CN112358645A - Polymethacrylimide aerogel and preparation method thereof - Google Patents
Polymethacrylimide aerogel and preparation method thereof Download PDFInfo
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Abstract
The invention relates to polymethacrylimide aerogel and a preparation method thereof, belonging to the technical field of aerogel preparation. Preparing a solution of polymethacrylimide prepolymer by using methacrylic acid and methacrylonitrile monomers; preparing PMI prepolymer quaternary ammonium salt from the PMI prepolymer solution; repeatedly washing to obtain white bulk solid, and drying; dissolving in water solution, freezing and solidifying; freeze-drying to obtain PMI prepolymer quaternary ammonium salt aerogel; and (4) after heat treatment, obtaining the polymethacrylimide aerogel. The polymethacrylimide aerogel is a three-dimensional reticular open-cell structure, expands the range of the polymethacrylimide porous material, and also expands the application of the polymethacrylimide porous material in the fields of sound absorption, catalysis, adsorption and the like. The polymethacrylimide aerogel has better mechanical property and heat resistance. The material has high mechanical property while ensuring enough heat resistance.
Description
Technical Field
The invention belongs to the technical field of aerogel preparation, and particularly relates to polymethacrylimide aerogel and a preparation method thereof
Background
The molecular structure of Polymethacrylimide (PMI) materials endows the materials with excellent mechanical properties and heat resistance: carboxyl and nitrile groups enable molecular chains to form hydrogen bonds; the molecular chain is rigid due to the steric hindrance of methyl, carboxyl and nitrile groups; the six-membered imide ring further increases the rigidity of the molecular chain; in addition, the molecular chains are also crosslinked to form a spatial network structure. Therefore, polymethacrylimide is a material with very excellent mechanical properties.
The polymethacrylimide products on the market are foams at present, the polymethacrylimide foam material is a typical thermosetting foam with excellent comprehensive performance, the natural color is off-white or light yellow, and the polymethacrylimide foam material has been developed for 60 years. The rigid closed cell structure of the foam determines the characteristics of low density, high energy absorption efficiency and the like of the material. Polymethacrylimide foams can withstand high temperatures of up to 220 ℃ and PMI foams have the highest specific strength and modulus at the same density compared with other foams and are easy to machine. The preparation route of polymethacrylimide foams generally adopts a two-step method: preparing a foamable prepolymerization plate in the first step, and preparing polymethacrylimide foam in the second step. During the preparation of the pre-polymeric sheet, the polymethacrylimide pre-polymer was found to have an extremely high melt strength. Therefore, the polymethacrylimide is a very good aerogel matrix material, the high melt strength of the prepolymer can enable the polymethacrylimide to well resist volume shrinkage in the drying process, and the polymethacrylimide has better performance on the mechanical property of the aerogel after being formed. In addition, the polymethacrylimide has higher thermal deformation temperature, and can also enable the polymethacrylimide aerogel to have better mechanical property at high temperature.
Aerogel (Aerogel) is a highly dispersed solid material in which colloidal particles or high polymer molecules are aggregated with each other to form a nanoporous network structure, and the voids are filled with a gaseous dispersion medium. Aerogel due to its ultra-low density (-0.03 g/cm)3) High porosity (up to 99%), very low thermal conductivity (0.02W/(m.K)), and high specific surface area (1000 m)2Excellent properties such as/g) are widely used in the fields of heat and sound insulating materials, catalyst carriers, filtration devices, and the like. Aerogels can be classified into inorganic aerogels and organic aerogels according to their chemical composition. Inorganic aerogels, such as silica aerogels and carbon aerogels, have excellent thermal insulation properties, but very poor mechanical properties. Organic aerogel generally has better performance than inorganic aerogel in mechanical properties, because high polymer aerogel forms three-dimensional space network structure more easily than inorganic material on molecular structure, consequently can regard as aerogel material's organic high polymer ten minutes various, can prepare out the unique aerogel of various performances, expands the development of aerogel in scientific research and application.
Most of the aerogel preparation methods adopt sol-gel line preparation at present, and generally are divided into three routes of a freeze drying method, a supercritical drying method and a normal pressure drying method according to different drying methods. Generally, monomers used for synthesizing polymethacrylimide materials are methacrylic acid and methacrylonitrile or methacrylic acid and acrylonitrile, the monomers are all monofunctional monomers, synthesized polymethacrylimide prepolymers are all linear polymers, and gel is difficult to directly form in the solution polymerization process, so that the method adopts a freeze drying route, and prepares polymethacrylimide aerogel by dissolving the polymers in water in a manner of preparing prepolymer quaternary ammonium salt and then in a freeze drying manner.
Disclosure of Invention
The invention provides polymethacrylimide aerogel and a preparation method thereof. Compared with a closed cell structure of polymethacrylimide foam, the preparation method of the aerogel through freeze drying is used for preparing the polymethacrylimide open-cell structure material, and the range and application of the polymethacrylimide porous material are expanded.
The method comprises the following steps:
step one, methacrylic acid and methacrylonitrile (acrylonitrile) are taken as monomers, a cross-linking agent, an organic solvent and an initiator are added, and under the condition of a constant-temperature water bath at 60 ℃, a solution of a PMI prepolymer is prepared through free radical solution polymerization.
And step two, adding a tertiary amine compound into the PMI prepolymer solution to react to prepare the PMI prepolymer quaternary ammonium salt. After continuous stirring, a uniform stable solution is formed, and then the standing reaction is continued.
And step three, separating the PMI prepolymer quaternary ammonium salt from the solvent by using acetone, repeatedly washing the PMI prepolymer quaternary ammonium salt to obtain a hard white bulk solid, and then drying the PMI prepolymer quaternary ammonium salt to remove the acetone.
And step four, dissolving the PMI prepolymer quaternary ammonium salt into water according to a certain solid content, and freezing and solidifying at low temperature.
And step five, freezing and drying the solidified PMI prepolymer quaternary ammonium salt to obtain the PMI prepolymer quaternary ammonium salt aerogel.
And step six, performing heat treatment on the PMI prepolymer quaternary ammonium salt aerogel to obtain polymethacrylimide aerogel.
Preferably, the raw materials comprise, by weight, 40-60 parts of first monomer methacrylic acid, 60-40 parts of second monomer methacrylonitrile or acrylonitrile, 0.1-2 parts of initiator and 0.1-3 parts of cross-linking agent. And the total mass of the monomers accounts for 10-35 wt% of the total mass of the organic solvent and the monomers.
Preferably, the crosslinking agent is any one of acrylamide, magnesium oxide, allyl methacrylate, methylene bisacrylamide and 1, 3-propylene glycol, the initiator is any one of azobisisobutyronitrile, azobisisoheptonitrile and dibenzoyl peroxide, the organic solvent is any one of dimethyl sulfoxide and N, N-dimethylformamide, and the tertiary amine compound is any one of triethylamine, tributylamine or N, N-diisopropylethylamine.
Preferably, the molar ratio of the amount of tertiary amine compound to the amount of methacrylic acid is in the range of 1: 1 to 3: 1.
Preferably, the mass of the PMI prepolymer quaternary ammonium salt is 3 wt% -10 wt% of the total mass of the deionized water and the PMI prepolymer quaternary ammonium salt.
Preferably, the drying time is 36h to 72 h.
Preferably, the heat treatment temperature is 180 ℃ and the heat treatment time is 6 h.
The invention has the beneficial effects that:
(1) compared with a polymethacrylimide foam closed cell structure, the polymethacrylimide aerogel is a three-dimensional reticular open cell structure, the range of the polymethacrylimide porous material is expanded, and the application of the polymethacrylimide porous material in the fields of sound absorption, catalysis, adsorption and the like is also expanded.
(2) Compared with polyimide aerogel prepared by polymerizing dicarboxylic anhydride and diamine, the polymethacrylimide aerogel has better mechanical property and heat resistance.
(3) Compared with inorganic aerogel, the composite material has high mechanical property while ensuring enough heat resistance.
Drawings
FIG. 1 is a schematic diagram of a polymethacrylimide preparation process;
FIG. 2 is a microscopic SEM (scanning electron microscope) spectrum of a freeze-dried polymethacrylimide aerogel in a macroscopic appearance and a three-dimensional network structure;
FIG. 3 is an infrared spectrum comparison of polymethacrylimide aerogel and polymethacrylimide foam;
the method comprises the following specific implementation steps:
the method comprises the following steps: solution polymerization
The solvent is dimethyl sulfoxide (DMSO), the monomer is Methyl Acrylonitrile (MAN) and methacrylic acid (MAA), the cross-linking agent is Acrylamide (AM), and the initiator is Azobisisobutyronitrile (AIBN). 7.5g of MAN and MAA, 0.39g of AM, 35g of DMSO and 0.1607g of AIBN were mixed uniformly, and free radical solution polymerization was carried out for 96 hours in a thermostatic water bath at 60 ℃ to obtain a PMI prepolymer solution.
Step two: preparation of quaternary ammonium salts
17.6309g of triethylamine was added to the solution of PMI prepolymer obtained in step one, stirred vigorously until the solution was homogeneous, and then allowed to stand for 24 hours. After the reaction is completed, the PMI prepolymer quaternary ammonium salt solution is uniform.
The PMI prepolymer quaternary ammonium salt is separated by a large amount of acetone, the polymer in a white thread shape appears in the first washing, and the PMI prepolymer quaternary ammonium salt in a white thread shape becomes a dough shape with the increase of the number of times of washing.
Step three: drying
After PMI prepolymer quaternary ammonium salt is precipitated, the PMI prepolymer quaternary ammonium salt is put into an oven for drying, acetone is volatilized, the drying temperature is 40 ℃, and the drying time is at least 48 hours.
Step four: preparing a quaternary ammonium salt aqueous solution
Dissolving the PMI prepolymer quaternary ammonium salt obtained in the third step into deionized water according to the solid content of 3 wt%, 4 wt%, 5 wt% and 6 wt%, and preparing the PMI prepolymer quaternary ammonium salt aqueous solution with the total mass of 20 g. The dissolution time is long, and continuous stirring is required.
Step five: preparation of aerogels
And (3) freezing and solidifying the completely dissolved solution at-20 ℃, and drying by using a freeze dryer to remove the solvent water in the gel to obtain the PMI prepolymer quaternary ammonium salt aerogel.
And (3) putting the aerogel into an oven for heat treatment, setting the temperature at 180 ℃, and carrying out heat treatment for 6h to obtain the polymethacrylimide aerogel.
When the PMI prepolymer quaternary ammonium salt is used for preparing aerogel with the solid content of 6 wt%, the density of the obtained aerogel is 0.0949g/cm, the compression modulus is 65.9MPa, and the thermal conductivity is 0.0618W/(m.K).
Example two
Different from the first embodiment, the first step: 6g of MAN, 9g of MAA, 0.1g of AM, 35g of DMSO and 0.015g of AIBN were mixed homogeneously. And carrying out free radical solution polymerization reaction for 96 hours under the condition of a constant-temperature water bath at 60 ℃ to obtain a PMI prepolymer solution.
Step two: preparation of quaternary ammonium salts
21.15g of triethylamine was added to the PMI prepolymer solution of step one, stirred vigorously until the solution was homogeneous, and then left to react for 24 hours. After the reaction is finished, PMI prepolymer quaternary ammonium salt solution is formed.
When the PMI prepolymer quaternary ammonium salt is used for preparing aerogel with the solid content of 6 wt%, the density of the aerogel is 0.1023g/cm, the compression modulus is 50.4MPa, and the thermal conductivity coefficient is 0.0620W/(m.K).
EXAMPLE III
Different from the first embodiment, the first step: 9g of MAN, 6g of MAA, 0.45g of AM, 35g of DMSO and 0.45g of AIBN were mixed homogeneously. And carrying out free radical solution polymerization reaction for 96 hours under the condition of a constant-temperature water bath at 60 ℃ to obtain a PMI prepolymer solution.
Step two: preparation of quaternary ammonium salts
And (3) adding 14.1g of triethylamine into the PMI prepolymer solution in the step one, continuously stirring until the solution is uniform, and reacting for 24 hours. After the reaction is finished, a uniform PMI prepolymer quaternary ammonium salt solution is formed.
When the obtained quaternary ammonium salt is used for preparing aerogel with the solid content of 6 wt%, the density of the obtained aerogel is 0.0923g/cm, the compression modulus is 68.4MPa, and the thermal conductivity is 0.0617W/(m.K).
Comparative example 1
10g of 4,4 ' -diaminodiphenyl ether (ODA) was mechanically stirred in a three-necked flask containing 80g of DMAc until completely dissolved, and then 10g of 3,3 ', 4,4 ' -biphenyltetracarboxylic acid (BPDA) was slowly added thereto and stirred in an ice-water bath for 3 hours to completely dissolve the same, thereby obtaining a polyamic acid solution having a solid content of 20%. Then, 29.08g of triethylamine was added dropwise at room temperature, and the reaction was continued for 24 hours after stirring to a stable and uniform solution. The resulting solution was washed with acetone to give a white filamentous material, which was dried to constant weight to give Polyamic Acid Salts (PAAs). And taking out 1.2g of PAAs, dissolving in 18.8g of deionized water, freezing and solidifying at the temperature of minus 20 ℃, freeze-drying, and then carrying out heat treatment at the temperature of 180 ℃ for 6 hours to obtain the polyimide aerogel with the solid content of 6 wt%.
From the infrared spectrum of the polymethacrylimide aerogel and the polymethacrylimide foam in FIG. 3, it can be seen that the wavelength is 2234cm-1Point of the neckThe peak is the stretching vibration peak of carbon-nitrogen triple bond (C ≡ N) in the methacrylonitrile chain unit and is 1690cm-1And 959cm-1The absorption peaks at (a) are out-of-plane bending vibration peaks of C ═ O in the carboxyl group of methacrylic acid and — OH in the carboxyl group, respectively. At 1222cm-1At which secondary amine (-R) appears1-NH-R2-) the C-N bond stretching vibration peak in the compound shows that carboxyl and nitrile groups in the polymer react after heat treatment to generate six-membered imide ring structures, and the peaks of the polymethacrylimide foam and the aerogel at the positions are completely consistent, thus showing that the polymethacrylimide aerogel is successfully prepared. FIG. 2 is an SEM image of PMI aerogel with a solid content of 6 wt%, and it can be seen that PMI aerogel forms a three-dimensional space net-shaped open-pore structure after freeze-drying, the pore diameter of the PMI aerogel is mostly distributed in a range from 5 μm to 50 μm, the pore diameter distribution is uniform, and a little net-shaped structure is broken.
The density, compressive modulus, thermal conductivity and heat distortion temperature of aerogels with different solid contents are shown in Table 1. The density measurement basis is GB/T6343-2009 as the method basis; the compression performance is taken as a method basis according to GB/T1041-2008; measuring the thermal conductivity of the aerogel at 65 ℃ according to GB/T34336-2017 as a method basis; the heat distortion temperature is measured according to the method of GB/T1634.1-2019, the heating rate is 120 ℃/h, and the applied load is 1.80 MPa.
From the performance data in table 1, it can be seen that, as the solid content of the polymethacrylimide aerogel prepared by the present invention increases, the density, the compressive modulus, and the thermal conductivity all show a rising trend, the thermal deformation temperature is between 220 and 226 ℃, which is in accordance with the thermal deformation temperature range of the polymethacrylimide porous material, compared with the polyimide aerogel, the polymethacrylimide aerogel has a higher thermal deformation temperature, which means that the PMI aerogel has better performance than the polyimide aerogel when used under a higher temperature condition.
Table 1 comparison of the properties of aerogels of different solids contents in example one and comparative example one
Claims (6)
1. The preparation method of the polymethacrylimide aerogel is characterized by comprising the following steps:
step one, using methacrylic acid and methacrylonitrile or methacrylic acid and acrylonitrile as monomers, adding a cross-linking agent, an initiator and an organic solvent, and preparing a solution of a Polymethacrylimide (PMI) prepolymer through free radical solution polymerization under the condition of constant-temperature water bath;
step two, adding a tertiary amine compound into the PMI prepolymer solution obtained in the step one to react to prepare PMI prepolymer quaternary ammonium salt, continuously stirring to form a uniform and stable solution, and then continuously standing for reaction;
step three, repeatedly washing the PMI prepolymer quaternary ammonium salt solution by using acetone, then changing the PMI prepolymer quaternary ammonium salt into a hard white massive solid, and then drying to remove the acetone;
step four, dissolving the PMI prepolymer quaternary ammonium salt obtained in the step three into an aqueous solution, and freezing and solidifying at low temperature;
step five, freezing and drying the solidified PMI prepolymer quaternary ammonium salt to obtain PMI prepolymer quaternary ammonium salt aerogel;
and step six, performing heat treatment on the PMI prepolymer quaternary ammonium salt aerogel to obtain polymethacrylimide aerogel.
2. The method for preparing polymethacrylimide aerogel according to claim 1, wherein the raw materials of step one comprise 40 to 60 parts by weight of first monomer methacrylic acid, 60 to 40 parts by weight of second monomer methacrylonitrile or acrylonitrile, 0.1 to 2 parts by weight of initiator, and 0.1 to 3 parts by weight of cross-linking agent, and the total mass of the monomers accounts for 10 wt% to 35 wt% of the total mass of the organic solvent and the monomers.
3. The method for preparing polymethacrylimide aerogel according to claim 1, wherein the cross-linking agent is any one of acrylamide, magnesium oxide, allyl methacrylate, methylene bisacrylamide or 1, 3-propanediol, the initiator is any one of azobisisobutyronitrile, azobisisoheptonitrile or dibenzoyl peroxide, the organic solvent is any one of dimethylsulfoxide or N, N-dimethylformamide, and the tertiary amine compound is any one of triethylamine, tributylamine or N, N-diisopropylethylamine.
4. The method for preparing polymethacrylimide aerogel according to claim 1, wherein the molar ratio of tertiary amine compound to methacrylic acid in the second step is 1: 1 to 3: 1.
5. The method for preparing polymethacrylimide aerogel as claimed in claim 1, wherein the aqueous solution of PMI prepolymer quaternary ammonium salt in step four has a solid content of 3-10 wt%.
6. The method for preparing polymethacrylimide aerogel according to claim 1, wherein the temperature of the heat treatment in the sixth step is 160-180 ℃.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20090029109A1 (en) * | 2007-07-23 | 2009-01-29 | 3M Innovative Properties Company | Aerogel composites |
| CN105713227A (en) * | 2016-04-18 | 2016-06-29 | 成都正威新材料研发有限公司 | Linear polyimide aerogel and preparing method thereof |
| CN109233174A (en) * | 2018-07-20 | 2019-01-18 | 长沙学院 | Based on a kind of Polymethacrylimide (PMI) foamed plastics |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090029109A1 (en) * | 2007-07-23 | 2009-01-29 | 3M Innovative Properties Company | Aerogel composites |
| CN105713227A (en) * | 2016-04-18 | 2016-06-29 | 成都正威新材料研发有限公司 | Linear polyimide aerogel and preparing method thereof |
| CN109233174A (en) * | 2018-07-20 | 2019-01-18 | 长沙学院 | Based on a kind of Polymethacrylimide (PMI) foamed plastics |
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