CN104177644A - Method for preparing polyimide-modified phenolic aerogel - Google Patents
Method for preparing polyimide-modified phenolic aerogel Download PDFInfo
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- CN104177644A CN104177644A CN201410396169.3A CN201410396169A CN104177644A CN 104177644 A CN104177644 A CN 104177644A CN 201410396169 A CN201410396169 A CN 201410396169A CN 104177644 A CN104177644 A CN 104177644A
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- polyimide
- aerogel
- phenolic aldehyde
- modified phenolic
- hydrogel
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- 239000004964 aerogel Substances 0.000 title claims abstract description 44
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Polymers C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 title claims abstract description 14
- 239000004642 Polyimide Substances 0.000 claims abstract description 70
- 229920001721 polyimide Polymers 0.000 claims abstract description 70
- 239000000017 hydrogel Substances 0.000 claims abstract description 30
- 239000002243 precursor Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 230000032683 aging Effects 0.000 claims abstract description 8
- 238000005554 pickling Methods 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- -1 modified phenolic aldehyde Chemical class 0.000 claims description 51
- 239000000203 mixture Substances 0.000 claims description 26
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 21
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical group CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 16
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000003643 water by type Substances 0.000 claims description 12
- 150000004985 diamines Chemical class 0.000 claims description 10
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 10
- 229960000549 4-dimethylaminophenol Drugs 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 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 description 6
- 150000001299 aldehydes Chemical class 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Chemical group COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 4
- 239000000920 calcium hydroxide Substances 0.000 claims description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 4
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical group C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims 1
- 238000009413 insulation Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract 1
- 238000004132 cross linking Methods 0.000 abstract 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 238000002604 ultrasonography Methods 0.000 description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 7
- 238000006073 displacement reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 229920006259 thermoplastic polyimide Polymers 0.000 description 1
Landscapes
- Phenolic Resins Or Amino Resins (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a method for preparing polyimide-modified phenolic aerogel. The polyimide modified phenolic aerogel is prepared from the following raw materials in parts by weight: 1 part of polyimide, 1-10 parts of phenol and aldehyde, 85-97 parts of deionized water, 0.5 part of ethylenetriamine, 0.4 part of catalyst A and 0.1 parts of catalyst B. The method comprises the following main steps: preparing a polyimide water-soluble precursor solution firstly; then, preparing phenolic hydrogel; and finally, sequentially carrying out crosslinking, acid pickling and aging on the polyimide water-soluble precursor solution and a network structure in the hydrogel, and carrying out solvent replacement and ambient-pressure drying on the obtained product, so that polyimide-modified phenolic aerogel is obtained finally. The apparent density of the prepared aerogel material is 0.03-0.5 g/cm<3>, the specific surface area is 400-900 m<2>/g, the aperture size of the aerogel is 5-50 nm, the heat conduction coefficient is 0.012-0.025 W/m.k, the temperature resistance range is minus 130-800 DEG C, and the aerogel is good in mechanical and processing properties, excellent in insulating properties, wide in applicable temperature and excellent in thermal insulation performance.
Description
Technical field
The invention belongs to foam material field, be specifically related to a kind of method of preparing polyimide modified phenolic aldehyde aerogel.
Background technology
Than conventional foam, aerogel has higher specific tenacity, specific surface area, and the more tiny even heat insulation performance in aperture is better, therefore has very high researching value; There is being mainly divided into so far inorganic aerogels and the large class of organic aerogel two from 1931 in aerogel, and than inorganic aerogels, because organic aerogel contains carbon, carbon has the ability of good absorptive thermal radiation, this effect is especially at high temperature obvious, and therefore its high temperature insulating performance is obviously better than inorganic aerogels; The heat-proof quality of phenol formaldehyde foam is best in all foams, but because slag is fallen in its easy efflorescence, fragility has limited its application, adopts the preparation method of phenolic aldehyde aerogel can improve to a great extent the shortcoming of its these aspects.
But in the preparation process of traditional phenolic aldehyde aerogel, drying step is the subject matter of its application of restriction, because aerogel frame strength is not high, if the method that adopts constant pressure and dry prepares unsuccessfully aerogel because the tension force effect of water and other stresses can cause skeleton to cave in, so must adopt supercritical co preparation method, too high, the operational difficulty of cost like this, therefore, how can under normal temperature, normal pressure, realize the preparation of phenolic aldehyde aerogel, be this area technical problem urgently to be resolved hurrily always.
Summary of the invention
For the toughness that solves existing phenolic aldehyde aerogel existence is the shortcomings and deficiencies such as shock strength is poor, strength rigid is not high, the difficult machine-shaping stability of drying means is bad, the usage period is too short, the invention provides the preparation method of a kind of polyimide (PI) modified phenolic aerogel, technique simple possible, can prepare the controlled modified phenolic aerogel of high comprehensive performance and density, the present invention is achieved in that economical and efficient
A method of preparing polyimide modified phenolic aldehyde aerogel, comprises the following steps, in weight part:
A) polyimide of 1 part is dissolved in the deionized water of the second triamine of 0.5 part and 18 parts, make polyimide precursor solution;
B) 1～10 part of phenolic aldehyde mixture is dissolved in 70～79 parts of deionized waters, then add 0.4 part of catalyst A, ultrasonic reaction at 70 DEG C, to being generated as light red transparence hydrogel; In described phenolic aldehyde mixture, the mol ratio of phenol and aldehyde is 1:2;
C) polyimide precursor solution step a being obtained adds in the hydrogel of step b acquisition, more slowly adds 0.1 part of catalyst B, and ultrasonic reaction at 80～95 DEG C, until generate orange-yellow transparence hydrogel;
D) gained hydrogel is put into aging 2 days of 5% acetic acid pickling, put into acetone solvent displacement 3 days, last constant pressure and dry, obtains polyimide modified phenolic aldehyde aerogel;
Described catalyst A is one or both in sodium carbonate, sodium hydroxide, hydrated barta, ammonium hydroxide, calcium hydroxide, ethamine; Described catalyst B is DMAP or pyridine.
In the present invention, preferred, in phenolic aldehyde mixture, phenol is a kind of in Resorcinol, Isosorbide-5-Nitrae Resorcinol or their mixing described in step b, and aldehyde is a kind of in formaldehyde, furfural or their mixing.
In the present invention, preferred, described polyimide is thermoplastic polyimide, and molecular weight is between 1～50,000, and molecular formula is:
wherein X is
or
in one.
In the present invention, preferably, described polyimide is to obtain like this: diamines is dissolved in N,N-DIMETHYLACETAMIDE, is adding dianhydride, to add the mol ratio of diamines and dianhydride be 1:1.05, stirring reaction 4h, drips 0.1mL3-aminopropyl trimethoxysilane, continues stirring reaction 4h, reaction product is first with deionized water wash, after filtration, again with after distilled water wash, 100 DEG C of oven dry, pulverize, obtain polyimide.
In the present invention, preferred, described dianhydride is pyromellitic acid anhydride, and described diamines is 4,4 '-diaminodiphenylmethane, DDS, 4, the one in 4 '-diaminodiphenyl oxide, mphenylenediamine.
In the present invention, the mechanism of polyimide modified phenolic aldehyde gel is: phenolic aldehyde aerogel microcosmic becomes tridimensional network, its aperture is between 5～50 nanometers, and gained polyimide molecule amount of the present invention is between 1～50,000, its size range in several nanometers between tens nanometers, therefore polyimide molecule can be present in its structure taking two kinds of forms in phenolic aldehyde aerogel: one as physical blending, and polyimide molecule chain can shuttle back and forth and between the hole of phenolic aldehyde aerogel, form interpenetrating(polymer)networks and reach the effect of physics enhancing; Two for copolymerization, the acid anhydrides of polyimide molecule chain end can with phenolic aldehyde aerogel network structure on hydroxyl (OH) thus crosslinked being connected in its structure, thereby arrive the effect of modification by copolymerization.
Be below the reaction formula of phenolic hydroxyl group and acid anhydrides on aerogel, wherein NR '
3for catalyst B
In the present invention, polyimide (PI) modified effect is embodied in:
1, polyimide has good mechanical property, on microcosmic, by being interspersed in phenolic aldehyde aerogel network hole and end group is crosslinked is attached to two kinds of modes in phenolic aldehyde aerogel network structure and strengthens its skeleton structure intensity, make it when dry, be difficult for causing the situation of caving in because of tension force and the various stress of water, thereby can adopt constant pressure and dry to replace supercritical co dry, thereby effectively reduce preparation cost;
2,, in macroscopic view, the mechanical property that polyimide can strongthener itself, can improve significantly its intensity and toughness, and to a certain degree improve its fragility, strengthens its toughness;
3, polyimide has higher heat-resisting scope than phenolic aldehyde, its heat resisting temperature is between-200 DEG C-400 DEG C, can increase significantly the heat-resisting scope of phenolic aldehyde aerogel, expand its application range, make it under more environment, bring into play its heat-insulating sound-insulating ability.
The present invention adopts polyimide to carry out enhancing modified phenolic aldehyde aerogel, strengthens its skeleton structure, can adopt the method for constant pressure and dry to be dried, and the cost greatly reducing, has simplified operation; The polyimide modified phenolic aldehyde aerogel apparent density that preparation in accordance with the present invention obtains is 0.03g/cm
3～0.5g/cm
3, specific surface area is 400～900M
2/ g, aerogel aperture are of a size of 5～50 nanometers, thermal conductivity is 0.012～0.025W/m.k, temperature resistant range-130～800 DEG C, its satisfactory mechanical property, and surface quality is excellent, processing characteristics excellence, insulativity excellent performance, Applicable temperature is wide, heat-proof quality excellence.Can be under partiting thermal insulation environment, adopt this material can be effectively heat insulation as protective layer such as spontaneous combustion easily occurs motor car engine; Some positions of the precision instruments such as computer can produce large calorimetric in the time of computing, tend to burn other close accurate electrical devices, at this moment just need an insulation and the good protective layer of heat-proof quality; Aerospace field needs the lagging material of lightweight etc., further researches and develops this material and has broad application prospects.
Brief description of the drawings
Fig. 1 is that the embodiment of the present invention is prepared polyimide modified phenolic aldehyde aerogel schematic flow sheet.
Embodiment
By specific embodiment, technical scheme of the present invention is further described below, but the present invention is not limited to these embodiment.
Embodiment 1 prepares polyimide
By diamines, (diamines selected of the present embodiment is 4,4 '-diaminodiphenylmethane) be dissolved in N,N-DIMETHYLACETAMIDE, adding pyromellitic acid anhydride, institute adds 4, the mol ratio of 4 '-diaminodiphenylmethane and pyromellitic acid anhydride is 1:1.05, stirring reaction 4h, drip again 0.1mL3-aminopropyl trimethoxysilane, continue stirring reaction 4h, reaction product, first with deionized water wash, is filtered, again with after distilled water wash, 100 DEG C of oven dry, pulverize, obtain polyimide, the polyimide molecule formula obtaining is:
In concrete operations, diamines also can use DDS, 4, and 4 '-diaminodiphenyl oxide or mphenylenediamine, be followed successively by as the molecular formula of the polyimide that diamines was obtained using them:
Embodiment 2
Feed composition is by weight: 1 part of the polyimide that embodiment 1 obtains, 1 part, phenolic aldehyde mixture (by Resorcinol and formaldehyde in molar ratio 1:2 mix acquisition), totally 97 parts of deionized waters, 0.5 part of second triamine, sodium carbonate is that 0.4 part, DMAP are 0.1 part, as shown in Figure 1:
(a) in proportion polyimide is dissolved in the deionized water of second triamine and 18 parts, make polyimide precursor solution;
(b) in proportion phenolic aldehyde mixture is dissolved in 79 parts of deionized waters, add sodium carbonate to react under 70 DEG C of constant temperature, 50KHz ultrasound environments, finish reaction until become the hydrogel of light red vitreous state;
(c) polyimide precursor solution step a being prepared adds in the hydrogel of step b acquisition, slowly add again DMAP, under 95 DEG C of constant temperature, 100KHz ultrasound environments, react, in the time that it becomes orange-yellow transparence hydrogel, reaction finishes;
(d) step c gained hydrogel is put into 5% acetic acid pickling aging 2 days, then put into acetone solvent displacement 3 days, last constant pressure and dry, obtains polyimide modified phenolic aldehyde airsetting after being dried, and recording its density is 0.03g/cm
3.
Embodiment 3
Feed composition is by weight: 1 part of the polyimide that embodiment 1 obtains, 4 parts, phenolic aldehyde mixture (by Isosorbide-5-Nitrae Resorcinol and furfural in molar ratio 1:2 mix acquisition), totally 94 parts of deionized waters, 0.5 part of second triamine, 0.4 part, calcium hydroxide, 0.1 part of DMAP;
(a) in proportion polyimide is dissolved in the deionized water of second triamine and 18 parts, make polyimide precursor solution;
(b) in proportion phenolic aldehyde mixture is dissolved in 76 parts of deionized waters, add calcium hydroxide to react under 70 DEG C of constant temperature, 50KHz ultrasound environments, finish reaction until become the hydrogel of light red vitreous state;
(c) polyimide precursor solution step a being prepared adds in the hydrogel of step b acquisition, slowly add again DMAP, under 95 DEG C of constant temperature, 100KHz ultrasound environments, react, in the time that it becomes orange-yellow transparence hydrogel, reaction finishes;
(d) step c gained hydrogel is put into 5% acetic acid pickling aging 2 days, then put into acetone solvent displacement 3 days, last constant pressure and dry, obtains polyimide modified phenolic aldehyde airsetting after being dried, and recording its density is 0.15g/cm
3.
Embodiment 4
Feed composition is by weight: embodiment 1 obtains 1 part of polyimide, 6 parts of (phenolic aldehyde mol ratio 1:2 of phenolic aldehyde mixture, in the present embodiment, phenol is by Resorcinol and 1,4 Resorcinol mix with mol ratio 1:1, and aldehyde is mixed with mol ratio 1:1 by formaldehyde and furfural), totally 92 parts of deionized waters, 0.5 part of second triamine, 0.4 part of hydrated barta, 0.1 part of pyridine;
(a) in proportion polyimide is dissolved in the deionized water of second triamine and 18 parts, make polyimide precursor solution;
(b) in proportion phenolic aldehyde mixture is dissolved in 74 parts of deionized waters, add hydrated barta to react under 70 DEG C of constant temperature, 50KHz ultrasound environments, finish reaction until become the hydrogel of light red vitreous state;
(c) polyimide precursor solution step a being prepared adds in the hydrogel of step b acquisition, more slowly adds pyridine, under 95 DEG C of constant temperature, 100KHz ultrasound environments, reacts, and in the time that it becomes orange-yellow transparence hydrogel, reaction finishes;
(d) step c gained hydrogel is put into 5% acetic acid pickling aging 2 days, then put into acetone solvent displacement 3 days, last constant pressure and dry, obtains polyimide modified phenolic aldehyde airsetting after being dried, and recording its density is 0.24g/cm
3.
Embodiment 5
Feed composition is by weight: 1 part of polyimide, (phenolic aldehyde mol ratio is 1:2 for 8 parts, phenolic aldehyde mixture, wherein phenol is by Resorcinol and 1,4 Resorcinol mix with mol ratio 1:3, aldehyde is formaldehyde), totally 90 parts of deionized waters, 0.5 part of second triamine, 0.4 part, sodium hydroxide, 0.1 part of DMAP;
A) in proportion polyimide is dissolved in the deionized water of second triamine and 18 parts, make polyimide precursor solution;
(b) in proportion phenolic aldehyde mixture is dissolved in 72 parts of deionized waters, add sodium hydroxide to react under 70 DEG C of constant temperature, 50KHz ultrasound environments, until become the hydrogel of light red vitreous state;
(c) polyimide precursor solution step a being prepared adds in the hydrogel of step b acquisition, slowly add again DMAP, under 95 DEG C of constant temperature, 100KHz ultrasound environments, react, in the time that it becomes orange-yellow transparence hydrogel, reaction finishes;
(d) step c gained hydrogel is put into 5% acetic acid pickling aging 2 days, put into acetone solvent displacement 3 days, last constant pressure and dry, obtains polyimide modified phenolic aldehyde airsetting, and recording its density is 0.35g/cm
3.
Embodiment 6
Feed composition is by weight:: 1 part of polyimide, 10 parts, phenolic aldehyde mixture (being mixed with mol ratio 1:2 by Resorcinol and furfural), totally 88 parts of deionized waters, 0.5 part of second triamine, 0.4 part of catalyst A (ethamine and ammonium hydroxide mix with mol ratio 1:2), 0.1 part of pyridine;
A) in proportion polyimide is dissolved in the deionized water of second triamine and 18 parts, make polyimide precursor solution;
(b) in proportion phenolic aldehyde mixture is dissolved in 72 parts of deionized waters, add catalyst A to react under 70 DEG C of constant temperature, 50KHz ultrasound environments, until become the hydrogel of light red vitreous state;
(c) polyimide precursor solution step a being prepared adds in the hydrogel of step b acquisition, more slowly adds pyridine, under 95 DEG C of constant temperature, 100KHz ultrasound environments, reacts, and in the time that it becomes orange-yellow transparence hydrogel, reaction finishes;
(d) step c gained hydrogel is put into 5% acetic acid pickling aging 2 days, put into acetone solvent displacement 3 days, last constant pressure and dry, obtains polyimide modified phenolic aldehyde airsetting, and recording its density is 0.5g/cm
3.
The above embodiment has only expressed embodiments of the present invention; it describes comparatively concrete and detailed; but can not therefore be interpreted as the restriction to the scope of the claims of the present invention; it should be noted that; to those skilled in the art; without departing from the inventive concept of the premise, can also make some improvement, these all belong to protection scope of the present invention.
Claims (5)
1. a method of preparing polyimide modified phenolic aldehyde aerogel, comprises the following steps, in weight part:
A) polyimide of 1 part is dissolved in the deionized water of the second triamine of 0.5 part and 18 parts, make polyimide precursor solution;
B) 1～10 part of phenolic aldehyde mixture is dissolved in 70～79 parts of deionized waters, then add 0.4 part of catalyst A, ultrasonic reaction at 70 DEG C, finishes reaction when being generated as light red transparence hydrogel; In described phenolic aldehyde mixture, the mol ratio of phenol and aldehyde is 1:2;
C) polyimide precursor solution step a being obtained adds in the hydrogel that step b obtains, then adds 0.1 part of catalyst B, and ultrasonic reaction at 80～95 DEG C, until finish reaction while generating orange-yellow transparence hydrogel;
D) by aging the pickling of step c gained hydrogel, after solvent exchange, constant pressure and dry, obtain polyimide modified phenolic aldehyde aerogel;
Described catalyst A is one or both in sodium carbonate, sodium hydroxide, hydrated barta, ammonium hydroxide, calcium hydroxide, ethamine; Described catalyst B is DMAP or pyridine.
2. the method for polyimide modified phenolic aldehyde aerogel according to claim 1, it is characterized in that, described in step b, in phenolic aldehyde mixture, phenol is a kind of in Resorcinol, Isosorbide-5-Nitrae Resorcinol or their mixing, and aldehyde is a kind of in formaldehyde, furfural or their mixing.
3. according to the method for polyimide modified phenolic aldehyde aerogel described in claim 1 or 2, it is characterized in that, described polyimide molecule formula is:
, wherein X is
,
,
, or
in one.
4. the method for polyimide modified phenolic aldehyde aerogel according to claim 3, is characterized in that, described polyimide is to obtain like this: diamines is dissolved in N,N-DIMETHYLACETAMIDE, add dianhydride, to add the mol ratio of diamines and dianhydride be 1:1.05, stirring reaction 4h, drips 0.1mL 3-aminopropyl trimethoxysilane, continue after stirring reaction 4h, reaction product, first with deionized water wash, is filtered, then with after distilled water wash, 100 DEG C of oven dry, pulverize, obtain polyimide.
5. the method for polyimide modified phenolic aldehyde aerogel according to claim 4, is characterized in that, described dianhydride is pyromellitic acid anhydride, described diamines is 4,4 '-diaminodiphenylmethane, DDS, 4, the one in 4 '-diaminodiphenyl oxide, mphenylenediamine.
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| CN116169399A (en) * | 2023-04-21 | 2023-05-26 | 柯灵爱尔(北京)环境技术中心 | High temperature resistant aerogel battery spacer |
| CN116715935A (en) * | 2023-06-29 | 2023-09-08 | 中交建筑集团有限公司 | Building thermal insulation material and preparation method thereof |
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2014
- 2014-08-12 CN CN201410396169.3A patent/CN104177644B/en active Active
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