CN107365497B - Polyimide-based composite aerogel with high flame retardant property as well as preparation method and application thereof - Google Patents
Polyimide-based composite aerogel with high flame retardant property as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a preparation method and a product of polyimide-based composite aerogel, and particularly relates to graphene-reinforced polyimide-based composite aerogel and a preparation method and application thereof. The composition comprises: the graphene-polyimide composite material comprises graphene and polyimide, wherein the mass ratio of the graphene to the polyimide is 6: 100-20: 100. the preparation process comprises the following steps: uniformly mixing graphene oxide and a water-soluble precursor polyamide acid of polyimide, and preparing graphene oxide-polyamide acid composite aerogel through a sol-gel process and a freeze-drying technology; and preparing the graphene-polyimide composite aerogel through a thermal imidization process. The polyimide-based composite aerogel prepared by the invention adopts a green chemical preparation method, and uses no phosphorus-containing flame retardant or halogen-containing flame retardant. In addition, the prepared polyimide-based composite aerogel has excellent mechanical property, heat resistance and flame retardance, so that the prepared polyimide-based composite aerogel is an ideal heat-insulating and flame-retardant material.
Description
Technical Field
The invention belongs to the technical field of novel nano-material-high-molecular-weight porous composite aerogel, and relates to a graphene-reinforced polyimide-based composite aerogel material and a preparation method and application thereof.
Background
The aerogel is a porous gel substance with a three-dimensional network structure and taking gas as a dispersion medium, the porosity is generally 80-99.8%, and the specific surface area is generally 200-1000 m2g-1The density is usually less than 0.1g cm-3. Due to the unique porous structure of the aerogel, the aerogel has many excellent properties in aspects of mechanics, acoustics, heat and the like, such as low apparent density, low acoustic impedance, low thermal conductivity and the like. Therefore, the aerogel has wide application prospects in the aspects of heat insulation, flame retardance, sound insulation and the like.
Compared with the traditional silica (SiO2) aerogel, the polymer-based aerogel is used as a matrix of materials for flame retardance, heat insulation and the like due to the unique properties of low cost, easiness in molding, high porosity, low density, low thermal conductivity and the like. At present, the polymer-based flame-retardant aerogel is usually prepared by using water-soluble polymer materials such as polyvinyl alcohol and the like as a matrix and environment-friendly nano materials such as clay, SiO2 and the like as flame retardants through a freeze-drying technology. However, the polymer-based flame retardant aerogel generally has the problems of poor mechanical properties (compressive modulus is usually 0.3-5.8 MPa), low thermal decomposition temperature (190-270 ℃), poor flame retardant properties (limiting oxygen index, LOI <34), and the like, so that the application of the polymer-based flame retardant aerogel is limited. On the one hand, the reason is caused by poor mechanical property of the polymer matrix and low thermal decomposition temperature; on the other hand, the flame-retardant nano filler is easy to agglomerate and is difficult to disperse in a polymer matrix. Therefore, the high-flame-retardant polymer-based aerogel needs to be prepared by selecting a water-soluble polymer matrix with good mechanical properties and high decomposition temperature, and solving the problem of dispersion of the flame-retardant filler in the matrix.
Disclosure of Invention
The invention provides a polyimide aerogel material reinforced by graphene as a flame retardant, and a preparation method and application thereof, aiming at the problems of poor mechanical, thermal and flame retardant properties, limited use and the like of a high-molecular-base composite aerogel taking water-soluble polymers such as polyvinyl alcohol and the like as main matrixes and clay and the like as main flame retardants.
The invention provides polyimide-based composite aerogel with high flame retardant property, which comprises graphene and polyimide, wherein the mass ratio of the graphene to the polyimide is 6: 100-20: 100. The cross-linking structure formed by the graphene and the polyamic acid improves the mechanical property and the thermal stability of the composite aerogel.
Further, the mass ratio of the graphene to the polyimide is 10: 100-18: 100.
Further, the polyimide-based composite aerogel also comprises montmorillonite.
The mass ratio of the graphene to the montmorillonite is not less than 0.3: 1.
Preferably, the mass ratio of the graphene to the montmorillonite is 0.6: 1-1.2: 1.
The invention also provides a method for preparing the polyimide-based composite aerogel, which comprises the following steps:
dispersing graphene oxide in deionized water, and performing ultrasonic treatment to obtain a stably dispersed graphene oxide dispersion solution, wherein the mass concentration of the graphene oxide dispersion solution is 2-10 mg/mL;
dissolving water-soluble polyamic acid in the stable graphene oxide dispersion liquid to obtain a graphene oxide-polyamic acid solution;
placing the graphene oxide-polyamic acid solution for 12-24 hours after ultrasonic treatment, and obtaining graphene oxide-polyamic acid hydrogel through a sol-gel process;
freezing the graphene oxide-polyamic acid hydrogel into a solid in a refrigerator or liquid nitrogen, and then freeze-drying the solid in a freeze dryer for 12-64 hours to obtain graphene oxide-polyamic acid aerogel which is marked as PAA/GO;
and carrying out thermal imidization on the graphene oxide-polyamic acid aerogel in a nitrogen atmosphere to prepare graphene-polyimide aerogel, and recording the graphene-polyimide aerogel as PI/G. The rich oxygen-containing groups on the surface of the graphene oxide can be subjected to a crosslinking reaction with the polyamic acid under a heating condition, so that the mechanical property and the thermal stability of the composite aerogel are improved.
Further, the preparation method comprises the following steps:
dispersing graphene oxide in deionized water, and performing ultrasonic treatment to obtain a stably dispersed graphene oxide dispersion solution, wherein the mass concentration of the graphene oxide dispersion solution is 2-10 mg/mL;
dispersing the peeled montmorillonite in deionized water, and mechanically stirring to obtain dispersed montmorillonite dispersion liquid;
dispersing graphene oxide and the peeled montmorillonite in deionized water according to a certain proportion, and performing ultrasonic treatment to obtain a stably dispersed graphene oxide/montmorillonite dispersion liquid, wherein the proportion of the graphene oxide to the peeled montmorillonite is more than or equal to 1: 2. The surface of the graphene oxide contains rich oxygen-containing groups such as carboxyl, hydroxyl, carbonyl and the like, and has negative charges, and the groups can be effectively combined with montmorillonite sheets containing positive charges to achieve the effect of synergistically dispersing the graphene oxide and the montmorillonite.
Dissolving water-soluble polyamic acid in the graphene oxide/montmorillonite dispersion liquid to obtain a graphene oxide/montmorillonite-polyamic acid solution;
carrying out ultrasonic treatment on the graphene oxide/montmorillonite-polyamide acid solution, then standing for 12-24 hours, and obtaining graphene oxide/montmorillonite-polyamide acid hydrogel through a sol-gel process;
freezing the graphene oxide/montmorillonite-polyamide acid hydrogel into a solid in a refrigerator or liquid nitrogen, and then freeze-drying the solid in a freeze dryer for 12 to 64 hours to obtain graphene oxide/montmorillonite-polyamide acid aerogel which is marked as PAA/GO/M;
carrying out thermal imidization on the graphene oxide/montmorillonite-polyamic acid aerogel in a nitrogen atmosphere to prepare the graphene oxide/montmorillonite-polyimide aerogel, and recording the graphene oxide/montmorillonite-polyamic acid aerogel as PI/GO/M.
Further, the exfoliated montmorillonite is prepared by the following steps: dispersing original montmorillonite in a certain amount of deionized water, heating at 70-95 deg.C while stirring for at least 0.5h, performing ultrasonic treatment for at least 1h, filtering, and drying.
Further, the thermal imidization process is as follows: and (3) carrying out sectional heating and heat preservation on the obtained polyamic acid-based composite aerogel in a tubular furnace in a nitrogen atmosphere, namely, respectively preserving the heat at 100 ℃, 200 ℃ and 300 ℃ for 0.5 to 2 hours. The reaction of the polyamide acid is sufficient under the condition of sectional heat preservation, and the formed crosslinked network of the polyamide is dense, thereby being beneficial to the promotion of the subsequent performance.
The invention also provides application of the polyimide-based composite aerogel as a heat insulation material and a flame retardant material, wherein the polyimide-based composite aerogel comprises graphene and polyimide, and the mass ratio of the graphene to the polyimide is 6: 100-20: 100.
The invention has the beneficial effects that:
(1) the mechanical property, heat resistance and flame retardance of the polyimide aerogel enhanced by taking the graphene as the flame retardant are obviously improved, so that the polyimide aerogel is used as a heat insulation and flame retardant material and is more widely applied.
(2) Due to the good synergistic dispersion effect between the graphene oxide and the montmorillonite, the problem that the flame-retardant nano filler is easy to agglomerate is solved, so that the mechanical property, the heat resistance and the flame retardance of the polyimide aerogel enhanced by taking the graphene/montmorillonite as a flame retardant are further improved.
(3) The invention has ingenious design idea, adopts a simple, convenient and environment-friendly preparation process to effectively compound the graphene or graphene/montmorillonite which is the material of the two-dimensional nanosheet layer with the polymer matrix material with excellent performance, and directly constructs the three-dimensional aerogel material with excellent flame retardant performance.
Drawings
FIG. 1 is a sedimentation experiment chart of the synergistic dispersion ratio of graphene oxide and montmorillonite in the invention;
FIG. 2-a is a scanning electron microscope image of polyimide-based composite aerogel PI in the invention;
FIG. 2-b shows polyimide-based composite aerogel PI/G according to the present invention1006 scanning electron microscope picture;
FIG. 2-c shows polyimide-based composite aerogel PI/G according to the present invention100:6Scanning electron micrograph of/M.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1
N, N-dimethylacetamide is used as a solvent, 4' -diaminodiphenyl ether and pyromellitic dianhydride in equal molar ratio are subjected to condensation polymerization reaction in an ice-water bath to prepare polyamic acid with the solid content of 15%. The specific process is as follows: at room temperature, firstly 8g of 4, 4' -diaminodiphenyl ether is fully dissolved in 95g N, N-dimethylacetamide, until the solution is clear and no particles are seen, then pyromellitic dianhydride with the same amount, namely 8.85g, is added in batches, and then the reaction is transferred to an ice-water bath for reaction for 2 hours. And adding triethylamine with the mass of diamine and the like, and continuously stirring for reacting for about 2 hours to obtain a polyamic acid solution with the solid content of 15%. And sealing and storing the prepared polyamic acid solution, standing for two days, slowly pouring the polyamic acid solution into ice water, washing, freezing and drying to obtain water-soluble polyamic acid for later use.
And (3) adding 2g of polyamic acid and 1g of triethylamine into 30mL of deionized water, performing ultrasonic treatment for 1h, and stirring for 0.5h to dissolve and uniformly disperse the polyamic acid to obtain a polyamic acid aqueous solution. The triethylamine can be coated on the terminal carboxyl functional group of the polyamic acid, so that the polyamic acid is easy to dissolve in deionized water. And then transferring the polyamide acid aerogel into a mold, carrying out ultrasonic treatment for 0.5h, transferring the mold into a refrigerator with the temperature of about 4 ℃ for precooling for 5h, then putting the mold into liquid nitrogen to rapidly freeze the mold into a solid, and then carrying out freeze drying for 48h under the vacuum degree of 10-20 Pa to obtain the polyamide acid aerogel.
Placing the obtained polyamic acid aerogel in a tubular furnace, controlling a heating program in a nitrogen atmosphere, namely heating the polyamic acid aerogel from room temperature to 100 ℃ for 30min, and keeping the temperature for 1 h; heating to 100-200 deg.C for 30min, and keeping the temperature for 1 h; and (3) heating to 200-300 ℃ for 30min, and preserving heat for 1h to obtain the polyimide aerogel, which is recorded as PI.
Example 2
The procedure for preparing a water-soluble polyamic acid was the same as in example 1.
The preparation method of the graphene reinforced polyimide-based composite aerogel comprises the following steps:
30mL of 5mg mL-12g of a polyimide was added to the graphene oxide dispersionAnd (3) ultrasonically treating amino acid and 1g of triethylamine for 1h, and stirring for 0.5h to dissolve and uniformly disperse the polyamide acid to obtain a polyamide acid aqueous solution. The rest of the procedure was the same as in example 1. And obtaining the graphene-reinforced polyimide-based composite aerogel. Through Thermal Gravimetric Analysis (TGA), in the graphene-reinforced polyimide-based composite aerogel, the mass ratio of graphene to polyimide is 6: 100. therefore, the graphene-reinforced polyimide-based composite aerogel obtained in example 2 is recorded as PI/G100:6。
Example 3
The procedure for preparing a water-soluble polyamic acid was the same as in example 1.
The preparation method of the graphene/montmorillonite synergistically enhanced polyimide-based composite aerogel comprises the following steps:
taking 30mL of prepared 5mg mL-1Adding 300mg of montmorillonite into the graphene oxide dispersion liquid, stirring for 0.5h, and performing ultrasonic treatment for 1 h. The rest of the procedure was the same as in example 1. Obtaining the polyimide-based composite aerogel material synergistically enhanced by graphene/montmorillonite, and recording the polyimide-based composite aerogel material as PI/G100:6/M。
Polyimide-based composite aerogel materials, PI, PI/G obtained in examples 1, 2, and 3100:6And PI/G100:6The results of the individual performance tests of/M are shown in Table 1. Wherein the thermal decomposition temperature is the thermal weight loss temperature of the sample at 10 wt%. The results show that PI/G is relative to PI100:6The compression modulus, the density, the specific modulus and the decomposition temperature of the polyimide aerogel are obviously improved, namely the mechanical property and the heat resistance of the polyimide aerogel are obviously improved under the enhancement of the graphene. And relative to PI, PI/G100:6The compression modulus, density, specific modulus, decomposition temperature and limiting oxygen index of/M are improved. And, PI/G100:6Compressive modulus, specific modulus, and limiting oxygen index of/M vs. PI/G100:6Is more excellent.
Table 1: performance of graphene or graphene/montmorillonite reinforced polyimide-based composite aerogel
Example 4
According to the method for preparing the graphene-reinforced polyimide-based composite aerogel in example 2, graphene-reinforced polyimide-based composite aerogels containing graphene and polyimide in the ratio of 40:100, 20:100, 18:100, 13:100 and 10:100, respectively, are prepared, and the prepared graphene-reinforced polyimide-based composite aerogels are respectively marked as PI/G100:40，PI/G100:20，PI/G100：18，PI/G100:13，PI/G100:10。
PI/G100:40，PI/G100:20，PI/G100：18，PI/G100:13，PI/G100:10，PI/G100:6The results of the performance test of (a) are shown in Table 2. The results show that PI/G100:20，PI/G100：18，PI/G100:13，PI/G100:10，PI/G100:6The mechanical property, heat resistance and flame retardance of the flame-retardant rubber are good.
Table 2: composite aerogel performance containing different mass ratios of graphene to polyimide
Example 5
As shown in FIG. 1, 5mg mL of the solution was taken-1The graphene oxide is used as a dispersion medium, and 0, 2.5, 5, 10, 20 and 30mg mL of the same volume are added from left to right respectively-1The montmorillonite is stirred for 0.5h and is subjected to ultrasonic treatment for 1h to form uniform brown dispersion liquid. Then left to stand for 24 hours. When 20mg mL of the solution is added-1When montmorillonite is used, obvious flocculent precipitate appears in the dispersion liquid. When 30mgmL of the solution is added-1The dispersion is completely precipitated in the presence of montmorillonite. The sedimentation experiment result shows that the graphene oxide can disperse montmorillonite with twice mass concentration at most. More preferably, when the mass ratio of the graphene oxide to the montmorillonite is 1: 1-2: 1, the synergistic dispersion effect of the graphene oxide and the montmorillonite is better.
When graphene oxide disperses montmorillonite with twice mass concentration, polyimide-based composite aerogel synergistically enhanced by graphene/montmorillonite is prepared according to the method in example 3, and the mass ratio of graphene to montmorillonite in the obtained polyimide-based composite aerogel is 0.3:1 through thermal weight loss analysis (TGA). When the mass ratio of the graphene oxide to the montmorillonite is 1: 1-2: 1, preparing the graphene oxide/montmorillonite synergistically enhanced polyimide-based composite aerogel according to the method in the embodiment 3, and performing thermal weight loss analysis (TGA) to obtain the polyimide-based composite aerogel, wherein the mass ratio of the graphene to the montmorillonite is 0.6: 1-1.2: 1.
Example 6
FIG. 2 is a scanning electron microscope image of the polyimide-based composite aerogel according to the present invention. SEM characterization showed that: PI/G prepared in the invention100:6And PI/G100:6Compared with PI, the PI/G has uniform and compact internal holes and is further more intuitively explained100:6And PI/G100:6Excellent mechanical property/M, heat resistance and flame retardance.
It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Claims (5)
1. A preparation method of polyimide-based composite aerogel with high flame retardant property is characterized by comprising the following steps: dispersing graphene oxide in deionized water, and performing ultrasonic treatment to obtain a stably dispersed graphene oxide dispersion solution, wherein the mass concentration of the graphene oxide dispersion solution is 2-10 mg/mL; dispersing the peeled montmorillonite in deionized water, and mechanically stirring to obtain dispersed montmorillonite dispersion liquid, wherein the mass concentration of the montmorillonite dispersion liquid is 2-50 mg/mL; dispersing graphene oxide and stripped montmorillonite in deionized water according to a certain proportion, and performing ultrasonic treatment to obtain a stably dispersed graphene oxide/montmorillonite dispersion liquid, wherein the mass ratio of the graphene oxide to the stripped montmorillonite is 1: 1-2: 1; dissolving water-soluble polyamic acid in the graphene oxide/montmorillonite dispersion liquid to obtain a graphene oxide/montmorillonite-polyamic acid solution; carrying out ultrasonic treatment on the graphene oxide/montmorillonite-polyamide acid solution, standing for 12-24h, and obtaining graphene oxide/montmorillonite-polyamide acid hydrogel through a sol-gel process; freezing the graphene oxide/montmorillonite-polyamide acid hydrogel into a solid in a refrigerator or liquid nitrogen, and then freeze-drying the solid in a freeze dryer for 12 to 64 hours to obtain graphene oxide/montmorillonite-polyamide acid aerogel which is marked as PAA/GO/M; carrying out thermal imidization on the graphene oxide/montmorillonite-polyamide acid aerogel in a nitrogen atmosphere to prepare graphene/montmorillonite-polyimide aerogel, and recording the graphene/montmorillonite-polyimide aerogel as PI/G/M, wherein the mass ratio of graphene to polyimide in the obtained graphene/montmorillonite-polyimide aerogel is 13: 100-18: 100, and the mass ratio of graphene to montmorillonite is 0.6: 1-1.2: 1.
2. The method for preparing polyimide-based composite aerogel according to claim 1, wherein the exfoliated montmorillonite is prepared by the following steps: dispersing original montmorillonite in deionized water, heating at 70-95 deg.C while stirring for at least 0.5 hr, performing ultrasonic treatment for at least 1 hr, filtering, and drying.
3. The method for preparing polyimide-based aerogel according to claim 1, wherein the thermal imidization process is: the obtained polyamide-based composite aerogel is heated and insulated in a tube furnace in a nitrogen atmosphere in sections, namely, the temperature is respectively kept at 100 ℃, 200 ℃ and 300 ℃ for 0.5 to 2 hours.
4. A polyimide-based composite aerogel prepared by the method of any one of claims 1-3.
5. The use of the polyimide-based composite aerogel of claim 4 as a thermal insulation material, a flame retardant material.
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| GB2587889B (en) * | 2018-02-22 | 2022-01-12 | Graphene Composites Ltd | Composite structure and method of manufacture |
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| TWI732195B (en) | 2018-05-17 | 2021-07-01 | 利機企業股份有限公司 | Flame-retardant and abrasion-resistant composite |
| GB2573810B (en) | 2018-05-18 | 2021-02-24 | Graphene Composites Ltd | Protective shield and shield wall |
| CN109467928A (en) * | 2018-11-29 | 2019-03-15 | 圣盟（廊坊）新材料研究院有限公司 | A kind of preparation method of graphene/composite conducting polymer material |
| CN109453743A (en) * | 2018-12-12 | 2019-03-12 | 郑州大学 | A kind of graphene oxide/bentonite nano piece aeroge, preparation method and application |
| CN110394128A (en) * | 2019-07-18 | 2019-11-01 | 复旦大学 | A kind of hydrophobic anti-flaming thermal-insulation aerogel composite and preparation method thereof |
| CN110642250B (en) * | 2019-09-12 | 2022-03-18 | 东华大学 | Cobalt-crosslinked composite carbon aerogel with adjustable pore diameter and preparation method thereof |
| CN113637107A (en) * | 2021-08-23 | 2021-11-12 | 合肥晋怡科技有限公司 | Preparation method of flame-retardant polymethacrylimide foam composite material |
| CN113929077A (en) * | 2021-11-10 | 2022-01-14 | 四川大学 | Polyimide/graphene-based composite carbon foam with ordered pore structure and preparation method and application thereof |
| CN114409956A (en) * | 2022-01-13 | 2022-04-29 | 武汉理工大学 | Flame-retardant thermal-insulation aerogel with fire early-warning function and preparation method and application thereof |
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