in the mixed solvent of 1200 gram tetrahydrofuran (THF)s and 400 gram methyl alcohol, stirring is all dissolved solid, adds 322 gram BTDA then, 30 ℃ were stirred 12 hours, add 20 gram carbon nanotubes again, continue to stir 3 hours～5 hours, this solution is pulverized after 18 hours 70 ℃ of oven dry is the polyimide foam precursor powder.
Other is with embodiment 9.
Embodiment 11
In being furnished with three neck round-bottomed flasks of agitator, add 200 grams 4,4 '-ODA, in the mixed solvent of 1200 gram tetrahydrofuran (THF)s and 400 gram methyl alcohol, stirring is all dissolved solid, add 322 gram BTDA then, 30 ℃ were stirred 12 hours, added 20 gram carbon nanotubes again, continued to stir 3 hours～5 hours, with this solution 70 ℃ the oven dry 18 hours after, pulverizing is the polyimide foam precursor powder.
Other is with embodiment 9.
Embodiment 12
In being furnished with three neck round-bottomed flasks of agitator, add 200 grams 4,4 '-ODA, in the mixed solvent of 1200 gram tetrahydrofuran (THF)s and 400 gram methyl alcohol, stirring is all dissolved solid, add 290 gram ODPA and 22 gram PMDA then, 30 ℃ were stirred 12 hours, added 20 gram carbon nanotubes again, continued to stir 3 hours～5 hours, with this solution 70 ℃ the oven dry 18 hours after, pulverizing is the polyimide foam precursor powder.
Other is with embodiment 9.
Comparative example 1
In being furnished with three neck round-bottomed flasks of agitator, add 400 grams 4,4 '-ODA, in the mixed solvent of 2400 gram tetrahydrofuran (THF)s and 800 gram methyl alcohol, stirring is all dissolved solid, add 620 gram ODPA then, 30 ℃ were stirred 12 hours, and this solution is pulverized after 18 hours 70 ℃ of oven dry is the polyimide foam precursor powder.
Other is with embodiment 1.
Comparative example 2
In being furnished with three neck round-bottomed flasks of agitator, add 200 grams 3,4 '-ODA, in the mixed solvent of 1200 gram tetrahydrofuran (THF)s and 400 gram methyl alcohol, stirring is all dissolved solid, add 310 gram ODPA then, 30 ℃ were stirred 12 hours, and this solution is pulverized after 18 hours 70 ℃ of oven dry is the polyimide foam precursor powder.
Other is with embodiment 9.
Density, second-order transition temperature and compressive strength by above-mentioned example 1 to embodiment 12 and comparative example 1 to 2 gained polyimide froth in situ filling honeycomb composite material are illustrated in the table 1.
Table 1 preparation polysiloxane acid imide foam material mixture ratio and multicellular glass transition temperature
| Example/sample number | Main component | Density/gcm -3 | Glass transition temperature Tg/℃ | Compressive strength/MPa |
| 1 | Quartzy honeycomb/4,4 '-ODA-ODPA/ carbon nanotube | 0.108 | 284 | 4.0 |
| 2 | Quartzy honeycomb/4,4 '-ODA-ODPA/ carbon nanotube | 0.120 | 285 | 4.3 |
| 3 | Quartzy honeycomb/4,4 '-ODA-ODPA/ carbon nanotube | 0.112 | 285 | 3.9 |
| 4 | Spin wheel honeycomb/4,4 '-ODA-ODPA/ carbon nanotube | 0.098 | 284 | 3.4 |
| 5 | Quartzy honeycomb/4,4 '-ODA-ODPA/ polycrystalline iron fiber | 0.118 | 286 | 4.4 |
| 6 | Quartzy honeycomb/4,4 '-ODA-ODPA/ polycrystalline iron fiber | 0.127 | 290 | 4.5 |
| 7 | Quartzy honeycomb/4,4 '-ODA-ODPA/ magnesium hydroxide | 0.110 | 288 | 4.1 |
| 8 | Quartzy honeycomb/4,4 '-ODA-ODPA/ organo montmorillonite | 0.108 | 291 | 4.2 |
| 9 | Aluminium honeycomb/3,4 '-ODA-ODPA/ glass microballon | 0.088 | 258 | 2.0 |
| 10 | Aluminium honeycomb/3,4 '-ODA-BTDA/ glass microballon | 0.092 | 272 | 2.1 |
| 11 | Aluminium honeycomb/4,4 '-ODA-BTDA/ organo montmorillonite | 0.092 | 315 | 2.1 |
| 12 | Aluminium honeycomb/4,4 '-ODA-ODPA-PMDA/ organo montmorillonite | 0.094 | 318 | 2.0 |
| Comparative example 1 | Quartzy honeycomb/4,4 '-ODA-ODPA | 0.101 | 278 | 3.8 |
| Comparative example 2 | Aluminium honeycomb/3,4 '-ODA-ODPA | 0.083 | 250 | 1.9 |
In 8GHz～18GHz scope, the reflection of electromagnetic wave rate of embodiment 1～6 is all less than the reflectivity of the comparative example 1 that does not add functional stuffing, and reflectivity reduces 4GHz～20dB, interpolation wave absorbtion filler be described after, the absorbing property of matrix material obviously improves; The limiting oxygen index(LOI) of embodiment 7～8 improves 8%～23% than the limiting oxygen index(LOI) of the comparative example 1 that does not add functional stuffing, the interpolation flame retardant filler be described after, the flame retardant properties of matrix material obviously improves; The sound wave transmitance of embodiment 9～12 is all less than the transmitance of the comparative example 2 that does not add functional stuffing, and transmitance reduces 3GHz～12dB, interpolation noise reduction filler be described after, the damping noise reduction performance of matrix material obviously improves.
Claims (8)
1. polyimide froth in situ filling honeycomb composite material, it is characterized in that: be filled with the polyimide foam that functional stuffing disperses modification in the honeycomb hole of described matrix material, described functional stuffing can give described matrix material different functions, described modified polyimides foam foam in place in honeycomb hole.
2. filling honeycomb composite material as claimed in claim 1 is characterized in that: foamable polyimide precursor powder or microballoon account for the 5%wt～89%wt of matrix material total mass; Functional stuffing accounts for the 0.01%wt～70%wt of matrix material total mass; Coupling agent accounts for 0～3%wt of matrix material total mass; Honeycomb accounts for 10%～94%wt of matrix material total mass.
3. as the described filling honeycomb composite material of claim 1～2, it is characterized in that: described functional stuffing is selected from inhales ripple filler, fire-retardant filler or noise reduction filler.
4. as the described filling honeycomb composite material of claim 1～3, it is characterized in that: inhale in the cenosphere etc. that the ripple filler is selected from carbon black, carbon nanotube, carbon fiber, silicon carbide fiber, silicon carbide/carbon fiber, polycrystalline iron fiber, metal oxide, surface metalation one or more; Fire-retardant filler is selected from one or more in aluminium hydroxide, magnesium hydroxide, antimonous oxide, wollastonite, polynite, kaolin, mica, porous mineral dust, silicon-dioxide, quartz sand, lime carbonate, the talcum powder etc.; The noise reduction filler is selected from one or more in polynite, kaolin, mica, terra alba, the glass microballon etc., and is to carry out surface-treated through coupling agent.
5. as each described filling honeycomb composite material in the claim 1～2, it is characterized in that: described polyimide is by aromatic series dianhydride or derivatives thereof A, aromatic diamine B and end-capping reagent C preparation, wherein the A component is selected from: 3,3 ', 4,4 '-phenyl ether tetracarboxylic dianhydride (ODPA), 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (s-BTDA), 2,3 ', 3,4 '-benzophenone tetracarboxylic dianhydride (a-BTDA), bisphenol A-type phenyl ether dianhydride (BPADA), 3,3 ', 4,4 '-BPDA (s-BPDA), 2,3 ', 3,4 '-BPDA (a-BPDA), 1,2,4,5-pyromellitic acid dianhydride (PMDA), 3,3 ', 4,4 '-phenyl ether tetracid, 3,3 ', 4,4 '-phenyl ether, two acid diesters, 3,3 ', 4,4 '-benzophenone tetracid, 3,3 ', 4,4 '-benzophenone, two acid diesters, 2,3 ', 3,4 '-benzophenone tetracid, 2,3 ', 3,4 '-benzophenone, two acid diesters, bisphenol A-type phenyl ether tetracid, bisphenol A-type phenyl ether two acid diesters, 3,3 ', 4,4 '-biphenyl tetracid, 3,3 ', 4,4 '-biphenyl acid diester, 2,3 ', 3,4 '-biphenyl tetracid, 2,3 ', 3,4 '-biphenyl acid diester, 1,2,4, the 5-pyromellitic acid, 1,2,4, the equal phthalic acid diester of 5-or its mixture; Described B component is selected from: 3,4 '-diaminodiphenyl oxide (3,4 '-ODA), 4,4 '-diaminodiphenyl oxide (4,4 ' ODA), 4,4 '-diaminobenzophenone (4,4 '-DABP), 3,4 '-diaminobenzophenone (3,4 '-DABP), 3,3 '-diaminobenzophenone (3,3 '-DABP), dihydroxyphenyl propane phenyl ether diamines (BAPP) or its mixture; Described C component is selected from: adjacent benzene tetracarboxylic acid acid anhydride, 4-ethynyl phthalic anhydride, the phenylacetylene phthalic anhydride, aniline, 3-ethynyl aniline, 4-ethynyl aniline, phenylacetylene aniline, N-(β-aminoethyl)-γ-aminopropyl methyl dimethoxysilane, N-(β-aminoethyl)-γ-An Bingjisanyiyangjiguiwan, N-(β-aminoethyl)-γ-An Bingjisanjiayangjiguiwan, γ-An Bingjisanyiyangjiguiwan, γ-An Bingjisanjiayangjiguiwan or γ-aminopropyl methyl dimethoxysilane or its mixture.
6. as each described filling honeycomb composite material in the claim 1～4, it is characterized in that: described coupling agent is selected from one or more in titanate coupling agent, silane coupling agent, acrylic acid or the like coupling agent, polymethyl siloxane, polydimethylsiloxane, polyether-modified polysiloxane, the vinyl polysiloxane etc.
7. the preparation method of filling honeycomb composite material as claimed in claim 1 is characterized in that: comprise the steps:
(1) aromatic series dianhydride or derivatives thereof or the mixture of the two, aromatic diamine and end-capping reagent were reacted in solvent 2 hours～24 hours, prepare the polyimide foam precursor solution;
(2) functional stuffing is evenly spread in above-mentioned (1) described polyimide foam precursor solution, make the polyimide foam compound precursor liquid solution that functional stuffing disperses modification;
(3) with the modified polyimides foam compound precursor liquid solution described in above-mentioned (2) at 35 ℃～100 ℃ internal heating, remove most of small molecules volatile matter, obtain the polyimide foam composite precursor powder that functional stuffing disperses modification;
(4) with the precursor powder described in above-mentioned (3) at 100 ℃～180 ℃ internal heating, pre-frothing obtains the polyimide foam presoma microballoon that functional stuffing disperses modification;
(5) functional stuffing described in above-mentioned (3) is disperseed the polyimide foam composite precursor powder of modification or the functional stuffing described in above-mentioned (4) disperse the quality such as polyimide foam presoma microballoon of modification to be filled in each honeycomb hole, disperse the polyimide froth in situ filling honeycomb composite material of modification at 250 ℃～400 ℃ lactim formation functional particles.
8. as each described filling honeycomb composite material being applied in aircraft, aircraft, weaponry, submarine, naval vessel, automobile, radar, building, microwave unreflected chamber or senior sports goods of claim 1～7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007101200467A CN101130632A (en) | 2007-08-08 | 2007-08-08 | Polyimide froth in situ filling honeycomb composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007101200467A CN101130632A (en) | 2007-08-08 | 2007-08-08 | Polyimide froth in situ filling honeycomb composite material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101130632A true CN101130632A (en) | 2008-02-27 |
Family
ID=39128045
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007101200467A Pending CN101130632A (en) | 2007-08-08 | 2007-08-08 | Polyimide froth in situ filling honeycomb composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101130632A (en) |
Cited By (36)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101787290A (en) * | 2010-02-11 | 2010-07-28 | 东华大学 | Method for preparing polyimide intercalated grafted magnesium hydroxide flame retardant |
| CN102061003A (en) * | 2010-11-25 | 2011-05-18 | 中国科学院长春应用化学研究所 | Preparation method of fiber reinforced polyimide foam composite material |
| CN102391830A (en) * | 2011-08-09 | 2012-03-28 | 中国科学院宁波材料技术与工程研究所 | Application of ferrite-carbon nano-tube composite material used as wave-absorbing material at low temperature |
| CN102675688A (en) * | 2011-03-09 | 2012-09-19 | 汉达精密电子(昆山)有限公司 | Inorganic reaction type flame retardant |
| CN103087347A (en) * | 2013-01-24 | 2013-05-08 | 北京市射线应用研究中心 | Polyimide composite wave absorbing foam material and preparation method thereof |
| CN103131182A (en) * | 2013-02-05 | 2013-06-05 | 焦作市天益科技有限公司 | Raw material composition of high-temperature-resistant polyimide resin heat-insulating plate |
| CN103347379A (en) * | 2013-07-10 | 2013-10-09 | 南京洛普电子工程研究所 | Fire-retardant type wide-frequency-band high-power compound wave-absorbing material and preparing method thereof |
| CN104804190A (en) * | 2015-04-30 | 2015-07-29 | 哈尔滨工程大学 | Flame-retardant polyimide foam material comprising honeycomb core space structure, and preparation method |
| CN104910380A (en) * | 2015-06-02 | 2015-09-16 | 哈尔滨工程大学 | Preparation method of honeycomb-reinforced polyimide foam composite material |
| CN105017769A (en) * | 2014-04-21 | 2015-11-04 | 中国科学院化学研究所 | Cellular reinforcement thermosetting hard closed-cell polyimide foam composite material as well as preparation method and application thereof |
| CN105369694A (en) * | 2015-09-29 | 2016-03-02 | 长春高琦聚酰亚胺材料有限公司 | Full-polyimide foam honeycomb and manufacturing method thereof |
| CN105437683A (en) * | 2014-08-19 | 2016-03-30 | 株洲时代新材料科技股份有限公司 | Flame-retardant lightweight structure core and preparation method thereof |
| CN106245076A (en) * | 2016-08-25 | 2016-12-21 | 山东清大银光金属海绵新材料有限责任公司 | The preparation of double whisker reinforcement sponge structure type nickel cobalt molybdenum evanohm high temperature energy-absorbing materials |
| CN106999907A (en) * | 2014-08-11 | 2017-08-01 | 康宁股份有限公司 | The method of honeycomb ceramics of the manufacture with the passage containing porous adsorbent |
| CN105783599B (en) * | 2016-05-17 | 2017-08-25 | 长沙达菲新材料科技有限公司 | A kind of stealthy armour of lightweight and preparation method thereof |
| CN107286594A (en) * | 2016-03-31 | 2017-10-24 | 深圳光启高等理工研究院 | Absorbing material and preparation method thereof |
| WO2018076772A1 (en) * | 2016-10-28 | 2018-05-03 | 深圳光启高等理工研究院 | Antenna housing, antenna structure and antenna system |
| CN108059729A (en) * | 2017-12-14 | 2018-05-22 | 中航复材（北京）科技有限公司 | A kind of heat-preservation and sound-absorption honeycomb and preparation method thereof |
| CN108164741A (en) * | 2017-12-12 | 2018-06-15 | 湖北航天化学技术研究所 | A kind of silicon substrate heat-insulating material of aramid fiber Honeycomb and preparation method thereof |
| CN108308777A (en) * | 2018-04-20 | 2018-07-24 | 智均安（苏州）科技有限公司 | Control temperature intelligent safety cap |
| CN108749229A (en) * | 2018-04-23 | 2018-11-06 | 西北工业大学 | A kind of sandwich structure Wave suction composite material and preparation method |
| CN109438703A (en) * | 2018-11-05 | 2019-03-08 | 株洲时代新材料科技股份有限公司 | Black polyamide microballoon and preparation method thereof and preparation method containing its film |
| CN109553905A (en) * | 2018-11-24 | 2019-04-02 | 浙江中科恒泰新材料科技有限公司 | A kind of preparation method of the polymethacrylimide foam composite material of enhancing |
| CN109955565A (en) * | 2017-12-14 | 2019-07-02 | 广州金发碳纤维新材料发展有限公司 | A kind of high-temperature-resistant thermoplastic honeycomb board |
| CN110039841A (en) * | 2018-01-15 | 2019-07-23 | 哈尔滨工业大学 | A kind of preparation method of the honeycomb sandwich structure Wave suction composite material of bowknot shape Co/C nano wave-absorbing material filling |
| CN110917865A (en) * | 2019-12-02 | 2020-03-27 | 北京工业大学 | PDMS plate-shaped filler and preparation method thereof |
| CN111721649A (en) * | 2020-06-29 | 2020-09-29 | 哈尔滨工程大学 | Method for testing compression resistance and peel strength of polyimide foam in honeycomb core material |
| CN112126116A (en) * | 2020-08-24 | 2020-12-25 | 航天特种材料及工艺技术研究所 | Wave-absorbing polyurethane sponge/hard foam composite material and preparation method thereof |
| CN112126114A (en) * | 2020-08-24 | 2020-12-25 | 航天特种材料及工艺技术研究所 | Wave-absorbing honeycomb/hard foam composite material and preparation method thereof |
| CN112679955A (en) * | 2020-12-29 | 2021-04-20 | 江苏中科聚合新材料产业技术研究院有限公司 | Low-temperature-resistant polyimide foam material, and preparation method and application thereof |
| CN112745502A (en) * | 2020-12-29 | 2021-05-04 | 江苏中科聚合新材料产业技术研究院有限公司 | Flame-retardant wave-absorbing polyimide foam material and preparation method and application thereof |
| CN112812561A (en) * | 2021-03-08 | 2021-05-18 | 辽宁省海洋水产科学研究院 | Preparation method of detachable floating layer material for fish sperm freezing liquid nitrogen fumigation frame |
| CN112880482A (en) * | 2021-01-26 | 2021-06-01 | 中国人民解放军陆军工程大学 | Military shelter plate and manufacturing method thereof |
| CN113185747A (en) * | 2021-05-11 | 2021-07-30 | 贵州航天天马机电科技有限公司 | Preparation method of hard polyimide foam material |
| CN115011121A (en) * | 2022-07-28 | 2022-09-06 | 青岛海洋新材料科技有限公司 | Polyimide foam material for sound absorption and preparation method thereof |
| CN115322430A (en) * | 2022-07-25 | 2022-11-11 | 成都飞机工业（集团）有限责任公司 | Wave-absorbing aerogel composite material and preparation method thereof |
-
2007
- 2007-08-08 CN CNA2007101200467A patent/CN101130632A/en active Pending
Cited By (49)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101787290B (en) * | 2010-02-11 | 2013-02-06 | 东华大学 | Method for preparing polyimide intercalated grafted magnesium hydroxide flame retardant |
| CN101787290A (en) * | 2010-02-11 | 2010-07-28 | 东华大学 | Method for preparing polyimide intercalated grafted magnesium hydroxide flame retardant |
| CN102061003A (en) * | 2010-11-25 | 2011-05-18 | 中国科学院长春应用化学研究所 | Preparation method of fiber reinforced polyimide foam composite material |
| CN102675688A (en) * | 2011-03-09 | 2012-09-19 | 汉达精密电子(昆山)有限公司 | Inorganic reaction type flame retardant |
| CN102391830B (en) * | 2011-08-09 | 2014-01-29 | 中国科学院宁波材料技术与工程研究所 | Application of ferrite-carbon nano-tube composite material used as wave-absorbing material at low temperature |
| CN102391830A (en) * | 2011-08-09 | 2012-03-28 | 中国科学院宁波材料技术与工程研究所 | Application of ferrite-carbon nano-tube composite material used as wave-absorbing material at low temperature |
| CN103087347A (en) * | 2013-01-24 | 2013-05-08 | 北京市射线应用研究中心 | Polyimide composite wave absorbing foam material and preparation method thereof |
| CN103131182A (en) * | 2013-02-05 | 2013-06-05 | 焦作市天益科技有限公司 | Raw material composition of high-temperature-resistant polyimide resin heat-insulating plate |
| CN103347379A (en) * | 2013-07-10 | 2013-10-09 | 南京洛普电子工程研究所 | Fire-retardant type wide-frequency-band high-power compound wave-absorbing material and preparing method thereof |
| CN103347379B (en) * | 2013-07-10 | 2016-03-23 | 南京洛普电子工程研究所 | High power combined absorbing material of nonflammable wide-band and preparation method thereof |
| CN105017769B (en) * | 2014-04-21 | 2018-08-14 | 中国科学院化学研究所 | Honeycomb thermosetting property rigid closed cell Polyimide foam composite material and the preparation method and application thereof |
| CN105017769A (en) * | 2014-04-21 | 2015-11-04 | 中国科学院化学研究所 | Cellular reinforcement thermosetting hard closed-cell polyimide foam composite material as well as preparation method and application thereof |
| CN106999907A (en) * | 2014-08-11 | 2017-08-01 | 康宁股份有限公司 | The method of honeycomb ceramics of the manufacture with the passage containing porous adsorbent |
| CN105437683A (en) * | 2014-08-19 | 2016-03-30 | 株洲时代新材料科技股份有限公司 | Flame-retardant lightweight structure core and preparation method thereof |
| EP3184294A4 (en) * | 2014-08-19 | 2018-02-28 | Zhuzhou Times New Material Technology Co., Ltd. | Flame-retardant lightweight structural core and manufacturing method therefor |
| CN104804190A (en) * | 2015-04-30 | 2015-07-29 | 哈尔滨工程大学 | Flame-retardant polyimide foam material comprising honeycomb core space structure, and preparation method |
| CN104910380A (en) * | 2015-06-02 | 2015-09-16 | 哈尔滨工程大学 | Preparation method of honeycomb-reinforced polyimide foam composite material |
| CN105369694A (en) * | 2015-09-29 | 2016-03-02 | 长春高琦聚酰亚胺材料有限公司 | Full-polyimide foam honeycomb and manufacturing method thereof |
| CN107286594A (en) * | 2016-03-31 | 2017-10-24 | 深圳光启高等理工研究院 | Absorbing material and preparation method thereof |
| CN105783599B (en) * | 2016-05-17 | 2017-08-25 | 长沙达菲新材料科技有限公司 | A kind of stealthy armour of lightweight and preparation method thereof |
| CN106245076B (en) * | 2016-08-25 | 2018-03-02 | 山东清大银光金属海绵新材料有限责任公司 | The preparation of double whisker reinforcement sponge structure type nickel cobalt molybdenum evanohm high temperature energy-absorbing materials |
| CN106245076A (en) * | 2016-08-25 | 2016-12-21 | 山东清大银光金属海绵新材料有限责任公司 | The preparation of double whisker reinforcement sponge structure type nickel cobalt molybdenum evanohm high temperature energy-absorbing materials |
| WO2018076772A1 (en) * | 2016-10-28 | 2018-05-03 | 深圳光启高等理工研究院 | Antenna housing, antenna structure and antenna system |
| CN108164741A (en) * | 2017-12-12 | 2018-06-15 | 湖北航天化学技术研究所 | A kind of silicon substrate heat-insulating material of aramid fiber Honeycomb and preparation method thereof |
| CN108164741B (en) * | 2017-12-12 | 2021-03-26 | 湖北航天化学技术研究所 | Silicon-based heat-insulating material reinforced by aramid honeycomb and preparation method thereof |
| CN108059729A (en) * | 2017-12-14 | 2018-05-22 | 中航复材（北京）科技有限公司 | A kind of heat-preservation and sound-absorption honeycomb and preparation method thereof |
| CN109955565A (en) * | 2017-12-14 | 2019-07-02 | 广州金发碳纤维新材料发展有限公司 | A kind of high-temperature-resistant thermoplastic honeycomb board |
| CN110039841A (en) * | 2018-01-15 | 2019-07-23 | 哈尔滨工业大学 | A kind of preparation method of the honeycomb sandwich structure Wave suction composite material of bowknot shape Co/C nano wave-absorbing material filling |
| CN108308777A (en) * | 2018-04-20 | 2018-07-24 | 智均安（苏州）科技有限公司 | Control temperature intelligent safety cap |
| CN108749229A (en) * | 2018-04-23 | 2018-11-06 | 西北工业大学 | A kind of sandwich structure Wave suction composite material and preparation method |
| CN109438703A (en) * | 2018-11-05 | 2019-03-08 | 株洲时代新材料科技股份有限公司 | Black polyamide microballoon and preparation method thereof and preparation method containing its film |
| CN109553905A (en) * | 2018-11-24 | 2019-04-02 | 浙江中科恒泰新材料科技有限公司 | A kind of preparation method of the polymethacrylimide foam composite material of enhancing |
| CN110917865A (en) * | 2019-12-02 | 2020-03-27 | 北京工业大学 | PDMS plate-shaped filler and preparation method thereof |
| CN111721649A (en) * | 2020-06-29 | 2020-09-29 | 哈尔滨工程大学 | Method for testing compression resistance and peel strength of polyimide foam in honeycomb core material |
| CN111721649B (en) * | 2020-06-29 | 2022-04-22 | 哈尔滨工程大学 | Method for testing compression resistance and peel strength of polyimide foam in honeycomb core material |
| CN112126116A (en) * | 2020-08-24 | 2020-12-25 | 航天特种材料及工艺技术研究所 | Wave-absorbing polyurethane sponge/hard foam composite material and preparation method thereof |
| CN112126114A (en) * | 2020-08-24 | 2020-12-25 | 航天特种材料及工艺技术研究所 | Wave-absorbing honeycomb/hard foam composite material and preparation method thereof |
| CN112679955A (en) * | 2020-12-29 | 2021-04-20 | 江苏中科聚合新材料产业技术研究院有限公司 | Low-temperature-resistant polyimide foam material, and preparation method and application thereof |
| CN112745502A (en) * | 2020-12-29 | 2021-05-04 | 江苏中科聚合新材料产业技术研究院有限公司 | Flame-retardant wave-absorbing polyimide foam material and preparation method and application thereof |
| CN112880482A (en) * | 2021-01-26 | 2021-06-01 | 中国人民解放军陆军工程大学 | Military shelter plate and manufacturing method thereof |
| CN112880482B (en) * | 2021-01-26 | 2023-02-21 | 中国人民解放军陆军工程大学 | Military shelter plate and manufacturing method thereof |
| CN112812561B (en) * | 2021-03-08 | 2022-04-19 | 辽宁省海洋水产科学研究院 | Preparation method of detachable floating layer material for fish sperm freezing liquid nitrogen fumigation frame |
| CN112812561A (en) * | 2021-03-08 | 2021-05-18 | 辽宁省海洋水产科学研究院 | Preparation method of detachable floating layer material for fish sperm freezing liquid nitrogen fumigation frame |
| CN113185747A (en) * | 2021-05-11 | 2021-07-30 | 贵州航天天马机电科技有限公司 | Preparation method of hard polyimide foam material |
| CN113185747B (en) * | 2021-05-11 | 2022-07-05 | 贵州航天天马机电科技有限公司 | Preparation method of hard polyimide foam material |
| CN115322430A (en) * | 2022-07-25 | 2022-11-11 | 成都飞机工业（集团）有限责任公司 | Wave-absorbing aerogel composite material and preparation method thereof |
| CN115322430B (en) * | 2022-07-25 | 2023-10-03 | 成都飞机工业（集团）有限责任公司 | Wave-absorbing aerogel composite material and preparation method thereof |
| CN115011121A (en) * | 2022-07-28 | 2022-09-06 | 青岛海洋新材料科技有限公司 | Polyimide foam material for sound absorption and preparation method thereof |
| CN115011121B (en) * | 2022-07-28 | 2023-09-01 | 青岛海洋新材料科技有限公司 | Polyimide foam material for sound absorption and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101130632A (en) | Polyimide froth in situ filling honeycomb composite material | |
| EP1515796B1 (en) | Aerogel and hollow particle binder composition, insulation composite therewith, and method of preparation | |
| AU2003299511B2 (en) | Heat resistant insulation composite, and method for preparing the same | |
| EP0116759B1 (en) | Production of macro balloon structures | |
| US6084000A (en) | Hollow polyimide microspheres | |
| CN102850905B (en) | Aqueous expansion-type steel structure fireproof paint and preparation method thereof | |
| US7816428B2 (en) | Inorganic hollow particle, process for producing the same, and composition containing the same | |
| CN102942668A (en) | Preparation method for polyimide composite foamed material filled with functional filling material | |
| JP2007191711A (en) | Fire resistant coating material | |
| CN103087347B (en) | Polyimide composite wave absorbing foam material and preparation method thereof | |
| JP5358273B2 (en) | Inorganic hollow powder, its production method and its use | |
| JP4112540B2 (en) | Manufacturing method of spherical inorganic hollow powder. | |
| CN109880423A (en) | A kind of heat-insulated protective coating of novel flame-retardant and preparation method thereof | |
| CN105779806A (en) | Preparing method for foam metal composite material | |
| Zeng et al. | EMI shielding performance of phenolic-based carbon foam modified with GO/SiO2 hybrid nanomaterials | |
| JP4244323B2 (en) | Spherical inorganic hollow powder, method for producing the same, and resin composition | |
| CN109651821A (en) | A kind of organosilicon foam and preparation method thereof | |
| JP5519489B2 (en) | Method for producing inorganic hollow powder and resin composition used therefor | |
| Zhan et al. | Influences of surface area of graphene on fire protection of waterborne intumescent fire resistive coating | |
| CN107286343B (en) | A kind of Halogen composite flame-proof Polyimide foams and preparation method thereof | |
| CN113502077A (en) | Preparation method of graphene high-performance fireproof coating | |
| CN112745502A (en) | Flame-retardant wave-absorbing polyimide foam material and preparation method and application thereof | |
| CN112430013A (en) | High-molecular two-component high-temperature-resistant heat-insulating material and application thereof | |
| CN107722814A (en) | A kind of damping paint for forming multi-layer compound structure | |
| CN112940457B (en) | Flame-retardant epoxy electromagnetic shielding material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Open date: 20080227 |