CN115850703B - Preparation method of bio-based intrinsic photosensitive shape memory polyimide and three-dimensional intelligent polyimide - Google Patents
Preparation method of bio-based intrinsic photosensitive shape memory polyimide and three-dimensional intelligent polyimide Download PDFInfo
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- 239000004642 Polyimide Substances 0.000 title claims abstract description 111
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 53
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 229920005610 lignin Polymers 0.000 claims abstract description 31
- 238000007639 printing Methods 0.000 claims abstract description 28
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000016 photochemical curing Methods 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 50
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 39
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 38
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 33
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 33
- 238000010438 heat treatment Methods 0.000 claims description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
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- 239000013067 intermediate product Substances 0.000 claims description 28
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 25
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- 239000000243 solution Substances 0.000 claims description 19
- 125000001424 substituent group Chemical group 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 17
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 16
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- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 claims description 10
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- 235000012141 vanillin Nutrition 0.000 claims description 8
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
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- WFQDTOYDVUWQMS-UHFFFAOYSA-N 1-fluoro-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(F)C=C1 WFQDTOYDVUWQMS-UHFFFAOYSA-N 0.000 claims description 5
- FWIZOFDVGZCRTB-UHFFFAOYSA-N 2-methyl-4-nitroisoindole-1,3-dione Chemical compound C1=CC([N+]([O-])=O)=C2C(=O)N(C)C(=O)C2=C1 FWIZOFDVGZCRTB-UHFFFAOYSA-N 0.000 claims description 5
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 5
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 5
- KCDXJAYRVLXPFO-UHFFFAOYSA-N syringaldehyde Chemical compound COC1=CC(C=O)=CC(OC)=C1O KCDXJAYRVLXPFO-UHFFFAOYSA-N 0.000 claims description 5
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- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-N 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
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- 239000004952 Polyamide Substances 0.000 claims description 3
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 3
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- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention provides a preparation method of bio-based intrinsic photosensitive shape memory polyimide and three-dimensional intelligent polyimide. The invention takes lignin derivatives as raw materials to synthesize bio-diamine and dianhydride, and then prepares SMPI which contains a photosensitive structure capable of undergoing cross-linking reaction under ultraviolet light and has a shape memory function in a main chain structure of a PI macromolecular chain; can realize SMPI application in the field of photo-curing 4D printing additive manufacturing. The lignin derivative is used as a raw material, so that the biomass resource is recycled, and the problems of energy shortage, environmental pollution and the like can be solved; the method can not only avoid the damage of monomers synthesized by petroleum-based compounds as raw materials to human bodies, but also endow the prepared PI with more functional characteristics. The invention solves the problems of reduced resolution, performance degradation and the like of a three-dimensional PI intelligent structure caused by the fact that photosensitive groups grafted on a precursor of PI or a side chain of a macromolecular chain of PI are easy to lose in a high-temperature treatment process.
Description
Technical Field
The invention relates to a preparation method of bio-based intrinsic photosensitive shape memory polyimide and three-dimensional intelligent polyimide, belonging to the technical field of intelligent materials and additive manufacturing.
Background
Polyimide (PI) is a polymer having an imide ring in its main chain, and has been widely used in the fields of heat insulating films, fuel cells, heaters, liquid crystals, separation films, lasers, and the like. PI, which has been studied at present, has excellent mechanical properties, thermal stability, solvent resistance, irradiation resistance and dielectric properties, generally has a benzene ring structure. Such aromatic PI generally has strong intermolecular/intramolecular forces in the molecular chain structure, but such strong forces make it difficult to reprocess, and are relatively expensive, limiting its further use. In addition, diamine and dianhydride monomers synthesized from petrochemicals are often used in the synthesis of aromatic PI. In the synthesis of functional PI, the existing diamine and dianhydride monomers in the market also limit to some extent the imparting of more properties, such as bio-based properties, to PI. Moreover, some diamine and dianhydride monomers synthesized from petrochemicals are toxic and pose a potential threat to human health, so that green, safe and effective solutions are sought in the future.
The method for preparing PI with excellent mechanical properties, reworkability and thermal stability by synthesizing safe, green and effective novel diamine and dianhydride monomers by using renewable resources is an effective method facing increasingly exhausted non-renewable petroleum resources. In recent years, researchers have achieved some success in the research of preparing bio-based PI from renewable resources. However, research hotspots of scientific research staff are mainly focused on imparting PI bio-based characteristics, but research on synthesizing PI with multifunctional type by using bio-based monomers, such as shape memory function, photosensitive characteristics, three-dimensional intelligent structure thereof, etc., is less, and needs further promotion.
In converting a PI of a two-dimensional shape into a three-dimensional PI structure, 3D or 4D printing additive manufacturing techniques are currently commonly employed. In order to meet the requirement that PI can be applied to photocuring 3D or 4D printing additive manufacturing technology, photosensitive groups are grafted on a precursor of PI or a side chain of a macromolecular chain of PI to increase the photosensitive characteristic of PI, but grafted photosensitive substances are lost in a high-temperature treatment process, so that the structural resolution of three-dimensional intelligent polyimide (Shape memory polyimide, SMPI for short) is reduced, and the performance is degraded. Although the preparation of "Li Xiao.4D printed shape memory polyimide and its performance study [ D ] university of the chinese academy of sciences, 2019," a one-step chemical imide process SMPI was used to solve the above problems, it still was to graft a photosensitive functional group on the SMPI molecular chain, increasing the photosensitive properties of SMPI. However, the method still does not introduce a photosensitive structure capable of undergoing a crosslinking reaction under ultraviolet light irradiation on the main chain structure of the macromolecular chain of PI. Therefore, there is an urgent need for a novel photosensitive SMPI compatible photocuring 4D printing additive manufacturing technology that has a photosensitive structure in the PI macromolecular chain main chain structure that can undergo a crosslinking reaction under ultraviolet irradiation and that does not have a material loss during high temperature processing.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a preparation method of bio-based intrinsic photosensitive shape memory polyimide and three-dimensional intelligent polyimide. The invention takes lignin derivatives as raw materials to synthesize bio-based diamine and dianhydride monomers, and then prepares bio-based intrinsic photosensitive Shape Memory Polyimide (SMPI) which contains a photosensitive structure capable of undergoing a crosslinking reaction under ultraviolet light and has a shape memory function in a main chain structure of a PI macromolecular chain; the method can realize SMPI application in the field of photocuring 4D printing additive manufacturing, so as to prepare a three-dimensional PI intelligent structure with high precision and excellent mechanical property, solve the problem of conversion from a two-dimensional PI to a three-dimensional PI intelligent structure, solve the problem of resolution reduction and performance degradation of the three-dimensional PI intelligent structure caused by easy loss of a photosensitive group grafted on a precursor of PI or a side chain of a macromolecular chain of PI in a high-temperature treatment process, and further enrich a photocuring 4D printing material system. The lignin derivative is used as a raw material, so that the biomass resource is recycled, the problems of energy shortage, environmental pollution and the like can be solved, and the energy consumption can be reduced; the method can not only avoid the damage of aromatic diamine and dianhydride monomers synthesized by petroleum-based compounds as raw materials to human bodies, but also endow the prepared PI with more functional characteristics.
The technical scheme of the invention is as follows:
a preparation method of bio-based intrinsic photosensitive shape memory polyimide comprises the following steps:
(1) Preparation of diamine:
i. Dissolving lignin derivative in ethyl acetate, adding tributyl borate and acetylacetone-B 2O3 complex, and mixing uniformly; dripping n-butylamine at 70-80 ℃, stirring at 70-80 ℃ for 4-5h, and standing at 70-80 ℃ for 10-16h after dripping; then adding an aqueous solution of acid with the mass concentration of 1-10wt% and the temperature of 40-70 ℃ to stir and react for 1-6h at 70-80 ℃; cooling to room temperature, filtering, washing, recrystallizing with acetic acid, and drying to obtain intermediate I; the lignin derivative is vanillin, syringaldehyde or 4-hydroxybenzaldehyde;
ii. Uniformly mixing the intermediate product I, p-fluoronitrobenzene, DMF and potassium carbonate, and reacting for 4-8 hours at 70-80 ℃ under the protection of nitrogen; pouring the obtained reaction solution into a sodium hydroxide aqueous solution with the mass concentration of 3-10%, separating out solid, washing the obtained solid to be neutral, recrystallizing with DMF/water, filtering, and drying to obtain an intermediate product II;
iii, fully and uniformly mixing the intermediate product II, dioxane and palladium-carbon under the protection of nitrogen, dropwise adding hydrazine hydrate at room temperature, and carrying out reflux reaction for 4-8h under the protection of nitrogen after the dropwise adding; filtering while the mixture is hot, pouring the filtrate into deionized water to obtain a white product, and drying the white product to diamine;
Diamines
Wherein the substituent R' is phenyl; the substituent R is:
(2) Preparation of dianhydride:
i. Uniformly mixing lignin derivatives, p-hydroxyacetophenone and piperidine, and stirring and reacting for 20-30h at 60-100 ℃ under the protection of nitrogen; pouring the obtained reaction solution into water, adding 0.5-3mol/L dilute hydrochloric acid to adjust the pH to be less than 1, and standing at room temperature for 10-15h; then filtering, recrystallizing and drying to obtain an intermediate product III; the lignin derivative is vanillin, syringaldehyde or 4-hydroxybenzaldehyde;
ii. Fully and uniformly mixing an intermediate product III, anhydrous potassium carbonate, DMF and toluene, carrying out nitrogen protection, and carrying out water diversion at 130-150 ℃ for 4-6 hours, adding N-methyl-3-nitrophthalimide after the system is cooled to room temperature, and carrying out reaction for 15-25 hours at 120-140 ℃ under the nitrogen protection; cooling to room temperature, slowly pouring the reaction solution into dilute hydrochloric acid with pH=2-3 to separate out precipitate, washing the obtained precipitate with water, recrystallizing with acetic acid, and drying to obtain an intermediate product IV;
iii, fully and uniformly mixing the intermediate product IV, deionized water and sodium hydroxide, carrying out reflux reaction for 30-40h at 120-160 ℃ under the protection of nitrogen, cooling to room temperature, and filtering; adding 5-6mol/L hydrochloric acid to acidify until the pH value of the system is=1-3, and then filtering, recrystallizing with acetic acid and recrystallizing with acetic anhydride to obtain dianhydride.
Wherein, substituent R is:
(3) Dissolving diamine and dianhydride in a low boiling point organic solvent, and stirring and reacting for 12-24 hours at the temperature of 10-20 ℃ under the protection of nitrogen to obtain polyimide precursor solution-polyamide acid; then standing for 2-4h at 30-50deg.C to remove bubbles; finally, performing high-temperature imidization reaction to obtain the bio-based intrinsic photosensitive shape memory polyimide;
bio-based intrinsic photosensitive shape memory polyimide
Wherein n=10-200;
The substituent R' is:
the meaning of the substituent R 'and the substituent R are the same as the meaning of the substituent R' and the substituent R in diamine in sequence.
According to a preferred embodiment of the invention, in step (1) i, the ratio of the mass of lignin derivative to the volume of ethyl acetate is (8-12): (15-30) g/mL; the mass ratio of lignin derivative and tributyl borate is (8-12): (10-20) g/mL.
According to a preferred embodiment of the present invention, in the step (1) i, the preparation method of the acetylacetonate-B 2O3 complex comprises the steps of: refluxing acetylacetone and boric anhydride with a molar ratio of 1:1 in ethyl acetate at 76 ℃ for 40min; the volume ratio of the mass of the acetylacetone to the ethyl acetate is (0.1-0.5): 1g/mL; the molar ratio of lignin derivative to acetylacetone is (1-5): (1-3), preferably 2:1.
According to a preferred embodiment of the invention, in step (1) i, the mass of n-butylamine is 5-15% of the mass of the lignin derivative.
Preferably according to the invention, in step (1) i, the acid is hydrochloric acid, sulfuric acid, acetic acid or phosphoric acid; the volume ratio of the aqueous acid solution to the ethyl acetate is (10-20): (1-3).
According to a preferred embodiment of the invention, in step (1) ii, the molar ratio of intermediate I, p-fluoronitrobenzene and potassium carbonate is (0.05-2): (0.1-4); (0.1-1); the mass and DMF volume ratio of the intermediate product I is: (1-5): (10-300).
According to the present invention, in the step (1) ii), the volume ratio of the reaction solution to the aqueous sodium hydroxide solution is (2-5): (3-10).
According to the invention, in step (1) iii, the ratio of the mass of the intermediate II to the volume of the dioxane is 1 (1-10) g/mL; the mass of palladium-carbon is (25-30)% of the mass of the intermediate product II; the mass ratio of the intermediate product II to the hydrazine hydrate is (2-3): 1.
According to a preferred embodiment of the invention, in step (1) iii, the hydrazine hydrate is added at a rate of 3 to 7mL/h.
According to a preferred embodiment of the invention, in step (2) i, the molar ratio of lignin derivative to p-hydroxyacetophenone is 1:1; the molar amount of lignin derivative and the volume ratio of piperidine are 1: (1-10) mol/L; the volume ratio of the reaction liquid to the water is 1: (40-60).
According to a preferred embodiment of the invention, in step (2) ii, the molar ratio of intermediate III to anhydrous potassium carbonate is 1 (1-2): the molar amount of intermediate III and the volume ratio of DMF was 1: (1-5) mol/L; the volume ratio of DMF to toluene is (10-20): (4-10); the molar ratio of N-methyl-3-nitrophthalimide to intermediate III was 2:1.
According to the invention, in step (2) iii, the mass ratio of intermediate IV, deionized water and sodium hydroxide is (3-10): 100-200): 10-20.
According to a preferred embodiment of the present invention, in step (2) iii, the method for recrystallizing acetic anhydride comprises the steps of: refluxing the crude product and acetic anhydride for 12 hours at 140 ℃, wherein the mass ratio of the crude product to the acetic anhydride is as follows: (3-10): (10-20).
According to a preferred embodiment of the present invention, in the step (3), the low boiling point organic solvent is one or a combination of two or more of N-methylpyrrolidone, N-dimethylformamide, and N, N-dimethylacetamide; the molar amount of diamine and the volume ratio of the low boiling point organic solvent are 0.1-0.5mol/L.
According to the invention, the molar ratio of diamine to dianhydride in step (3) is preferably 1 (0.94-1.02).
According to the present invention, preferably, in the step (3), the high-temperature imidization reaction method comprises the steps of: heating the reaction solution from room temperature to 70-90 ℃ at a heating rate of 0.5-2 ℃/min, and preserving heat for 1-3h under the condition that the temperature is 70-90 ℃; then heating to 110-130 ℃ at a heating rate of 0.5-2 ℃/min, and preserving heat for 1-3h under the condition of 110-130 ℃; then heating to 160-180 ℃ at a heating rate of 0.5-2 ℃/min, and preserving heat for 1-3h under the condition of 160-180 ℃; continuously heating to 220-240 ℃ at a heating rate of 0.5-2 ℃/min, and preserving heat for 1-3h under the condition that the temperature is 220-240 ℃; then heating to 290-310 ℃ at a heating rate of 0.5-2 ℃/min, and preserving heat for 1-3h under the condition of 290-310 ℃; finally, the temperature is increased to 350-370 ℃ at the heating rate of 0.5-2 ℃/min, and the temperature is kept for 1-3 hours under the condition of 350-370 ℃ to obtain the bio-based intrinsic photosensitive shape memory polyimide.
According to the invention, the lignin derivative can be prepared by the existing method, such as extraction from lignin by alkaline oxidation method.
The bio-based intrinsic photosensitive shape memory polyimide is prepared by the method.
A preparation method of three-dimensional intelligent polyimide comprises the following steps:
(1) Preparing the bio-based intrinsic photosensitive shape memory polyimide according to the method;
(2) The photo-curing 4D printing method is adopted to prepare the three-dimensional polyimide.
According to the invention, the photo-curing 4D printing method is just the existing method. Preferably, in the step (2), the method for preparing the three-dimensional polyimide by adopting the photo-curing 4D printing method comprises the following steps:
(1) Dissolving the bio-based intrinsic photosensitive shape memory polyimide in a low boiling point solvent to obtain printing ink with the viscosity of 100-300 mPa.s at 25 ℃; the low boiling point solvent is N-methyl pyrrolidone, N-dimethylformamide or N, N-dimethylacetamide;
(2) Adopting a photo-curing printer with ultraviolet irradiation wavelength of 300-410nm, and photo-curing 4D printing layer by layer at room temperature according to the established 3D model and the equivalent thickness of the 3D model slice; setting the exposure time and thickness of each layer of 4D printing to be 20-40s and 20-60 mu m respectively;
(3) And after the photo-curing printing is finished, continuing to photo-cure for 0.5-1h at room temperature under the ultraviolet irradiation wavelength of 300-410nm, and finally drying in vacuum for 6-12h at the temperature of 150-250 ℃ to obtain the three-dimensional intelligent polyimide.
A three-dimensional intelligent polyimide is prepared by the method.
The reaction route of the invention is as follows:
The synthetic route for diamine is as follows:
the synthesis route of dianhydride is as follows:
the synthetic route of the bio-based intrinsic photosensitive shape memory polyimide is as follows:
Wherein, substituent R is:
The substituent R' is:
The substituent R' is phenyl.
n＝10～200。
The invention has the technical characteristics and beneficial effects that:
1. The invention takes biological base such as vanillin extracted from lignin as a reaction monomer, introduces the biological base unit and cinnamoyl and chalcone photosensitive groups into diamine and dianhydride monomers through nucleophilic addition, nucleophilic substitution, reduction, acidification and other chemical reactions, and synthesizes a molecular chain structure containing a photosensitive structure capable of undergoing cross-linking reaction under ultraviolet irradiation by a low-temperature polycondensation-high-temperature imide method, and the biological base has a shape memory function and is intrinsic photosensitive SMPI. By researching the relation between the photosensitive structure and PI performance, a regulating mechanism is found so as to optimize the molecular chain structure of SMPI to ensure that the photosensitive structure has optimal photosensitive property and shape memory function. And finally, an optimal photocuring 4D printing method is explored, and the three-dimensional intelligent SMPI with the performances of high precision, small dimensional shrinkage, excellent mechanical property and the like is prepared.
2. The invention takes vanillin and the like extracted from lignin as bio-based monomers, realizes the reutilization of biomass resources, can solve the problems of energy shortage, environmental pollution and the like, and can also reduce energy consumption; the method can avoid the damage of aromatic diamine and dianhydride monomers synthesized by using petroleum-based compounds as raw materials to human bodies, is environment-friendly and safe, and can endow the prepared PI with more functional characteristics.
3. The method solves the problems of reduced resolution, performance degradation and large volume shrinkage of the three-dimensional intelligent SMPI structure caused by the fact that photosensitive groups are easily lost in the high-temperature treatment process when grafted on the precursor of PI or the side chain of the macromolecular chain of PI. The main chain of the macromolecular chain of PI obtained by the method contains photosensitive groups, has high-temperature stability, can generate photo-crosslinking reaction under ultraviolet irradiation, utilizes a photo-curing 4D printing method to prepare a three-dimensional intelligent SMPI structure, and the prepared SMPI and the three-dimensional intelligent SMPI structure thereof have excellent performances.
4. The polyimide prepared by the method has excellent photosensitive property and shape memory function. The bio-based intrinsic photosensitive polyimide prepared by the invention has photosensitive characteristics, so that the bio-based intrinsic photosensitive polyimide can be used as photoresist, and is used for reducing the photo-curing time and photo-curing strength of the photoresist, slowing down the processing procedures and improving the production efficiency. The shape memory characteristic of the bio-based intrinsic photosensitive polyimide can be used as a packaging material, and the shape deformation characteristic of the bio-based intrinsic photosensitive polyimide can increase the fun and convenience of national life. Meanwhile, the three-dimensional intelligent SMPI prepared by the method has low heat conductivity, excellent mechanical strength, no toxicity and the like, and has wide application prospect in the fields of building heat preservation and insulation, biomedical supports, aerospace expandable structures, automobile filters and the like.
5. The preparation method has the advantages of fine preparation process, low cost and good repeatability, and can be used for preparing the bio-based shape memory polyimide and the three-dimensional intelligent structure thereof on a large scale.
6. In the process of preparing polyimide from diamine and dianhydride, the temperature programming of the high-temperature imidization reaction is important, the temperature programming condition is unsuitable, a large amount of bubbles can be generated, and the performance of the obtained polyimide is adversely affected; the polyimide material obtained is brittle and unfavorable for application due to too high or too low temperature. Meanwhile, the molar ratio of diamine to dianhydride is too high or too low, the obtained polyimide material also has the phenomenon of breakage, and the mechanical strength, shape memory performance and the like are reduced. The preparation method provided by the invention is used as a whole, the effect of the preparation method can be realized under the combined action of all conditions and steps, the yield of the polyimide material can be influenced by changing any condition, and the performance of the obtained polyimide material can be influenced.
Drawings
FIG. 1 is an ultraviolet absorption spectrum of the bio-based intrinsic photosensitive SMPI prepared in example 1;
FIG. 2 is an infrared spectrum of the bio-based intrinsic photosensitive SMPI prepared in example 1 before (a) and after (b) irradiation with ultraviolet light;
FIG. 3 is a thermogravimetric curve of the bio-based intrinsic photosensitive SMPI prepared in example 1 after uv irradiation;
FIG. 4 is a graph showing the shape memory state (a) and the recovery state (b) of the bio-based intrinsic photosensitive SMPI prepared in example 1 after ultraviolet irradiation;
Fig. 5 is a picture of the three-dimensional smart SMPI structure prepared in example 4.
Detailed Description
The invention is further illustrated, but not limited, by the following examples.
Meanwhile, the experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available unless otherwise specified.
Example 1
A preparation method of bio-based intrinsic photosensitive shape memory polyimide comprises the following steps:
(1) Preparation of diamine:
i. 100g of vanillin is dissolved by 200mL of anhydrous ethyl acetate, and then 180mL of tributyl borate and 65g of acetylacetone-B 2O3 complex are added and mixed uniformly; 15mL of n-butylamine is added dropwise at 75 ℃ for 1 hour, the mixture is stirred at 75 ℃ for 4.5 hours, and the mixture is stood at 75 ℃ for 12 hours; then 1500mL of hydrochloric acid with a mass concentration of 2% at 60℃was added thereto, and stirring was continued at 75℃for 1 hour to complete the reaction. Cooling to room temperature, filtering, washing with water for 3-4 times, filtering out the product, washing with ethyl acetate for 2-3 times to obtain a crude product, finally recrystallizing with acetic acid, and drying to obtain an intermediate product I, wherein the product yield is 91%.
The preparation method of the acetylacetone-B 2O3 complex comprises the following steps: acetylacetone (50 g) and boric anhydride in a molar ratio of 1:1 were refluxed in 200mL of ethyl acetate at 76 ℃ for 40min; the molar ratio of lignin derivative to acetylacetone was 2:1.
Ii. 18.4g of intermediate I, 14.11g of p-fluoronitrobenzene, 200mL of DMF and 13.8g of potassium carbonate are added into a 300mL three-necked flask equipped with a mechanical stirring paddle, a nitrogen inlet (nitrogen protection), a condenser tube and a thermometer, the mixture is uniformly mixed, the mixture is reacted for 6 hours at 75 ℃, and after the reaction is finished, the system is poured into 500mL of 5wt% sodium hydroxide aqueous solution to separate out the product. Repeatedly washing the product to be neutral after filtration, recrystallizing with DMF/water (volume ratio is 1:20), and carrying out suction filtration to obtain a pale yellow product, and carrying out vacuum drying at 80 ℃ for 10 hours to obtain an intermediate product II, wherein the product yield is 97%.
Iii, under the protection of nitrogen, 30mL of dioxane, 24.45g of intermediate product II and 7g of palladium-carbon are added into a 100mL three-neck flask equipped with a mechanical stirring device, a condenser tube and a dropping funnel, the mixture is fully and uniformly mixed, wen Dijia mL of hydrazine hydrate (the mass concentration is 80%) is arranged in an inner chamber for two hours, reflux reaction is carried out for 6 hours under the protection of nitrogen, the product is filtered by heat, the filtrate is poured into 500mL of deionized water to obtain a white product, and vacuum drying is carried out at 80 ℃ for 10 hours to obtain diamine. The yield of the product is 90%.
(2) Preparation of dianhydride:
i. 0.01mol of vanillin and 0.01mol of p-hydroxyacetophenone are added into a three-neck flask containing 20ml of piperidine, and the mixture is uniformly mixed, and magnetically stirred and reacted for 24 hours under the protection of nitrogen at the temperature of 80 ℃. After the reaction is finished, pouring the dark red viscous solution in the flask into 1000 ml of water, adding enough 1mol/L dilute hydrochloric acid, adjusting the pH to be lower than 1, and standing at room temperature for 12 hours; the product was collected by filtration and recrystallized from a mixed solution of ethanol and water (volume ratio=1:10), and dried to give intermediate product III in 92% yield.
Ii. 0.09mol of intermediate III, 15g of anhydrous potassium carbonate, 200 mM MF and 50mL of toluene are added into a branched flask equipped with a magnetic stirrer, a water separator and a condenser, water is separated at 140 ℃ for 5 hours under the protection of nitrogen, and after the system is cooled to room temperature, 0.045mol of N-methyl-3-nitrophthalimide is added. The temperature was raised to 130 degrees celsius under nitrogen and reacted at this reaction temperature for 20 hours. After cooling to room temperature, slowly pouring the solution into dilute hydrochloric acid (pH=2-3) to precipitate, washing with water, vacuum drying at 100 ℃ to obtain an off-white solid, recrystallizing with acetic acid, and drying to obtain an intermediate product IV with a product yield of 93%.
Iii, adding 10g of intermediate IV and 200mL of deionized water, adding 15g of sodium hydroxide into a branched flask equipped with a magnetic stirring, water diversion and condensation pipe, heating and refluxing for reaction for 36 hours at 140 ℃ under the protection of nitrogen, cooling to room temperature and filtering to obtain a red solution. Acidifying with 6mol/L hydrochloric acid until the pH value of the system is 2-3, filtering to obtain a white solid, recrystallizing the crude product with acetic acid to obtain a white solid, and recrystallizing acetic anhydride (reflux the crude product and acetic anhydride at 140 ℃ for 12h, wherein the mass ratio of the crude product to the acetic anhydride is 5:15) to obtain dianhydride, wherein the product yield is 96%.
(3) 5Mmol of diamine and 5mmol of dianhydride are added into a three-neck flask containing 20 ml of low-boiling point organic solvent (DMF), magnetic stirring is carried out for 24 hours under the protection of nitrogen and low-temperature (15 ℃) environment, polyimide precursor solution-polyamide acid is obtained, then the precursor solution is placed in a vacuum oven at 40 ℃ for 3 hours to remove bubbles, and then high Wen Xianya amination technology is carried out in a gradual heating and heat preservation mode, so that the bio-based intrinsic photosensitive shape memory polyimide film is obtained, and the product yield is 92%.
The way of carrying out the thermal amidation by the way of gradually heating and preserving heat is as follows: the low-temperature pre-polymerization solution is heated to 80 ℃ from room temperature at a heating rate of 1 ℃/min, is kept at the temperature of 80 ℃ for 2 hours, is heated to 120 ℃ at the heating rate of 1 ℃/min, is kept at the temperature of 120 ℃ for 2 hours, is heated to 170 ℃ at the heating rate of 1 ℃/min, is kept at the temperature of 170 ℃ for 2 hours, is continuously heated to 230 ℃ at the heating rate of 1 ℃/min, is kept at the temperature of 230 ℃ for 2 hours, is heated to 300 ℃ at the heating rate of 1 ℃/min, is kept at the temperature of 300 ℃ for 2 hours, is heated to 360 ℃ at the heating rate of 1 ℃/min, is kept at the temperature of 360 ℃ for 2 hours, and the high-temperature thermal amidation process in a gradual heating and heat-preserving mode is completed.
The ultraviolet absorption spectrum curve of the bio-based intrinsic photosensitive shape memory polyimide prepared in the embodiment is shown in figure 1, and the obtained material has the characteristic of sensitivity to ultraviolet light in the ultraviolet light region of 300-400nm and has the maximum absorption at 350 nm.
The bio-based intrinsic photosensitive polyimide prepared in the embodiment is irradiated for 10min under ultraviolet light with the wavelength of 365 nm; the infrared spectrum of (a) before and (b) after the irradiation of ultraviolet light is shown in FIG. 2. The association absorption peak in the range of 3500-3100 cm -1 of the infrared spectrum is caused by the stretching vibration of the-NH and-OH functional groups on the PI macromolecular chain; however, the telescopic vibration absorption peak of C=O at 1680-1630cm -1 of the ketocarbonyl function in the diamine and dianhydride monomers became weak on the macromolecular chain of PI, which to a certain extent indicated a substantial reduction in the content of photosensitive carbonyl functions and a new absorption peak of C-O function at 1076cm -1. The above results verify that PI macromolecular chains undergo a crosslinking reaction under uv irradiation.
The thermal weight curve of the bio-based intrinsic photosensitive shape memory polyimide prepared in the embodiment after the ultraviolet irradiation is shown in fig. 3, and the obtained material has excellent thermal stability, no loss of small molecular substances is detected in a low temperature stage, and the thermal decomposition temperature at the maximum mass loss is 480 ℃, which indicates that the bio-based intrinsic photosensitive SMPI prepared in the embodiment has excellent thermal stability, and when the bio-based intrinsic photosensitive polyimide is used for photocuring a 4D printing three-dimensional intelligent PI structure, the process for removing the solvent does not influence the molecular chain structure of the PI, namely, the performance loss is not caused, so that the problems of volume shrinkage, precision reduction and mechanical property degradation of the existing three-dimensional intelligent PI structure are effectively solved.
The shape memory state (a) and the recovery state (b) of the bio-based intrinsic photosensitive shape memory polyimide prepared in this example after the ultraviolet irradiation are shown in fig. 4, which can recover 98% of the shape to the original shape, showing that the material prepared in this invention has excellent shape memory function.
Example 2
A method for preparing bio-based intrinsic photosensitive shape memory polyimide, as described in example 1, except that: the lignin derivative used for preparing diamine and dianhydride is syringaldehyde; other steps and conditions were consistent with example 1.
Example 3
A method for preparing bio-based intrinsic photosensitive shape memory polyimide, as described in example 1, except that: the lignin derivative used for preparing diamine and dianhydride is 4-hydroxy benzaldehyde; other steps and conditions were consistent with example 1.
Example 4
A preparation method of three-dimensional intelligent polyimide comprises the following steps:
(1) The bio-based intrinsic photosensitive shape memory polyimide was prepared as in example 1;
(2) The method for preparing the three-dimensional intelligent polyimide by adopting the photocuring 4D printing method comprises the following steps:
i. Dissolving the bio-based intrinsic photosensitive shape memory polyimide in a solvent (DMF) with a low boiling point to obtain printing ink with a viscosity of 200 mPa.s at 25 ℃;
ii. Adopting a photo-curing printer with ultraviolet irradiation wavelength of 355-410nm, and performing photo-curing 4D printing layer by layer at room temperature according to the established 3D model and the equivalent thickness of the 3D model slice; setting the exposure time and thickness of each layer of 4D printing to be 30s and 20 mu m respectively;
and iii, after the photo-curing printing is finished, continuing to photo-cure for 1h at room temperature under the ultraviolet irradiation wavelength of 361nm, and finally drying for 6h at the temperature of 200 ℃ in vacuum to obtain the three-dimensional intelligent polyimide.
The three-dimensional intelligent polyimide prepared by printing in this example 4D is shown in fig. 5 as a hollow cylinder.
Claims (10)
1. A preparation method of bio-based intrinsic photosensitive shape memory polyimide comprises the following steps:
(1) Preparation of diamine:
i. Dissolving lignin derivative in ethyl acetate, adding tributyl borate and acetylacetone-B 2O3 complex, and mixing uniformly; dripping n-butylamine at 70-80 ℃, stirring at 70-80 ℃ for 4-5h, and standing at 70-80 ℃ for 10-16h after dripping; then adding an aqueous solution of acid with the mass concentration of 1-10wt% and the temperature of 40-70 ℃ to stir and react for 1-6h at 70-80 ℃; cooling to room temperature, filtering, washing, recrystallizing with acetic acid, and drying to obtain intermediate I; the lignin derivative is vanillin, syringaldehyde or 4-hydroxybenzaldehyde;
ii. Uniformly mixing the intermediate product I, p-fluoronitrobenzene, DMF and potassium carbonate, and reacting for 4-8 hours at 70-80 ℃ under the protection of nitrogen; pouring the obtained reaction solution into a sodium hydroxide aqueous solution with the mass concentration of 3-10%, separating out solid, washing the obtained solid to be neutral, recrystallizing with DMF/water, filtering, and drying to obtain an intermediate product II;
iii, fully and uniformly mixing the intermediate product II, dioxane and palladium-carbon under the protection of nitrogen, dropwise adding hydrazine hydrate at room temperature, and carrying out reflux reaction for 4-8h under the protection of nitrogen after the dropwise adding; filtering while the mixture is hot, pouring the filtrate into deionized water to obtain a white product, and drying the white product to diamine;
Wherein the substituent R' is phenyl; the substituent R is:
(2) Preparation of dianhydride:
i. Uniformly mixing lignin derivatives, p-hydroxyacetophenone and piperidine, and stirring and reacting for 20-30h at 60-100 ℃ under the protection of nitrogen; pouring the obtained reaction solution into water, adding 0.5-3mol/L dilute hydrochloric acid to adjust the pH value to be less than 1, and standing at room temperature for 10-15h; then filtering, recrystallizing and drying to obtain an intermediate product III; the lignin derivative is vanillin, syringaldehyde or 4-hydroxybenzaldehyde;
ii. Fully and uniformly mixing an intermediate product III, anhydrous potassium carbonate, DMF and toluene, carrying out nitrogen protection, and carrying out water diversion at 130-150 ℃ for 4-6 hours, adding N-methyl-3-nitrophthalimide after the system is cooled to room temperature, and carrying out reaction for 15-25 hours at 120-140 ℃ under the nitrogen protection; cooling to room temperature, slowly pouring the reaction solution into dilute hydrochloric acid with pH=2-3 to separate out precipitate, washing the obtained precipitate with water, recrystallizing with acetic acid, and drying to obtain an intermediate product IV;
iii, fully and uniformly mixing the intermediate product IV, deionized water and sodium hydroxide, carrying out reflux reaction for 30-40h at 120-160 ℃ under the protection of nitrogen, cooling to room temperature, and filtering; adding 5-6mol/L hydrochloric acid to acidify until the pH value of the system is 1-3, and then filtering, recrystallizing with acetic acid, and recrystallizing with acetic anhydride to obtain dianhydride;
Wherein, substituent R is:
(3) Dissolving diamine and dianhydride in a low boiling point organic solvent, and stirring and reacting for 12-24 hours at the temperature of 10-20 ℃ under the protection of nitrogen to obtain polyimide precursor solution-polyamide acid; then standing for 2-4h at 30-50deg.C to remove bubbles; finally, the bio-based intrinsic photosensitive shape memory polyimide with the following structure is obtained through high-temperature imidization reaction;
Wherein n=10-200;
The substituent R' is:
the meaning of the substituent R 'and the substituent R are the same as the meaning of the substituent R' and the substituent R in diamine in sequence.
2. The method of preparing a bio-based intrinsic type photosensitive shape memory polyimide according to claim 1, wherein in step (1) i, one or more of the following conditions are included:
i. The volume ratio of lignin derivative mass and ethyl acetate is (8-12): (15-30) g/mL; the mass ratio of lignin derivative and tributyl borate is (8-12): 10-20 g/mL;
ii. The preparation method of the acetylacetone-B 2O3 complex comprises the following steps: refluxing acetylacetone and boric anhydride with a molar ratio of 1:1 in ethyl acetate at 76 ℃ for 40min; the volume ratio of the mass of the acetylacetone to the ethyl acetate is (0.1-0.5): 1g/mL; the molar ratio of lignin derivative to acetylacetone is (1-5): (1-3);
iii, the mass of the n-butylamine is 5-15% of the mass of the lignin derivative;
iv, the acid is hydrochloric acid, sulfuric acid, acetic acid or phosphoric acid; the volume ratio of the aqueous acid solution to the ethyl acetate is (10-20): (1-3).
3. The method of preparing a bio-based intrinsic type photosensitive shape memory polyimide according to claim 1, wherein in step (1) ii), one or more of the following conditions are included:
i. the molar ratio of the intermediate product I to the p-fluoronitrobenzene to the potassium carbonate is (0.05-2): (0.1-4); (0.1-1); the mass and DMF volume ratio of the intermediate product I is: (1-5): (10-300);
ii. The volume ratio of the reaction solution to the sodium hydroxide aqueous solution is (2-5): (3-10).
4. The method of preparing a bio-based intrinsic type photosensitive shape memory polyimide according to claim 1, wherein in step (1) iii, one or more of the following conditions are included:
i. The volume ratio of the mass of the intermediate product II to the dioxane is 1 (1-10) g/mL; the mass of palladium-carbon is (25-30)% of the mass of the intermediate product II; the mass ratio of the intermediate product II to the hydrazine hydrate is (2-3) 1;
ii. The dripping rate of the hydrazine hydrate is 3-7mL/h.
5. The method of preparing a bio-based intrinsic type photosensitive shape memory polyimide according to claim 1, wherein in step (2), one or more of the following conditions are included:
i. In the step (2) i, the molar ratio of the lignin derivative to the p-hydroxyacetophenone is 1:1; the molar amount of lignin derivative and the volume ratio of piperidine are 1: (1-10) mol/L; the volume ratio of the reaction liquid to the water is 1: (40-60);
ii. In step (2) ii, the molar ratio of intermediate III to anhydrous potassium carbonate is 1 (1-2): the molar amount of intermediate III and the volume ratio of DMF was 1: (1-5) mol/L; the volume ratio of DMF to toluene is (10-20): (4-10); the molar ratio of N-methyl-3-nitrophthalimide to intermediate III is 2:1;
iii, in the step (2) iii, the mass ratio of the intermediate product IV to deionized water to sodium hydroxide is (3-10): 100-200): 10-20;
in step iv, step (2) iii, the method for recrystallizing acetic anhydride comprises the steps of: refluxing the crude product and acetic anhydride for 12 hours at 140 ℃, wherein the mass ratio of the crude product to the acetic anhydride is as follows: (3-10): (10-20).
6. The method of preparing a bio-based intrinsic type photosensitive shape memory polyimide according to claim 1, wherein in step (3), one or more of the following conditions are included:
i. The low-boiling point organic solvent is one or the combination of more than two of N-methyl pyrrolidone, N, N-dimethylformamide or N, N-dimethylacetamide; the volume ratio of the molar quantity of diamine to the low-boiling point organic solvent is 0.1-0.5mol/L;
ii. The molar ratio of diamine to dianhydride is 1 (0.94-1.02);
The high-temperature imidization reaction method comprises the following steps: heating the reaction solution from room temperature to 70-90 ℃ at a heating rate of 0.5-2 ℃/min, and preserving heat for 1-3h under the condition that the temperature is 70-90 ℃; then heating to 110-130 ℃ at a heating rate of 0.5-2 ℃/min, and preserving heat for 1-3h under the condition of 110-130 ℃; then heating to 160-180 ℃ at a heating rate of 0.5-2 ℃/min, and preserving heat for 1-3h under the condition of 160-180 ℃; continuously heating to 220-240 ℃ at a heating rate of 0.5-2 ℃/min, and preserving heat for 1-3h under the condition that the temperature is 220-240 ℃; then heating to 290-310 ℃ at a heating rate of 0.5-2 ℃/min, and preserving heat for 1-3h under the condition of 290-310 ℃; finally, the temperature is increased to 350-370 ℃ at the heating rate of 0.5-2 ℃/min, and the temperature is kept for 1-3 hours under the condition of 350-370 ℃ to obtain the bio-based intrinsic photosensitive shape memory polyimide.
7. The bio-based intrinsic photosensitive shape memory polyimide prepared by the method of any one of claims 1 to 6.
8. A preparation method of three-dimensional intelligent polyimide comprises the following steps:
(1) Preparing a bio-based intrinsic photosensitive shape memory polyimide according to the method of any one of claims 1 to 6;
(2) The photo-curing 4D printing method is adopted to prepare the three-dimensional polyimide.
9. The method for preparing three-dimensional intelligent polyimide according to claim 8, wherein in the step (2), the method for preparing three-dimensional polyimide by using the photo-curing 4D printing method comprises the steps of:
(1) Dissolving the bio-based intrinsic photosensitive shape memory polyimide in a low boiling point solvent to obtain printing ink with the viscosity of 100-300 mPa.s at 25 ℃; the low boiling point solvent is N-methyl pyrrolidone, N-dimethylformamide or N, N-dimethylacetamide;
(2) Adopting a light curing printer with the illumination wavelength of 300-410nm, and performing light curing 4D printing layer by layer at room temperature according to the established 3D model and the equivalent thickness of the 3D model slice; setting the exposure time and thickness of each layer of 4D printing to be 20-40s and 20-60 mu m respectively;
(3) And after the photo-curing printing is finished, continuing to photo-cure for 0.5-1h at room temperature under the illumination wavelength of 300-410nm, and finally drying in vacuum for 6-12h at the temperature of 150-250 ℃ to obtain the three-dimensional intelligent polyimide.
10. A three-dimensional intelligent polyimide prepared by the method of claim 8 or 9.
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| CN115850703A (en) | 2023-03-28 |
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