CN115873246B - High-temperature-resistant high-solidity supermolecule shape memory polyimide and preparation method thereof - Google Patents
High-temperature-resistant high-solidity supermolecule shape memory polyimide and preparation method thereof Download PDFInfo
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- 229910021389 graphene Inorganic materials 0.000 claims abstract description 42
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- 239000002904 solvent Substances 0.000 claims abstract description 19
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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 8
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 7
- 150000008064 anhydrides Chemical class 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 7
- 230000001681 protective effect Effects 0.000 claims description 7
- ZPKSAIWDCQVXSQ-UHFFFAOYSA-N (4-aminophenoxy)boronic acid Chemical compound NC1=CC=C(OB(O)O)C=C1 ZPKSAIWDCQVXSQ-UHFFFAOYSA-N 0.000 claims description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 6
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 6
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 4
- UTHULKKJYXJZLV-UHFFFAOYSA-N (3-aminophenoxy)boronic acid Chemical compound NC1=CC=CC(OB(O)O)=C1 UTHULKKJYXJZLV-UHFFFAOYSA-N 0.000 claims description 3
- GGYKKZSFEXVNTD-UHFFFAOYSA-N 4-(2-propylphenoxy)aniline Chemical compound CCCC1=CC=CC=C1OC1=CC=C(N)C=C1 GGYKKZSFEXVNTD-UHFFFAOYSA-N 0.000 claims description 3
- JCRRFJIVUPSNTA-UHFFFAOYSA-N 4-[4-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 JCRRFJIVUPSNTA-UHFFFAOYSA-N 0.000 claims description 3
- ZIQBFAAPJOGAHV-UHFFFAOYSA-N [4-(aminomethyl)phenoxy]boronic acid Chemical compound NCC1=CC=C(OB(O)O)C=C1 ZIQBFAAPJOGAHV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004305 biphenyl Substances 0.000 claims description 3
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- NMARXKNYACRWOS-UHFFFAOYSA-N OC(C)(C)C(C)(C)O.NC1=CC=C(C=C1)OB(O)O Chemical compound OC(C)(C)C(C)(C)O.NC1=CC=C(C=C1)OB(O)O NMARXKNYACRWOS-UHFFFAOYSA-N 0.000 claims 1
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- AJYDKROUZBIMLE-UHFFFAOYSA-N 4-[2-[2-[2-(4-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=CC=C(OC=2C=CC(N)=CC=2)C=1C(C)(C)C1=CC=CC=C1OC1=CC=C(N)C=C1 AJYDKROUZBIMLE-UHFFFAOYSA-N 0.000 description 5
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- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 2
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Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention provides high-temperature-resistant high-solidity supermolecule shape memory polyimide and a preparation method thereof, and relates to the technical field of shape memory materials. Mixing graphene oxide, an organic solvent, diamine and dianhydride for polycondensation reaction to obtain dianhydride-terminated polyamic acid solution; mixing a boron source containing an amino group with the dianhydride end-capped polyamic acid solution for polycondensation reaction, and sequentially removing solvent and carrying out thermal imidization on the obtained boric acid ester end-capped polyamic acid solution to obtain the high-temperature-resistant high-temperature-curing supermolecule shape memory polyimide. The thermosetting supermolecular shape memory polyimide prepared by the invention can generate rapid boron-oxygen bond exchange reaction at high temperature, so that stress is relaxed, complex shape forming is realized, and excellent high-temperature plasticity and welding function are realized; the invention realizes the functions of thermoset polyimide light response shape memory, light control shape reshaping and welding by means of the graphene oxide light-heat conversion function; and the glass transition temperature of the prepared polyimide is high.
Description
Technical Field
The invention relates to the technical field of shape memory materials, in particular to high-temperature-resistant high-solidity supermolecule shape memory polyimide and a preparation method thereof.
Background
The shape memory polymer and the composite material thereof have the advantages of light weight, adjustable performance and excellent performance, and are widely applied to the fields of aerospace, biomedicine and the like. The shape memory polyimide has the advantages of high glass transition temperature, high mechanical strength, good thermal stability, excellent shape memory performance and the like, is widely researched and focused in recent years, and has a huge application prospect in severe complex environments such as aerospace, high temperature and the like. For example, chinese patent CN104004188A discloses a high-temperature resistant thermosetting shape memory polyimide, wherein T g is 235-245 ℃, and the shape memory performance is stimulated by heating; chinese patent CN105542205A discloses a method for preparing electrically driven shape memory polyimide, T g is 220-238 ℃, the shape fixation rate of electrically driven shape memory is 96%, and the shape recovery rate is 97%.
Although the shape memory polyimide materials with high deformation temperature and different driving response modes are obtained in the prior reports, the shape memory polyimide materials are based on simple shapes, and the forming of the complex shapes and the welding function of the materials cannot be realized; moreover, there is no report of light control to realize shape reshaping and welding performance of high temperature shape memory polyimide, thus limiting the application of high temperature shape memory polymer as a driver in complex environments.
Disclosure of Invention
In view of the above, the present invention aims to provide a high temperature resistant thermosetting supermolecule shape memory polyimide and a preparation method thereof. The high-temperature-resistant high-solidity supermolecule shape memory polyimide prepared by the invention can realize complex shape remolding, welding and reprocessing, and has a light response shape memory function.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of high-temperature-resistant high-solidity supermolecule shape memory polyimide, which comprises the following steps:
(1) Mixing graphene oxide, an organic solvent, diamine and dianhydride for polycondensation reaction to obtain dianhydride-terminated polyamic acid solution;
(2) Mixing a boron source containing an amine group with the dianhydride end-capped polyamic acid solution to perform polycondensation reaction to obtain a borate end-capped polyamic acid solution; the boron source containing the amino group comprises boric acid ester containing the amino group and/or boric acid containing the amino group;
(3) Sequentially removing solvent and carrying out thermal imidization on the boric acid ester end-capped polyamic acid solution to obtain the high-temperature-resistant high-temperature-curable supermolecule shape memory polyimide.
Preferably, the diamine in the step (1) comprises one or more of 4,4 '-diaminodiphenyl ether, 4' -diaminodiphenyl sulfone, 1, 4-bis (4-aminophenoxy) benzene, 2-bis [ (4-aminophenoxy) phenyl ] propane, 4 '-diamino-2, 2' -bistrifluoromethyl biphenyl, ethylenediamine and hexamethylenediamine; the dianhydride comprises one or more of 4,4 '-diphenyl ether tetracarboxylic dianhydride, bisphenol A type diether dianhydride and 4,4' - (hexafluoroisopropenyl) diphthalic anhydride; the molar ratio of the diamine to the dianhydride is 0.8:1-0.98:1.
Preferably, the mass of the graphene oxide is 0.5-3% of the sum of the mass of the diamine and the dianhydride.
Preferably, the polycondensation reaction in the step (1) is performed under a protective atmosphere; the temperature of the polycondensation reaction is 0-5 ℃ and the time is 5-12 h.
Preferably, the boron source containing the amino group in the step (2) comprises one or more of 4-aminophenylboric acid, 3-aminophenylboric acid, 4-aminophenylpinacol ester, 3-aminophenylboric acid pinacol ester and 4-aminomethylphenylboric acid; the molar quantity of the boron source containing the amino groups is 2-15% of the total molar quantity of diamine and dianhydride.
Preferably, the polycondensation reaction in the step (2) is performed under a protective atmosphere; the temperature of the polycondensation reaction is room temperature and the time is 5-15 h.
Preferably, the temperature of the solvent removed in the step (3) is 50-100 ℃ and the time is 5-24 h.
Preferably, the thermal imidization in the step (3) includes: heating from the solvent removal temperature to a first temperature at a first heating rate, and performing first heat preservation at the first temperature; heating from the first temperature to a second temperature at a second heating rate, and performing second heat preservation at the second temperature; heating from the second temperature to a third temperature at a third heating rate, and performing third heat preservation at the third temperature; heating from the third temperature to a fourth temperature at a fourth heating rate, and performing fourth heat preservation at the fourth temperature; the first temperature, the second temperature, the third temperature and the fourth temperature are 120-160 ℃, 180-200 ℃, 210-240 ℃ and 250-280 ℃, the time of the first heat preservation, the second heat preservation, the third heat preservation and the fourth heat preservation is independently 1-3 h, and the first heating rate, the second heating rate, the third heating rate and the fourth heating rate are independently 3-10 ℃/min.
The invention provides the high-temperature-resistant high-solidity supermolecule shape memory polyimide prepared by the preparation method; the high-temperature-resistant high-temperature-curing supramolecular shape memory polyimide contains a dynamic borate crosslinked network, and graphene oxide is doped in the high-temperature-resistant high-temperature-curing supramolecular shape memory polyimide.
Preferably, the glass transition temperature of the high temperature resistant thermosetting supermolecule shape memory polyimide is greater than 180 ℃.
The invention provides a preparation method of high-temperature-resistant high-solidity supermolecule shape memory polyimide, which comprises the following steps: (1) Mixing graphene oxide, an organic solvent, diamine and dianhydride for polycondensation reaction to obtain dianhydride-terminated polyamic acid solution; (2) Mixing a boron source containing an amine group with the dianhydride end-capped polyamic acid solution to perform polycondensation reaction to obtain a borate end-capped polyamic acid solution; the boron source containing the amino group comprises boric acid ester containing the amino group and/or boric acid containing the amino group; (3) Sequentially removing solvent and carrying out thermal imidization on the boric acid ester end-capped polyamic acid solution to obtain the high-temperature-resistant high-temperature-curable supermolecule shape memory polyimide. The invention synthesizes polyamide acid oligomer with terminal group containing borate functional group capable of dynamic exchange through polycondensation method, and forms supermolecule polyimide crosslinked by borate through high temperature thermal imidization, the supermolecule polyimide can realize complex shape remolding, welding and reprocessing (superposition, hot pressing, etc.) functions of thermosetting polyimide through dynamic borate exchange reaction at high temperature; in addition, the functionalized graphene oxide is introduced into the system, the photo-thermal conversion function of the graphene oxide is utilized to realize the photo-response shape memory function of the thermosetting polyimide, and the light-control shaping and welding functions are realized at the same time, so that the application of the high-temperature shape memory polyimide is greatly enriched.
The invention provides the high-temperature-resistant high-solidity supermolecule shape memory polyimide prepared by the preparation method; the high-temperature-resistant high-temperature-curing supramolecular shape memory polyimide contains a dynamic borate crosslinked network, and graphene oxide is doped in the high-temperature-resistant high-temperature-curing supramolecular shape memory polyimide. The supermolecule polyimide material prepared by the invention shows excellent reshaping and shape memory functions under the drive of light; the glass transition temperature of the supramolecular polyimide composite material is more than 180 ℃, and the supramolecular polyimide composite material can be applied to severe environments such as high temperature and the like.
Drawings
FIG. 1 is a graph of the thermo-mechanical properties of the thermoset supramolecular shape memory polyimide prepared in example 1;
FIG. 2 is a graph showing the effect of demonstrating the welding performance of the thermosetting supermolecule shape memory polyimide prepared in example 1;
FIG. 3 is an explanatory view of optically controlled deformation of the thermosetting supermolecular shape memory polyimide prepared in example 1;
FIG. 4 is a physical diagram of a complex structure of optically controlled shape reconstruction of the thermosetting supermolecule shape memory polyimide prepared in example 1.
Detailed Description
The invention provides a preparation method of high-temperature-resistant high-solidity supermolecule shape memory polyimide, which comprises the following steps:
(1) Mixing graphene oxide, an organic solvent, diamine and dianhydride for polycondensation reaction to obtain dianhydride-terminated polyamic acid solution;
(2) Mixing a boron source containing an amine group with the dianhydride end-capped polyamic acid solution to perform polycondensation reaction to obtain a borate end-capped polyamic acid solution; the boron source containing the amino group comprises boric acid ester containing the amino group and/or boric acid containing the amino group;
(3) Sequentially removing solvent and carrying out thermal imidization on the boric acid ester end-capped polyamic acid solution to obtain the high-temperature-resistant high-temperature-curable supermolecule shape memory polyimide.
In the present invention, unless otherwise specified, all the materials involved are commercially available products well known to those skilled in the art.
According to the invention, graphene oxide, an organic solvent, diamine and dianhydride are mixed for polycondensation reaction, so as to obtain dianhydride end-capped polyamic acid solution. The graphene oxide is not particularly required, and graphene oxide which is well dispersed in an organic solvent and is well known to a person skilled in the art can be adopted. In the present invention, the mass of the graphene oxide is preferably 0.5 to 3%, more preferably 1 to 2.5%, and even more preferably 1 to 1.5% of the sum of the mass of the diamine and the dianhydride. In the present invention, the organic solvent is preferably N-methyl-2-pyrrolidone, N-dimethylformamide, N-dimethylacetamide or chloroform, more preferably N-methyl-2-pyrrolidone or N, N-dimethylformamide; the invention has no special requirement on the dosage of the organic solvent, and can fully disperse the graphene oxide. In the present invention, the diamine preferably includes one or more of 4,4 '-diaminodiphenyl ether, 4' -diaminodiphenyl sulfone, 1, 4-bis (4-aminophenoxy) benzene, 2-bis [ (4-aminophenoxy) phenyl ] propane, 4 '-diamino-2, 2' -bistrifluoromethyl biphenyl, ethylenediamine and hexamethylenediamine, more preferably one or two of 4,4 '-diaminodiphenyl ether, 4' -diaminodiphenyl sulfone or 2, 2-bis [ (4-aminophenoxy) phenyl ] propane and ethylenediamine, and when a mixture of both is preferred, the molar ratio of mixing is preferably 1:1. In the present invention, the dianhydride preferably includes one or more of 4,4 '-biphenyl ether tetracarboxylic dianhydride, bisphenol a type diether dianhydride and 4,4' - (hexafluoroisopropenyl) diphthalic anhydride, more preferably one or two of 4,4 '-biphenyl ether tetracarboxylic dianhydride, bisphenol a type diether dianhydride and 4,4' - (hexafluoroisopropenyl) diphthalic anhydride, and when a mixture of the two is preferred, the molar ratio of the mixture is preferably 1:1. In the present invention, the molar ratio of the diamine to the dianhydride is preferably 0.8:1 to 0.98:1, more preferably 0.88:1 to 0.96:1.
In the present invention, the mixing method is preferably: adding graphene oxide into an organic solvent for ultrasonic dispersion to obtain graphene oxide dispersion liquid; and adding diamine into the graphene oxide dispersion liquid, stirring and mixing, and adding dianhydride into the obtained mixed liquid. In the present invention, the time of the ultrasonic dispersion is preferably 30 to 60 minutes, more preferably 30 to 40 minutes; and uniformly dispersing the graphene oxide in the organic solvent through the ultrasonic dispersion. In the invention, the stirring and mixing are preferably carried out at room temperature, and the stirring and mixing time is not particularly required, so that diamine is ensured to be completely dissolved in graphene oxide dispersion liquid; the stirring and mixing are preferably carried out under a protective atmosphere, preferably a dry nitrogen atmosphere. In the present invention, the dianhydride is preferably added stepwise in several steps.
In the present invention, the temperature of the polycondensation reaction is preferably 0 to 5 ℃, and in the embodiment of the present invention, the polycondensation reaction is specifically performed under the condition of ice water bath; the time of the polycondensation reaction is preferably 5 to 12 hours, more preferably 10 to 12 hours, and is calculated from the completion of the dianhydride addition; the polycondensation reaction is preferably carried out under a protective atmosphere, preferably a nitrogen atmosphere; the polycondensation reaction is preferably carried out with stirring. In the invention, taking diamine as 4,4' -diaminodiphenyl ether and dianhydride as bisphenol A type diether dianhydride as examples, the reaction formula of the polycondensation reaction is shown as formula A:
After the dianhydride end-capped polyamic acid solution is obtained, the boron source containing the amino group is mixed with the dianhydride end-capped polyamic acid solution for polycondensation reaction to obtain the borate end-capped polyamic acid solution. In the present invention, the boron source containing an amine group includes an amine group-containing boric acid ester and/or an amine group-containing boric acid, preferably includes one or more of 4-aminophenylboric acid, 3-aminophenylboric acid, 4-aminophenylpinacol ester, 3-aminophenylpinacol borate and 4-aminomethylphenylboric acid, more preferably 4-aminophenylboric acid or 4-aminophenylpinacol ester; the molar amount of the boron source containing an amine group is preferably 2 to 15%, more preferably 4 to 13%, still more preferably 8 to 13% of the total molar amount of diamine and dianhydride; the boron source containing amine groups is preferably added to the dianhydride-terminated polyamic acid solution. In the present invention, the temperature of the polycondensation reaction is preferably room temperature, and the time is preferably 5 to 15 hours, more preferably 12 hours; the polycondensation reaction is preferably carried out under a protective atmosphere, preferably nitrogen; the polycondensation reaction is preferably carried out under stirring. In the invention, dianhydride end-capped polyamide acid is taken as a reaction product of a formula A, a boron source containing an amino group is 4-aminophenylboronic acid pinacol ester for example, and the reaction formula of the polycondensation reaction is shown as a formula B; in the polycondensation reaction process, graphene oxide is uniformly dispersed in the solution, does not participate in the reaction, and has non-covalent physical interaction with polyamide acid.
After the borate end-capped polyamic acid solution is obtained, the borate end-capped polyamic acid solution is sequentially subjected to solvent removal and thermal imidization to obtain the high-temperature-resistant high-solidity supermolecule shape memory polyimide. In the present invention, the temperature of the solvent is preferably 50 to 100 ℃, more preferably 80 ℃, and the time is preferably 5 to 24 hours, more preferably 24 hours; the invention preferably comprises the steps of spreading the borate terminated polyamic acid solution on a horizontal glass plate, then placing the glass plate in an oven, and volatilizing the solvent at 50-100 ℃ to remove the solvent; the thickness of the blade coating is preferably 50 to 200. Mu.m. In the present invention, the thermal imidization preferably includes: heating from the solvent removal temperature to a first temperature at a first heating rate, and performing first heat preservation at the first temperature; heating from the first temperature to a second temperature at a second heating rate, and performing second heat preservation at the second temperature; heating from the second temperature to a third temperature at a third heating rate, and performing third heat preservation at the third temperature; heating from the third temperature to a fourth temperature at a fourth heating rate, and performing fourth heat preservation at the fourth temperature; the first temperature, the second temperature, the third temperature and the fourth temperature are preferably 120 to 160 ℃, 180 to 200 ℃, 210 to 240 ℃ and 250 to 280 ℃, respectively, more preferably 120 ℃, 200 ℃, 240 ℃ and 280 ℃, respectively; the time of the first heat preservation, the second heat preservation, the third heat preservation and the fourth heat preservation is independently preferably 1-3 h, more preferably 1h; the first heating rate, the second heating rate, the third heating rate and the fourth heating rate are preferably 3 to 10 ℃/min, more preferably 5 ℃/min. During the thermal imidization, a borate cross-linking reaction also occurs simultaneously, forming a six-membered borate ring. In the invention, taking borate end capped polyamide acid as a product of a formula B as an example, the reaction formula of the thermal imidization reaction is shown as a formula C:
After the thermal imidization, the invention also preferably puts the glass substrate into hot water to enable the polyimide product obtained after the thermal imidization to fall off from the surface of the glass plate, and then sequentially washes and dries the fallen polyimide product with distilled water to obtain the high-temperature-resistant high-solid supermolecular shape memory polyimide. In the present invention, the drying temperature is preferably 50 to 80 ℃, and the drying time is based on sufficient removal of moisture.
The invention provides the high-temperature-resistant high-solidity supermolecule shape memory polyimide prepared by the preparation method; the high-temperature-resistant high-temperature-curing supramolecular shape memory polyimide contains a dynamic borate crosslinked network, and graphene oxide is doped in the high-temperature-resistant high-temperature-curing supramolecular shape memory polyimide. The thermosetting supermolecular shape memory polyimide provided by the invention can generate rapid boron-oxygen bond exchange reaction (one boron-oxygen bond and the other boron-oxygen bond are subjected to bond exchange reaction as shown in a formula D) at high temperature due to dynamic covalent crosslinking of the borate (the borate is a dynamic covalent bond), so that stress is relaxed, the molding of a complex shape can be realized, and excellent high-temperature plasticity and welding functions are realized; according to the invention, graphene oxide is introduced into the system, and the photo-thermal conversion function of the graphene oxide is used for realizing the photo-response shape memory function of thermosetting polyimide and the light-operated shape reshaping and welding functions; in the invention, the welding function specifically means that two materials are lapped together, and when the temperature is higher than the boron-oxygen bond exchange reaction temperature, external force is applied, and the two materials are stuck together through dynamic covalent exchange reaction.
In the present invention, the glass transition temperature of the high temperature resistant thermosetting supermolecule shape memory polyimide is preferably more than 180 ℃, more preferably more than 200 ℃; the thermosetting supermolecule shape memory polyimide has high glass transition temperature and can be applied to severe environments such as high temperature and the like.
The high temperature resistant thermosetting supermolecule shape memory polyimide and the preparation method thereof provided by the invention are described in detail below with reference to examples, but they are not to be construed as limiting the scope of the invention.
Example 1
Dispersing graphene oxide (1% of the sum of the mass of 4,4' -diamino diphenyl sulfone and bisphenol A type diether dianhydride) into an N-methyl-2-pyrrolidone solvent, and carrying out ultrasonic treatment for 30min to obtain uniformly dispersed graphene oxide dispersion; then adding 4,4' -diamino diphenyl sulfone (4.8 mmol) into the graphene oxide dispersion liquid, and stirring at room temperature under a dry nitrogen atmosphere until the solution is dissolved; then adding bisphenol A type diether dianhydride (5 mmol), stirring for 12h under the condition of nitrogen atmosphere and ice water bath, and carrying out polycondensation reaction to obtain dianhydride end-capped polyamide acid solution; then, 4-aminophenylboric acid (0.4 mmol) was added to the dianhydride-terminated polyamic acid solution, and the reaction was continued under stirring for 12 hours in a nitrogen atmosphere to obtain a borate-terminated polyamic acid solution.
Uniformly coating the borate-terminated polyamic acid solution on a horizontal glass plate, heating in an oven at 80 ℃ to volatilize a solvent for 24 hours, then gradually heating to 120 ℃ to keep the temperature for 1 hour, heating to 200 ℃ to keep the temperature for 1 hour, heating to 240 ℃ to keep the temperature for 1 hour, and heating to 280 ℃ to keep the temperature for 1 hour to obtain an imidized and crosslinked supermolecule shape memory polyimide film; and then the glass plate is put into hot water to peel off the polyimide film from the glass plate, distilled water is used to wash the obtained peeled off matter clean, and the thermosetting supermolecule shape memory polyimide is obtained after drying at 80 ℃.
The thermal mechanical properties of the thermosetting supermolecular shape memory polyimide prepared in example 1 were tested using a dynamic mechanical analyzer, and the results are shown in fig. 1. Fig. 1 is a thermal mechanical property curve of the shape memory polyimide composite material prepared in example 1, which shows the change trend of the storage modulus and loss factor of the prepared thermosetting supermolecular shape memory polyimide with temperature, and the glass transition temperature of the material is 208 ℃ from the highest point of the loss factor.
The thermosetting supermolecule shape memory polyimide prepared in the example 1 is subjected to light control welding performance demonstration, and the specific operation is as follows: and (3) joining the two prepared materials, irradiating with 808nm (illumination intensity of 2W) infrared light, testing the surface temperature to 280 ℃, maintaining for 1min, and removing the infrared light to completely cool to obtain the welded material. FIG. 2 is a graph showing the effect of demonstrating the welding performance of the thermosetting supermolecule shape memory polyimide prepared in example 1. FIG. 2 shows the performance of the prepared thermosetting supermolecular polyimide for realizing material welding by means of dynamic covalent exchange reaction of boric acid ester, and the interface of the welded manually stretched material is not easy to break, and has good mechanical performance and tensile strength of 84MPa.
The thermoset supramolecular shape memory polyimide prepared in example 1 was subjected to light-operated deformation demonstration, and the specific operations are as follows: irradiating a flat sample with 808nm (illumination intensity of 0.5W) infrared light, wherein the surface temperature reaches 230 ℃, then manually bending the sample, wherein the sample is easy to deform due to the fact that the temperature of the sample at the irradiation position reaches above the glass transition temperature, and the sample obtains a temporary shape after infrared light is removed: after which the bent sample was irradiated with 808nm (illumination intensity 0.5W) infrared light at the bend, it was seen that shape recovery occurred when the temperature reached above the glass transition temperature. Fig. 3 is a light-operated deformation demonstration diagram of the supermolecule shape memory polyimide prepared in example 1, which shows that the prepared supermolecule polyimide realizes near infrared light driven shape recovery by means of the efficient photo-thermal conversion function of graphene oxide, and a curved sample quickly returns to a flat state after infrared light irradiation.
The thermoset supermolecule shape memory polyimide prepared in example 1 is subjected to light control shaping demonstration, and the specific operation is as follows: and bending a sample with a planar shape to obtain a required shape, sequentially irradiating the sample with 808nm (illumination intensity of 2W) infrared light at a crease, enabling the surface temperature to reach 280 ℃, carrying out a boron ester bond exchange reaction, and removing the infrared light to obtain a complex shape. Fig. 4 is a reconstructed shape physical diagram of a slice realized by local light control dynamic exchange reaction of planar shape, which shows that the material can realize light control complex shape reshaping by means of graphene photo-thermal conversion function and boron ester bond exchange reaction under temperature stimulation.
Example 2
Dispersing graphene oxide (1.5% of the sum of the mass of 2, 2-bis [ (4-aminophenoxy) phenyl ] propane, ethylenediamine and 4,4' - (hexafluoro-isopropenyl) diphthalic anhydride) into N, N-dimethylformamide, and carrying out ultrasonic treatment for 40min to obtain a uniformly dispersed graphene oxide dispersion; then adding 2, 2-bis [ (4-aminophenoxy) phenyl ] propane (2.2 mmol) and ethylenediamine (2.2 mmol) into the graphene oxide dispersion liquid, and stirring the mixture at room temperature under a dry nitrogen atmosphere until the mixture is dissolved; adding 4,4' - (hexafluoroisopropenyl) isophthalic acid anhydride (5 mmol), stirring for 12 hours under the conditions of nitrogen atmosphere and ice water bath, and performing polycondensation reaction to obtain dianhydride end-capped polyamic acid solution; then, 4-aminophenylboronic acid pinacol ester (1.2 mmol) was added to the dianhydride-terminated polyamic acid solution, and the reaction was continued under nitrogen atmosphere for 12 hours to obtain a boric acid ester-terminated polyamic acid solution.
Uniformly coating the borate-terminated polyamic acid solution on a horizontal glass plate, heating in an oven at 80 ℃ to volatilize a solvent for 24 hours, then gradually heating to 120 ℃ to keep the temperature for 1 hour, heating to 200 ℃ to keep the temperature for 1 hour, heating to 240 ℃ to keep the temperature for 1 hour, and heating to 280 ℃ to keep the temperature for 1 hour to obtain an imidized and crosslinked supermolecule shape memory polyimide film; and then the glass plate is put into hot water to peel off the polyimide film from the glass plate, distilled water is used to wash the obtained peeled off matter clean, and the thermosetting supermolecule shape memory polyimide is obtained after drying at 80 ℃.
Example 3
Dispersing graphene oxide (1.0% of the sum of the mass of 4,4 '-diaminodiphenyl ether (2.3 mmol), ethylenediamine and 4,4' - (hexafluoroisopropenyl) diphthalic anhydride) into N, N-dimethylformamide, and carrying out ultrasonic treatment for 30min to obtain a uniformly dispersed graphene oxide dispersion; then adding 4,4' -diaminodiphenyl ether (2.3 mmol) and ethylenediamine (2.3 mmol) into the graphene oxide dispersion liquid, and stirring at room temperature under a dry nitrogen atmosphere until the mixture is dissolved; adding 4,4' - (hexafluoroisopropenyl) isophthalic acid anhydride (5 mmol), stirring for 12 hours under the conditions of nitrogen atmosphere and ice water bath, and performing polycondensation reaction to obtain dianhydride end-capped polyamic acid solution; then, 4-aminophenylboronic acid pinacol ester (0.8 mmol) was added to the dianhydride-terminated polyamic acid solution, and the reaction was continued under nitrogen atmosphere for 12 hours to obtain a boric acid ester-terminated polyamic acid solution.
Uniformly coating the borate-terminated polyamic acid solution on a horizontal glass plate, heating in an oven at 80 ℃ to volatilize a solvent for 24 hours, then gradually heating to 120 ℃ to keep the temperature for 1 hour, heating to 200 ℃ to keep the temperature for 1 hour, heating to 240 ℃ to keep the temperature for 1 hour, and heating to 280 ℃ to keep the temperature for 1 hour to obtain an imidized and crosslinked supermolecule shape memory polyimide film; and then the glass plate is put into hot water to peel off the polyimide film from the glass plate, distilled water is used to wash the obtained peeled off matter clean, and the thermosetting supermolecule shape memory polyimide is obtained after drying at 80 ℃.
Example 4
Dispersing 2.5% of the sum of graphene oxide (2, 2-bis [ (4-aminophenoxy) phenyl ] propane, 4'- (hexafluoro-isopropenyl) phthalic anhydride and 4,4' -diphenyl ether tetracarboxylic dianhydride) into N, N-dimethylformamide, and carrying out ultrasonic treatment for 60min to obtain uniformly dispersed graphene oxide dispersion; then adding 2, 2-bis [ (4-aminophenoxy) phenyl ] propane (4.6 mmol) into the graphene oxide dispersion liquid, and stirring at room temperature under a dry nitrogen atmosphere until the graphene oxide dispersion liquid is dissolved; then adding 4,4'- (hexafluoroisopropenyl) diphthalic anhydride (2.5 mmol) and 4,4' -diphenyl ether tetracarboxylic dianhydride (2.5 mmol), stirring for 12h under the conditions of nitrogen atmosphere and ice water bath, and carrying out polycondensation reaction to obtain dianhydride end-capped polyamic acid solution; then, 4-aminophenylboric acid (0.8 mmol) was added to the dianhydride-terminated polyamic acid solution, and the reaction was continued under stirring for 12 hours in a nitrogen atmosphere to obtain a borate-terminated polyamic acid solution.
Uniformly coating the borate-terminated polyamic acid solution on a horizontal glass plate, heating in an oven at 80 ℃ to volatilize a solvent for 24 hours, then gradually heating to 120 ℃ to keep the temperature for 1 hour, heating to 200 ℃ to keep the temperature for 1 hour, heating to 240 ℃ to keep the temperature for 1 hour, and heating to 280 ℃ to keep the temperature for 1 hour to obtain an imidized and crosslinked supermolecule shape memory polyimide film; and then the polyimide is peeled off from the glass plate, the obtained peeled off matter is washed clean by distilled water, and the obtained product is dried at 80 ℃ to obtain the thermosetting supermolecule shape memory polyimide.
The thermoset supramolecular shape memory polyimides prepared in examples 2 to 4 were subjected to light control welding performance demonstration, light control deformation demonstration and light control complex shape reshaping according to the method of example 1, and the thermoset supramolecular shape memory polyimides prepared in examples 2 to 4 all have similar test effects as the thermoset supramolecular shape memory polyimide of example 1, namely: all have the welding function, the interface of the manual stretching material is not easy to break after welding; the shape recovery driven by near infrared light can be realized, and the bent sample quickly returns to a straight state after being irradiated by infrared light; can realize light-operated complex-shape reshaping.
From the above examples, it can be seen that the thermosetting supramolecular polyimide prepared by the invention has high glass transition temperature and high temperature resistance, so that the thermosetting supramolecular polyimide can be applied to severe environments such as high temperature; the thermosetting supermolecular polyimide prepared by the invention can realize complex shape reshaping and welding, and has a light response shape memory function.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (9)
1. The preparation method of the high-temperature-resistant high-solidity supramolecular shape memory polyimide is characterized by comprising the following steps of:
(1) Mixing graphene oxide, an organic solvent, diamine and dianhydride for polycondensation reaction to obtain dianhydride-terminated polyamic acid solution;
(2) Mixing a boron source containing an amine group with the dianhydride end-capped polyamic acid solution to perform polycondensation reaction to obtain a borate end-capped polyamic acid solution; the boron source containing the amino group comprises one or more of 4-aminophenylboric acid, 3-aminophenylboric acid, 4-aminophenylboric acid pinacol ester, 3-aminophenylboric acid pinacol ester and 4-aminomethylphenylboric acid; the molar weight of the boron source containing the amino is 2-15% of the total molar weight of diamine and dianhydride;
(3) Sequentially removing solvent and carrying out thermal imidization on the boric acid ester end-capped polyamic acid solution to obtain the high-temperature-resistant high-temperature-curable supermolecule shape memory polyimide.
2. The method according to claim 1, wherein the diamine in the step (1) comprises one or more of 4,4 '-diaminodiphenyl ether, 4' -diaminodiphenyl sulfone, 1, 4-bis (4-aminophenoxy) benzene, 2-bis [ (4-aminophenoxy) phenyl ] propane, 4 '-diamino-2, 2' -bistrifluoromethyl biphenyl, ethylenediamine and hexamethylenediamine; the dianhydride comprises one or more of 4,4 '-diphenyl ether tetracarboxylic dianhydride, bisphenol A type diether dianhydride and 4,4' - (hexafluoroisopropenyl) diphthalic anhydride; the molar ratio of the diamine to the dianhydride is 0.8:1-0.98:1.
3. The production method according to claim 1 or 2, wherein the mass of the graphene oxide is 0.5 to 3% of the sum of the mass of the diamine and the dianhydride.
4. The method according to claim 1, wherein the polycondensation reaction in step (1) is carried out under a protective atmosphere; the temperature of the polycondensation reaction is 0-5 ℃ and the time is 5-12 h.
5. The method according to claim 1, wherein the polycondensation reaction in the step (2) is carried out under a protective atmosphere; the temperature of the polycondensation reaction is room temperature and the time is 5-15 h.
6. The method according to claim 1, wherein the solvent removal in the step (3) is performed at a temperature of 50 to 100 ℃ for a time of 5 to 24 hours.
7. The method of claim 6, wherein the thermal imidization in step (3) comprises: heating from the solvent removal temperature to a first temperature at a first heating rate, and performing first heat preservation at the first temperature; heating from the first temperature to a second temperature at a second heating rate, and performing second heat preservation at the second temperature; heating from the second temperature to a third temperature at a third heating rate, and performing third heat preservation at the third temperature; heating from the third temperature to a fourth temperature at a fourth heating rate, and performing fourth heat preservation at the fourth temperature; the first temperature, the second temperature, the third temperature and the fourth temperature are 120-160 ℃, 180-200 ℃, 210-240 ℃ and 250-280 ℃, the time of the first heat preservation, the second heat preservation, the third heat preservation and the fourth heat preservation is independently 1-3 h, and the first heating rate, the second heating rate, the third heating rate and the fourth heating rate are independently 3-10 ℃/min.
8. The heat-resistant thermosetting supramolecular shape memory polyimide prepared by the preparation method of any one of claims 1 to 7; the high-temperature-resistant high-temperature-curing supramolecular shape memory polyimide contains a dynamic borate crosslinked network, and graphene oxide is doped in the high-temperature-resistant high-temperature-curing supramolecular shape memory polyimide.
9. The high temperature resistant thermosetting supramolecular shape memory polyimide as recited in claim 8, wherein the glass transition temperature of the thermosetting supramolecular shape memory polyimide is greater than 180 ℃.
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| CN104004188A (en) * | 2014-06-19 | 2014-08-27 | 冷劲松 | High-temperature-resistant thermoset shape memory polyimide and preparing method thereof |
| CN107805311A (en) * | 2016-09-09 | 2018-03-16 | 翁秋梅 | A kind of dynamic aggregation thing and its application with hybrid cross-linked network |
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| CN114874440A (en) * | 2022-05-27 | 2022-08-09 | 中国科学院兰州化学物理研究所 | Polyimide/reduced graphene oxide composite material and preparation method and application thereof |
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| CN107805311A (en) * | 2016-09-09 | 2018-03-16 | 翁秋梅 | A kind of dynamic aggregation thing and its application with hybrid cross-linked network |
| CN108341944A (en) * | 2017-01-25 | 2018-07-31 | 翁秋梅 | A kind of energy-absorbing method based on dynamic aggregation object |
| CN113136032A (en) * | 2021-04-26 | 2021-07-20 | 中国科学院兰州化学物理研究所 | Space atomic oxygen-resistant optically transparent thermosetting shape memory polyimide, and preparation method and application thereof |
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