CN105778091A - Preparation method of high-modulus low-shrinkage crosslinked polyimide aerogel material - Google Patents
Preparation method of high-modulus low-shrinkage crosslinked polyimide aerogel material Download PDFInfo
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- CN105778091A CN105778091A CN201510947816.XA CN201510947816A CN105778091A CN 105778091 A CN105778091 A CN 105778091A CN 201510947816 A CN201510947816 A CN 201510947816A CN 105778091 A CN105778091 A CN 105778091A
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- modulus
- aerogel material
- polyimide aerogel
- crosslinking agent
- dianhydride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Abstract
The invention relates to a preparation method of a high-modulus low-shrinkage crosslinked polyimide aerogel material. According to the invention, a sol-gel method is adopted. Flexible diamine and dianhydride monomers are mixed to synthesize polyamide acid; cheap aminosilane is used for promoting crosslinking; a gel is formed through chemical imidization; and with a supercritical drying process, the polyimide aerogel material with a spherical crosslinked structure is prepared. The method provided by the invention has the characteristics of wide applicability, simple reaction process, low overall cost, and the like. The obtained material has a nano-scale pearl chain structure which is different from that of prior arts. A sample has shrinkage rate of 8-15% and density of 120-170mg/cm<3>. With the use of mixed diamine, the mechanical property and thermal stability of the prepared polyimide aerogel material are greatly improved. The material has a modulus range of 28-35MPa, a specific modulus up to 236J/g, and initial thermal decomposition temperature of 560 DEG C. The type of low-density high-modulus hydrophobic polyimide aerogel material has important application values in the fields of spacecraft thermal insulation parts, building thermal insulation layers, commercial thermal insulation products, and the like.
Description
Technical field
The invention belongs to aerogel material preparing technical field, be specifically related to a kind of high-modulus, the preparation method of lower shrinkage insulation crosslinked polyimide aeroge.
Background technology
Aeroge, as there being the specific function material of nanometer open-celled structure, due to the performance that it is superior, is widely used in numerous areas.The maximum bottleneck restricting its industrialized production and application at present is exactly the mechanical property of its extreme difference, and the aeroge therefore obtaining high-modulus is the target of researcher's effort all the time.Polyimide aerogels is preferable as a kind of mechanical property, and heat endurance is high, and the organic aerogel that heat-proof quality is good gets more and more people's extensive concerning in recent years.
Shrinking is greatly more scabrous problem in polyimide aerogels preparation process, and bigger contraction causes the density of aeroge typically the highest.Owing to this performance of thermal conductivity of heat-barrier material and the density of material are closely related, usual density is low means that effect of heat insulation is more preferable, thus the density reducing polyimide aerogels is an up the effective means of its heat-proof quality.Meanwhile, relatively low density also results in the modulus of material and declines, and affects its mechanical property.So, it is thus achieved that low-density, high-modulus, namely the polyimide aerogels of high ratio modulus is the key problem really promoting its using value.
Summary of the invention
It is an object of the invention to provide a kind of applied widely, with low cost, reaction time is short, may industry amplify low-density, the preparation method of high-modulus crosslinked polyimide aerogel material.Its basic ideas are to substitute the crosslinking agent of other costlinesses by adding cheap ammonification silane, use the preparation of the hybrid diamine containing methyl to have the polyimide aerogels of hydrophobic performance.First the silane containing imino group mixes generation acid anhydride end capping reaction with polyamic acid oligomer solution, then polyamic acid oligomer realizes the process being cross-linked with each other by self poly-condensation and hydrolysis of ammonification silane, then pass through chemistry imines process and form polyimides wet gel, after be dried to obtain crosslinked polyimide aeroge through CO 2 supercritical.Particular content is as follows:
The present invention proposes a kind of high-modulus, the preparation method of lower shrinkage crosslinked polyimide aeroge, it is characterised in that uses sol-gal process, specifically comprises the following steps that
(1) dianhydride and the diamine monomer containing methyl are dissolved in organic solvent, make polyamic acid solution；
(2) add crosslinking agent to the polyamic acid solution of step (1) gained to stir, add dehydrating agent, after at room temperature standing, obtain gel；Wherein: the adding proportion of dianhydride, diamines and crosslinking agent is 8.68mmol:8.35mmol:225ul；Described crosslinking agent is amino silane；
(3) it is dried after the most aging for step (2) gained gel, i.e. obtains required crosslinked polyimide aeroge.
Wherein: the organic solvent in step (1) is 1-METHYLPYRROLIDONE；
Described in step (1), dianhydride is 3,3'4,4'-bibenzene tetracarboxylic dianhydride；
Described in step (1), the hybrid diamine containing methyl includes 4,4'-diaminodiphenyl ether and double [4-(the 4-phenalgin epoxide) phenyl] propane of 2,2-；
Crosslinking agent amino silane described in step (2) is double [3-(trimethoxy is silica-based) propyl group] amine；
Dehydrating agent described in step (2) is ethanedioic acid and the mixed solution of pyridine composition；
Drying means described in step (3) is that supercritical fluid drying, freeze-drying, heat de-airing are dried or the mode such as normal pressure natural drying.
The beneficial effects of the present invention is:
The present invention has the features such as applicability is extensive, raw material is cheap and easily-available, course of reaction is simple, overall low cost, and obtained material has the multistage microstructural of nanoscale, has the spherical micro-structural of uniqueness.Sample shrinkage factor is less than 15%, and density is 120-170mg/cm3, thermal conductivity is at 0.03-0.05 (W/mK), and modulus is at 28-35 MPa, and specific modulus is up to 236J/g, and temperature of initial decomposition, more than 550 degrees Celsius, is the insulation aerogel material of a kind of high intensity, high thermal stability.
Accompanying drawing explanation
The photo of Fig. 1 embodiment 1 sample；
The FFIR figure of Fig. 2 embodiment 1 sample；
The electron scanning micrograph of Fig. 3 embodiment 1 sample；
Fig. 4 embodiment 1 stress-strain diagram；
The thermogravimetric curve of Fig. 5 embodiment 1 sample；
The nitrogen adsorption desorption curve of Fig. 6 embodiment 1 sample；
The pore size distribution curve of Fig. 7 embodiment 1 sample.
Detailed description of the invention
By the following examples and accompanying drawing is further elaborated with the present invention.(each raw material is marketable material, is chemical pure without special instruction purity or analyzes pure grade).
Embodiment 1: the preparation of crosslinked polyimide aeroge
By hybrid diamine and dianhydride (diaminodiphenyl ether: 2, double [4-(4-phenalgin epoxide) phenyl] propane of 2-: 3,3', 4,4'-biphenyl tetracarboxylic dianhydride=0.418g:2.574g:2.556g) it is dissolved in the 1-METHYLPYRROLIDONE of 38mL, synthesizing polyamides acid solution, it is subsequently added double [3-(trimethoxy the is silica-based) propyl group] amine of 225uL crosslinking agent, and quickly stir one hour, add dehydrating agent 12.1mL(ethanedioic acid: pyridine=6.5mL:5.6mL), rapidly as gel in room temperature after stirring.Carry out 3 solution with the mixed solution of 1-METHYLPYRROLIDONE Yu acetone after 24h to replace, each 8-12h.With pure acetone, gel being carried out 3 solvents again to replace, each 8-12h, finally carry out supercritical drying, obtaining density is 172mg/cm3Polyimide aerogels.Pictorial diagram is as shown in Figure 1.
Embodiment 2: the preparation of crosslinked polyimide aeroge
By hybrid diamine and dianhydride (diaminodiphenyl ether: 2, double [4-(4-phenalgin epoxide) phenyl] propane of 2-: 3,3', 4,4'-biphenyl tetracarboxylic dianhydride=0.836g:1.716g:2.556g) it is dissolved in the 1-METHYLPYRROLIDONE of 38mL, synthesizing polyamides acid solution, it is subsequently added double [3-(trimethoxy the is silica-based) propyl group] amine of 225uL crosslinking agent, quickly stirring one hour, add dehydrating agent 12.1mL(ethanedioic acid: pyridine=6.5mL:5.6mL), rapidly as gel in room temperature after stirring.Carry out 3 solution with the mixed solution of 1-METHYLPYRROLIDONE Yu acetone after 24h to replace, each 8-12h.With pure acetone, gel being carried out 3 solvents again to replace, each 8-12h, finally carry out supercritical drying, obtaining density is 137mg/cm3Polyimide aerogels.
Embodiment3: the preparation of crosslinked polyimide aeroge
By hybrid diamine and dianhydride (diaminodiphenyl ether: 2, double [4-(4-phenalgin epoxide) phenyl] propane of 2-: 3,3', 4,4'-biphenyl tetracarboxylic dianhydride=1.254g:0.858g:2.556g) it is dissolved in the 1-METHYLPYRROLIDONE of 38mL, synthesizing polyamides acid solution, it is subsequently added double [3-(trimethoxy the is silica-based) propyl group] amine of 225uL crosslinking agent, quickly stirring one hour, add dehydrating agent 12.1mL(ethanedioic acid: pyridine=6.5mL:5.6mL), rapidly as gel in room temperature after stirring.Carry out 3 solution with the mixed solution of 1-METHYLPYRROLIDONE Yu acetone subsequently to replace, each 8-12h.With pure acetone, gel being carried out 3 solvents again to replace, each 8-12h, finally carry out supercritical drying, obtaining density is 120mg/cm3Polyimide aerogels.
Shown in Fig. 2, the FFIR of sample then shows, material has the obvious characteristic peak (1776cm-of polyimides1、1716cm-1、1375cm-1), indicate the integrality of imidization.The electron scanning micrograph of Fig. 3 then shows, the nanofibre-like structure of various conventional crosslinked polyimide aeroge, and the microstructure of this aeroge is the pearl chain-shaped network of nanometer scale, and particle diameter is at about 30nm.The stress-strain diagram of Fig. 4 shows, this material has bigger elastic deformation district (nearly 10%), and elastic modelling quantity is left and right.Relative to pressure rising of adsorption curve at 0.9, the nitrogen adsorption desorption curve of Fig. 6 shows that the pore structure of material is that this conclusion have also been obtained the confirmation of Fig. 7 pore size distribution curve based on mesoporous and macropore.Integration test result shows, this material is based on mesoporous, has the High Strength Polyimide aeroge of multilevel hierarchy.
Embodiment described above is only for illustrating technological thought and the feature of the present invention; its object is to make those of ordinary skill in the art will appreciate that present disclosure and implement according to this; the scope of this patent is not limited merely to above-mentioned specific embodiment; the most all equal changes made according to disclosed spirit or modification, still contain within the scope of the present invention.
Claims (7)
1. a high-modulus, the preparation method of lower shrinkage crosslinked polyimide aerogel material, it is characterised in that use sol-gal process, specifically comprise the following steps that
(1) hybrid diamine containing methyl and dianhydride monomer are dissolved in organic solvent, make polyamic acid solution；
(2) in the polyamic acid solution of step (1) gained, add crosslinking agent and dehydrating agent, stir, after at room temperature standing, obtain gel；Wherein: the adding proportion of dianhydride, hybrid diamine and crosslinking agent is 8.68mmol:8.35mmol:225ul；Crosslinking agent is amino silane；
(3) it is dried after the most aging for step (2) gained gel, i.e. obtains required crosslinked polyimide aeroge.
Method the most according to claim 1, it is characterised in that the organic solvent described in step (1) is 1-METHYLPYRROLIDONE.
Method the most according to claim 1, it is characterised in that the dianhydride described in step (1) is 3,3'4,4'-bibenzene tetracarboxylic dianhydride.
Method the most according to claim 1, it is characterised in that the hybrid diamine containing methyl described in step (1) includes 4,4'-diaminodiphenyl ether and 2, double [4-(the 4-phenalgin epoxide) phenyl] propane of 2-.
Method the most according to claim 1, it is characterised in that the crosslinking agent amino silane described in step (2) is double [3-(trimethoxy is silica-based) propyl group] amine.
Method the most according to claim 1, it is characterised in that the dehydrating agent described in step (2) is ethanedioic acid and the mixed solution of pyridine composition.
Method the most according to claim 1, it is characterised in that drying means described in step (3) is that supercritical fluid drying, freeze-drying, heat de-airing are dried or one in normal pressure natural drying.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110229340A (en) * | 2019-06-17 | 2019-09-13 | 中国科学院宁波材料技术与工程研究所 | A kind of polyimide aerogels and preparation method thereof based on silane hydrophobically modified |
| CN110437470A (en) * | 2018-05-04 | 2019-11-12 | 中国科学院苏州纳米技术与纳米仿生研究所 | A kind of polyimide aerogels and the preparation method and application thereof with lotus leaf effect |
| CN113462012A (en) * | 2021-07-19 | 2021-10-01 | 中国科学技术大学 | Flexible linear high-temperature-resistant polyimide aerogel battery diaphragm, preparation method thereof and lithium ion battery |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014189560A1 (en) * | 2013-05-23 | 2014-11-27 | Nexolve Corporation | Method of aerogel synthesis |
| CN104341594A (en) * | 2014-10-20 | 2015-02-11 | 同济大学 | Preparation method of crosslinked polyimide silicon dioxide mixed gas gel |
| US20150141544A1 (en) * | 2012-02-03 | 2015-05-21 | U.S. Government as represented by the Administrator of the National Aeronautics and Spac | Porous cross-linked polyimide networks |
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- 2015-12-17 CN CN201510947816.XA patent/CN105778091A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150141544A1 (en) * | 2012-02-03 | 2015-05-21 | U.S. Government as represented by the Administrator of the National Aeronautics and Spac | Porous cross-linked polyimide networks |
| WO2014189560A1 (en) * | 2013-05-23 | 2014-11-27 | Nexolve Corporation | Method of aerogel synthesis |
| CN104341594A (en) * | 2014-10-20 | 2015-02-11 | 同济大学 | Preparation method of crosslinked polyimide silicon dioxide mixed gas gel |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110437470A (en) * | 2018-05-04 | 2019-11-12 | 中国科学院苏州纳米技术与纳米仿生研究所 | A kind of polyimide aerogels and the preparation method and application thereof with lotus leaf effect |
| CN110437470B (en) * | 2018-05-04 | 2021-11-02 | 中国科学院苏州纳米技术与纳米仿生研究所 | Polyimide aerogel with lotus leaf effect and preparation method and application thereof |
| CN110229340A (en) * | 2019-06-17 | 2019-09-13 | 中国科学院宁波材料技术与工程研究所 | A kind of polyimide aerogels and preparation method thereof based on silane hydrophobically modified |
| CN110229340B (en) * | 2019-06-17 | 2022-03-08 | 中国科学院宁波材料技术与工程研究所 | Polyimide aerogel based on silane hydrophobic modification and preparation method thereof |
| CN113462012A (en) * | 2021-07-19 | 2021-10-01 | 中国科学技术大学 | Flexible linear high-temperature-resistant polyimide aerogel battery diaphragm, preparation method thereof and lithium ion battery |
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Application publication date: 20160720 |