CN102964834B - High temperature-resistant anti-compression cross-linking polyimide foam material and preparation method and application thereof - Google Patents
High temperature-resistant anti-compression cross-linking polyimide foam material and preparation method and application thereof Download PDFInfo
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- 0 CC1OC1C(C1C=C(*)C2C1)C2C(C=C*C(C)(C)N(C(C(C1C(N2*C(C)(C)N(C(C3C4C5C(*)=CC3C5)=O)C4=O)=O)C3C1C2=O)=O)C3=O)=O Chemical compound CC1OC1C(C1C=C(*)C2C1)C2C(C=C*C(C)(C)N(C(C(C1C(N2*C(C)(C)N(C(C3C4C5C(*)=CC3C5)=O)C4=O)=O)C3C1C2=O)=O)C3=O)=O 0.000 description 1
- LRSDMTARWGKQDI-UHFFFAOYSA-N Cc(cc1)c(C)cc1-c1c(C)c(C)ccc1 Chemical compound Cc(cc1)c(C)cc1-c1c(C)c(C)ccc1 LRSDMTARWGKQDI-UHFFFAOYSA-N 0.000 description 1
- YXBIAYXZUDJVEB-UHFFFAOYSA-N Cc(cc1)c(C)cc1-c1cc(C)c(C)cc1 Chemical compound Cc(cc1)c(C)cc1-c1cc(C)c(C)cc1 YXBIAYXZUDJVEB-UHFFFAOYSA-N 0.000 description 1
- FKFVCCPWFITRSN-UHFFFAOYSA-N Cc(cc1)c(C)cc1C(c1cc(C)c(C)cc1)=O Chemical compound Cc(cc1)c(C)cc1C(c1cc(C)c(C)cc1)=O FKFVCCPWFITRSN-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention discloses a novel high temperature-resistant anti-compression cross-linking polyimide foam material, a precursor and a preparation method and an application thereof. The structural formula of the cross-linking polyimide foam material precursor is shown as a formula I. The preparation method comprises the following steps: mixing organic tetracarboxylic dianhydride or malonate ester of organic tetracid, norbornene mono acid monoester and aromatic diamine mixture in organic solvent to form a polyimide precursor resin solution, removing part solvent, drying and grinding to obtain precursor powder, and heating the precursor powder to 300-400 DEG C and foaming to obtain the cross-linking polyimide foam. The method has the characteristics of simple process and low forming temperature, and the obtained foam material is high in temperature resistance, strength and toughness and low in compression deformation at high temperature. The material can be applied to preparing high temperature-resistant sandwich materials, high temperature-resistant thermal insulation materials, high temperature-resistant damping materials and high temperature-resistant wave-transmitting materials.
Description
Technical field
The present invention relates to a kind of high temperature resistant height incompressible crosslinked polyimide class A foam A material and preparation method thereof and application.
Background technology
Polyimide foams comes across the sixties in 20th century the earliest, utilizes the polyamic acid solution foamable that with the addition of whipping agent to obtain by Monsanto and Dupont company (US3249561).Subsequently, many patents (US Patent No. 3483144, US6084000, US4296208, US5994418, US2006063848, European patent EP 0048119, Chinese patent CN1528808) disclose Polyimide foams prepared by the methods such as the foaming of multiple employing powder, the foaming of presoma microballoon, microwave foaming.Compared with other polymer foams, Polyimide foams has high temperature resistant, low temperature resistant, low dielectric, does not burn, radiation hardness, rate of being fuming are low and decompose the plurality of advantages such as release toxic gas is few, thus causes showing great attention to of people.At present, polyimide foam has been widely used in the high-tech sectors such as Aeronautics and Astronautics, naval vessel, bullet train as heat insulation, the critical material such as damping noise reduction and insulation.
Polyimide foams can be divided into thermoplasticity and thermoset two class according to chemical structure.At present, the research of polyimide foam mainly concentrates on thermoplastic polyimide foam.Earlier U.S. Patents (US 3310506,3483144,4296208,4305796,4439381) disclosed polyimide foam manufacture method is only limited to preparation low rate of closed hole, low density (< 8kg/m3) polyimide foam.Unique business-like product is the Solimide series froth product of American I nspec company.Subsequently, the people such as Weiser (Proc.43rd Int.SAMPE Symp., May 31,1998, P730-44; HighPerform.Polym.2000,12,1-12; US4241193; EP0437821 B1) aromatic diamine of aromatic diacid dimethyl ester formed by esterification by aromatic series tetracarboxylic dianhydride and methyl alcohol and composition thereof and design weight and composition thereof is formed stable salt polyimide precursor toner in organic solution, then under whipping agent effect, foamable forms thermoplastic polyimide foam.Unitika company of the U.S. has formed seriation commerical prod, comprises the TEEK-HH be combined to form by ODPA and 3,4 '-ODA, the TEEK-LL be combined to form by BTDA and 4,4 '-ODA, the TEEK-CL etc. be combined to form by BTDA and 4,4 '-DDS.The density range of the soft open celled foam of these thermoplastic polyimide is 8-320 kg/m
3, rate of closed hole lower than 32%, under room temperature 10% distortion time compressive strength in 0.098-0.84MPa scope, second-order transition temperature (T
g) within the scope of 237-321 DEG C.Its T
glower (< 321 DEG C), more than T
gunder the high temperature of temperature, intensity obviously declines, and can not meet the application demand under worst hot case.Therefore, the shortcomings such as thermoplastic polyimide open celled foam also exists resistance to elevated temperatures difference, and compressive strength is lower.
The people such as Yamaguchi (US2002/0040068 A1) disclose a kind of by 2,3,3 ', the corresponding list that 4 '-BPDA (α-BPDA) is formed through esterification under alcohol compound exists or diester compound and aromatic diamine and the reaction of siliceous diamine mixture form polyimide precursor resin solid powder, and then heated by microwave is to the 300-500 DEG C of method forming thermoplastic polyimide foam.The T of prepared polyimide foam
g> 300 DEG C, but the polyimide foam density prepared by the method is the highest is no more than 70kg/m
3, and undercapacity, foaming process is complicated simultaneously, and the microwave foaming method cost adopted is higher.
In the high polymer main chain of polyimide foam, introducing crosslinking structure, by being cross-linked to form thermosetting foams, resistance toheat and the anti-compression properties of foam materials can be improved simultaneously.But thermoset polyimide resin normally infusibility indissoluble, both cannot be dissolved in organic solvent and form solution, also cannot form mobility melt by heating and melting, and thus prepare Thermocurable polyimide foam materials and there is larger difficulty.2008, Chinese patent (CN101402795) disclosed and a kind ofly adopts reactive phenylacetylene base end-capping reagent to prepare the method for Thermocurable polyimide foam materials.The method is by 2,3,3 ', mixture esterification in fatty alcohol of 4 '-BPDA and other aromatic series tetracarboxylic dianhydride forms corresponding aromatic diacid diester, then add aromatic diamines (as Ursol D and 4,4 '-diaminodiphenyl oxide etc.) and phenylacetylene base end-capping reagent (as phenylacetylene base aniline etc.) reaction formation resin solution, add suds-stabilizing agent, add heat extraction small molecules volatile matter, obtain polyimide precursor powder; Polyimide precursor powder is inserted mould, and the high temperature post-foaming being heated to 360 DEG C obtains polyimide foam.But, this patent openly data such as the rate of closed hole of foam and mechanical property.Because the solidification value of the phenylacetylene base end-capping reagent of employing is up to 360-380 DEG C, easily causes shaping abscess softening transform, therefore be difficult to the Polyimide foams obtaining high rate of closed hole, high compression-strength.
Summary of the invention
The object of this invention is to provide a kind of novel fire resistant, high incompressible crosslinked polyimide class A foam A material, presoma and preparation method thereof, namely by introducing the norbornylene class dicarboxylic anhydride of heat cross-linking as end-capping reagent in the building-up process of polyimide foam presoma, by the crosslinked mechanical property improving fire resistant polyimide foam further.
High temperature resistant, high incompressible crosslinked polyimide (PI) class A foam A material of the present invention is that the presoma containing the END CAPPED GROUP of norborneol class dicarboxylic anhydride by it is obtained by foaming, curing cross-linked.
The structural formula of described crosslinked polyimide (PI) class A foam A material precursor is as follows:
In above-mentioned formula I, Ar can be selected from following any one or a few:
R can be selected from following any one or a few:
X can be hydrogen or methyl;
N is the integer of 1 ~ 50.
Presoma shown in above-mentioned formula I is made up of the feed composition comprising following mass parts:
Organic tetracid dicarboxylic anhydride and/or organic four acid mono 1-100,
Organic diamine monomer 1-100,
Norbornylene class dicarboxylic anhydride 1-100;
Wherein, described organic tetracarboxylic dianhydride or organic four acid mono comprise: 2, 3, 3 ', 4 '-BPDA (α-BPDA), 3, 3 ', 4, 4 '-BPDA (s-BPDA), 3, 3 ', 4, 4 '-two methyl-phenoxide tetracarboxylic dianhydride (ODPA), 3, 3 ', 4, 4 '-benzophenone tetracarboxylic dianhydride (BTDA), 1, 2, 4, 5-pyromellitic acid anhydride (PMDA), 1, 2, 3, 4-tetramethylene tetracarboxylic dianhydride (CBDA), 1, 2, 4, 5-cyclopentanetetracarboxylic dianhydride (CHDA) and tetracid corresponding to each tetracarboxylic dianhydride, or its mixture.
Described organic diamine monomer comprises: mphenylenediamine (m-PDA), Ursol D (p-PDA), 3,4 '-diaminodiphenyl oxide (3,4 '-ODA), 4,4 '-diaminodiphenyl oxide (4,4 '-ODA), 4,4 '-diaminodiphenyl-methane (MDA), 4,4 '-diaminodiphenylsulfone(DDS) (DDS), 1, two (4-amino-benzene oxygen) benzene (1 of 3-, 3,4 '-APB), DAP (2,6-DAP), 2,2-two [4-(4-amino-benzene oxygen) phenyl] propane (BAPP) or its mixtures.
Described norbornylene class dicarboxylic anhydride comprises: norbornene dicarboxylic anhydride (NA), methyl norbornene dioic anhydride (MNA) or its mixture.
The mass parts of described organic tetracid dicarboxylic anhydride and/or organic four acid mono can be 3-31 further; The mass parts of described organic diamine monomer can be 14-33 further; The mass parts of described norbornylene class dicarboxylic anhydride can be 11-36 further;
Preparation method comprises the steps:
(1) described organic tetracarboxylic dianhydride and/or organic tetracid are mixed with lower boiling aliphatic alcohols solvent, aprotic polar solvent and ether solvent, reflux 3-8 hour, form the solution of organic diacid diester; By described norbornylene class dicarboxylic anhydride and lower boiling aliphatic alcohols solvent, reflux 3 ~ 8 hours, forms its esterification solution; Mix after the solution of described organic diacid diester and described esterification solution are cooled to room temperature, obtain homogeneous mixed solution;
Or described organic tetracarboxylic dianhydride and/or organic tetracid, norbornylene class dicarboxylic anhydride are mixed with lower boiling aliphatic alcohols solvent, aprotic polar solvent and ether solvent, reflux 3-8 hour, form homogeneous mixed solution and be also cooled to room temperature;
(2) in described mixing solutions, add organic diamine monomer, and add imide reaction catalyzer, tensio-active agent, react 15 minutes ~ 6 hours under nitrogen protection, obtain homogeneous phase polyimide foam precursor solution;
(3) polyimide precursor solution described in step (2) is placed in baking oven for heating, removing small molecules volatile matter, grinds, sieves, obtain polyimide foam precursor powder.
Above-mentioned preparation process, the mass parts of the solvent added, tensio-active agent and catalyzer is as follows:
Described lower boiling aliphatic alcohols solvent comprises the mixture that methyl alcohol, ethanol, Virahol, propyl carbinol and arbitrary proportion thereof mix.
Described ether solvent comprises tetrahydrofuran (THF), Polyethylene glycol dimethyl ether, diglyme, dioxane and mixture in any proportion thereof.
Described aprotic polar solvent comprises the mixture of N-Methyl pyrrolidone (NMP), DMF (DMF), N,N-dimethylacetamide (DMAc) and arbitrary proportion thereof.
Described tensio-active agent comprise polyoxyethylene groups ethers non-ionic type fluorocarbon surfactant (as
fSO-100), polymethyl siloxane, polydimethylsiloxane, organosilicon glycol copolymer, vinyl polysiloxane, cation fluorine carbon surface active agent (as INTECHEM-03L) and composition thereof.
Described catalyzer comprises isoquinoline 99.9,1,2 dimethylimidazole, 2-ethyl-4-methylimidazole, benzoglyoxaline and substituted pyridines (as α-methylpyridine) and the mixture mixed in any proportion thereof.
The mass parts of described lower boiling aliphatic alcohols solvent can be 18 ~ 67 further; The mass parts of described ether solvent can be 14 ~ 29 further; The mass parts of described aprotic polar solvent can be 0 ~ 7 further; The mass parts of tensio-active agent can be 0.18 ~ 0.31 further; The mass parts of described catalyzer can be 0 ~ 0.2 further.
Described high temperature resistant, high incompressible crosslinked polyimide (PI) class A foam A material is filled in mould by described polyimide foam precursor powder, in baking oven or thermocompressor, 300 ~ 400 DEG C are risen to from room temperature, foaming, curing cross-linked 2 ~ 7 hours, obtain described crosslinked polyimide foam materials.
Polyimide foam provided by the invention has the features such as rate of closed hole is high, resistance to elevated temperatures good, incompressible intensity is high, toughness is better.The density of prepared foam can reach 500kg/m
3, rate of closed hole > 80%, second-order transition temperature > 320 DEG C, room temperature lower density > 100kg/m
3, the ultimate compression strength > 1MPa of foam; Under 320 DEG C of high temperature and 0.5MPa pressure, density is 250kg/m
3the compressed shape variability of foam after constant temperature process in 2 hours lower than < 2%.
Its typical performance is as shown in table 1.
The typical performance of table 1 the present invention the is high temperature resistant incompressible Polyimide foams of height
The application of above-mentioned high temperature resistant, high incompressible crosslinked polyimide class A foam A material also belongs to protection scope of the present invention.Described application is included in the application in the following material of preparation: high temperature resistant sandwich material, high temperature resistant heat insulation material, high temperature resistant sound absorbent material and high temperature resistant wave-permeable material etc.
Described high temperature resistant sandwich material means the core of carbon (glass or aramid fiber etc.) fiber-reinforced resin matrix compound material sandwich structure.Crosslinked polyimide class A foam A material of the present invention is under 320 DEG C of high temperature and 0.5MPa pressure, deformation ratio after 2 hours, lower than 2%, can meet the resistance to elevated temperatures requirement of carbon (glass or aramid fiber etc.) fiber/polyimide resin composite material sandwich structure.
Described high temperature resistant heat insulation material means the lagging material in the hot environments such as space flight, aviation, boats and ships.
Described high temperature resistant sound absorbent material means the sound absorbent material in the hot environments such as space flight, aviation, boats and ships.
Described high temperature resistant wave-permeable material means the electromagnetic wave transparent material in the hot environments such as space flight, aviation, boats and ships.
Tool of the present invention has the following advantages:
(1) preparation technology of the Polyimide foams described in is simple, is convenient to industrialization;
(2) by introducing the norbornylene class dicarboxylic anhydride of heat cross-linked type as end-capping reagent, while imidization, there is heat cross-linking, improving on the basis of foamed heat-resistance further, improve the mechanical property of foam, and can by thermotolerance and the mechanical property regulating the consumption of end-capping reagent to control foam.
(3) adopt norbornylene class dicarboxylic anhydride, have lower solidification value (250 DEG C ~ 320 DEG C), the cyclopentadiene gas discharged during solidification can as whipping agent, and the feature that resin melting is good.It can be used as end-capping reagent, little on the foam performance impact of foam precursor powder, the cost that lower solidification value makes Foam machining shaping simultaneously reduces greatly.
Accompanying drawing explanation
Fig. 1 is the infrared spectrum that embodiment 1 prepares gained foam precursor powder.
Fig. 2 is the infrared spectrum that embodiment 2 prepares gained foam precursor powder.
Fig. 3 is the infrared spectrum that embodiment 3 prepares gained foam precursor powder.
Fig. 4 is the infrared spectrum that embodiment 12 prepares gained foam precursor powder.
Fig. 5 is the infrared spectrum that embodiment 14 prepares gained foam precursor powder.
Fig. 6 is the infrared spectrum that embodiment 15 prepares gained foam precursor powder.
Fig. 7 is the infrared spectrum that embodiment 16 prepares gained foam precursor powder.
Fig. 8 is the infrared spectrum that embodiment 17 prepares gained foam precursor powder.
Fig. 9 is the infrared spectrum that embodiment 18 prepares gained foam precursor powder.
Figure 10 is the infrared spectrum that embodiment 19 prepares gained foam precursor powder.
Figure 11 is the infrared spectrum that embodiment 20 prepares gained foam precursor powder.
Figure 12 is the infrared spectrum that embodiment 21 prepares gained foam precursor powder.
Figure 13 is the infrared spectrum that embodiment 22 prepares gained foam precursor powder.
Embodiment
Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Described method is ordinary method if no special instructions.In following each embodiment, described part is mass fraction.Described reactant all can obtain from open commercial sources if no special instructions.
The rate of closed hole of foam materials prepared by the present invention adopts Micromeritics Accupyc ∏ 1340 to record, and testing standard is with reference to GB/T 10799-2008 standard.
The second-order transition temperature of foam materials prepared by the present invention adopts means of differential scanning calorimetry (DSC) to record.
The ultimate compression strength of foam materials prepared by the present invention and compression deformation rate adopt Instron 5567 universal testing machine to record, and intensity test standard is with reference to GB/T 9641-88.
Embodiment 1
1) in the there-necked flask that mechanical stirrer, spherical reflux condensing tube and thermometer are housed, add 29 parts of α-BPDA, 37 parts of dehydrated alcohols, 29 parts of anhydrous tetrahydro furans, under the condition stirred, reflux 3 hours, obtains homogeneous phase solution.
2) in the single port bottle that electromagnetic mixing apparatus, spherical reflux condensing tube are housed, add 33 parts of NA, 67 parts of dehydrated alcohols, under the condition stirred, heating 3 hours, obtains homogeneous phase solution.After being cooled to room temperature, this solution is added the step 1 being cooled to room temperature) in the solution prepared, and add 22 parts of p-PDA, 0.13 part of isoquinoline 99.9, under the condition of nitrogen protection, reflux stirs 15min, obtains homogeneous phase solution.After being cooled to room temperature, add 0.25 portion of polyoxyethylene groups ethers non-ionic type fluorocarbon surfactant
fSO-100, stirring at normal temperature 20min under the condition of nitrogen protection, obtain polyimide precursor resin solution.
3) by step 2) in polyimide precursor resin solution 60 DEG C of rotary evaporations to pouring in enamel tray after thick, then put into baking oven and carry out drying and obtain solid resin; Foam precursor powder is obtained after pulverizing.
Formula I is the structural formula of above-mentioned foam precursor powder.
In formula I general structure, X is hydrogen bond, and Ar is 2,3,3 ', 4 '-xenyl, and R is to phenyl, and n is 1.Fig. 1 is the infrared spectrum that this embodiment prepares gained polyimide, as seen from the figure, and 1779cm
-1and 1720cm
-1asymmetric and the symmetrical stretching vibration absorption peak of carbonyl for imide group, 1369cm
-1for the C-N stretching vibration absorption peak of imide group, illustrate and define imide ring.As from the foregoing, it is correct that this embodiment prepares products therefrom structure, is polymkeric substance shown in formula I.
4) by 20g step 3) in foam precursor powder put into 80mm × 80mm × 30mm stainless steel mould, mould is put into thermocompressor, pressurization fixed mould, then by room temperature to 320 DEG C, and constant temperature 3 hours; Be cooled to die sinking after room temperature, obtain the Polyimide foams of complete crosslinking curing, the density of foam is 100kg/m
3, second-order transition temperature is 365 DEG C, and ultimate compression strength is 1.2MPa, and concrete performance is listed in table 2.
Comparative example 1
1) be equipped with in the there-necked flask of mechanical stirrer, spherical reflux condensing tube and thermometer and add 29 parts of α-BPDA, 37 parts of dehydrated alcohols, 29 parts of anhydrous tetrahydro furans, under the condition stirred, reflux 3 hours, obtains homogeneous phase solution.
2) until step 1) in solution be cooled to room temperature after, add 22 parts of p-PDA, 0.13 part of isoquinoline 99.9, under the condition of nitrogen protection reflux stir 15min, obtain homogeneous phase solution.After being cooled to room temperature, add 0.25 part
fSO-100, stirring at normal temperature 20min under the condition of nitrogen protection, obtain polyimide precursor resin solution.
3) by step 2) in polyimide precursor resin solution 60 DEG C of rotary evaporations to pouring in enamel tray after thick, then put into baking oven and carry out drying and obtain solid resin; Foam precursor powder is obtained after pulverizing.
4) by 20g step 3) in foam precursor powder put into 80mm × 80mm × 30mm stainless steel mould, mould is put into thermocompressor, pressurization fixed mould, then by room temperature to 320 DEG C, and constant temperature 3 hours; Be down to die sinking after room temperature, obtain thermoplastic soft foam.The compression performance of gained foam is poor, and adding of end-capping reagent NA is described, can by the crosslinked ultimate compression strength significantly improving foam.
Embodiment 2
1) in the there-necked flask that mechanical stirrer, spherical reflux condensing tube and thermometer are housed, add 29 parts of α-BPDA, 37 parts of dehydrated alcohols, 29 parts of anhydrous tetrahydro furans, under the condition stirred, reflux 3 hours, obtains homogeneous phase solution.
2) in the single port bottle that electromagnetic mixing apparatus, spherical reflux condensing tube are housed, add 36 parts of MNA, 67 parts of dehydrated alcohols, under the condition stirred, heating 3 hours, obtains homogeneous phase solution.After being cooled to room temperature, this solution is added the step 1 being cooled to room temperature) in solution in, and add 22 parts of p-PDA, 0.13 part of isoquinoline 99.9, under the condition of nitrogen protection, reflux stirs 15min, obtains homogeneous phase solution.After being cooled to room temperature, add 0.25 part
fSO-100, stirring at normal temperature 20min under the condition of nitrogen protection, obtain polyimide precursor resin solution.
3) by step 2) in polyimide precursor resin solution 60 DEG C of rotary evaporations to pouring in enamel tray after thick, then put into baking oven and carry out drying and obtain solid resin; Foam precursor powder is obtained after pulverizing.
Formula I is the structural formula of above-mentioned foam precursor powder.
In described formula I general structure, X is methyl, and Ar is 2,3,3 ', 4 '-xenyl, and R is to phenyl, and n is 1.Fig. 2 is the infrared spectrum that this embodiment prepares gained polyimide, as seen from the figure, and 1779cm
-1and 1720cm
-1asymmetric and the symmetrical stretching vibration absorption peak of carbonyl for imide group, 1369cm
-1for the C-N stretching vibration absorption peak of imide group, illustrate and define imide ring.As from the foregoing, it is correct that this embodiment prepares products therefrom structure, is polymkeric substance shown in formula I.
4) by 20g step 3) in foam precursor powder put into 80mm × 80mm × 30mm stainless steel mould, mould is put into thermocompressor, pressurization fixed mould, then by room temperature to 320 DEG C, and constant temperature 3 hours; Be cooled to die sinking after room temperature, obtain the Polyimide foams of complete crosslinking curing, the density of foam is 100kg/m
3, second-order transition temperature is 345 DEG C, and ultimate compression strength is 1.1MPa, and concrete performance is listed in table 2.
Embodiment 3
1) in the there-necked flask that mechanical stirrer, spherical reflux condensing tube and thermometer are housed, add 29 parts of α-BPDA, 37 parts of dehydrated alcohols, 29 parts of anhydrous tetrahydro furans, under the condition stirred, reflux 3 hours, obtains homogeneous phase solution.
2) in the single port bottle that electromagnetic mixing apparatus, spherical reflux condensing tube are housed, add 11 parts of NA, 25 parts of dehydrated alcohols, under the condition stirred, heating 3 hours, obtains homogeneous phase solution.After being cooled to room temperature, this solution is added the step 1 being cooled to room temperature) in solution in, and add 14 parts of p-PDA, 0.13 part of isoquinoline 99.9, under the condition of nitrogen protection, reflux stirs 15min, obtains homogeneous phase solution.After being cooled to room temperature, add 0.22 part
fSO-100, stirring at normal temperature 20min under the condition of nitrogen protection, obtain polyimide precursor resin solution.
3) by step 2) in polyimide precursor resin solution 60 DEG C of rotary evaporations to pouring in enamel tray after thick, then put into baking oven and carry out drying and obtain solid resin; Foam precursor powder is obtained after pulverizing.Formula I is the structural formula of above-mentioned foam precursor powder.
In described formula I general structure, X is hydrogen bond, and Ar is 2,3,3 ', 4 '-xenyl, and R is to phenyl, and n is 3.Fig. 3 is the infrared spectrum that this embodiment prepares gained polyimide, as seen from the figure, and 1779cm
-1and 1720cm
-1asymmetric and the symmetrical stretching vibration absorption peak of carbonyl for imide group, 1369cm
-1for the C-N stretching vibration absorption peak of imide group, illustrate and define imide ring.As from the foregoing, it is correct that this embodiment prepares products therefrom structure, is polymkeric substance shown in formula I.
4) by 10g step 3) in foam precursor powder put into 80mm × 80mm × 30mm stainless steel mould, mould is put into thermocompressor, pressurization fixed mould, then by room temperature to 320 DEG C, and constant temperature 3 hours; Be cooled to die sinking after room temperature, obtain the Polyimide foams of complete crosslinking curing, the density of foam is 50kg/m
3, second-order transition temperature is 350 DEG C, and ultimate compression strength is 0.2MPa, and concrete performance is listed in table 2.
Embodiment 4
1) in the there-necked flask that mechanical stirrer, spherical reflux condensing tube and thermometer are housed, add 29 parts of α-BPDA, 11 parts of NA, 61 parts of dehydrated alcohols, 29 parts of anhydrous tetrahydro furans, under the condition stirred, reflux 3 hours, obtains homogeneous phase solution.
2) after being cooled to room temperature, add 14 parts of p-PDA, 0.13 part of isoquinoline 99.9, under the condition of nitrogen protection, reflux stirs 15min, obtains homogeneous phase solution.After being cooled to room temperature, add 0.22 part
fSO-100, stirring at normal temperature 20min under the condition of nitrogen protection, obtain polyimide precursor resin solution.
3) by step 2) in polyimide precursor resin solution 60 DEG C of rotary evaporations to pouring in enamel tray after thick, then put into baking oven and carry out drying and obtain solid resin; Foam precursor powder is obtained after pulverizing.
4) by 10g step 3) in foam precursor powder put into 80mm × 80mm × 30mm stainless steel mould, mould is put into thermocompressor, pressurization fixed mould, then by room temperature to 320 DEG C, and constant temperature 3 hours; Be cooled to die sinking after room temperature, obtain the Polyimide foams of complete crosslinking curing, the density of foam is 50kg/m
3, second-order transition temperature is 350 DEG C, and ultimate compression strength is 0.2MPa, and its performance is identical with the performance of gained foam materials in embodiment 3, illustrate by α-BPDA and NA together esterification on the performance of gained foam without impact.
Embodiment 5
Step 3 by 20g embodiment 3) in foam precursor powder put into stainless steel mould, mould is put into thermocompressor, pressurization fixed mould, then by room temperature to 320 DEG C, and constant temperature 3 hours; Be cooled to die sinking after room temperature, obtain the Polyimide foams of complete crosslinking curing, the density of foam is 100kg/m
3, second-order transition temperature is 350 DEG C, and ultimate compression strength is 1.4MPa, and concrete performance is listed in table 2.
Embodiment 6
Step 3 by 20g embodiment 3) in foam precursor powder put into stainless steel mould, mould is put into thermocompressor, pressurization fixed mould, then by room temperature to 350 DEG C, and constant temperature 7 hours; Be cooled to die sinking after room temperature, obtain the Polyimide foams of complete crosslinking curing, the density of foam is 100kg/m
3, second-order transition temperature is 360 DEG C, and ultimate compression strength is 1.0MPa, and concrete performance is listed in table 2.
Embodiment 7
Step 3 by 40g embodiment 3) in foam precursor powder put into stainless steel mould, mould is put into thermocompressor, pressurization fixed mould, then by room temperature to 320 DEG C, and constant temperature 3 hours; Be cooled to die sinking after room temperature, obtain the Polyimide foams of complete crosslinking curing, the density of foam is 200kg/m
3, second-order transition temperature is 350 DEG C, and ultimate compression strength is 4.2MPa, and concrete performance is listed in table 2.
Embodiment 8
Step 3 by 50g embodiment 3) in foam precursor powder put into stainless steel mould, mould is put into thermocompressor, pressurization fixed mould, then by room temperature to 320 DEG C, and constant temperature 3 hours; Be cooled to die sinking after room temperature, obtain the Polyimide foams of complete crosslinking curing, the density of foam is 250kg/m
3, second-order transition temperature is 350 DEG C, and ultimate compression strength is 6.1MPa, and concrete performance is listed in table 2.
Embodiment 9
Step 3 by 60g embodiment 3) in foam precursor powder put into stainless steel mould, mould is put into thermocompressor, pressurization fixed mould, then by room temperature to 320 DEG C, and constant temperature 3 hours; Be cooled to die sinking after room temperature, obtain the Polyimide foams of complete crosslinking curing, the density of foam is 300kg/m
3, second-order transition temperature is 350 DEG C, and ultimate compression strength is 7.9MPa, and concrete performance is listed in table 2.
Embodiment 10
Step 3 by 80g embodiment 3) in foam precursor powder put into stainless steel mould, mould is put into thermocompressor, pressurization fixed mould, then by room temperature to 320 DEG C, and constant temperature 3 hours; Be cooled to die sinking after room temperature, obtain the Polyimide foams of complete crosslinking curing, the density of foam is 400kg/m
3, second-order transition temperature is 350 DEG C, and ultimate compression strength is 10.8MPa, and concrete performance is listed in table 2.
Embodiment 11
Step 3 by 100g embodiment 3) in foam precursor powder put into stainless steel mould, mould is put into thermocompressor, pressurization fixed mould, then by room temperature to 320 DEG C, and constant temperature 3 hours; Be cooled to die sinking after room temperature, obtain the Polyimide foams of complete crosslinking curing, the density of foam is 500kg/m
3, second-order transition temperature is 350 DEG C, and ultimate compression strength is 14.1MPa, and concrete performance is listed in table 2.
Embodiment 12
1) in the there-necked flask that mechanical stirrer, spherical reflux condensing tube and thermometer are housed, add 15 parts of α-BPDA, 18 parts of dehydrated alcohols, 14 parts of anhydrous tetrahydro furans, under the condition stirred, reflux 3 hours, obtains homogeneous phase solution.
2) in the single port bottle that electromagnetic mixing apparatus, spherical reflux condensing tube are housed, add 15 parts of s-BPDA, 18 parts of dehydrated alcohols, 14 parts of anhydrous tetrahydro furans, 7 parts of N,N-dimethylacetamide, under the condition stirred, reflux 6 hours, obtains homogeneous phase solution.
3) in the single port bottle that electromagnetic mixing apparatus, spherical reflux condensing tube are housed, add 11 parts of NA, 25 parts of dehydrated alcohols, under the condition stirred, heating 3 hours, obtains homogeneous phase solution.
4) will the step 2 after room temperature be cooled to), step 3) in solution add the step 1 being cooled to room temperature) in solution in; and add 14 parts of p-PDA; 0.13 part of isoquinoline 99.9, under the condition of nitrogen protection, reflux stirs 15min, obtains homogeneous phase solution.After being cooled to room temperature, add 0.22 part
fSO-100, stirring at normal temperature 20min under the condition of nitrogen protection, obtain polyimide precursor resin solution.
5) by step 4) in polyimide precursor resin solution 60 DEG C of rotary evaporations to pouring in enamel tray after thick, then put into baking oven and carry out drying and obtain solid resin; Foam precursor powder is obtained after pulverizing.
Formula I is the structural formula of above-mentioned foam precursor powder.
In described formula I general structure, X is hydrogen bond, and Ar is 2,3,3 ', 4 '-xenyl and 3,3 ', 4, and 4 '-xenyl, the mol ratio of two kinds of dianhydrides is 1: 1, R is to phenyl, and n is 3.Fig. 4 is the infrared spectrum that this embodiment prepares gained polyimide, as seen from the figure, and 1779cm
-1and 1720cm
-1asymmetric and the symmetrical stretching vibration absorption peak of carbonyl for imide group, 1369cm
-1for the C-N stretching vibration absorption peak of imide group, illustrate and define imide ring.As from the foregoing, it is correct that this embodiment prepares products therefrom structure, is polymkeric substance shown in formula I.
6) by 20g step 5) in foam precursor powder put into 80mm × 80mm × 30mm stainless steel mould, mould is put into thermocompressor, pressurization fixed mould, then by room temperature to 320 DEG C, and constant temperature 3 hours; Be cooled to die sinking after room temperature, obtain the Polyimide foams of complete crosslinking curing, the density of foam is 100kg/m
3, second-order transition temperature is 350 DEG C, and ultimate compression strength is 1.0MPa, and concrete performance is listed in table 2.
Embodiment 13
1) in the there-necked flask that mechanical stirrer, spherical reflux condensing tube and thermometer are housed, 15 parts of α-BPDA are added, 15 parts of s-BPDA, 37 parts of dehydrated alcohols, 29 parts of anhydrous tetrahydro furans, 7 parts of N,N-dimethylacetamide, under the condition stirred, reflux 6 hours, obtains homogeneous phase solution.
2) in the single port bottle that electromagnetic mixing apparatus, spherical reflux condensing tube are housed, add 11 parts of NA, 25 parts of dehydrated alcohols, under the condition stirred, heating 3 hours, obtains homogeneous phase solution.After being cooled to room temperature, this solution is added the step 1 being cooled to room temperature) in solution in, and add 14 parts of p-PDA, 0.13 part of isoquinoline 99.9, under the condition of nitrogen protection, reflux stirs 15min, obtains homogeneous phase solution.After being cooled to room temperature, add 0.22 part
fSO-100, stirring at normal temperature 20min under the condition of nitrogen protection, obtain polyimide precursor resin solution.
3) by step 2) in polyimide precursor resin solution 60 DEG C of rotary evaporations to pouring in enamel tray after thick, then put into baking oven and carry out drying and obtain solid resin; Foam precursor powder is obtained after pulverizing.
4) by 20g step 3) in foam precursor powder put into 80mm × 80mm × 30mm stainless steel mould, mould is put into thermocompressor, pressurization fixed mould, then by room temperature to 320 DEG C, and constant temperature 3 hours; Be cooled to die sinking after room temperature, obtain the Polyimide foams of complete crosslinking curing, the density of foam is 100kg/m
3, second-order transition temperature is 350 DEG C, and ultimate compression strength is 1.0MPa, and its performance is consistent with gained foam performance in embodiment 12, illustrate by α-BPDA and other aromatic series tetracarboxylic dianhydrides together esterification on the performance of gained foam without impact.
Embodiment 14
1) in the there-necked flask that mechanical stirrer, spherical reflux condensing tube and thermometer are housed, add 27 parts of α-BPDA, 3 parts of ODPA, 37 parts of dehydrated alcohols, 29 parts of anhydrous tetrahydro furans, under the condition stirred, reflux 3 hours, obtains homogeneous phase solution.
2) in the single port bottle that electromagnetic mixing apparatus, spherical reflux condensing tube are housed, add 11 parts of NA, 25 parts of dehydrated alcohols, under the condition stirred, heating 3 hours, obtains homogeneous phase solution.After being cooled to room temperature, this solution is added the step 1 being cooled to room temperature) in solution in, and add 14 parts of p-PDA, 0.13 part of isoquinoline 99.9, under the condition of nitrogen protection, reflux stirs 15min, obtains homogeneous phase solution.After being cooled to room temperature, add 0.22 part
fSO-100, stirring at normal temperature 20min under the condition of nitrogen protection, obtain polyimide precursor resin solution.
3) by step 2) in polyimide precursor resin solution 60 DEG C of rotary evaporations to pouring in enamel tray after thick, then put into baking oven and carry out drying and obtain solid resin; Foam precursor powder is obtained after pulverizing.Formula I is the structural formula of above-mentioned foam precursor powder.
In described formula I general structure, X is hydrogen bond, and Ar is 2,3,3 ', 4 '-xenyl and 3,3,4 ', 4 '-hexichol ether, and the mol ratio of two kinds of dianhydrides is 9: 1, R is to phenyl, and n is 3.Fig. 5 is the infrared spectrum that this embodiment prepares gained polyimide, as seen from the figure, and 1779cm
-1and 1720cm
-1asymmetric and the symmetrical stretching vibration absorption peak of carbonyl for imide group, 1369cm
-1for the C-N stretching vibration absorption peak of imide group, illustrate and define imide ring.As from the foregoing, it is correct that this embodiment prepares products therefrom structure, is polymkeric substance shown in formula I.
4) by 20g step 3) in foam precursor powder put into 80mm × 80mm × 30mm stainless steel mould, mould is put into thermocompressor, pressurization fixed mould, then by room temperature to 320 DEG C, and constant temperature 3 hours; Be cooled to die sinking after room temperature, obtain the Polyimide foams of complete crosslinking curing, the density of foam is 100kg/m
3, second-order transition temperature is 340 DEG C, and ultimate compression strength is 1.3MPa, and specific performance is listed in table 2.
Embodiment 15
1) in the there-necked flask that mechanical stirrer, spherical reflux condensing tube and thermometer are housed, add 18 parts of α-BPDA, 13 parts of BTDA, 37 parts of dehydrated alcohols, 29 parts of anhydrous tetrahydro furans, under the condition stirred, reflux 4 hours, obtains homogeneous phase solution.
2) in the single port bottle that electromagnetic mixing apparatus, spherical reflux condensing tube are housed, add 11 parts of NA, 25 parts of dehydrated alcohols, under the condition stirred, heating 3 hours, obtains homogeneous phase solution.After being cooled to room temperature, this solution is added the step 1 being cooled to room temperature) in solution in, and add 14 parts of p-PDA, 0.13 part of isoquinoline 99.9, under the condition of nitrogen protection, reflux stirs 15min, obtains homogeneous phase solution.After being cooled to room temperature, add 0.23 part
fSO-100, stirring at normal temperature 20min under the condition of nitrogen protection, obtain polyimide precursor resin solution.
3) by step 2) in polyimide precursor resin solution 60 DEG C of rotary evaporations to pouring in enamel tray after thick, then put into baking oven and carry out drying and obtain solid resin; Foam precursor powder is obtained after pulverizing.
Formula I is the structural formula of above-mentioned foam precursor powder.
In described formula I general structure, X is hydrogen bond, and Ar is 2,3,3 ', 4 '-xenyl and 3,3 ', 4, and 4 '-benzophenone base, the mol ratio of two kinds of dianhydrides is 6: 4, R is to phenyl, and n is 3.Fig. 6 is the infrared spectrum that this embodiment prepares gained polyimide, as seen from the figure, and 1779cm
-1and 1720cm
-1asymmetric and the symmetrical stretching vibration absorption peak of carbonyl for imide group, 1369cm
-1for the C-N stretching vibration absorption peak of imide group, illustrate and define imide ring.As from the foregoing, it is correct that this embodiment prepares products therefrom structure, is polymkeric substance shown in formula I.
4) by 20g step 3) in foam precursor powder put into 80mm × 80mm × 30mm stainless steel mould, mould is put into thermocompressor, pressurization fixed mould, then by room temperature to 320 DEG C, and constant temperature 3 hours; Be cooled to die sinking after room temperature, obtain the Polyimide foams of complete crosslinking curing, the density of foam is 100kg/m
3, second-order transition temperature is 341 DEG C, and ultimate compression strength is 1.2MPa, and specific performance is listed in table 2.
Embodiment 16
1) in the there-necked flask that mechanical stirrer, spherical reflux condensing tube and thermometer are housed, add 3 parts of α-BPDA, 20 parts of PMDA, 37 parts of dehydrated alcohols, 29 parts of anhydrous tetrahydro furans, under the condition stirred, reflux 3 hours, obtains homogeneous phase solution.
2) in the single port bottle that electromagnetic mixing apparatus, spherical reflux condensing tube are housed, add 11 parts of NA, 25 parts of dehydrated alcohols, under the condition stirred, heating 3 hours, obtains homogeneous phase solution.After being cooled to room temperature, this solution is added the step 1 being cooled to room temperature) in solution in, and add 14 parts of p-PDA, 0.13 part of isoquinoline 99.9, under the condition of nitrogen protection, reflux stirs 15min, obtains homogeneous phase solution.After being cooled to room temperature, add 0.18 part
fSO-100, stirring at normal temperature 20min under the condition of nitrogen protection, obtain polyimide precursor resin solution.
3) by step 2) in polyimide precursor resin solution 60 DEG C of rotary evaporations to pouring in enamel tray after thick, then put into baking oven and carry out drying and obtain solid resin; Foam precursor powder is obtained after pulverizing.
Formula I is the structural formula of above-mentioned foam precursor powder.
In described formula I general structure, X is hydrogen bond, and Ar is 2,3,3 ', 4 '-xenyl and the equal phenyl of 1,2,4,5-, and the mol ratio of two kinds of dianhydrides is 1: 9, R is to phenyl, and n is 3.Fig. 7 is the infrared spectrum that this embodiment prepares gained polyimide, as seen from the figure, and 1779cm
-1and 1720cm
-1asymmetric and the symmetrical stretching vibration absorption peak of carbonyl for imide group, 1369cm
-1for the C-N stretching vibration absorption peak of imide group, illustrate and define imide ring.As from the foregoing, it is correct that this embodiment prepares products therefrom structure, is polymkeric substance shown in formula I.
4) by 20g step 3) in foam precursor powder put into 80mm × 80mm × 30mm stainless steel mould, mould is put into thermocompressor, pressurization fixed mould, then by room temperature to 320 DEG C, and constant temperature 3 hours; Be cooled to die sinking after room temperature, obtain the Polyimide foams of complete crosslinking curing, the density of foam is 100kg/m
3, second-order transition temperature is 356 DEG C, and ultimate compression strength is 1.1MPa, and specific performance is listed in table 2.
Embodiment 17
1) in the there-necked flask that mechanical stirrer, spherical reflux condensing tube and thermometer are housed, add 29 parts of α-BPDA, 37 parts of dehydrated alcohols, 29 parts of anhydrous tetrahydro furans, under the condition stirred, reflux 3 hours, obtains homogeneous phase solution.
2) in the single port bottle that electromagnetic mixing apparatus, spherical reflux condensing tube are housed, add 11 parts of NA, 25 parts of dehydrated alcohols, under the condition stirred, heating 3 hours, obtains homogeneous phase solution.After being cooled to room temperature, this solution is added the step 1 being cooled to room temperature) in solution in, and add 7 parts of m-PDA, 7 parts of p-PDA, 0.13 part of isoquinoline 99.9, under the condition of nitrogen protection, reflux stirs 15min, obtains homogeneous phase solution.After being cooled to room temperature, add 0.22 part
fSO-100, stirring at normal temperature 20min under the condition of nitrogen protection, obtain polyimide precursor resin solution.
3) by step 2) in polyimide precursor resin solution 60 DEG C of rotary evaporations to pouring in enamel tray after thick, then put into baking oven and carry out drying and obtain solid resin; Foam precursor powder is obtained after pulverizing.Formula I is the structural formula of above-mentioned foam precursor powder.
In described formula I general structure, X is hydrogen bond, and Ar is 2,3,3 ', 4 '-xenyl, and R is to phenyl and a phenyl, and the mol ratio of two kinds of diamines is 1: 1, n is 3.Fig. 8 is the infrared spectrum that this embodiment prepares gained polyimide, as seen from the figure, and 1779cm
-1and 1720cm
-1asymmetric and the symmetrical stretching vibration absorption peak of carbonyl for imide group, 1369cm
-1for the C-N stretching vibration absorption peak of imide group, illustrate and define imide ring.As from the foregoing, it is correct that this embodiment prepares products therefrom structure, is polymkeric substance shown in formula I.
4) by 20g step 3) in foam precursor powder put into 80mm × 80mm × 30mm stainless steel mould, mould is put into thermocompressor, pressurization fixed mould, then by room temperature to 320 DEG C, and constant temperature 3 hours; Be cooled to die sinking after room temperature, obtain the Polyimide foams of complete crosslinking curing, the density of foam is 100kg/m
3, second-order transition temperature is 340 DEG C, and ultimate compression strength is 1.2MPa, and specific performance is listed in table 2.
Embodiment 18
1) in the there-necked flask that mechanical stirrer, spherical reflux condensing tube and thermometer are housed, add 29 parts of α-BPDA, 37 parts of dehydrated alcohols, 29 parts of anhydrous tetrahydro furans, under the condition stirred, reflux 3 hours, obtains homogeneous phase solution.
2) in the single port bottle that electromagnetic mixing apparatus, spherical reflux condensing tube are housed, add 11 parts of NA, 25 parts of dehydrated alcohols, under the condition stirred, heating 3 hours, obtains homogeneous phase solution.After being cooled to room temperature, this solution is added the step 1 being cooled to room temperature) in solution in, and add 7 parts of p-PDA, 13 part 3,4 '-ODA, 0.13 part of isoquinoline 99.9, under the condition of nitrogen protection, reflux stirs 15min, obtains homogeneous phase solution.After being cooled to room temperature, add 0.22 part
fSO-100, stirring at normal temperature 20min under the condition of nitrogen protection, obtain polyimide precursor resin solution.
3) by step 2) in polyimide precursor resin solution 60 DEG C of rotary evaporations to pouring in enamel tray after thick, then put into baking oven and carry out drying and obtain solid resin; Foam precursor powder is obtained after pulverizing.
Formula I is the structural formula of above-mentioned foam precursor powder.
In described formula I general structure, X is hydrogen bond, and Ar is 2,3,3 ', 4 '-xenyl, and R is to phenyl and 3,4 '-hexichol ether, and the mol ratio of two kinds of diamines is 1: 1, n is 3.Fig. 9 is the infrared spectrum that this embodiment prepares gained polyimide, as seen from the figure, and 1779cm
-1and 1720cm
-1asymmetric and the symmetrical stretching vibration absorption peak of carbonyl for imide group, 1369cm
-1for the C-N stretching vibration absorption peak of imide group, illustrate and define imide ring.As from the foregoing, it is correct that this embodiment prepares products therefrom structure, is polymkeric substance shown in formula I.
4) by 20g step 3) in foam precursor powder put into 80mm × 80mm × 30mm stainless steel mould, mould is put into thermocompressor, pressurization fixed mould, then by room temperature to 320 DEG C, and constant temperature 3 hours; Be cooled to die sinking after room temperature, obtain the Polyimide foams of complete crosslinking curing, the density of foam is 100kg/m
3, second-order transition temperature is 320 DEG C, and ultimate compression strength is 1.0MPa, and specific performance is listed in table 2.
Embodiment 19
1) in the there-necked flask that mechanical stirrer, spherical reflux condensing tube and thermometer are housed, add 29 parts of α-BPDA, 37 parts of dehydrated alcohols, 29 parts of anhydrous tetrahydro furans, under the condition stirred, reflux 3 hours, obtains homogeneous phase solution.
2) in the single port bottle that electromagnetic mixing apparatus, spherical reflux condensing tube are housed, add 11 parts of NA, 25 parts of dehydrated alcohols, under the condition stirred, heating 3 hours, obtains homogeneous phase solution.After being cooled to room temperature, this solution is added the step 1 being cooled to room temperature) in solution in, and add 27 part 4,4 '-ODA, 0.13 part of isoquinoline 99.9, under the condition of nitrogen protection, reflux stirs 6h, obtains homogeneous phase solution.After being cooled to room temperature, add 0.28 part
fSO-100, stirring at normal temperature 20min under the condition of nitrogen protection, obtain polyimide precursor resin solution.
3) by step 2) in polyimide precursor resin solution 60 DEG C of rotary evaporations to pouring in enamel tray after thick, then put into baking oven and carry out drying and obtain solid resin; Foam precursor powder is obtained after pulverizing.
Formula I is the structural formula of above-mentioned foam precursor powder.
In described formula I general structure, X is hydrogen bond, and Ar is 2,3,3 ', 4 '-xenyl, and R is 4,4 '-hexichol ether, and n is 3.Figure 10 is the infrared spectrum that this embodiment prepares gained polyimide, as seen from the figure, and 1779cm
-1and 1720cm
-1asymmetric and the symmetrical stretching vibration absorption peak of carbonyl for imide group, 1369cm
-1for the C-N stretching vibration absorption peak of imide group, illustrate and define imide ring.As from the foregoing, it is correct that this embodiment prepares products therefrom structure, is polymkeric substance shown in formula I.
4) by 40g step 3) in foam precursor powder put into 80mm × 80mm × 30mm stainless steel mould, mould is put into thermocompressor, pressurization fixed mould, then by room temperature to 320 DEG C, and constant temperature 3 hours; Be cooled to die sinking after room temperature, obtain the Polyimide foams of complete crosslinking curing, the density of foam is 200kg/m
3, second-order transition temperature is 337 DEG C, and ultimate compression strength is 3.2MPa, and specific performance is listed in table 2.
Embodiment 20
1) in the there-necked flask that mechanical stirrer, spherical reflux condensing tube and thermometer are housed, add 29 parts of α-BPDA, 37 parts of dehydrated alcohols, 29 parts of anhydrous tetrahydro furans, under the condition stirred, reflux 3 hours, obtains homogeneous phase solution.
2) in the single port bottle that electromagnetic mixing apparatus, spherical reflux condensing tube are housed, add 11 parts of NA, 25 parts of dehydrated alcohols, under the condition stirred, heating 3 hours, obtains homogeneous phase solution.After being cooled to room temperature, this solution is added the step 1 being cooled to room temperature) in solution in, and add 26 parts of MDA, 0.13 part of isoquinoline 99.9, under the condition of nitrogen protection, reflux stirs 15min, obtains homogeneous phase solution.After being cooled to room temperature, add 0.28 part
fSO-100, stirring at normal temperature 20min under the condition of nitrogen protection, obtain polyimide precursor resin solution.
3) by step 2) in polyimide precursor resin solution 60 DEG C of rotary evaporations to pouring in enamel tray after thick, then put into baking oven and carry out drying and obtain solid resin; Foam precursor powder is obtained after pulverizing.
Formula I is the structural formula of above-mentioned foam precursor powder.
In described formula I general structure, X is hydrogen bond, and Ar is 2,3,3 ', 4 '-xenyl, and R is 4,4 '-diphenylmethane group, and n is 3.Figure 11 is the infrared spectrum that this embodiment prepares gained polyimide, as seen from the figure, and 1779cm
-1and 1720cm
-1asymmetric and the symmetrical stretching vibration absorption peak of carbonyl for imide group, 1369cm
-1for the C-N stretching vibration absorption peak of imide group, illustrate and define imide ring.As from the foregoing, it is correct that this embodiment prepares products therefrom structure, is polymkeric substance shown in formula I.
4) by 40g step 3) in foam precursor powder put into 80mm × 80mm × 30mm stainless steel mould, mould is put into thermocompressor, pressurization fixed mould, then by room temperature to 320 DEG C, and constant temperature 3 hours; Be cooled to die sinking after room temperature, obtain the Polyimide foams of complete crosslinking curing, the density of foam is 200kg/m
3, second-order transition temperature is 343 DEG C, and ultimate compression strength is 2.9MPa, and specific performance is listed in table 2.
Embodiment 21
1) in the there-necked flask that mechanical stirrer, spherical reflux condensing tube and thermometer are housed, add 29 parts of α-BPDA, 37 parts of dehydrated alcohols, 29 parts of anhydrous tetrahydro furans, under the condition stirred, reflux 3 hours, obtains homogeneous phase solution.
2) in the single port bottle that electromagnetic mixing apparatus, spherical reflux condensing tube are housed, add 11 parts of NA, 25 parts of dehydrated alcohols, under the condition stirred, heating 3 hours, obtains homogeneous phase solution.After being cooled to room temperature, this solution is added the step 1 being cooled to room temperature) in solution in, and add 33 parts of DDS, 0.13 part of isoquinoline 99.9, under the condition of nitrogen protection, reflux stirs 15min, obtains homogeneous phase solution.After being cooled to room temperature, add 0.31 part
fSO-100, stirring at normal temperature 20min under the condition of nitrogen protection, obtain polyimide precursor resin solution.
3) by step 2) in polyimide precursor resin solution 60 DEG C of rotary evaporations to pouring in enamel tray after thick, then put into baking oven and carry out drying and obtain solid resin; Foam precursor powder is obtained after pulverizing.
Formula I is the structural formula of above-mentioned foam precursor powder.
In described formula I general structure, X is hydrogen bond, and Ar is 2,3,3 ', 4 '-xenyl, and R is 4,4 '-diphenyl sulfone, and n is 3.Figure 12 is the infrared spectrum that this embodiment prepares gained polyimide, as seen from the figure, and 1779cm
-1and 1720cm
-1asymmetric and the symmetrical stretching vibration absorption peak of carbonyl for imide group, 1369cm
-1for the C-N stretching vibration absorption peak of imide group, illustrate and define imide ring.As from the foregoing, it is correct that this embodiment prepares products therefrom structure, is polymkeric substance shown in formula I.
4) by 40g step 3) in foam precursor powder put into 80mm × 80mm × 30mm stainless steel mould, mould is put into thermocompressor, pressurization fixed mould, then by room temperature to 320 DEG C, and constant temperature 3 hours; Be cooled to die sinking after room temperature, obtain the Polyimide foams of complete crosslinking curing, the density of foam is 200kg/m
3, second-order transition temperature is 354 DEG C, and ultimate compression strength is 2.3MPa, and specific performance is listed in table 2.
Embodiment 22
1) in the there-necked flask that mechanical stirrer, spherical reflux condensing tube and thermometer are housed, add 29 parts of α-BPDA, 0.66 part of NA, 38 parts of dehydrated alcohols, 29 parts of anhydrous tetrahydro furans, under the condition stirred, reflux 3 hours, obtains homogeneous phase solution.
2) after being cooled to room temperature, add 25 parts of DDS, 0.13 part of isoquinoline 99.9, under the condition of nitrogen protection, reflux stirs 15min, obtains homogeneous phase solution.After being cooled to room temperature, add 0.27 part
fSO-100, stirring at normal temperature 20min under the condition of nitrogen protection, obtain polyimide precursor resin solution.
3) by step 2) in polyimide precursor resin solution 60 DEG C of rotary evaporations to pouring in enamel tray after thick, then put into baking oven and carry out drying and obtain solid resin; Foam precursor powder is obtained after pulverizing.
Formula I is the structural formula of above-mentioned foam precursor powder.
In described formula I general structure, X is hydrogen bond, and Ar is 2,3,3 ', 4 '-xenyl, and R is 4,4 '-diphenyl sulfone, and n is 50.Figure 13 is the infrared spectrum that this embodiment prepares gained polyimide, as seen from the figure, and 1779cm
-1and 1720cm
-1asymmetric and the symmetrical stretching vibration absorption peak of carbonyl for imide group, 1369cm
-1for the C-N stretching vibration absorption peak of imide group, illustrate and define imide ring.As from the foregoing, it is correct that this embodiment prepares products therefrom structure, is polymkeric substance shown in formula I.
4) by 40g step 3) in foam precursor powder put into 80mm × 80mm × 30mm stainless steel mould, mould is put into thermocompressor, pressurization fixed mould, then by room temperature to 320 DEG C, and constant temperature 3 hours; Be cooled to die sinking after room temperature, obtain the Polyimide foams of complete crosslinking curing, the density of foam is 200kg/m
3, second-order transition temperature is 340 DEG C, and ultimate compression strength is 1.3MPa, and specific performance is listed in table 2.
Embodiment 23
1) in the there-necked flask that mechanical stirrer, spherical reflux condensing tube and thermometer are housed, add 29 parts of α-BPDA, 37 parts of dehydrated alcohols, 29 parts of anhydrous tetrahydro furans, under the condition stirred, reflux 3 hours, obtains homogeneous phase solution.
2) in the single port bottle that electromagnetic mixing apparatus, spherical reflux condensing tube are housed, add 11 parts of NA, 25 parts of dehydrated alcohols, under the condition stirred, heating 3 hours, obtains homogeneous phase solution.After being cooled to room temperature, this solution is added the step 1 being cooled to room temperature) in solution in, and add 33 parts of DDS, 0.13 part of 1,2 dimethylimidazole, under the condition of nitrogen protection, reflux stirs 15min, obtains homogeneous phase solution.After being cooled to room temperature, adding 0.31 part of polymethyl siloxane, stirring at normal temperature 20min under the condition of nitrogen protection, obtain polyimide precursor resin solution.
3) by step 2) in polyimide precursor resin solution 60 DEG C of rotary evaporations to pouring in enamel tray after thick, then put into baking oven and carry out drying and obtain solid resin; Foam precursor powder is obtained after pulverizing.
4) by 40g step 3) in foam precursor powder put into 80mm × 80mm × 30mm stainless steel mould, mould is put into thermocompressor, pressurization fixed mould, then by room temperature to 320 DEG C, and constant temperature 3 hours; Be cooled to die sinking after room temperature, obtain the Polyimide foams of complete crosslinking curing, the density of foam is 200kg/m
3, second-order transition temperature is 354 DEG C, and ultimate compression strength is 2.1MPa, and specific performance is listed in table 2.
The performance of the incompressible Polyimide foams of the high temperature resistant height of gained is prepared in table 2. embodiment
Claims (5)
1. a presoma for crosslinked polyimide foam materials, its structural formula is such as formula shown in I:
In formula I, Ar is selected from the mixture of α-BPDA or α-BPDA and one or more Ar following:
R is selected from following at least one:
X is hydrogen or methyl; N is the integer of 1 ~ 50.
2. prepare a method for crosslinked polyimide foam materials presoma according to claim 1, it is characterized in that: described crosslinked polyimide foam materials is made up of the raw material comprising following mass parts:
Organic tetracid dicarboxylic anhydride and/or organic four acid mono 1-100,
Organic diamine monomer 1-100,
Norbornylene class dicarboxylic anhydride 1-100;
Wherein, described organic tetracarboxylic dianhydride is selected from 2,3,3 ', 4 '-BPDA or 2,3, the mixture of 3 ', 4 '-BPDA and following at least one: 3,3 ', 4,4 '-BPDA, 3,3 ', 4,4 '-two methyl-phenoxide tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 1,2,4,5-pyromellitic acid anhydride, 1,2,3,4-tetramethylene tetracarboxylic dianhydride and 1,2,4,5-cyclopentanetetracarboxylic dianhydride;
Described organic four acid mono are selected from 2,3,3 ', 4 '-bibenzene tetracarboxylic or 2,3, the mixture of 3 ', 4 '-bibenzene tetracarboxylic and following at least one: 3,3 ', 4,4 '-bibenzene tetracarboxylic, 3,3 ', 4,4 '-two methyl-phenoxide tetracarboxylic acid, 3,3 ', 4,4 '-benzophenone tetracarboxylic, 1,2,4,5-Pyromellitic Acid, 1,2,3,4-cyclobutanetetracarboxylic and 1,2,4,5-cyclopentanetetracarboxylic;
Described organic diamine monomer is selected from following at least one: mphenylenediamine, Ursol D, 3,4 '-diaminodiphenyl oxide, 4,4 '-diaminodiphenyl oxide, 4,4 '-diaminodiphenyl-methane, 4,4 '-diaminodiphenylsulfone(DDS), 1, two [4-(4-amino-benzene oxygen) phenyl] propane of two (4-amino-benzene oxygen) benzene, DAP and 2, the 2-of 3-;
Described norbornylene class dicarboxylic anhydride is selected from norbornene dicarboxylic anhydride and/or methyl norbornene dioic anhydride;
Described method comprises the steps:
(1) described organic tetracarboxylic dianhydride and/or organic tetracid are mixed with lower boiling aliphatic alcohols solvent, aprotic polar solvent and ether solvent, reflux 3-8 hour, form the solution of organic diacid diester; By described norbornylene class dicarboxylic anhydride and lower boiling aliphatic alcohols solvent, reflux 3 ~ 8 hours, forms its esterification solution; Mix after the solution of described organic diacid diester and described esterification solution are cooled to room temperature, obtain homogeneous mixed solution;
Or described organic tetracarboxylic dianhydride and/or organic tetracid, norbornylene class dicarboxylic anhydride are mixed with lower boiling aliphatic alcohols solvent, aprotic polar solvent and ether solvent, reflux 3-8 hour, form homogeneous mixed solution and be also cooled to room temperature;
(2) in described mixing solutions, add organic diamine monomer, and add imide reaction catalyzer, tensio-active agent, react 15 minutes ~ 6 hours under nitrogen protection, obtain homogeneous phase polyimide foam precursor solution;
(3) polyimide precursor solution described in step (2) is placed in baking oven for heating, removing small molecules volatile matter, grinds, sieves, obtain polyimide foam precursor powder;
In described method, the mass parts of the solvent added, tensio-active agent and catalyzer is as follows, and identical in quality representated by every part of mass parts of every part of mass parts of described solvent, tensio-active agent and catalyzer and described raw material:
3. method according to claim 2, is characterized in that: described lower boiling aliphatic alcohols solvent be selected from following any one: methyl alcohol, ethanol, Virahol and propyl carbinol;
Described ether solvent be selected from following any one: tetrahydrofuran (THF), Polyethylene glycol dimethyl ether, diglyme and dioxane;
Described aprotic polar solvent be selected from following any one: N-Methyl pyrrolidone, DMF and N,N-dimethylacetamide;
Described tensio-active agent comprises polyoxyethylene groups ethers non-ionic type fluorocarbon surfactant, polymethyl siloxane, polydimethylsiloxane, organosilicon glycol copolymer, vinyl polysiloxane, cation fluorine carbon surface active agent and composition thereof;
Described catalyzer be selected from following any one: isoquinoline 99.9,1,2 dimethylimidazole, 2-ethyl-4-methylimidazole, benzoglyoxaline and substituted pyridines.
4. a crosslinked polyimide foam materials, prepare according to the method comprised the steps: by the precursor powder shown in claim 1 Chinese style I 300 ~ 400 DEG C of foaming and curing cross-linked 2 ~ 7 hours, obtain described crosslinked polyimide foam materials.
5. the application of crosslinked polyimide foam materials according to claim 4 in the following material of preparation: high temperature resistant sandwich material, high temperature resistant heat insulation material, high temperature resistant sound absorbent material and high temperature resistant wave-permeable material.
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| CN103788649B (en) * | 2013-12-20 | 2016-11-16 | 苏州市万泰真空炉研究所有限公司 | A kind of preparation method of high strength hard polyimide foam |
| 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 |
| CN104877112A (en) * | 2015-03-03 | 2015-09-02 | 北京理工大学 | Norbornene imide heat-resistant polymer porous material and preparation method thereof |
| CN107540841B (en) * | 2017-08-04 | 2020-07-14 | 航天材料及工艺研究所 | Preparation method of hard closed-cell polyimide foam |
| CN109593199B (en) * | 2018-11-30 | 2020-05-22 | 中国科学院化学研究所 | Soft polyimide foam, preparation method and application thereof |
| CN110342954A (en) * | 2019-06-28 | 2019-10-18 | 西安工程大学 | A kind of preparation method of high strength carbon foamed material |
| CN114044903B (en) * | 2021-12-29 | 2022-12-16 | 四川大学 | Hard polyimide foam and preparation method and application thereof |
| CN115895254A (en) * | 2022-11-23 | 2023-04-04 | 中国科学院化学研究所 | Polyimide foam material and preparation method thereof |
| CN116082637B (en) * | 2023-02-10 | 2023-07-28 | 富优特(山东)新材料科技有限公司 | Thermosetting polyimide foam material based on 2, 3',4' -biphenyl tetracarboxylic dianhydride and preparation method thereof |
| CN116199884A (en) * | 2023-02-20 | 2023-06-02 | 四川大学 | High-performance high-temperature-resistant heat-insulation polyimide foam and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1389494A (en) * | 2001-06-04 | 2003-01-08 | 中国科学院化学研究所 | Thermosetting polyimide base resin and its prepn. |
| CN101058639A (en) * | 2006-04-19 | 2007-10-24 | 中国科学院化学研究所 | Fluorine-containing polyimide basal body resin and preparation method thereof |
| WO2010087918A1 (en) * | 2009-01-31 | 2010-08-05 | General Electric Company | Autoclave cure cycle design process and curing method |
| CN102690415A (en) * | 2012-06-05 | 2012-09-26 | 中国科学院化学研究所 | Polyimide microspheres and preparation method and application thereof |
-
2012
- 2012-11-22 CN CN201210477864.3A patent/CN102964834B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1389494A (en) * | 2001-06-04 | 2003-01-08 | 中国科学院化学研究所 | Thermosetting polyimide base resin and its prepn. |
| CN101058639A (en) * | 2006-04-19 | 2007-10-24 | 中国科学院化学研究所 | Fluorine-containing polyimide basal body resin and preparation method thereof |
| WO2010087918A1 (en) * | 2009-01-31 | 2010-08-05 | General Electric Company | Autoclave cure cycle design process and curing method |
| CN102690415A (en) * | 2012-06-05 | 2012-09-26 | 中国科学院化学研究所 | Polyimide microspheres and preparation method and application thereof |
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