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CN116253882A - Preparation method of amino hyperbranched siloxane and modified polyimide aerogel material thereof - Google Patents

Preparation method of amino hyperbranched siloxane and modified polyimide aerogel material thereof Download PDF

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CN116253882A
CN116253882A CN202211099609.XA CN202211099609A CN116253882A CN 116253882 A CN116253882 A CN 116253882A CN 202211099609 A CN202211099609 A CN 202211099609A CN 116253882 A CN116253882 A CN 116253882A
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amino
aerogel material
polyimide aerogel
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hyperbranched siloxane
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袭锴
徐阳
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Nanjing University
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    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
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    • 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
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Abstract

The invention discloses an amino hyperbranched siloxane and a preparation method of a modified polyimide aerogel material thereof. Firstly, under the condition of sub-stoichiometric ratio, the alkoxy silane X with amino active functional group, the alkoxy silane Y with non-active functional group and water are undergone the process of autocatalysis controllable hydrolytic condensation so as to obtain the invented amino hyperbranched siloxane liquid (HPSi-NH) 2 ) Then HPSi-NH 2 Reacting a cross-linking agent with an anhydride-terminated polyamic acid solution to obtain a functionalized polyamic acidStirring the amino hyperbranched siloxane modified polyimide aerogel material with tertiary amine and deionized water to obtain functional polyamic acid wet gel, and performing freeze drying and high-temperature imidization treatment on the wet gel to obtain the amino hyperbranched siloxane modified polyimide aerogel material. The material has excellent flexibility, rebound resilience, heat resistance and flame retardance, and can be applied to the fields of aerospace, communication, catalysis and filtration.

Description

Preparation method of amino hyperbranched siloxane and modified polyimide aerogel material thereof
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to an amino hyperbranched siloxane and a preparation method of a modified polyimide aerogel material thereof.
Background
The organic silicon resin has excellent performances of high and low temperature resistance, weather resistance, aging resistance, electrical insulation and the like, has been widely applied to the fields of aerospace, electronic and electrical appliances, light industry and the like, and becomes an indispensable novel polymer material in national economy. However, the traditional organic silicon resin has the advantages of simple synthesis, high functional group density and low viscosity because of high viscosity of the organic silicon resin and interaction force between hydroxyl groups, and the hyperbranched polymer is derived from dendritic polymer, but the hyperbranched siloxane synthesized at present has single active group and can not be regulated and controlled according to the use condition, and the preparation process is complicated.
Polyimide aerogel materials have excellent mechanical strength, high temperature resistance, radiation resistance and the like, so that research on polyimide aerogel materials has been continuously increased in recent years. The freeze drying technology has the advantages of simple process and no need of using organic solvents, and becomes one of the main methods for preparing polyimide aerogel materials, but the polyimide aerogel materials prepared by the method have poor rebound performance, and the prepared polyimide aerogel has low mechanical strength because of no chemical crosslinking points between the linear polyamic acids, and meanwhile, the polyimide aerogel body lacks functionality, so that the further development of the polyimide aerogel materials is limited.
Disclosure of Invention
Aiming at the problems in the prior art, the technical problem to be solved by the invention is to provide the amino hyperbranched siloxane which is liquid at normal temperature, contains a large amount of amino groups, alkoxy groups and other active groups, can regulate and control the content of the amino groups and the alkoxy groups, and can select the types of the other active groups according to the use requirements. The invention aims to provide a preparation method of an amino hyperbranched siloxane modified polyimide aerogel material, which can regulate and control the amino and alkoxy content of the amino hyperbranched siloxane so as to regulate and control the performance of the obtained material. The invention finally aims to solve the technical problem of providing the material prepared by the preparation method of the amino hyperbranched siloxane modified polyimide aerogel material, which has excellent flexibility, rebound resilience, small volume shrinkage, heat resistance and excellent flame retardant property.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
1) Mixing and stirring the alkoxy silane X with the amino active functional group and the alkoxy silane Y with the inactive functional group in an organic solvent at 0-80 ℃ for 1-4 h; slowly dripping water with a metering ratio into the system to react for 1-24 h at the temperature of 0-80 ℃, and finally distilling under reduced pressure at the temperature of 40-90 ℃ and the pressure of minus 0.1-0 MPa for 1-3 h to remove the solvent to obtain hyperbranched aminosiloxane (HPSi-NH) 2 )；
2) Reacting dianhydride compound and diamine compound in organic solvent at-10-25 deg.c for 2-12 hr; after that HPSi-NH 2 Adding the modified polyamide acid solution into a reaction system, and reacting for 1-8 hours at the temperature of minus 10-25 ℃ to obtain a modified polyamide acid solution of the functionalized siloxane;
3) Adding tertiary amine into the polyamide acid solution modified by the functionalized siloxane, slowly adding deionized water into the system to fully precipitate after the reaction is completed, filtering the precipitate, and vacuum drying to obtain functionalized polyamide acid powder;
4) Stirring the functionalized polyamic acid powder obtained in the step 3), tertiary amine and deionized water for 2-24 hours at the temperature of 0-80 ℃ to obtain functionalized polyamic acid wet gel; freezing the wet gel at-197 to-20 ℃ for 1-24 hours, and freeze-drying to obtain the functionalized polyamic acid xerogel;
5) The multifunctional polyamic acid xerogel obtained in the step 4) is treated by a method of N 2 Or imidizing for 2-12 h in Ar atmosphere at the high temperature of 150-300 ℃ to obtain the amino hyperbranched siloxane modified polyimide aerogel material.
The molar ratio of the alkoxy silane X with the amino active functional group to the alkoxy silane Y with the non-active functional group is 1:0.1-9; the mol ratio of the X+Y to the water is 1:0.5-1.5; the molar ratio of the dianhydride compound to the diamino compound is 1:0.5-0.95; the dianhydride compoundWith HPSi-NH 2 The molar ratio is 1:0.05-0.5.
Further, in step 1), the alkoxysilane X having an amino active functional group is selected from one or more of 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane, N- (2-aminoethyl) -3-aminopropyl triethoxysilane, p-aminophenyl trimethoxysilane, p-aminophenyl triethoxysilane, aniline methyltriethoxysilane, aniline methyltrimethoxysilane, and has the specific general formula:
Figure BDA0003833123750000031
the alkoxy silane Y with an inactive functional group is selected from one or more of methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 1- (trimethoxysilyl) naphthalene, 1- (triethoxysilyl) naphthalene, p-chlorophenyl trimethoxysilane and p-chlorophenyl triethoxysilane, and the specific general formula is as follows:
Figure BDA0003833123750000032
further, in the step 1), the organic solvent is one or more selected from anhydrous methanol, anhydrous ethanol, anhydrous n-butanol, anhydrous tetrahydrofuran and anhydrous acetone; the content of the organic solvent is 40-80 wt%; stirring temperature is 0-80 ℃; the stirring reaction time is 1-4 h.
Further, the content of the organic solvent is 50 to 70wt%.
Further, in the step 1), the molar ratio of the alkoxy silane X with the amino active functional group to the alkoxy silane Y with the non-active functional group is 1:0.1-9; in the step 1), the mol ratio of X+Y to water is 1:0.5-1.5; the reaction temperature is 0-80 ℃; the reaction time is 1-24 h.
Further, the molar ratio of X+Y to water is 3:1-1.3; the reaction temperature is 50-70 ℃; the reaction time is 8-12 h.
Further, HPSi-NH obtained in step 1) 2 The specific general formula is as follows:
Figure BDA0003833123750000041
further, in step 2), the dianhydride compound is selected from the group consisting of pyromellitic dianhydride, 3',4' -diphenyl sulfone tetracarboxylic dianhydride, 2, 3',4' -diphenyl ether tetracarboxylic dianhydride, 3', one or more of 4,4' -diphenyl ether tetracarboxylic dianhydride, 3',4' -benzophenone tetracarboxylic dianhydride and 3,3',4' -biphenyl tetracarboxylic dianhydride, the specific general formula of which is as follows;
Figure BDA0003833123750000042
the diamine compound is selected from one or more of 4,4' -diaminodiphenyl ether, 2, 6-diaminopyridine, 4' -diaminodiphenyl sulfone, m-phenylenediamine, p-phenylenediamine, 4' -di (3-aminophenoxy) biphenyl, 2, 5-di (4-aminophenyl) pyridine, bisphenol A diether diamine and 1, 3-bis (3-aminopropyl) tetramethyl disiloxane.
Further, in the step 2), the organic polar solvent is selected from one or more of N-methyl pyrrolidone, N-ethyl pyrrolidone, N-dimethylformamide and N, N-dimethylacetamide; the content of the organic solvent is 50-90 wt%; the reaction temperature is-10 to 25 ℃; the reaction time is 5-12 h.
Further, the content of the organic solvent is 75-85 wt%; the reaction temperature is 0-10 ℃; the reaction time is 8-10 h.
Further, the molar ratio of the dianhydride compound to the diamino compound is 1:0.5-0.95; the reaction time is 2-12 h; the reaction temperature is-10 to 25 ℃.
Further, dianhydride compound and HPSi-NH 2 The mol ratio of (2) is 1:0.05-0.5; the reaction temperature is-10 to 25 ℃ and the reaction time is 1 to 8 hours.
Further, the reaction temperature is between-5 and 10 ℃ and the reaction time is between 2 and 4 hours.
Further, in the step 3), the tertiary amine is one or more of triethylamine, trimethylamine, N-dimethylaniline, N-dimethylcyclopentylamine, N-methyl-N-ethyl-p-methylaniline and N, N-dimethylbenzylamine; the mass ratio of the small-molecule tertiary amine to the polyamide acid is 0.1-0.7:1.
Further, the mass ratio of the tertiary amine to the polyamic acid is 0.4 to 0.6:1
Further, in the step 4), the mass ratio of the tertiary amine to the polyamic acid is 0.4-0.9:1; the content of deionized water is 50-90 wt%; the mixing temperature is 0-80 ℃; the mixing time is 2-24 h.
Further, the mass ratio of the tertiary amine to the polyamic acid is 0.4-0.6:1; the content of deionized water is 60-80 wt%; the mixing temperature is 25-60 ℃; mixing time is 6-12 h;
further, in the step 4), the freezing temperature of the polyamide acid wet gel is minus 197 ℃ to minus 20 ℃; the freezing time is 1-24 h.
Further, in step 5), the thermal imine temperature of the polyimide acid xerogel is 150-300 ℃; the thermal imidization time is 2-12 h.
The amino hyperbranched siloxane modified polyimide aerogel material prepared by the preparation method is prepared.
Compared with the prior art, the invention has the beneficial effects that:
the invention carries out autocatalysis controllable hydrolytic condensation on alkoxy silane X with amino active functional groups, alkoxy silane Y with inactive functional groups and water under the sub-stoichiometric ratio to obtain multi-functional groups (such as other active groups, alkoxy groups and amino groups) with controllable amino content, namely amino hyperbranched siloxane liquid (HPSi-NH) 2 ) Is liquid at normal temperature, contains a large amount of amino, alkoxy and other active groups, and can be used for carrying out the variety of other active groups according to the use requirementAnd (5) selecting. Compared with the traditional polyimide aerogel material, the amino hyperbranched siloxane modified polyimide aerogel material provided by the invention has more excellent flexibility and rebound resilience, functional groups can be regulated and controlled according to the use condition, and meanwhile, the prepared amino hyperbranched siloxane modified polyimide aerogel material has small volume shrinkage, excellent heat resistance and flame retardance, and can be applied to the fields of aerospace, communication, catalysis and filtration.
Drawings
FIG. 1 is a flow chart of a process for preparing an amino hyperbranched siloxane and a modified polyimide aerogel material thereof;
FIG. 2 is HPSi-NH of example 1 2 Is a physical diagram of (a);
FIG. 3 is an infrared spectrum of a method of preparing an amino hyperbranched siloxane and a modified polyimide aerogel material thereof;
FIG. 4 is a scanning electron microscope image of a method of preparing an amino hyperbranched siloxane and a modified polyimide aerogel material thereof;
FIG. 5 is a graph of thermal stability (air atmosphere and nitrogen atmosphere) of a method of preparing an amino hyperbranched siloxane and a modified polyimide aerogel material thereof;
FIG. 6 is a cyclic compression diagram at 80% strain of a method of preparing an amino hyperbranched siloxane and modified polyimide aerogel material thereof;
FIG. 7 is a compressed physical view of an amino hyperbranched siloxane and a modified polyimide aerogel material thereof.
Detailed Description
The invention is further described below in connection with specific embodiments. These examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. In the following examples, unless otherwise specified, the experimental procedures used were conventional. The raw materials used are commercially available from public sources unless otherwise specified.
Example 1
The preparation method of the amino hyperbranched siloxane and the preparation method of the modified polyimide aerogel material thereof is shown in figure 1, and comprises the following steps:
1) Into a 500mL three-necked flask equipped with a mechanical stirring and condensing tube, 24.37g (0.1 mol) of phenyl trimethoxysiloxane, 221.37g (1 mol) of amino trimethoxysiloxane and 105.32g (30 wt%) of absolute methanol were added, and stirred at 0℃for 4 hours to mix uniformly; slowly dripping 9.9g (0.55 mol) of water into the reaction system for reaction, wherein the reaction temperature is 0 ℃ and the reaction time is 24 hours; distilling under reduced pressure at 40deg.C and-0.1 MPa for 3 hr to remove solvent to obtain HPSi-NH 2 。
2) Into a 1000mL three-necked flask equipped with a mechanical stirring and condensing tube, 19.02g (0.095 mol) of 4,4' -diaminoanisole, 32.22g (0.1 mol) of 3,3',4' -benzophenone tetracarboxylic dianhydride and 461.16g of N, N-dimethylformamide (content of organic solvent: 90% by weight) were charged, and reacted at a temperature of-10℃for 12 hours; 0.005mol of HPSi-NH 2 Adding the mixture into a reaction system, and reacting for 8 hours at the temperature of minus 10 ℃ to obtain the phenylsiloxane modified polyamide acid solution.
3) Adding 5.12g of triethylamine (the mass ratio of the triethylamine to the polyamic acid is 0.1:1) into the phenylsiloxane modified polyamic acid solution obtained in the step 2), slowly adding deionized water into the system to fully precipitate after the reaction is completed, and filtering and vacuum drying the precipitate to obtain phenyl functionalized polyamic acid powder.
4) The phenyl-functionalized polyamic acid powder obtained in the step 3) was stirred with 46.112g of triethylamine (the mass ratio of triethylamine to the polyamic acid powder is 0.9:1) and 102.48g of deionized water (the content of deionized water is 50 wt%) at 0℃for 24 hours to obtain a phenyl-functionalized polyamic acid wet gel. After the wet gel is frozen at the temperature of-197 ℃ for 1 hour, the phenyl functionalized polyamic acid xerogel is obtained through freeze drying.
5) The phenyl functionalized polyamic acid xerogel obtained in the step 4) is treated in N 2 Imidizing for 12 hours in the atmosphere at the temperature of 150 ℃ to obtain the amino hyperbranched siloxane modified polyimide aerogel material.
HPSi-NH prepared by test example 1 2 The basic performance is as follows:
viscosity: 1500cps
Amino content: 4.89mmol/g
The basic performances of the prepared amino hyperbranched siloxane and the preparation method of the modified polyimide aerogel material thereof are as follows:
density: 0.063g/cm 3
Porosity: 92 percent of
Compressive strength at 50% compressive strain: 23kPa
Example 2
The preparation method of the amino hyperbranched siloxane and the preparation method of the modified polyimide aerogel material thereof is shown in figure 1, and comprises the following steps:
1) Into a 1000mL three-necked flask equipped with a mechanical stirring and condensing tube, 210.97g (0.9 mol) of octyl trimethoxy silane, 21.33g (0.1 mol) of p-aminophenyl trimethoxy silane and 929.2g (80 wt%) of absolute ethyl alcohol were added, and stirred at 80℃for 1 hour to mix uniformly; slowly dripping 27g (1.5 mol) of water into the reaction system for reaction, wherein the reaction temperature is 80 ℃ and the reaction time is 1h; distilling under reduced pressure at 80deg.C and pressure of-0.05 MPa for 1 hr to remove solvent to obtain HPSi-NH 2 。
2) Into a 250mL three-necked flask equipped with a mechanical stirrer and a condenser, 12.42g (0.05 mol) of 4,4' -diaminodiphenyl sulfone, 21.82g (0.1 mol) of pyromellitic anhydride and 34.24g of N, N-diethylformamide (content of organic solvent: 50 wt%) were charged, and reacted at 25℃for 2 hours. 0.05mol of HPSi-NH 2 Adding the mixture into a system, and reacting for 1h at 25 ℃ to obtain the octyl siloxane modified polyamide acid solution.
3) 23.97g of trimethylamine (the mass ratio of trimethylamine to polyamic acid is 0.7:1) is added into the octyl siloxane modified polyamic acid solution obtained in the step 2), deionized water is slowly added into the system to fully precipitate after the reaction is completed, and the precipitate is filtered and dried in vacuum to obtain octyl functionalized polyamic acid powder.
4) After stirring the octyl functionalized polyamic acid powder obtained in the step 3) with 10.27g of trimethylamine (the mass ratio of trimethylamine to polyamic acid powder is 0.3:1) and 616.32g of deionized water (the content of deionized water is 90 wt%) at 80 ℃ for 2 hours, an octyl functionalized polyamic acid wet gel is obtained. Freezing the octyl functionalized polyamic acid wet gel at the temperature of minus 20 ℃ for 24 hours, and freeze-drying to obtain octyl functionalized polyamic acid xerogel;
6) And 5) imidizing the octyl functionalized polyamide acid xerogel obtained in the step 5) in Ar atmosphere at a high temperature of 300 ℃ for 2 hours to obtain the amino hyperbranched siloxane modified polyimide aerogel material.
HPSi-NH prepared by test example 2 2 The basic performance is as follows:
viscosity: 3000cps
Amino content: 0.824mmol/g
The basic properties of the prepared amino hyperbranched siloxane modified polyimide aerogel material are as follows:
density: 0.0521g/cm 3
Porosity: 89%
Example 3
The preparation method of the amino hyperbranched siloxane modified polyimide aerogel material comprises the following steps:
1) Into a 500mL three-necked flask equipped with a mechanical stirring and condensing tube, 99.15g (0.5 mol) of phenyl trimethoxysiloxane, 111.18g (0.5 mol) of N- (2-aminoethyl) -3-aminopropyl trimethoxysilane and 140.22g (40 wt%) of anhydrous tetrahydrofuran were added and stirred at room temperature for 2 hours to mix uniformly; slowly dripping 18g (1 mol) of water into the reaction system for reaction, wherein the reaction temperature is 50 ℃, and the reaction time is 12 hours; distilling under reduced pressure at 50deg.C and 0MPa for 2 hr to remove solvent to obtain HPSi-NH 2 。
2) Into a 500mL three-necked flask equipped with a mechanical stirrer and a condenser, 8.73g (0.08 mol) of 2, 6-diaminopyridine, 31.02g (0.1 mol) of 3,3',4' -diphenylether tetracarboxylic dianhydride and 119.25g of N-methylpyrrolidone (content of organic solvent: 75% by weight) were charged, and reacted at a temperature of 10℃for 8 hours. 0.02mol of HPSi-NH 2 Adding the mixture into a system, and reacting for 6 hours at the temperature of 10 ℃ to obtain the phenylsiloxane modified polyamide acid solution.
3) 15.9g of N, N-dimethylaniline (the mass ratio of the N, N-dimethylaniline to the polyamic acid is 0.4:1) is added into the phenylsiloxane modified polyamic acid solution obtained in the step 2), deionized water is slowly added into the system for full precipitation after the reaction is completed, and the precipitation is filtered and dried in vacuum to obtain phenyl functionalized polyamic acid powder.
4) Stirring phenyl-functionalized polyamic acid powder obtained in the step 3) and 23.85g of N, N-dimethylaniline (the mass ratio of the N, N-dimethylaniline to the polyamic acid powder is 0.6:1) and 145.75g of deionized water (the content of the deionized water is 60 wt%) for 12 hours at 25 ℃ to obtain phenyl-functionalized polyamic acid wet gel, freezing the wet gel at-10 ℃ for 18 hours, and freeze-drying to obtain phenyl-functionalized polyamic acid xerogel;
5) And 5) imidizing the phenyl functionalized polyamide acid xerogel obtained in the step 5) at a high temperature of 270 ℃ for 8 hours in Ar atmosphere to obtain the amino hyperbranched siloxane modified polyimide aerogel material.
Preparation of HPSi-NH according to test example 3 2 The basic performance is as follows:
viscosity: 2700cps
Amino content: 3.68mmol/g
The basic properties of the prepared amino hyperbranched siloxane modified polyimide aerogel material are as follows:
density: 0.0368g/cm 3
Porosity: 94.2%
Thermal conductivity: 0.0279W/mK
Example 4
The preparation method of the amino hyperbranched siloxane modified polyimide aerogel material comprises the following steps:
1) 120.4g (0.5 mol) of 3-chloropropyl triethoxysilane, 22.14g (0.1 mol) of aminopropyl triethoxysilane and 280.72g (70 wt%) of anhydrous acetone are added into a 1000mL three-neck flask provided with a mechanical stirring and condensing tube, and the mixture is stirred for 2 hours at 40 ℃ to be uniformly mixed; slowly dripping 14.04g (0.78 mol) of water into the reaction system for reaction, wherein the reaction temperature is 70 ℃ and the reaction time is 8 hours; distilling under reduced pressure at 50deg.C and-0.03 MPa for 2 hr to remove solvent to obtain HPSi-NH 2 。
2) Is provided with an organic deviceA500 mL three-necked flask equipped with a mechanical stirrer and a condenser was charged with 24.63g (0.06 mol) of bisphenol A diether diamine, 29.42g (0.1 mol) of 3,3',4' -biphenyltetracarboxylic acid dianhydride and 306.28g of N-ethylpyrrolidone (content of organic solvent: 85% by weight), and reacted at a temperature of 10℃for 8 hours. 0.04mol of HPSi-NH 2 Adding the mixture into a system, and reacting for 6 hours at the temperature of 10 ℃ to obtain the chlorsiloxane-modified polyamide acid solution.
3) Adding 32.43g of N, N-dimethylbenzylamine (the mass ratio of the N, N-dimethylbenzylamine to the polyamic acid is 0.6:1) into the chlorsiloxane-modified polyamic acid solution obtained in the step 2), slowly adding deionized water into the system to fully precipitate after the reaction is completed, and filtering and vacuum drying the precipitate to obtain chlorided functionalized polyamic acid powder.
4) The chlorine-containing functionalized polyamic acid powder obtained in the step 3) and 21.64g of N, N-dimethylbenzylamine (the mass ratio of N, N-dimethylbenzylamine to the polyamic acid powder is 0.4:1) and 486.45g of deionized water (the content of deionized water is 80 wt%) were stirred at 60℃for 6 hours, and then a chlorine-containing functionalized polyamic acid wet gel was obtained. The wet gel is frozen for 18 hours at the temperature of minus 10 ℃ and then is frozen and dried to obtain the chlorine-containing functionalized polyamic acid xerogel.
5) Imidizing the chlorine-containing functionalized polyamide acid xerogel obtained in the step 4) for 8 hours in Ar atmosphere at 270 ℃ to obtain the amino hyperbranched siloxane modified polyimide aerogel material.
The amino hyperbranched siloxane-based properties prepared by test example 4 were as follows:
viscosity: 3500cps
Amino content: 1.598mmol/g
The basic properties of the chlorine-containing amino hyperbranched siloxane modified polyimide aerogel material are as follows:
density: 0.0443g/cm -3
Porosity: 93.2%
The specific surface area is: 12.3m 2 /g
Example 5
The HPSi and amino hyperbranched siloxane modified polyimide aerogel materials prepared in the above examples are subjected to chemical characterization and performance test, and the results are shown in figures 2-7:
FIG. 2 is HPSi-NH of example 1 2 From the physical image of (C), the HPSi-NH can be seen 2 Is liquid at normal temperature and has low viscosity.
FIG. 3 is an infrared spectrum of an amino hyperbranched siloxane-modified polyimide aerogel material of example 1, which can be seen at 800cm -1 The bending vibration peak of Si-O-Si appears at 1787cm -1 、1720cm -1 、1375cm -1 The C=O symmetrical vibration peak on the imine ring and the C=O antisymmetric vibration peak on the imine ring and the C-N stretching vibration peak on the imine ring appear respectively, which illustrate the amino hyperbranched siloxane modified polyimide aerogel material.
FIG. 4 is a scanning electron microscope image of an amino hyperbranched siloxane modified polyimide aerogel material of example 3, from which it can be seen that the aerogel material exhibits a layered porous structure with an interlayer spacing of about 10 μm, and it is this unique layered structure that imparts excellent rebound properties to the amino hyperbranched siloxane modified polyimide aerogel material.
FIG. 5 is a graph showing the thermal stability of an amino hyperbranched siloxane-modified polyimide aerogel material of example 3 (a) an air atmosphere (b) a nitrogen atmosphere, from which it can be seen that the T of the multifunctional flexible polyimide aerogel material was under an air, nitrogen atmosphere 10％ 434 ℃, 459 ℃, respectively, is superior to other polymer aerogel materials (such as polyimide aerogel, polystyrene aerogel, polypyrrolidone aerogel, etc.).
FIG. 6 example 4 is a cyclic compression diagram of an amino hyperbranched siloxane modified polyimide aerogel material at 80% strain, from which it can be seen that the aerogel material has a compressive strength of 21kPa at 80% strain, while still maintaining a higher compressive strength after 10 compression cycles, meaning that the aerogel material has excellent mechanical strength.
Fig. 7 is a compressed physical diagram of the amino hyperbranched siloxane and the modified polyimide aerogel material thereof according to example 4, from which it can be seen that the aerogel material can be restored to the original state when the external force is released after the external force is compressed, and exhibits excellent rebound performance.

Claims (10)

1. An amino hyperbranched siloxane, characterized in that the HPSi-NH 2 The preparation method of (2) comprises the following steps: mixing and stirring the alkoxy silane X with the amino active functional group and the alkoxy silane Y with the inactive functional group in an organic solvent at 0-80 ℃ for 1-4 h; slowly dripping water with a metering ratio into the system to react for 1-24 h at 0-80 ℃, and finally distilling at 40-90 ℃ under reduced pressure of minus 0.1-0 MPa for 1-3 h to obtain the HPSi-NH 2 。
2. The amino hyperbranched siloxane according to claim 1, wherein:
the alkoxy silane X with amino active functional groups is selected from one or more of 3-aminopropyl triethoxy silane, 3-aminopropyl trimethoxy silane, N- (2-aminoethyl) -3-aminopropyl triethoxy silane, p-aminophenyl trimethoxy silane, p-aminophenyl triethoxy silane, aniline methyl triethoxy silane and aniline methyl trimethoxy silane;
the alkoxy silane Y with the non-active functional group is selected from one or more of methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 1- (trimethoxysilyl) naphthalene, 1- (triethoxysilyl) naphthalene, p-chlorophenyl trimethoxysilane and p-chlorophenyl triethoxysilane.
3. The preparation method of the amino hyperbranched siloxane modified polyimide aerogel material is characterized by comprising the following steps of:
1) Subjecting a dianhydride compound and a diamine compound to ring-opening reaction in an organic solvent, and then subjecting the following claims to1 HPSi-NH 2 Adding the modified polyamide acid solution into a reaction system, and continuing to react to obtain a modified polyamide acid solution of the functional siloxane;
2) Adding tertiary amine into the polyamide acid solution modified by the functionalized siloxane, slowly adding deionized water into the system to fully precipitate after the reaction is completed, filtering the precipitate, and vacuum drying to obtain functionalized polyamide acid powder;
3) Stirring the functionalized polyamic acid powder, tertiary amine and deionized water to obtain functionalized polyamic acid wet gel, and then performing freeze drying treatment on the wet gel to obtain functionalized polyamic acid xerogel;
4) And (3) carrying out high-temperature imidization treatment on the functionalized polyamide acid xerogel in an inert atmosphere to obtain the amino hyperbranched siloxane modified polyimide aerogel material.
4. The method for preparing an amino hyperbranched siloxane-modified polyimide aerogel material according to claim 1, wherein in step 1):
the dianhydride compound is selected from pyromellitic dianhydride, 3',4' -diphenyl sulfone tetracarboxylic dianhydride, 2, 3',4' -diphenyl ether tetracarboxylic dianhydride and 3,3', one or more of 4,4' -diphenyl ether tetracarboxylic dianhydride, 3',4' -benzophenone tetracarboxylic dianhydride, 3',4' -biphenyl tetracarboxylic dianhydride;
the diamine compound is selected from one or more of 4,4' -diaminodiphenyl ether, 2, 6-diaminopyridine, 4' -diaminodiphenyl sulfone, m-phenylenediamine, p-phenylenediamine, 4' -di (3-aminophenoxy) biphenyl, 2, 5-di (4-aminophenyl) pyridine, bisphenol A diether diamine and 1, 3-bis (3-aminopropyl) tetramethyl disiloxane;
the organic solvent is selected from one or more of N-methyl pyrrolidone, N-ethyl pyrrolidone, N-dimethylformamide and N, N-dimethylacetamide.
5. The method for preparing an amino hyperbranched siloxane-modified polyimide aerogel material according to claim 3, wherein in step 1):
the molar ratio of the dianhydride compound to the diamino compound is 1:0.5-0.95, and the reaction time is 2-12 h; the reaction temperature is-10 to 25 ℃; the dianhydride compound and HPSi-NH 2 The mol ratio is 1:0.05-0.5, the reaction temperature is-10-25 ℃, and the reaction time is 1-8 h.
6. The method for preparing an amino hyperbranched siloxane modified polyimide aerogel material according to claim 3, wherein the tertiary amine is one or more of triethylamine, trimethylamine, N-dimethylaniline, N-dimethylcyclopentylamine, N-methyl-N-ethyl-p-methylaniline, N-dimethylbenzylamine.
7. The method for preparing an amino hyperbranched siloxane-modified polyimide aerogel material according to claim 3, wherein the mass ratio of the tertiary amine to the polyamic acid in the step 3) is 0.3-0.9:1; the deionized water content is 50-90 wt%, the mixing temperature is 0-80 ℃, and the mixing time is 2-24 h.
8. The method for preparing an amino hyperbranched siloxane-modified polyimide aerogel material according to claim 3, wherein the temperature at which the polyamic acid wet gel in the step 3) is frozen is-197 to-20 ℃ and the freezing time is 1 to 24 hours.
9. The method for preparing an amino hyperbranched siloxane-modified polyimide aerogel material according to claim 3, wherein the thermal imine temperature of the polyamic acid xerogel in the step 4) is 150-300 ℃ and the reaction time is 2-12 h.
10. A material prepared by the method for preparing an amino hyperbranched siloxane modified polyimide aerogel material according to any one of claims 3 to 9.
CN202211099609.XA 2022-09-05 2022-09-05 Preparation method of amino hyperbranched siloxane and modified polyimide aerogel material thereof Pending CN116253882A (en)

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CN117943264B (en) * 2024-03-26 2024-06-14 锦绣防水科技有限公司 Waterproof and heat-insulating modified asphalt coiled material and preparation method thereof
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