CN104017215A - Polyimide resin, preparation method thereof and polyimide foam - Google Patents
Polyimide resin, preparation method thereof and polyimide foam Download PDFInfo
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- CN104017215A CN104017215A CN201310066026.1A CN201310066026A CN104017215A CN 104017215 A CN104017215 A CN 104017215A CN 201310066026 A CN201310066026 A CN 201310066026A CN 104017215 A CN104017215 A CN 104017215A
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- dianhydride
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 85
- 239000009719 polyimide resin Substances 0.000 title claims abstract description 48
- 239000006260 foam Substances 0.000 title claims abstract description 42
- 239000004642 Polyimide Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims description 14
- 150000004982 aromatic amines Chemical class 0.000 claims abstract description 27
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- -1 NVP Chemical compound 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 2
- 229940100630 metacresol Drugs 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 10
- 150000003949 imides Chemical class 0.000 abstract description 8
- 238000005187 foaming Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 description 7
- 101000608720 Helianthus annuus 10 kDa late embryogenesis abundant protein Proteins 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 0 C*C(c1c(C=O)cc(*)cc1)=O Chemical compound C*C(c1c(C=O)cc(*)cc1)=O 0.000 description 3
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 3
- 125000006159 dianhydride group Chemical group 0.000 description 3
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 230000003245 working effect Effects 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- UENRXLSRMCSUSN-UHFFFAOYSA-N 3,5-diaminobenzoic acid Chemical group NC1=CC(N)=CC(C(O)=O)=C1 UENRXLSRMCSUSN-UHFFFAOYSA-N 0.000 description 2
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- OHBQPCCCRFSCAX-UHFFFAOYSA-N COc(cc1)ccc1OC Chemical compound COc(cc1)ccc1OC OHBQPCCCRFSCAX-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 150000008064 anhydrides Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000001739 density measurement Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical group CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention provides polyimide resin which contains structural units represented by a formula I or II or III shown in descriptions. The invention further provides a method for preparing the polyimide resin. The method comprises the steps of adding aromatic amine, polylactide and dianhydride into a solvent, and removing the solvent after reaction, thereby obtaining the polyimide resin. Finally, the invention further provides polyimide foam which is prepared through crushing the polyimide resin provided by the invention, then, tabletting, and then, carrying out heated foaming. An imide structural unit contained by the polyimide resin provided by the invention has good reaction activity, so that the polyimide foam with good thermal stability, chemical stability and mechanical properties and relatively long service life can be obtained after heated foaming.
Description
Technical field
The invention belongs to polyimide material field, relate in particular to a kind of polyimide resin and preparation method thereof and a kind of polyimide foam.
Background technology
Along with the appearance of polymer artificial synthetic materials, porous material is used widely in synthetic plastics industry, and each type of foam is seen everywhere.Compared to transmission foam materialss such as urethane, polyethylene, polystyrene, polyimide foam has excellent resistance toheat, high temperature barrier, noise reduction, shock resistance, dimensional stability, wave penetrate capability and flame retardant properties, can be used as heat insulation, sound insulation and flame retardant properties, in field application such as aircraft, spacecraft, weaponry, naval vessel, bullet train and automobiles.
At present, the polyimide foam of available technology adopting, is generally by adding fatty alcohol to foam and make as whipping agent in methacrylic acid and methacrylonitrile monomer mixture.But because self-polymerization all can occur for methacrylic acid and these two kinds of monomers of methacrylonitrile, cause the imide rate of the two lower, the use temperature of the foam materials obtaining is lower, and mechanical property is also poor.
Summary of the invention
The invention solves the polyimide foam of being prepared by methacrylic acid and methacrylic nitrile monomer in prior art and have that use temperature is low, the technical problem of bad mechanical property, propose a kind of novel polyimide resin and preparation method thereof and a kind of polyimide foam.
Particularly, the invention provides a kind of polyimide resin, in described polyimide resin, contain the structural unit shown in formula I, formula II or formula III:
Formula I:
Formula II:
Formula III:
R
1be selected from any one in lower array structure:
N is 20～50 integer; ;
R
2be selected from any one in O, S or lower array structure:
The present invention also provides the preparation method of described polyimide resin, comprises aromatic amine, polylactide, dianhydride are added in solvent, after reaction, except desolventizing, obtains described polyimide resin;
Wherein, described aromatic amine is
Described dianhydride is
Finally, the invention provides a kind of polyimide foam, described polyimide foam is by compressing tablet after polyimide resin provided by the invention is pulverized, and then foamable obtains.
Polyimide resin provided by the invention, contained imide structure unit has good reactive behavior, it can decompose the homodisperse nanometer foam of generation in the time of foamable, thereby obtain polyimide foam provided by the invention, this polyimide foam at high temperature also has good thermostability, chemical stability, mechanical property, and work-ing life is longer.Meanwhile, in the preparation method of polyimide resin provided by the invention, by the species structure of synthesis material (comprising aromatic amine, polylactide and dianhydride) is specifically selected, while ensureing reaction, there is higher imide rate.
Embodiment
The invention provides a kind of polyimide resin, in described polyimide resin, contain the structural unit shown in formula I, formula II or formula III:
Formula I:
Formula II:
Formula III:
R
1be selected from any one in lower array structure:
N is 20～50 integer;
R
2be selected from any one in O, S or lower array structure:
Polyimide resin provided by the invention, contained imide structure unit has good reactive behavior, it can decompose the homodisperse nanometer foam of generation in the time of foamable, thereby obtain polyimide foam provided by the invention, this polyimide foam at high temperature also has good thermostability, chemical stability, mechanical property, and work-ing life is longer.
In the present invention, the second-order transition temperature of described polyimide resin is more than 300 DEG C, is even more than 350 DEG C, thereby can ensure follow-up foamable time, serious softening transform can not occur resin.Accordingly, the number-average molecular weight of described polyimide resin is 50000～500000.
As a kind of preferred implementation of the present invention, R
1for
r
2for
but be not limited to this.
The present invention also provides the preparation method of described polyimide resin, comprises aromatic amine, polylactide, dianhydride are added in solvent, after reaction, except desolventizing, obtains described polyimide resin;
Wherein, described aromatic amine is
Described dianhydride is
(pyromellitic acid anhydride),
In the present invention, described aromatic amine preferably adopts
its chemical name is 3,5-diaminobenzoic acid, but is not limited to this.
Polylactide, has another name called poly(lactic acid), and its structural formula is
Preparation in accordance with the present invention, in reaction process, react and form imide structure unit by the anhydride group in amino and dianhydride in aromatic amine, on aromatic amine, have neither part nor lot in the carboxyl of reaction or hydroxyl and continue and polylactide generation condensation reaction, obtain described polyimide resin.
Wherein, aromatic amine with
for example, dianhydride with
(3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride) is example, and the reaction mechanism relating to is:
Or, aromatic amine with
for example, dianhydride with
(being pyromellitic acid anhydride) is example, and the reaction mechanism relating to is:
Above-mentioned reaction is carried out in solvent, described solvent is the conventional all kinds of SOLVENTS of those skilled in the art, for example can be selected from N, dinethylformamide (DMF), N, one or more in N-N,N-DIMETHYLACETAMIDE (DMAc), dimethyl sulfoxide (DMSO), tetramethylene sulfone, dioxane, METHYLPYRROLIDONE (NMP), NVP, meta-cresol, benzene,toluene,xylene, tetrahydrofuran (THF), but be not limited to this.
In the present invention, the mol ratio of described aromatic amine and polylactide, dianhydride is 1:0.8～2.2:0.95～1.05.Under preferable case, the reaction times is 2～12h.
As a kind of preferred implementation of the present invention, be also included in and in reaction process, control the step that the viscosity of reaction system is 10000-100000CP.In reaction process, control for further improving the transformation efficiency (improving imide rate) of above-mentioned reaction, being also included in the step that the solid content of reaction system is 10-60wt%.
As previously mentioned, R
1be preferably
now corresponding aromatic amine is
3,5-diaminobenzoic acid is.R
2be preferably
now corresponding dianhydride is 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride.
In the preparation method of polyimide resin provided by the invention, by the structure of synthesis material (comprising aromatic amine, polylactide and dianhydride) is carried out preferably, while ensureing reaction, there is higher imide rate.
Finally, the invention provides a kind of polyimide foam, described polyimide foam is by compressing tablet after polyimide resin provided by the invention is pulverized, and then foamable obtains.
The step of described foamable is those skilled in the art's common practise.As previously mentioned, the second-order transition temperature of polyimide resin that the present invention improves is more than 300 DEG C, polyimide resin generation softening transform when preventing from foaming, and therefore the temperature of foamable is unsuitable too high.Under preferable case, the step of described foamable comprises: first preheating 20～30min at 100～120 DEG C, at 160～180 DEG C, heat 5～10min again, then in 30min, be warming up to 300～330 DEG C and keep 5～10min, finally in 10min, be warming up to 380～400 DEG C and keep 5～10min, obtain described polyimide foam.
In foaming process, polyimide resin generation thermolysis, produces rare gas element, thereby in resin structure, forms equally distributed bubble structure, and in this bubble structure, rear extended meeting is filled by air, obtains described polyimide foam.Because air is the material that specific inductivity is minimum, so the specific inductivity of the Polyimide foams obtaining is also lower.The density of described polyimide foam is 0.03-0.1g/cm3, and relative permittivity is less than 2.0.
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.Embodiment is that in comparative example, the raw material that adopts is all commercially available.
Embodiment 1
(1) accurately take the DMF of 233mL and the tetrahydrofuran (THF) of 167mL is placed in there-necked flask as mixed solvent, add the aromatic amine (3 of 11.23g, 5-diaminobenzoic acid), be stirred to after dissolving completely, add the dianhydride (3,3 ' of 30.91g, 4,4 '-benzophenone tetracarboxylic dianhydride), slowly quantitatively add in batches, under room temperature, react 3h.Then add the polylactide (molecular weight 2538 of 227.1g, be n=35), the mol ratio that is aromatic amine, polylactide and dianhydride is 1:0.87:0.96, then at 80 DEG C, continues to stir after 4h then underpressure distillation, except desolventizing, continue vacuum-drying, obtain the faint yellow polyimide resin solid of the present embodiment, be designated as S1, it contains the structural unit shown in formula III, wherein R
1for
n=35, R
2for
(2) S1 is pulverized, and be at room temperature pressed into thin slice, preheating 30min at 120 DEG C, at 180 DEG C, heat 5min again, in 30min, be warming up to 330 DEG C and keep 10min, finally in 10min, be warming up to 400 DEG C and keep 10min, obtain the polyimide foam S10 of the present embodiment.
Embodiment 2
Adopt the method identical with embodiment 1 to prepare polyimide resin S2 and the polyimide foam S20 of the present embodiment, difference is:
In step (1), adopt
as 3,3 ', 4 in the dianhydride alternate embodiment 1 of the present embodiment, 4 '-benzophenone tetracarboxylic dianhydride, and the mol ratio of aromatic amine, polylactide (molecular weight is 2538, i.e. n=35) and dianhydride is 1:0.87:1;
The polyimide resin S2 obtaining by above-mentioned steps, obtains it and contains the structural unit shown in formula II, wherein R
1for
n=35.
Embodiment 3
Adopt the method identical with embodiment 1 to prepare polyimide resin S3 and the polyimide foam S30 of the present embodiment, difference is:
In step (1), adopt
(pyromellitic acid anhydride) as 3,3 ', 4 in the dianhydride alternate embodiment 1 of the present embodiment, 4 '-benzophenone tetracarboxylic dianhydride, and aromatic amine, polylactide (molecular weight is 2538, i.e. n=35) are 1:1:1 with the mol ratio of dianhydride;
The polyimide resin S3 obtaining by above-mentioned steps, obtains it and contains the structural unit shown in formula I, wherein R
1for
n=35.
Embodiment 4
Adopt the method identical with embodiment 1 to prepare polyimide resin S4 and the polyimide foam S40 of the present embodiment, difference is:
In step (1), aromatic amine is
dianhydride structural formula is
and R
2for
aromatic amine, polylactide (molecular weight is 2538, i.e. n=35) are 1:1:1.05 with the mol ratio of dianhydride;
The polyimide resin S4 obtaining by above-mentioned steps, obtains it and contains the structural unit shown in formula III, wherein R
1for
n=35, R
2for
Embodiment 5
Adopt the method identical with embodiment 1 to prepare polyimide resin S5 and the polyimide foam S50 of the present embodiment, difference is:
In step (1), aromatic amine is
dianhydride structural formula is
and R
2for
aromatic amine, polylactide (molecular weight is 1458, i.e. n=20) are 1:1.2:0.96 with the mol ratio of dianhydride;
The polyimide resin S5 obtaining by above-mentioned steps, obtains it and contains the structural unit shown in formula III, wherein R
1for
n=20, R
2for
Embodiment 6
Adopt the method identical with embodiment 1 to prepare polyimide resin S6 and the polyimide foam S60 of the present embodiment, difference is:
In step (1), aromatic amine is
dianhydride structural formula is
and R
2for
aromatic amine, polylactide (molecular weight is 3618, i.e. n=50) are 1:2.1:1 with the mol ratio of dianhydride;
The polyimide resin S6 obtaining by above-mentioned steps, obtains it and contains the structural unit shown in formula III, wherein R
1for
n=50, R
2for
Comparative example 1
Join 165g Virahol and 50g methane amide as whipping agent by 2850g methacrylic acid, 2190g methacrylonitrile and 15g propyl methacrylate form in mixture, by this mixture at 40 DEG C being of a size of polymerization 68h in the sheet glass of 50*50cm and chamber that the thick edge seal thing of 12mm forms by two.Polymerisate is slowly heated to 115 DEG C from 32 DEG C subsequently, and heating-up time 32h, completes polyreaction; Then foamable 2h at 205 DEG C.
By above-mentioned, obtain the polyimide foam DS10 of this comparative example.
Performance test
(1) density measurement
With reference to GB1033 plastic density and relative density testing method, adopt pycnometric method to test polyimide foam S10-S60 and DS10.
(2) specific inductivity
With reference to GB/T1408.1 insulating material electrical strength test method, adopt dielectrometer to test polyimide foam S10-S60 and DS10.
(3) mechanical property
With reference to GB/T1040 plastic tensile method for testing performance, GB/T9341 plastics bend test method, adopts electronic universal tester to test polyimide foam S10-S60 and DS10.
Test result is as shown in table 1.
Table 1
Can find out from the test result of upper table 1, polyimide foam S10-S60 density provided by the invention is 0.0339～0.0913g/cm
3, specific inductivity, lower than 2.0, has good mechanical property simultaneously, is obviously better than the foam sample DS10 of comparative example, and therefore its work-ing life is also corresponding longer.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (10)
1. a polyimide resin, is characterized in that, contains the structural unit shown in formula I, formula II or formula III in described polyimide resin:
Formula I:
Formula II:
Formula III:
R
1be selected from any one in lower array structure:
N is 20～50 integer;
R
2be selected from any one in O, S or lower array structure:
2. polyimide resin according to claim 1, is characterized in that, the number-average molecular weight of described polyimide resin is 50000～500000.
3. polyimide resin according to claim 1, is characterized in that, R
1for
r
2for
4. the preparation method of polyimide resin claimed in claim 1, is characterized in that, comprises aromatic amine, polylactide, dianhydride are added in solvent, after reaction, except desolventizing, obtains described polyimide resin;
Wherein, described aromatic amine is
Described dianhydride is
5. preparation method according to claim 4, it is characterized in that, described solvent is selected from N, one or more in dinethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), tetramethylene sulfone, dioxane, METHYLPYRROLIDONE, NVP, meta-cresol, benzene,toluene,xylene, tetrahydrofuran (THF).
6. preparation method according to claim 4, is characterized in that, the mol ratio of described aromatic amine and polylactide, dianhydride is 1:0.8～2.2:0.95～1.05, and the time of reaction is 2～12h.
7. preparation method according to claim 4, is characterized in that, is also included in and in reaction process, controls the step that the viscosity of reaction system is 10000-100000CP.
8. according to the preparation method described in claim 4 or 7, it is characterized in that, be also included in and in reaction process, control the step that the solid content of reaction system is 10-60wt%.
9. a polyimide foam, is characterized in that, described polyimide foam is by compressing tablet after polyimide resin claimed in claim 1 is pulverized, and then foamable obtains.
10. polyimide foam according to claim 9, it is characterized in that, the step of described foamable comprises: first preheating 20～30min at 100～120 DEG C, at 160～180 DEG C, heat 5～10min again, then in 30min, be warming up to 300～330 DEG C and keep 5～10min, finally in 10min, be warming up to 380～400 DEG C and keep 5～10min, obtain described polyimide foam.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310066026.1A CN104017215B (en) | 2013-02-28 | 2013-02-28 | A kind of polyimide resin and preparation method thereof and a kind of polyimide foam |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310066026.1A CN104017215B (en) | 2013-02-28 | 2013-02-28 | A kind of polyimide resin and preparation method thereof and a kind of polyimide foam |
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| Publication Number | Publication Date |
|---|---|
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| CN104017215B CN104017215B (en) | 2016-09-07 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111363305A (en) * | 2018-12-25 | 2020-07-03 | 比亚迪股份有限公司 | Foamed plastic composition, foamed plastic, preparation method of foamed plastic and engine hood |
| CN115785417A (en) * | 2022-12-14 | 2023-03-14 | 华南理工大学 | Polyimide-polyester copolymer and preparation and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN101735457A (en) * | 2010-01-15 | 2010-06-16 | 新阳桥科技有限公司 | Production method of soft polyimide foam |
| CN102174198A (en) * | 2011-03-22 | 2011-09-07 | 中国科学院长春应用化学研究所 | Method for preparing polyimide foam material |
| CN102838745A (en) * | 2012-09-19 | 2012-12-26 | 中国科学院长春应用化学研究所 | Preparation method of polyimide foam |
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| JPH07179757A (en) * | 1993-07-28 | 1995-07-18 | Mitsui Toatsu Chem Inc | Polyimide resin composition |
| CN101735457A (en) * | 2010-01-15 | 2010-06-16 | 新阳桥科技有限公司 | Production method of soft polyimide foam |
| CN102174198A (en) * | 2011-03-22 | 2011-09-07 | 中国科学院长春应用化学研究所 | Method for preparing polyimide foam material |
| CN102838745A (en) * | 2012-09-19 | 2012-12-26 | 中国科学院长春应用化学研究所 | Preparation method of polyimide foam |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111363305A (en) * | 2018-12-25 | 2020-07-03 | 比亚迪股份有限公司 | Foamed plastic composition, foamed plastic, preparation method of foamed plastic and engine hood |
| CN111363305B (en) * | 2018-12-25 | 2021-08-10 | 比亚迪股份有限公司 | Foamed plastic composition, foamed plastic, preparation method of foamed plastic and engine hood |
| CN115785417A (en) * | 2022-12-14 | 2023-03-14 | 华南理工大学 | Polyimide-polyester copolymer and preparation and application thereof |
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| CN104017215B (en) | 2016-09-07 |
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