CN115873246A - High-temperature-resistant thermosetting supramolecular shape memory polyimide and preparation method thereof - Google Patents
High-temperature-resistant thermosetting supramolecular shape memory polyimide and preparation method thereof Download PDFInfo
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- CN115873246A CN115873246A CN202211521516.1A CN202211521516A CN115873246A CN 115873246 A CN115873246 A CN 115873246A CN 202211521516 A CN202211521516 A CN 202211521516A CN 115873246 A CN115873246 A CN 115873246A
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- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 37
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- 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
- 239000012298 atmosphere Substances 0.000 claims description 7
- 230000001681 protective effect Effects 0.000 claims description 7
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 6
- QHHKLPCQTTWFSS-UHFFFAOYSA-N 5-[2-(1,3-dioxo-2-benzofuran-5-yl)-1,1,1,3,3,3-hexafluoropropan-2-yl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)(C(F)(F)F)C(F)(F)F)=C1 QHHKLPCQTTWFSS-UHFFFAOYSA-N 0.000 claims description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 5
- ZSKXYSCQDWAUCM-UHFFFAOYSA-N 1-(chloromethyl)-2-dodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1CCl ZSKXYSCQDWAUCM-UHFFFAOYSA-N 0.000 claims description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 4
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 4
- YMXIIVIQLHYKOT-UHFFFAOYSA-N 3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC=CC(N)=C1 YMXIIVIQLHYKOT-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
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- KMWLUGSVWULTHR-UHFFFAOYSA-N [4-(aminomethyl)phenyl]boronic acid Chemical compound NCC1=CC=C(B(O)O)C=C1 KMWLUGSVWULTHR-UHFFFAOYSA-N 0.000 claims description 3
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Abstract
The invention provides high-temperature-resistant thermosetting supramolecular 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 to carry out a polycondensation reaction to obtain a dianhydride-terminated polyamide acid solution; mixing a boron source containing amido with a polyamide acid solution terminated by dianhydride for polycondensation, and sequentially carrying out solvent removal and thermal imidization on the obtained polyamide acid solution terminated by borate to obtain the high-temperature-resistant thermosetting supramolecular shape memory polyimide. The thermosetting supermolecule shape memory polyimide prepared by the invention can generate rapid boron-oxygen bond exchange reaction at high temperature, so that the stress is relaxed, the complex shape forming is realized, and the thermosetting supermolecule shape memory polyimide has excellent high-temperature plasticity and welding functions; according to the invention, the functions of thermosetting polyimide photoresponse shape memory, light-operated shape remolding and welding are realized by means of the graphene oxide photothermal conversion function; and the prepared polyimide has high glass transition temperature.
Description
Technical Field
The invention relates to the technical field of shape memory materials, in particular to high-temperature-resistant thermosetting supramolecular 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, so that the shape memory polyimide is widely researched and paid attention to 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, T g 235-245 ℃, and stimulating the shape memory performance by heating; chinese patent CN105542205A discloses a preparation method of electro-driven shape memory polyimide, T g The temperature is 220-238 ℃, the shape fixing rate of the electro-driven shape memory is 96%, and the shape recovery rate is 97%.
Although 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 all based on simple shapes, and the forming of complex shapes and the welding function of the materials cannot be realized; in addition, no report on the shape remolding and welding performance of the high-temperature shape memory polyimide realized by light control exists, so that the application of the high-temperature shape memory polymer as a driver in a complex environment is limited.
Disclosure of Invention
In view of this, the present invention aims to provide a high temperature resistant thermosetting supramolecular shape memory polyimide and a preparation method thereof. The high-temperature resistant thermosetting supramolecular shape memory polyimide prepared by the invention can realize complex shape remolding, welding and remolding and has a photoresponse 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 thermosetting supramolecular shape memory polyimide, which comprises the following steps:
(1) Mixing graphene oxide, an organic solvent, diamine and dianhydride to carry out a polycondensation reaction to obtain a dianhydride-terminated polyamic acid solution;
(2) Mixing a boron source containing amino with the dianhydride-terminated polyamic acid solution for polycondensation reaction to obtain a polyamic acid solution terminated by boric acid ester; the boron source containing amine groups comprises boric acid ester containing amine groups and/or boric acid containing amine groups;
(3) And sequentially carrying out solvent removal and thermal imidization on the polyamic acid solution terminated by the boric acid ester to obtain the high-temperature-resistant thermosetting supramolecular shape memory polyimide.
Preferably, the diamine in step (1) 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' -bistrifluoromethylbiphenyl, ethylenediamine and hexamethylenediamine; the dianhydride comprises one or more of 4,4 '-diphenyl ether tetracarboxylic dianhydride, bisphenol A type diether dianhydride and 4,4' - (hexafluoroisopropylidene) diphthalic anhydride; the molar ratio of the diamine to the dianhydride is 0.8.
Preferably, the mass of the graphene oxide is 0.5-3% of the sum of the masses of the diamine and the dianhydride.
Preferably, 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.
Preferably, the boron source containing amine groups in the step (2) comprises one or more of 4-aminophenylboronic acid, 3-aminophenylboronic acid, 4-aminophenylboronic acid pinacol ester, 3-aminophenylboronic acid pinacol ester and 4-aminomethyl phenylboronic acid; the molar weight of the boron source containing the amido is 2-15% of the total molar weight of the diamine and the dianhydride.
Preferably, 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.
Preferably, the temperature of the solvent removal in the step (3) is 50-100 ℃, and the time is 5-24 h.
Preferably, the thermal imidization in the step (3) includes: raising the temperature of the desolventizing agent to a first temperature at a first temperature raising rate, and carrying out first heat preservation at the first temperature; raising the temperature from the first temperature to a second temperature at a second temperature raising rate, and carrying out second heat preservation at the second temperature; raising the temperature from the second temperature to a third temperature at a third temperature raising rate, and carrying out third heat preservation at the third temperature; raising the temperature from the third temperature to a fourth temperature at a fourth temperature raising rate, and carrying out fourth heat preservation at the fourth temperature; the first temperature, the second temperature, the third temperature and the fourth temperature are respectively 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 high-temperature resistant thermosetting supramolecular shape memory polyimide prepared by the preparation method in the technical scheme; the high-temperature-resistant thermosetting supramolecular shape memory polyimide contains a dynamic borate cross-linked network, and graphene oxide is doped in the high-temperature-resistant thermosetting supramolecular shape memory polyimide.
Preferably, the glass transition temperature of the high temperature resistant thermosetting supramolecular shape memory polyimide is greater than 180 ℃.
The invention provides a preparation method of high-temperature-resistant thermosetting supramolecular shape memory polyimide, which comprises the following steps: (1) Mixing graphene oxide, an organic solvent, diamine and dianhydride to carry out a polycondensation reaction to obtain a dianhydride-terminated polyamic acid solution; (2) Mixing a boron source containing amino with the dianhydride-terminated polyamic acid solution for polycondensation reaction to obtain a polyamic acid solution terminated by boric acid ester; the boron source containing amine groups comprises boric acid ester containing amine groups and/or boric acid containing amine groups; (3) And sequentially carrying out solvent removal and thermal imidization on the polyamic acid solution terminated by the boric acid ester to obtain the high-temperature-resistant thermosetting supramolecular shape memory polyimide. Firstly, polyamide acid oligomer with end groups containing dynamically exchangeable borate functional groups is synthesized by a polycondensation method, and then high-temperature thermal imidization is carried out to form borate crosslinked supermolecule polyimide which can be subjected to rapid stress relaxation by dynamic borate exchange reaction at high temperature, so that the complex shape remolding, welding and reprocessing (stacking, hot pressing and the like) functions of thermosetting polyimide are realized; 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 photo-control shaping and welding functions, and the application of the high-temperature shape memory polyimide is greatly enriched.
The invention provides high-temperature resistant thermosetting supramolecular shape memory polyimide prepared by the preparation method in the technical scheme; the high-temperature resistant thermosetting supramolecular shape memory polyimide contains a dynamic borate cross-linked network, and graphene oxide is doped in the high-temperature resistant thermosetting supramolecular shape memory polyimide. The supramolecular polyimide material prepared by the invention has excellent reshaping and shape memory functions under the drive of light; the glass transition temperature of the supramolecular polyimide composite material is larger than 180 ℃, and the supramolecular polyimide composite material can be applied to harsh 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 supramolecular shape memory polyimide prepared in example 1;
FIG. 3 is a representation of the light-controlled deformation of the thermoset supramolecular shape memory polyimide prepared in example 1;
fig. 4 is a diagram of a complex structure for reconstructing the optically controlled shape of the thermosetting supramolecular shape-memory polyimide prepared in example 1.
Detailed Description
The invention provides a preparation method of high-temperature-resistant thermosetting supramolecular shape memory polyimide, which comprises the following steps:
(1) Mixing graphene oxide, an organic solvent, diamine and dianhydride to carry out a polycondensation reaction to obtain a dianhydride-terminated polyamic acid solution;
(2) Mixing a boron source containing amino with the dianhydride-terminated polyamic acid solution for polycondensation reaction to obtain a polyamic acid solution terminated by boric acid ester; the boron source containing amine groups comprises boric acid ester containing amine groups and/or boric acid containing amine groups;
(3) And sequentially carrying out solvent removal and thermal imidization on the polyamic acid solution terminated by the boric acid ester to obtain the high-temperature-resistant thermosetting supramolecular shape memory polyimide.
In the present invention, the starting materials are all commercially available products known to those skilled in the art unless otherwise specified.
According to the invention, graphene oxide, an organic solvent, diamine and dianhydride are mixed for a polycondensation reaction to obtain a dianhydride-terminated polyamic acid solution. The graphene oxide is not particularly required by the present invention, and graphene oxide well dispersed in an organic solvent, which is well known to those skilled in the art, may be used, and in the embodiment of the present invention, the graphene oxide is purchased from southbound graphene technologies ltd. In the present invention, the mass of the graphene oxide is preferably 0.5 to 3%, more preferably 1 to 2.5%, and still more preferably 1 to 1.5% of the sum of the masses 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, and more preferably N-methyl-2-pyrrolidone or N, N-dimethylformamide; the invention has no special requirement on the dosage of the organic solvent, and the graphene oxide can be fully dispersed. 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' -bistrifluoromethylbiphenyl, ethylenediamine and hexamethylenediamine, more preferably one or both of 4,4 '-diaminodiphenyl ether, 4' -diaminodiphenyl sulfone or 2, 2-bis [ (4-aminophenoxy) phenyl ] propane and ethylenediamine, and when a mixture of the two is preferred, the molar ratio of the mixture is preferably 1. In the present invention, the dianhydride preferably comprises one or more of 4,4 '-biphenylethertetracarboxylic dianhydride, bisphenol a type diether dianhydride and 4,4' - (hexafluoroisopropylene) diphthalic anhydride, more preferably one or two of 4,4 '-biphenylethertetracarboxylic dianhydride, bisphenol a type diether dianhydride and 4,4' - (hexafluoroisopropylene) diphthalic anhydride, and when a mixture of the two is preferred, the mixing molar ratio is preferably 1. In the present invention, the molar ratio of the diamine to the dianhydride is preferably 0.8.
In the present invention, the method of mixing is preferably: adding graphene oxide into an organic solvent for ultrasonic dispersion to obtain a graphene oxide dispersion liquid; adding diamine into the graphene oxide dispersion liquid, stirring and mixing, and then adding dianhydride into the obtained mixed liquid. In the present invention, the time of the ultrasonic dispersion is preferably 30 to 60min, and more preferably 30 to 40min; 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, the stirring and mixing time is not particularly required, and the diamine is ensured to be completely dissolved in the graphene oxide dispersion liquid; the stirring and mixing is preferably carried out under a protective atmosphere, preferably a dry nitrogen atmosphere. In the present invention, the dianhydride is preferably added stepwise in portions.
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 ice-water bath conditions; the time of the polycondensation reaction is preferably 5 to 12 hours, more preferably 10 to 12 hours, and the time of the polycondensation reaction is calculated from the end 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 under stirring. In the present invention, the diamine is 4,4' -diaminodiphenyl ether, and the dianhydride is bisphenol a type diether dianhydride, and the reaction formula of the polycondensation reaction is shown as formula a:
after the dianhydride end-capped polyamic acid solution is obtained, a boron source containing amino and the dianhydride end-capped polyamic acid solution are mixed for polycondensation reaction to obtain the borate end-capped polyamic acid solution. In the present invention, the boron source containing amine groups comprises boric acid ester containing amine groups and/or boric acid containing amine groups, preferably comprises one or more of 4-aminophenylboronic acid, 3-aminophenylboronic acid, 4-aminophenylboronic acid pinacol ester, 3-aminophenylboronic acid pinacol ester and 4-aminomethyl phenylboronic acid, and more preferably comprises 4-aminophenylboronic acid or 4-aminophenylboronic acid pinacol ester; the molar amount of the boron source containing the amino group is preferably 2 to 15%, more preferably 4 to 13%, and further preferably 8 to 13% of the total molar amount of the diamine and the dianhydride; the invention preferably adds the amine group-containing boron source 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, and 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 conditions. In the invention, the dianhydride-terminated polyamic acid is taken as a reaction product of formula A, and the amino-containing boron source is 4-aminophenylboronic acid pinacol ester, and the reaction formula of the polycondensation reaction is shown as formula B; in the process of the polycondensation reaction, the graphene oxide is uniformly dispersed in the solution, does not participate in the reaction, and has non-covalent physical interaction with the polyamic acid.
After the polyamic acid solution terminated by the borate is obtained, the polyamic acid solution terminated by the borate is sequentially subjected to solvent removal and thermal imidization to obtain the high-temperature-resistant thermosetting supramolecular shape memory polyimide. In the invention, the temperature of the desolvation is preferably 50-100 ℃, more preferably 80 ℃, and the time is preferably 5-24 h, more preferably 24h; the polyamic acid solution with the borate end capping is preferably blade-coated on a horizontal glass plate, then the glass plate is placed in an oven, and the solvent is volatilized at the temperature of 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: raising the temperature of the desolventizing agent to a first temperature at a first temperature raising rate, and carrying out first heat preservation at the first temperature; raising the temperature from the first temperature to a second temperature at a second temperature raising rate, and carrying out second heat preservation at the second temperature; raising the temperature from the second temperature to a third temperature at a third temperature raising rate, and carrying out third heat preservation at the third temperature; raising the temperature from the third temperature to a fourth temperature at a fourth temperature raising rate, and carrying out 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, and are 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 preferably 1-3 h independently, and more preferably 1h; the first temperature rise rate, the second temperature rise rate, the third temperature rise rate, and the fourth temperature rise rate are preferably 3 to 10 ℃/min, and more preferably 5 ℃/min. In the thermal imidization process, a borate ester crosslinking reaction is also simultaneously carried out to form a six-membered borate ring. In the present invention, the reaction formula of the thermal imidization reaction is shown as formula C, taking the polyamic acid end-capped by borate ester as the product of formula B as an example:
after the thermal imidization, the invention preferably puts the glass substrate into hot water to make the polyimide product obtained after the thermal imidization fall off from the surface of the glass substrate, and then sequentially washes and dries the fallen polyimide product with distilled water to obtain the high-temperature resistant thermosetting supramolecular 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 high-temperature resistant thermosetting supramolecular shape memory polyimide prepared by the preparation method in the technical scheme; the high-temperature resistant thermosetting supramolecular shape memory polyimide contains a dynamic borate cross-linked network, and graphene oxide is doped in the high-temperature resistant thermosetting supramolecular shape memory polyimide. Due to dynamic covalent crosslinking of borate (the borate is a dynamic covalent bond), the thermosetting supramolecular shape memory polyimide provided by the invention can perform rapid boron-oxygen bond exchange reaction at high temperature (one boron-oxygen bond and the other boron-oxygen bond perform bond exchange reaction as shown in a formula D), so that stress is relaxed, forming of complex shapes can be realized, and the thermosetting supramolecular shape memory polyimide has excellent high-temperature plasticity and welding functions; according to the invention, graphene oxide is introduced into a system, and the photo-thermal conversion function of the graphene oxide is used for realizing the photo-responsive shape memory function of thermosetting polyimide and the photo-controlled shape remolding and welding functions; in the invention, the welding function specifically means that two materials are overlapped together, and when the temperature is higher than the temperature of boron-oxygen bond exchange reaction, external force is applied to bond the two materials together through dynamic covalent exchange reaction.
In the present invention, the glass transition temperature of the high temperature resistant thermosetting supramolecular shape memory polyimide is preferably greater than 180 ℃, more preferably greater than 200 ℃; the thermosetting supramolecular shape memory polyimide has high glass transition temperature and can be applied to harsh environments such as high temperature and the like.
The high temperature resistant thermosetting supramolecular shape memory polyimide and the preparation method thereof provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Dispersing graphene oxide (1 percent of the mass sum of 4,4' -diaminodiphenyl sulfone and bisphenol A type diether dianhydride) into an N-methyl-2-pyrrolidone solvent, and performing ultrasonic treatment for 30min to obtain a uniformly dispersed graphene oxide dispersion liquid; 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 graphene oxide dispersion liquid is dissolved; then adding bisphenol A type diether dianhydride (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-aminobenzeneboronic acid (0.4 mmol) is added into the dianhydride terminated polyamic acid solution, and stirring reaction is continued for 12h in a nitrogen atmosphere to obtain a borate terminated polyamic acid solution.
Uniformly coating the polyamic acid solution terminated by the boric acid ester on a horizontal glass plate, heating in an oven at 80 ℃ to volatilize the solvent for 24 hours, then gradually heating to 120 ℃ and preserving heat for 1 hour, heating to 200 ℃ and preserving heat for 1 hour, heating to 240 ℃ and preserving heat for 1 hour, and heating to 280 ℃ and preserving heat for 1 hour to obtain the imidized and crosslinked supramolecular shape memory polyimide film; and then putting the glass plate into hot water to peel the polyimide film from the glass plate, washing the obtained peeled object with distilled water, and drying at 80 ℃ to obtain the thermosetting supramolecular shape memory polyimide.
The thermo-mechanical property test of the thermosetting supramolecular shape memory polyimide prepared in example 1 is performed by using a dynamic mechanical analyzer, and the result is shown in fig. 1, fig. 1 is a thermo-mechanical property curve of the shape memory polyimide composite material prepared in example 1, the curve shows the variation trend of the storage modulus and the loss factor of the prepared thermosetting supramolecular shape memory polyimide along with the temperature, and the glass transition temperature of the material can be obtained from the highest point of the loss factor to be 208 ℃.
The thermosetting supramolecular shape memory polyimide prepared in the embodiment 1 is subjected to light control welding performance demonstration, and the specific operation is as follows: the two prepared materials are lapped together, and irradiated by infrared light with the wavelength of 808nm (the illumination intensity is 2W), the surface temperature is tested to 280 ℃, the temperature is kept for 1min, and after the infrared light is removed and the materials are completely cooled, the welded materials are obtained. Fig. 2 is a graph showing the effect of demonstrating the welding performance of the thermosetting supramolecular shape-memory polyimide prepared in example 1. Fig. 2 shows the performance of the prepared thermosetting supramolecular polyimide for realizing material welding by virtue of boric acid ester dynamic covalent exchange reaction, the interface of a manually-stretched material after welding is not easy to break, the material has good mechanical performance, and the tensile strength can reach 84MPa.
The thermosetting supramolecular shape memory polyimide prepared in example 1 is subjected to light-operated deformation demonstration, and the specific operation is as follows: irradiating a flat sample with 808nm (illumination intensity of 0.5W) of infrared light at a surface temperature of 230 ℃, and then manually bending the sample, wherein the sample is easily deformed due to the temperature of the sample at the irradiation position being above the glass transition temperature, and a temporary shape is obtained after removing the infrared light: the bent sample was then irradiated with 808nm (illumination intensity 0.5W) infrared light at the bend, and it was seen that shape recovery occurred when the temperature reached above the glass transition temperature. Fig. 3 is an illustration of the light-controlled deformation of the supramolecular shape memory polyimide prepared in example 1, which shows that the prepared supramolecular polyimide realizes near-infrared light-driven shape recovery by virtue of the efficient photo-thermal conversion function of graphene oxide, and a bent sample rapidly recovers to a straight state after infrared light irradiation.
The thermosetting supramolecular shape memory polyimide prepared in the example 1 is subjected to light-operated shaping demonstration, and the specific operation is as follows: bending a planar sample to obtain a required shape, irradiating the crease with 808nm (illumination intensity of 2W) infrared light in sequence, allowing the surface temperature to reach 280 ℃, performing a boron ester bond exchange reaction, and removing the infrared light to obtain a complex shape. Fig. 4 is a diagram of a reconstructed shape object obtained by performing a dynamic exchange reaction on a planar shape of a sheet through local light control, and shows that the material can realize light-controlled complex shape remodeling by virtue of a graphene photothermal conversion function and a boron ester bond exchange reaction under temperature stimulation.
Example 2
Dispersing graphene oxide (1.5 percent of the mass sum of 2, 2-bis [ (4-aminophenoxy) phenyl ] propane, ethylenediamine and 4,4' - (hexafluoroisopropylidene) diphthalic anhydride) into N, N-dimethylformamide, and carrying out ultrasonic treatment for 40min to obtain a uniformly dispersed graphene oxide dispersion liquid; then 2, 2-bis [ (4-aminophenoxy) phenyl ] propane (2.2 mmol) and ethylenediamine (2.2 mmol) were added to the graphene oxide dispersion, and stirred at room temperature under a dry nitrogen atmosphere until dissolved; then adding 4,4' - (hexafluoroisopropylidene) phthalic anhydride (5 mmol), stirring for 12h under the conditions of nitrogen atmosphere and ice water bath, and carrying out polycondensation reaction to obtain dianhydride capped polyamic acid solution; then 4-aminobenzeneboronic acid pinacol ester (1.2 mmol) is added into the dianhydride terminated polyamic acid solution, and stirring reaction is continued for 12 hours in a nitrogen atmosphere to obtain a boronic acid ester terminated polyamic acid solution.
Uniformly coating the polyamic acid solution terminated by the boric acid ester on a horizontal glass plate, heating in an oven at 80 ℃ to volatilize the solvent for 24 hours, then gradually heating to 120 ℃ and preserving heat for 1 hour, heating to 200 ℃ and preserving heat for 1 hour, heating to 240 ℃ and preserving heat for 1 hour, and heating to 280 ℃ and preserving heat for 1 hour to obtain the imidized and crosslinked supramolecular shape memory polyimide film; and then putting the glass plate into hot water to peel the polyimide film from the glass plate, washing the obtained peeled object with distilled water, and drying at 80 ℃ to obtain the thermosetting supramolecular shape memory polyimide.
Example 3
Dispersing graphene oxide (1.0% of the mass sum of 4,4 '-diaminodiphenyl ether (2.3 mmol), ethylenediamine and 4,4' - (hexafluoroisopropylidene) diphthalic anhydride) into N, N-dimethylformamide, and carrying out ultrasonic treatment for 30min to obtain a uniformly dispersed graphene oxide dispersion liquid; 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 graphene oxide dispersion liquid is dissolved; then adding 4,4' - (hexafluoroisopropylidene) diphthalic anhydride (5 mmol), stirring for 12h under the conditions of nitrogen atmosphere and ice-water bath, and carrying out polycondensation reaction to obtain dianhydride terminated polyamic acid solution; then 4-aminobenzeneboronic acid pinacol ester (0.8 mmol) is added into the dianhydride terminated polyamic acid solution, and stirring reaction is continued for 12 hours in a nitrogen atmosphere to obtain a boronic acid ester terminated polyamic acid solution.
Uniformly coating the polyamic acid solution terminated by the boric acid ester on a horizontal glass plate, heating in an oven at 80 ℃ to volatilize the solvent for 24 hours, then gradually heating to 120 ℃ and preserving heat for 1 hour, heating to 200 ℃ and preserving heat for 1 hour, heating to 240 ℃ and preserving heat for 1 hour, and heating to 280 ℃ and preserving heat for 1 hour to obtain the imidized and crosslinked supramolecular shape memory polyimide film; and then putting the glass plate into hot water to peel the polyimide film from the glass plate, washing the obtained peeled object with distilled water, and drying at 80 ℃ to obtain the thermosetting supramolecular shape memory polyimide.
Example 4
Dispersing graphene oxide (2, 2-bis [ (4-aminophenoxy) phenyl ] propane, 4'- (hexafluoroisopropylidene) diphthalic anhydride and 2.5% of the sum of 4,4' -diphenyl ether tetracarboxylic dianhydride) into N, N-dimethylformamide, and performing ultrasonic treatment for 60min to obtain a uniformly dispersed graphene oxide dispersion liquid; 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'- (hexafluoroisopropylidene) phthalic anhydride (2.5 mmol) and 4,4' -diphenyl ether tetracarboxylic dianhydride (2.5 mmol), stirring for 12 hours under the conditions of nitrogen atmosphere and ice-water bath, and carrying out polycondensation reaction to obtain dianhydride-terminated polyamic acid solution; then 4-aminobenzeneboronic acid (0.8 mmol) is added into the dianhydride terminated polyamic acid solution, and stirring reaction is continued for 12h in a nitrogen atmosphere to obtain a borate terminated polyamic acid solution.
Uniformly coating the polyamic acid solution terminated by the boric acid ester on a horizontal glass plate, heating in an oven at 80 ℃ to volatilize the solvent for 24 hours, then gradually heating to 120 ℃ and preserving heat for 1 hour, heating to 200 ℃ and preserving heat for 1 hour, heating to 240 ℃ and preserving heat for 1 hour, and heating to 280 ℃ and preserving heat for 1 hour to obtain the imidized and crosslinked supramolecular shape memory polyimide film; then peeling the polyimide from the glass plate, washing the obtained peeled object with distilled water, and drying at 80 ℃ to obtain the thermosetting supramolecular shape memory polyimide.
The thermosetting supramolecular shape memory polyimides prepared in examples 2 to 4 were subjected to light-operated welding performance demonstration, light-operated deformation demonstration and light-operated complex shape remodeling according to the method of example 1, and all of the thermosetting supramolecular shape memory polyimides prepared in examples 2 to 4 had similar test effects to the thermosetting supramolecular shape memory polyimide of example 1, that is: the material has a welding function, and the interface of a manually-stretched material is not easy to break after welding; the shape recovery driven by near infrared light can be realized, and the bent sample can be quickly recovered to a straight state after being irradiated by infrared light; the light-operated re-molding of complex shapes can be realized.
The above embodiments show 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 harsh environments such as high temperature and the like; the thermosetting supermolecule polyimide prepared by the invention can realize the remolding and welding of complex shapes and has the photoresponse shape memory function.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of high-temperature-resistant thermosetting supramolecular shape memory polyimide is characterized by comprising the following steps:
(1) Mixing graphene oxide, an organic solvent, diamine and dianhydride to carry out a polycondensation reaction to obtain a dianhydride-terminated polyamic acid solution;
(2) Mixing a boron source containing amino with the dianhydride-terminated polyamic acid solution for polycondensation reaction to obtain a polyamic acid solution terminated by boric acid ester; the boron source containing amine groups comprises boric acid ester containing amine groups and/or boric acid containing amine groups;
(3) And sequentially carrying out solvent removal and thermal imidization on the polyamic acid solution terminated by the boric acid ester to obtain the high-temperature-resistant thermosetting supramolecular shape memory polyimide.
2. The method according to claim 1, wherein the diamine in the step (1) comprises one or more selected from the group consisting of 4,4 '-diaminodiphenyl ether, 4' -diaminodiphenyl sulfone, 1, 4-bis (4-aminophenoxy) benzene, 2-bis [ (4-aminophenoxy) phenyl ] propane, 4 '-diamino-2, 2' -bistrifluoromethylbiphenyl, ethylenediamine and hexamethylenediamine; the dianhydride comprises one or more of 4,4 '-diphenyl ether tetracarboxylic dianhydride, bisphenol A type diether dianhydride and 4,4' - (hexafluoroisopropylidene) diphthalic anhydride; the molar ratio of the diamine to the dianhydride is 0.8.
3. The method according to claim 1 or 2, wherein the mass of the graphene oxide is 0.5 to 3% of the sum of the masses of the diamine and the dianhydride.
4. The production method according to claim 1, wherein the polycondensation reaction in the 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 boron source containing an amine group in the step (2) comprises one or more of 4-aminophenylboronic acid, 3-aminophenylboronic acid, 4-aminophenylboronic acid pinacol ester, 3-aminophenylboronic acid pinacol ester and 4-aminomethylphenylboronic acid; the molar weight of the boron source containing the amido is 2-15% of the total molar weight of the diamine and the dianhydride.
6. The production method according to claim 1 or 5, 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.
7. The method according to claim 1, wherein the temperature of the solvent removal in step (3) is 50 to 100 ℃ and the time is 5 to 24 hours.
8. The production method according to claim 7, wherein the thermal imidization in the step (3) includes: heating the temperature of the desolventizing agent to a first temperature at a first heating rate, and carrying out first heat preservation at the first temperature; raising the temperature from the first temperature to a second temperature at a second temperature raising rate, and carrying out second heat preservation at the second temperature; raising the temperature from the second temperature to a third temperature at a third temperature raising rate, and carrying out third heat preservation at the third temperature; raising the temperature from the third temperature to a fourth temperature at a fourth temperature raising rate, and carrying out fourth heat preservation at the fourth temperature; the first temperature, the second temperature, the third temperature and the fourth temperature are respectively 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.
9. High temperature resistant thermosetting supramolecular shape memory polyimide prepared by the preparation method of any one of claims 1 to 8; the high-temperature-resistant thermosetting supramolecular shape memory polyimide contains a dynamic borate cross-linked network, and graphene oxide is doped in the high-temperature-resistant thermosetting supramolecular shape memory polyimide.
10. The high temperature resistant thermoset supramolecular shape memory polyimide as claimed in claim 9, characterized in that glass transition temperature of high temperature resistant thermoset supramolecular shape memory polyimide is greater than 180 ℃.
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