CN105820571B - A kind of carbon fiber Honeycomb Polyimide foams and preparation method thereof - Google Patents
A kind of carbon fiber Honeycomb Polyimide foams and preparation method thereof Download PDFInfo
- Publication number
- CN105820571B CN105820571B CN201610305153.6A CN201610305153A CN105820571B CN 105820571 B CN105820571 B CN 105820571B CN 201610305153 A CN201610305153 A CN 201610305153A CN 105820571 B CN105820571 B CN 105820571B
- Authority
- CN
- China
- Prior art keywords
- carbon fiber
- honeycomb
- polyimides
- polyimide foams
- mould
- 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.)
- Active
Links
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/0088—Multi-face stack moulds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/34—Auxiliary operations
- B29C44/60—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/30—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core
- B29C70/38—Automated lay-up, e.g. using robots, laying filaments according to predetermined patterns
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/14—Applications used for foams
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Robotics (AREA)
- Composite Materials (AREA)
- Laminated Bodies (AREA)
- Reinforced Plastic Materials (AREA)
- Nonwoven Fabrics (AREA)
Abstract
The present invention provides a kind of carbon fiber Honeycomb Polyimide foams and preparation method thereof, the foamed material is reacted by aggressiveness powder before polyimides and carbon fiber cellular material and obtained, and the preparation method of aggressiveness powder is before the polyimides：1.5 ~ 2.5h is reacted by BTDA and methanol at reflux and is made 3, 3 ', 4, 4 ' benzophenone tetracarboxylic diformazan ester solutions, 10 ~ 11h is reacted by BPDA and methanol at reflux and is made 3, 3 ', 4, 4 ' biphenyltetracarboxyacid acid diformazan ester solutions, by gained 3, 3 ', 4, 4 ' benzophenone tetracarboxylic diformazan ester solutions and gained 3, 3 ', 4, 4 ' biphenyltetracarboxyacid acid diformazan ester solutions mix, add MDA, 0.5 ~ 1h is stirred at room temperature, add foam stabilizer, continue 0.5 ~ 3h of stirring, oligomer solution before obtained polyimides, oligomer solution before gained polyimides is drying to obtain aggressiveness powder before polyimides；Wherein BTDA is 6 ~ 8: 2 ~ 4 with BPDA molar ratios.The carbon fiber Honeycomb Polyimide foams uniform foam cell of the present invention, has very high mechanical property, and production cost is low.
Description
Technical field
The present invention relates to a kind of modified polyimides foam material and preparation method thereof, more particularly, to a kind of carbon fiber bee
Nest enhancing Polyimide foams and preparation method thereof.
Background technology
Polyimides is the heat-proof macromolecule material of a kind of excellent combination property, not only has very high hot property, machinery
Performance and chemical stability, also with relatively low dielectric constant and thermal coefficient of expansion.Polyimide foams not only have bubble
Foam material weight is light, low density feature, but also can not with polyurethane foam, polyethylene and polystyrene foam etc.
Heat resistance, anti-flammability and the dimensional stability of analogy, great attention is received in aerospace field, and is used as various flights
The heat-and sound-insulating material of device.But Polyimide foams production cost is high, foam uniformity is difficult to control, and is limited poly-
The popularization and application of acid imide foam material.
The content of the invention
It is an object of the invention to provide a kind of carbon fiber Honeycomb Polyimide foams and preparation method thereof, with
Solve the problems, such as Polyimide foams production cost height, poor mechanical property.
The carbon fiber Honeycomb Polyimide foams of the present invention are by aggressiveness powder before polyimides and carbon fiber bee
Nest material is reacted and obtained, and the preparation method of aggressiveness powder is before the polyimides：By 3,3', 4,4'- benzophenone tetracarboxylics
Dianhydride and methanol in mass ratio 1: 4 react 1.5 ~ 2.5h and 3,3', 4,4'- benzophenone tetracarboxylic diformazans are made at reflux
Ester solution；By 3,3', 4,4'- biphenyl tetracarboxylic dianhydrides and methanol in mass ratio 1: 4 react 10 ~ 11h and are made at reflux
3,3', 4,4'- biphenyltetracarboxyacid acid diformazan ester solution；By gained 3,3', 4,4'- benzophenone tetracarboxylic diformazan ester solutions and gained
3,3 ', 4, the mixing of 4 '-biphenyltetracarboxyacid acid diformazan ester solution, adds diaminodiphenyl-methane, stirs 0.5 ~ 1h at room temperature, add
Foam stabilizer, continues 0.5 ~ 3h of stirring, and oligomer solution before polyimides is made, oligomer solution before gained polyimides is drying to obtain
Aggressiveness powder before polyimides；Wherein 3,3', 4,4'- benzophenone tetracarboxylic dianhydride and 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride
Molar ratio be 6 ~ 8: 2 ~ 4, its preparation flow is as shown in Figure 1.
Preferably, the molar ratio of the BTDA and BPDA are 6 ~ 7: 3 ~ 4.It is highly preferred that mole of the BTDA and BPDA
Than for 7: 3.
Preferably, the mole dosage of the MDA is the sum of mole dosage of BTDA and BPDA.
Preferably, the addition of the foam stabilizer is the 0.5 ~ 1.0% of the quality sum of BTDA, BPDA and MDA.
The foam stabilizer is at least one of silicone oil, silicone glycol copolymer and polysiloxane-polyether copolymer, is had
Body, at least one of foam stabilizer TN-3038, DC-193, AK-8805.
The preparation method of the carbon fiber cellular material comprises the following steps：
A, the carbon cloth cut leaching is subjected to dipping process in a binder, the carbon cloth after dipping process is dried
It is dry, obtain carbon fiber prepreg；
B, by carbon fiber prepreg laying in a mold, the mould includes semi-hexagon shape mould and for forming honeycomb hole
Hexagonal prisms core, the end face of the hexagonal prisms core is regular hexagon, if the semi-hexagon shape mould be upper surface be equipped with
Dry strip fin, the shape size of the fin section institute with by plane where the hexagonal prisms core along its two opposite rib
The shape size of the half hexagonal prisms core formed is identical, is formed between adjacent two fins and is embedded the half hexagonal prisms core
Groove；
During laying, first on the semi-hexagon shape mould spread first layer carbon fiber prepreg, with the first layer carbon
The corresponding each concave part of fiber prepreg material is respectively put into hexagonal prisms core, then spreads the second layer above each hexagonal prisms core
Carbon fiber prepreg, then hexagonal prisms core is put into each concave part corresponding with second layer carbon fiber prepreg, then each
Third layer carbon fiber prepreg is spread on hexagonal prisms core, and so on, until top carbon fiber prepreg is completed, laying is complete
Finish；
C, the good carbon fiber prepreg of above-mentioned laying and mould are integrally put into hot press and carry out hot pressing, hot pressing terminates
Afterwards, treat that temperature is down to room temperature, demould, that is, obtain carbon fiber cellular material.
The phosphorus content of the carbon fiber cellular material more than 90%, the height of the carbon fiber cellular material for 5.0 ~
10.0cm, the aperture size of the carbon fiber cellular material is 9.6 ~ 12.8mm.
Aggressiveness powder is 3 ~ 10: 1 in mass ratio with carbon fiber cellular material before polyimides, is preferably 3 ~ 5: 1.
The density of the carbon fiber Honeycomb Polyimide foams is 30 ~ 60kg/m3, the carbon fiber honeycomb increasing
Compression stress is 2.0 ~ 2.5MPa during 50% deformation of strong Polyimide foams, and L directions shear strength is 2.8 ~ 3.0MPa, W
Direction shear strength is 1.5 ~ 2.0MPa, and thermal conductivity is 0.020 ~ 0.050W/（m•k）.L directions represent gained foamed material
Longitudinal direction, W directions represent its transverse direction.
The present invention carbon fiber Honeycomb Polyimide foams uniform foam cell, thermal insulation, heat resistance, it is sound absorption properties and
Anti-flammability is good, has very high mechanical property, can the long-time service at 300 DEG C, be particularly suitable for high-low temperature resistant, resistance to
Pressure, heat-insulated and sound absorption have the component of demand.Importantly, the present invention greatly reduces carbon fiber Honeycomb polyimides bubble
The production cost of foam material, condition is provided for its popularization and application.
Carbon fiber cellular material used in the present invention is prepared using one-step method, the cellular structural stability of carbon fiber
Good, intensity height, will not be destroyed in foaming process by foaming and intumescing, so as to significantly increase the mechanical strength of foamed material.
The method provided by the invention for preparing carbon fiber Honeycomb Polyimide foams, comprises the following steps：
Carbon fiber cellular material is put into mould, aggressiveness powder before polyimides is uniformly filled in carbon fiber honeycomb
In material, then mould is put into baking oven, at 100 ~ 150 DEG C, foam 1.0 ~ 1.5h；Then mould is put into resistance furnace,
After 200 DEG C keep the temperature 0.5 ~ 1h, 300 DEG C are warming up to, 0.5 ~ 1.0h is kept the temperature, that is, obtains carbon fiber Honeycomb polyimide foam
Material.
The method of the present invention step is extremely simple, and operation is very easy, not only increases production efficiency, is also greatly reduced life
Produce cost.The method of the present invention is that first aggressiveness powder before polyimides is uniformly filled in carbon fiber honeycomb, then is put into the lump
Foamable reaction is carried out in baking oven, so that foaming is more uniform, foamed material and the mutual enhancing effect of cellular material are brighter
It is aobvious.
Brief description of the drawings
Fig. 1 is the preparation flow figure of aggressiveness powder before polyimides.
Fig. 2 is the structure diagram of carbon fiber cellular material.
Fig. 3 is the structure diagram of semi-hexagon shape mould.
Fig. 4 is the lay-up process schematic diagram of carbon fiber prepreg.
Fig. 5 is the structure diagram of the good carbon fiber prepreg of laying.
Fig. 6 is the scanning electron microscope image of 4 products obtained therefrom of embodiment.
Fig. 7 is the scanning electron microscope image of 1 products obtained therefrom of comparative example.
In Fig. 3,4,5：1st, semi-hexagon shape mould, 2, hexagonal prisms core, 3, carbon fiber prepreg.
Embodiment
Below in an example, the various processes and method not being described in detail are conventional methods as known in the art,
Agents useful for same do not show source, specification be it is commercially available analysis it is pure or chemical pure.
Embodiment 1：The preparation of carbon fiber cellular material.
Carbon fiber cellular material used in the present invention is that a hot pressing forms in a mold by carbon fiber prepreg laying, its
Structure is as shown in Figure 2.Mould therefor includes semi-hexagon shape mould 1 and to form the hexagonal prisms core 2 of honeycomb hole, such as Fig. 3 and
Shown in Fig. 4.Hexagonal prisms core 2 is the prism that end face is in regular hexagon, its material is aluminium alloy or stainless steel.Semi-hexagon shape mould
1 is to be equipped with some identical strip fins on the upper surface of which, and the end face of fin is trapezoidal, with two phases of hexagonal prisms core 2
To rib where plane hexagonal prisms core 2 is cut into identical two parts, be called half hexagonal prisms, shape, the size of fin are equal
It is identical with half hexagonal prisms.Groove is formed between adjacent two fins, groove matches with half hexagonal prisms, for being embedded hexagonal prisms core
The latter half of mould 2.
Specifically preparation method is：
Carbon cloth is cut into growth 40cm, the carbon fiber cloth of wide 10cm；Carbon fiber cloth is immersed in polyamic acid to glue
Dipping process is carried out in knot agent, 15min is kept, is then taken out, is put into baking oven, dried at 100 DEG C, obtain carbon fibre initial rinse
Material.
As shown in figure 4, spread first layer carbon fiber prepreg on semi-hexagon shape mould 1, and make carbon fiber prepreg with
The upper surface of semi-hexagon shape mould 1 is adjacent to, and makes first layer carbon fiber prepreg with the fin and groove on semi-hexagon shape mould 1
Distribution and it is raised or sunken；
Hexagonal prisms core 2 is respectively put into the corresponding each depressed area of first layer carbon fiber prepreg, and makes six ribs
Three faces of the lower part of column core 2 are adjacent to first layer carbon fiber prepreg respectively；
Then second layer carbon fiber prepreg is laid with the top of hexagonal prisms core 2, and makes second layer carbon fiber prepreg
It is adjacent to respectively with three faces of 2 top half of hexagonal prisms core, at this time the concave part and first layer of second layer carbon fiber prepreg
The lug boss of carbon fiber prepreg is adjacent to；
Then hexagonal prisms core 2 is respectively put into the corresponding each depressed area of second layer carbon fiber prepreg again, with such
Push away, until the carbon fiber prepreg of top is laid, that is, complete the laying of carbon fiber prepreg, the good carbon fibre initial rinse of laying
Expect that structure is as shown in Figure 5.
The good carbon fiber prepreg of laying and mould are integrally put into hot press and carry out hot pressing, hot pressing condition is：Temperature
For 200 DEG C, pressure 0.5MPa, soaking time 1.0h.After hot pressing, treat that temperature is down to room temperature, demould, that is, obtain carbon fibre
Tie up honeycomb.
Embodiment 2：The preparation of carbon fiber Honeycomb Polyimide foams.
The preparation of aggressiveness powder before polyimides：BTDA is 6: 4 with the ratio between BPDA moles.
120g methanol is added in the four-hole boiling flask with blender, reflux condensing tube and thermometer, under stirring condition
It is heated to methanol to start to flow back, is slowly added to 30gBTDA, BTDA and methanol is reacted 1.5h, system at reflux
Transparent pale yellow solution is gradually become by suspension, that is, obtains 3,3 ', 4,4 '-benzophenone tetracarboxylic diformazan ester solution.
73.04g methanol is added in the four-hole boiling flask with blender, reflux condensing tube and thermometer, stirring condition
Under be heated to methanol and start to flow back, be slowly added to 18.26gBPDA, BPDA and methanol is reacted at reflux
10.0h, system are gradually become transparent pale yellow solution by suspension, that is, obtain 3,3 ', 4,4 '-biphenyltetracarboxyacid acid dimethyl ester is molten
Liquid.
By gained 3,3 ', 4,4 '-benzophenone tetracarboxylic diformazan ester solution and 3,3 ', 4,4 '-biphenyltetracarboxyacid acid of gained two
Methyl ester solution mixes, and 30.77gMDA is added into mixed liquor, stirs 40min, obtains polyesteramide solution, added into solution
0.40gTN-3038 foam stabilizers, stir 2 ~ 3h.It will be dried again added with the polyimide solution of foam stabilizer at 80 DEG C, to obtain the final product
Aggressiveness powder before to polyimides.
Foaming and post processing：
Highly it is that the regular hexagon carbon fiber honeycomb that 5cm, length of side 1.5cm, honeycomb aperture size are 12.8cm is put by 10g
Enter in mould, weigh aggressiveness powder before 50g polyimides, and filled uniformly with the carbon fiber honeycomb in mould, then
Mould is put into baking oven, foam 1h at 120 DEG C.Then mould is taken out and be put into high temperature resistance furnace, in 200 DEG C of holdings
0.5h, is then adjusted to 300 DEG C by temperature, keeps the temperature 0.5h, that is, obtains carbon fiber Honeycomb Polyimide foams.
Gained foam densities are 33kg/m3, compression stress is 2.0MPa during 50% deformation, and L directions shear strength is
2.83MPa, W direction shear strength are 1.55MPa, thermal conductivity 0.048W/（m•k).
Embodiment 3：The preparation of carbon fiber Honeycomb Polyimide foams.
The preparation of aggressiveness powder before polyimides：BTDA is 2 with the ratio between BPDA moles:1.
80g methanol is added in the four-hole boiling flask with blender, reflux condensing tube and thermometer, is added under stirring condition
Heat starts to flow back to methanol, is slowly added to 20gBTDA, makes BTDA and methanol reacts 1.5h at reflux, system by
Suspension gradually becomes transparent pale yellow solution, that is, obtains 3,3 ', 4,4 '-benzophenone tetracarboxylic diformazan ester solution.
36.5g methanol is added in the four-hole boiling flask with blender, reflux condensing tube and thermometer, under stirring condition
It is heated to methanol to start to flow back, is slowly added to 9.13gBPDA, BPDA and methanol is reacted 10.0h, body at reflux
System is gradually become transparent pale yellow solution by suspension, that is, obtains 3,3 ', 4,4 '-biphenyltetracarboxyacid acid diformazan ester solution.
By gained 3,3 ', 4,4 '-benzophenone tetracarboxylic diformazan ester solution and 3,3 ', 4,4 '-biphenyltetracarboxyacid acid of gained two
Methyl ester solution mixes, and 18.46gMDA is added into mixed liquor, stirs 40min, obtains polyesteramide solution, added into solution
0.24gTN-3038 foam stabilizers, stir 2 ~ 3h.It will be dried again added with the polyimide solution of foam stabilizer at 100 DEG C, i.e.,
Obtain aggressiveness powder before polyimides.
Foaming and post processing：
Highly it is the carbon fiber honeycomb for the regular hexagon that 5cm, length of side 1.5cm, honeycomb aperture size are 12.8cm by 10g
It is put into mould, weighs aggressiveness powder before 30g polyimides, and is filled uniformly with the carbon fiber honeycomb in mould,
Mould is put into baking oven again, foam 1h at 120 DEG C.Then mould is taken out and be put into high temperature resistance furnace, in 200 DEG C of holdings
0.5h, is then adjusted to 300 DEG C by temperature, keeps the temperature 0.5h, that is, obtains carbon fiber Honeycomb Polyimide foams.
Gained foam densities are 35kg/m3, compression stress is 2.2MPa during 50% deformation, and L directions shear strength is
2.85MPa, W direction shear strength are 1.6MPa, thermal conductivity 0.040W/（m•k).
Embodiment 4：The preparation of carbon fiber Honeycomb Polyimide foams.
The preparation of aggressiveness powder before polyimides：BTDA is 7 with the ratio between BPDA moles:3.
280g methanol is added in the four-hole boiling flask with blender, reflux condensing tube and thermometer, under stirring condition
Be heated to methanol to start to flow back, be slowly added to 70gBTDA, make BTDA and methanol reacts 2h at reflux, system by
Suspension gradually becomes transparent pale yellow solution, that is, obtains 3,3 ', 4,4 '-benzophenone tetracarboxylic diformazan ester solution.
109.6g methanol is added in the four-hole boiling flask with blender, reflux condensing tube and thermometer, stirring condition
Under be heated to methanol and start to flow back, be slowly added to 27.4gBPDA, BPDA and methanol is reacted 10.0h at reflux,
System is gradually become transparent pale yellow solution by suspension, that is, obtains 3,3 ', 4,4 '-biphenyltetracarboxyacid acid diformazan ester solution.
By gained 3,3 ', 4,4 '-benzophenone tetracarboxylic diformazan ester solution and 3,3 ', 4,4 '-biphenyltetracarboxyacid acid of gained two
Methyl ester solution mixes, and 61.53gMDA is added into mixed liquor, stirs 40min, obtains polyesteramide solution, added into solution
0.80gTN-3038 foam stabilizers, stir 0.5 ~ 1h.It will be dried again added with the polyimide solution of foam stabilizer at 90 DEG C, i.e.,
Obtain aggressiveness powder before polyimides.
Foaming and post processing：
Highly it is the carbon fiber honeycomb for the regular hexagon that 5cm, length of side 1.5cm, honeycomb aperture size are 12.8cm by 10g
It is put into mould, weighs aggressiveness powder before 40g polyimides, and is filled uniformly with the carbon fiber honeycomb in mould,
Mould is put into baking oven again, foam 1h at 130 DEG C.Then mould is taken out and be put into high temperature resistance furnace, in 200 DEG C of holdings
1.0h, is then adjusted to 300 DEG C by temperature, keeps the temperature 1.0h, that is, obtains carbon fiber Honeycomb Polyimide foams.
Gained foam densities are 38kg/m3, compression stress is 2.3MPa during 50% deformation, and L directions shear strength is
3.0MPa, W direction shear strength are 2.0MPa, thermal conductivity 0.030W/（m•k）.
Comparative example 1：The preparation of carbon fiber Honeycomb Polyimide foams.
The preparation of aggressiveness powder before polyimides：BTDA is 1 with the ratio between BPDA moles:1.
40g methanol is added in the four-hole boiling flask with blender, reflux condensing tube and thermometer, is added under stirring condition
Heat starts to flow back to methanol, is slowly added to 10gBTDA, makes BTDA and methanol reacts 1.5h at reflux, system by
Suspension gradually becomes transparent pale yellow solution, that is, obtains 3,3 ', 4,4 '-benzophenone tetracarboxylic diformazan ester solution.
36.52g methanol is added in the four-hole boiling flask with blender, reflux condensing tube and thermometer, stirring condition
Under be heated to methanol and start to flow back, be slowly added to 9.13gBPDA, BPDA and methanol is reacted 10.0h at reflux,
System is gradually become transparent pale yellow solution by suspension, that is, obtains 3,3 ', 4,4 '-biphenyltetracarboxyacid acid diformazan ester solution.
By gained 3,3 ', 4,4 '-benzophenone tetracarboxylic diformazan ester solution and 3,3 ', 4,4 '-biphenyltetracarboxyacid acid of gained two
Methyl ester solution mixes, and 12.3gMDA is added into mixed liquor, stirs 40min, obtains polyesteramide solution, added into solution
0.16g TN-3038 foam stabilizers, stir 2 ~ 3h.It will be dried again added with the polyimide solution of foam stabilizer at 80 DEG C, i.e.,
Obtain aggressiveness powder before polyimides.
Foaming and post processing：
Highly it is that the regular hexagon carbon fiber honeycomb that 5cm, length of side 1.5cm, honeycomb aperture size are 12.8cm is put by 10g
Enter in mould, weigh aggressiveness powder before 40g polyimides, and filled uniformly with the carbon fiber honeycomb in mould, then
Mould is put into baking oven, foam 1h at 120 DEG C.Then mould is taken out and be put into high temperature resistance furnace, in 200 DEG C of holdings
0.5h, is then adjusted to 300 DEG C by temperature, keeps the temperature 0.5h, that is, obtains carbon fiber Honeycomb Polyimide foams.
Gained foam densities are 30.5kg/m3, compression stress is 1.85MPa during 50% deformation, L directions shear strength
For 2.70MPa, W directions shear strength is 1.41MPa, thermal conductivity 0.055W/（m•k）.
Comparative example 2：The preparation of carbon fiber Honeycomb Polyimide foams.
The preparation of aggressiveness powder before polyimides：
Added in the there-necked flask equipped with mechanical agitator, spherical reflux condensing tube and thermometer 64g tetracarboxylic dianhydrides α-
BTDA, 72g tetracarboxylic dianhydride DSDA, 155g low boiling point solvent absolute ethyl alcohol, be heated to reflux under conditions of stirring 3 it is small when, obtain
To aromatic diacid diester homogeneous phase solution.
Equipped with electromagnetic mixing apparatus, spherical reflux condensing tube single port bottle in add 54g reactivity end-capping reagent NA,
120g low boiling point solvent absolute ethyl alcohols, when heating 3 is small under conditions of stirring, the mono-acid monoesters for obtaining reactive end-capping reagent is homogeneous
Solution, is cooled to room temperature.
The mono-acid monoesters homogeneous phase solution of gained reactivity end-capping reagent is added to mixing for gained aromatic diacid diester
In liquid, and 60g aromatic diamines m-PDA, 0.52g imidization accelerating agent isoquinolin is added, heated under conditions of nitrogen protection
Back flow reaction 15min, obtains homogeneous phase solution.After being cooled to room temperature, the non-ionic fluorine carbon of 1.02g polyoxyethylene groups ethers is added
Surfactant Zonyl®FSO-100, the stirring at normal temperature 30min under conditions of nitrogen protection, obtains polyimide precursor tree
The solution of fat.
By 60 DEG C of rotary evaporations of solution of polyimide precursor resin to pouring into enamel tray after thick, then put
Enter to obtain polyimide precursor resin solid powder in baking oven after dry, pulverize.
Foaming and post processing：
Highly it is the carbon fiber honeycomb for the regular hexagon that 5cm, length of side 1.5cm, honeycomb aperture size are 12.8cm by 10g
It is put into mould, weighs aggressiveness powder before 40g polyimides, and is filled uniformly with the carbon fiber honeycomb in mould,
Mould is put into baking oven again, foam 1h at 130 DEG C.Then mould is taken out and be put into high temperature resistance furnace, in 200 DEG C of holdings
1.0h, is then adjusted to 300 DEG C by temperature, keeps the temperature 1.0h, that is, obtains carbon fiber Honeycomb Polyimide foams.
Gained foam densities are 29.5kg/m3, compression stress is 1.70MPa during 50% deformation, L directions shear strength
For 2.50MPa, W directions shear strength is 1.36MPa, thermal conductivity 0.056W/（m•k）.
Embodiment products obtained therefrom and comparative example products obtained therefrom, the results are shown in Table 1, Fig. 6 and Fig. 7.
Table 1：
Claims (10)
1. a kind of carbon fiber Honeycomb Polyimide foams, it is characterized in that, it is fine by aggressiveness powder before polyimides and carbon
Dimension cellular material is reacted and obtained, and the preparation method of aggressiveness powder is before the polyimides：By 3,3', 4,4'- benzophenone four
Formic acid dianhydride and methanol in mass ratio 1: 4 react 1.5 ~ 2.5h and 3,3', 4,4'- benzophenone tetracarboxylics are made at reflux
Diformazan ester solution；By 3,3', 4,4'- biphenyl tetracarboxylic dianhydrides and methanol in mass ratio 1: 4 react 10 ~ 11h at reflux
3,3', 4,4'- biphenyltetracarboxyacid acid diformazan ester solutions is made；By gained 3,3', 4,4'- benzophenone tetracarboxylic diformazan ester solutions and
Gained 3,3 ', 4, the mixing of 4 '-biphenyltetracarboxyacid acid diformazan ester solution, adds diaminodiphenyl-methane, stirs 0.5 ~ 1h at room temperature,
Foam stabilizer is added, continues 0.5 ~ 3h of stirring, oligomer solution before polyimides is made, oligomer solution before gained polyimides is dried
Up to aggressiveness powder before polyimides；Wherein 3,3', 4,4'- benzophenone tetracarboxylic dianhydride and 3,3 ', 4,4 '-biphenyltetracarboxyacid acid
The molar ratio of dianhydride is 6 ~ 8: 2 ~ 4.
2. carbon fiber Honeycomb Polyimide foams according to claim 1, it is characterized in that, described 3,3 ', 4,
4 '-benzophenone tetracarboxylic dianhydride and 3,3 ', the molar ratio of 4,4 '-biphenyl tetracarboxylic dianhydride is 6 ~ 7: 3 ~ 4.
3. carbon fiber Honeycomb Polyimide foams according to claim 1, it is characterized in that, described 3,3 ', 4,
4 '-benzophenone tetracarboxylic dianhydride and 3,3 ', the molar ratio of 4,4 '-biphenyl tetracarboxylic dianhydride is 7: 3.
4. carbon fiber Honeycomb Polyimide foams according to claim 1, it is characterized in that, the diaminourea two
The mole dosage of phenylmethane is 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride and 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride
The sum of mole dosage；The addition of the foam stabilizer is 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-biphenyl
The 0.5 ~ 1.0% of the quality sum of tetracarboxylic dianhydride and diaminodiphenyl-methane.
5. carbon fiber Honeycomb Polyimide foams according to claim 1, it is characterized in that, the foam stabilizer is
At least one of silicone oil, silicone glycol copolymer and polysiloxane-polyether copolymer.
6. carbon fiber Honeycomb Polyimide foams according to claim 1, it is characterized in that, the carbon fiber bee
The preparation method of nest material comprises the following steps：
A, the carbon cloth cut leaching is subjected to dipping process in a binder, the carbon cloth after dipping process is dried,
Obtain carbon fiber prepreg；
B, by carbon fiber prepreg laying in a mold, the mould include semi-hexagon shape mould and for forming honeycomb hole six
Prism core, the end face of the hexagonal prisms core is regular hexagon, and the semi-hexagon shape mould is to be equipped with some in upper surface
Shape fin, the shape size of the fin to be formed with plane where the hexagonal prisms core along its two opposite rib is sectioned
Half hexagonal prisms core shape size it is identical, between adjacent two fins formed be embedded the recessed of the half hexagonal prisms core
Groove；
During laying, first on the semi-hexagon shape mould spread first layer carbon fiber prepreg, with the first layer carbon fiber
The corresponding each concave part of prepreg is respectively put into hexagonal prisms core, and second layer carbon fibre is then spread above each hexagonal prisms core
Prepreg is tieed up, then hexagonal prisms core is put into each concave part corresponding with second layer carbon fiber prepreg, then in each six rib
Third layer carbon fiber prepreg is spread on column core, and so on, until top carbon fiber prepreg is completed, laying finishes；
C, the good carbon fiber prepreg of above-mentioned laying and mould are integrally put into hot press and carry out hot pressing, after hot pressing, treated
Temperature is down to room temperature, and the demoulding, that is, obtain carbon fiber cellular material.
7. carbon fiber Honeycomb Polyimide foams according to claim 1, it is characterized in that, the carbon fiber bee
The phosphorus content of nest material is more than 90%, and the height of the carbon fiber cellular material is 5.0 ~ 10.0cm, the carbon fiber honeycomb material
The aperture size of material is 9.6 ~ 12.8mm.
8. carbon fiber Honeycomb Polyimide foams according to claim 1, it is characterized in that, gather before polyimides
The mass ratio of body powder and carbon fiber cellular material is 3 ~ 10:1.
9. carbon fiber Honeycomb Polyimide foams according to claim 1, it is characterized in that, the carbon fiber bee
The density of nest enhancing Polyimide foams is 30 ~ 60kg/m3, the carbon fiber Honeycomb Polyimide foams
Compression stress is 2.0 ~ 2.5MPa during 50% deformation, and L directions shear strength is 2.8 ~ 3.0MPa, W directions shear strength for 1.5 ~
2.0MPa, thermal conductivity are 0.020 ~ 0.050W/（m•k).
10. the method that one kind prepares any carbon fiber Honeycomb Polyimide foams in claim 1 ~ 9, it is special
Sign is to comprise the following steps：Carbon fiber cellular material is put into mould, aggressiveness powder before polyimides is uniformly filled in
In carbon fiber cellular material, then mould is put into baking oven, at 100 ~ 150 DEG C, foam 1.0 ~ 1.5h；Then mould is put into
In resistance furnace, after 200 DEG C keep the temperature 0.5 ~ 1h, 300 DEG C are warming up to, 0.5 ~ 1.0h is kept the temperature, that is, obtains carbon fiber Honeycomb and gather
Acid imide foam material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610305153.6A CN105820571B (en) | 2016-05-10 | 2016-05-10 | A kind of carbon fiber Honeycomb Polyimide foams and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610305153.6A CN105820571B (en) | 2016-05-10 | 2016-05-10 | A kind of carbon fiber Honeycomb Polyimide foams and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105820571A CN105820571A (en) | 2016-08-03 |
| CN105820571B true CN105820571B (en) | 2018-04-20 |
Family
ID=56529185
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610305153.6A Active CN105820571B (en) | 2016-05-10 | 2016-05-10 | A kind of carbon fiber Honeycomb Polyimide foams and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105820571B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108281132A (en) * | 2018-03-13 | 2018-07-13 | 吉林大学 | With Cylindrical Pit bionic non-smooth surface polyurethane foam board and preparation method |
| CN108840697B (en) * | 2018-06-29 | 2021-07-13 | 航天材料及工艺研究所 | Carbon/carbon composite material honeycomb and preparation method thereof |
| CN111040161B (en) * | 2019-12-30 | 2022-11-15 | 江苏中科聚合新材料产业技术研究院有限公司 | Heat-insulation polyimide foam material and preparation method thereof |
| 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 |
| 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 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5188879A (en) * | 1991-07-15 | 1993-02-23 | Sorrento Engineering Corporation | Polyimide foam filled structures |
| EP1002006B1 (en) * | 1998-05-29 | 2005-03-23 | The Government of the U.S.A., as represented by the Administrator of the National Aeronautics and Space Administration (NASA) | Aromatic polyimide foam |
| CN103737988A (en) * | 2014-01-06 | 2014-04-23 | 苏州芳磊蜂窝复合材料有限公司 | Honeycomb core based on carbon fibre paper and preparation method for same |
| CN104842593A (en) * | 2015-03-24 | 2015-08-19 | 中山大学 | Carbon fiber honeycomb structure and preparation method therefor |
| 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 |
-
2016
- 2016-05-10 CN CN201610305153.6A patent/CN105820571B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5188879A (en) * | 1991-07-15 | 1993-02-23 | Sorrento Engineering Corporation | Polyimide foam filled structures |
| EP1002006B1 (en) * | 1998-05-29 | 2005-03-23 | The Government of the U.S.A., as represented by the Administrator of the National Aeronautics and Space Administration (NASA) | Aromatic polyimide foam |
| CN103737988A (en) * | 2014-01-06 | 2014-04-23 | 苏州芳磊蜂窝复合材料有限公司 | Honeycomb core based on carbon fibre paper and preparation method for same |
| 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 |
| CN104842593A (en) * | 2015-03-24 | 2015-08-19 | 中山大学 | Carbon fiber honeycomb structure and preparation method therefor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105820571A (en) | 2016-08-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105820571B (en) | A kind of carbon fiber Honeycomb Polyimide foams and preparation method thereof | |
| CN105153422B (en) | A kind of Polyimide foams and preparation method thereof | |
| CN108727818A (en) | A kind of hydrophobic type silica/polyimides aerogel composite and preparation method | |
| CN105017769B (en) | Honeycomb thermosetting property rigid closed cell Polyimide foam composite material and the preparation method and application thereof | |
| CN108530673A (en) | A kind of linear polyimides aeroge and preparation method thereof | |
| CN102964834B (en) | High temperature-resistant anti-compression cross-linking polyimide foam material and preparation method and application thereof | |
| JP3687496B2 (en) | Foamed polyimide and process for producing the same | |
| CN102134395B (en) | Modified light flexible polyimide foam material and preparation method thereof | |
| CN101402795B (en) | Novel fire resistant polyimide foam and method of producing the same | |
| CN101812232A (en) | Polyimide foam and preparation method thereof | |
| CN102093714A (en) | Light flexible polymide foam material and preparation method thereof | |
| WO2015180063A1 (en) | Method for continuously preparing solvent-free open-cell and closed-cell polyimide foam | |
| CN102134396A (en) | Light flexible polyimide foam material and preparation method thereof | |
| CN103012793A (en) | Novel mould-pressing polyimide foamed plastic and preparation method thereof | |
| CN106457193A (en) | Process for producing aerogels by dielectric heating | |
| CN106883431A (en) | A kind of preparation method of low water absorbable polyimide resin film | |
| CN109880096A (en) | Polyimide foam and its preparation method and application | |
| CN102502575A (en) | Method for preparing carbon foam by using foaming agent | |
| CN110655790A (en) | Production method of polyimide foam material | |
| US6090861A (en) | Process for high temperature production of organic aerogels | |
| EP2348065B1 (en) | Polyimide foam and method for producing same | |
| CN104804190A (en) | Flame-retardant polyimide foam material comprising honeycomb core space structure, and preparation method | |
| CN1317233C (en) | Silica aerogel powder moulding method adopting gel injection molding method | |
| US6077876A (en) | Process for high temperature production of organic aerogels | |
| KR101228382B1 (en) | Manufacturing method of ion exchange membrane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |