CN114163637B - Azobenzene polyimide film material with reversible photoinduced deformation performance and preparation method thereof - Google Patents
Azobenzene polyimide film material with reversible photoinduced deformation performance and preparation method thereof Download PDFInfo
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- CN114163637B CN114163637B CN202010952926.6A CN202010952926A CN114163637B CN 114163637 B CN114163637 B CN 114163637B CN 202010952926 A CN202010952926 A CN 202010952926A CN 114163637 B CN114163637 B CN 114163637B
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- 239000000463 material Substances 0.000 title claims abstract description 51
- 229920001721 polyimide Polymers 0.000 title claims abstract description 48
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 230000002441 reversible effect Effects 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 23
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 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 10
- 239000003880 polar aprotic solvent Substances 0.000 claims abstract description 10
- 150000004985 diamines Chemical class 0.000 claims abstract description 9
- 238000012643 polycondensation polymerization Methods 0.000 claims abstract description 8
- 239000000758 substrate Substances 0.000 claims abstract description 6
- 239000011248 coating agent Substances 0.000 claims abstract description 4
- 238000000576 coating method Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 15
- 229920000642 polymer Polymers 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 230000009477 glass transition Effects 0.000 claims description 4
- 238000006317 isomerization reaction Methods 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 125000004427 diamine group Chemical group 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- DMLAVOWQYNRWNQ-YPKPFQOOSA-N (Z)-azobenzene Chemical compound C1=CC=CC=C1\N=N/C1=CC=CC=C1 DMLAVOWQYNRWNQ-YPKPFQOOSA-N 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000004642 Polyimide Substances 0.000 abstract description 12
- 238000005286 illumination Methods 0.000 abstract description 4
- 238000005452 bending Methods 0.000 description 14
- 239000004952 Polyamide Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 1
- WFKAJVHLWXSISD-UHFFFAOYSA-N anhydrous dimethyl-acetamide Natural products CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000007699 photoisomerization reaction Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1096—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors containing azo linkage in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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Abstract
The invention relates to an azobenzene polyimide film material with reversible photoinduced deformation performance, and preparation and application thereof, and the preparation method of the material comprises the following steps: 1) Dissolving diamine monomer containing azobenzene unit and dianhydride monomer containing X in polar aprotic solvent, and performing condensation polymerization reaction to obtain polyamic acid solution; 2) Coating the polyamic acid solution on a substrate, and performing thermal imidization to obtain a polyimide film material; 3) Carrying out hot stretching on the polyimide film material; when the device is applied, ultraviolet light and visible light are used as driving sources for photoinduced deformation. Compared with the prior art, the invention solves the problem that polyimide material can not realize rapid, reversible and large-amplitude deformation through different wavelength illumination by utilizing the photoinduced deformation of the ultraviolet-visible light driving material.
Description
Technical Field
The invention belongs to the technical field of photoinduced deformation materials, and relates to an azobenzene polyimide film material with reversible photoinduced deformation performance, and preparation and application thereof.
Background
The photoinduced deformation material can convert light energy into mechanical energy, so that macroscopic bending, torsion and other deformation of the material can be realized. The photoinduced deformation actuator has the characteristics of long distance, no contact, no damage, easy control and the like, and is expected to be applied to various fields of life medical treatment, aerospace, military detection and the like.
The photoinduced deformation polyimide combines the characteristics of excellent thermal stability, mechanical property and remote driving deformation, and is expected to be gradually applied to a high-temperature driver, a space expandable structure and a soft robot serving in a special environment. The introduction of photo-responsive azo phenyl groups into the polyimide molecular structure is the most straightforward method for preparing photo-deformable polyimides.
At present, the photo-induced deformation of azobenzene polyimide material utilizes the fact that azobenzene groups can be reoriented under polarized light illumination. With polarized light (442-532 nm), azobenzene on the surface of the film undergoes multiple isomerization conversion (Weigger effect) of trans-cis-trans, and finally long axes of the randomly arranged azobenzene groups gradually tend to be arranged along the polarization direction of perpendicular light (reorientation process), and the change of arrangement causes the film to form asymmetric shrinkage or expansion, so that the film bends towards or back to the light source. Achieving stable deformation using this mechanism often requires a long time of illumination (several minutes to several tens of minutes) to achieve a state of molecular reorientation. After the illumination is stopped, some materials can quickly return to the original state due to different molecular structures, and some samples can be placed for a long time to return. In the latter case, strain recovery may also be achieved by changing the polarization direction of the light, and the direction of reorientation of the azobenzene element. But no rapid, reversible deformation is currently achieved by alternating irradiation of uv/visible light.
Disclosure of Invention
The invention aims to provide an azobenzene polyimide film material with reversible photoinduced deformation performance, and preparation and application thereof, wherein ultraviolet light and visible light (green light) can be used as a driving source of photoinduced deformation polyimide, and the material can be rapidly and reversibly deformed.
The aim of the invention can be achieved by the following technical scheme:
the azobenzene polyimide film material with reversible photoinduced deformation performance is characterized by comprising the following chemical structural formula:
wherein m represents the degree of polymerization, X is a tetravalent aromatic or aliphatic hydrocarbon group, and Y is a diamine residue containing an azobenzene moiety.
Further, m is more than or equal to 10.
Further, X is preferably selected from one of the following groups:
further, the chemical structural formula of Y is as follows:
wherein R is selected from C 1 、C 2 、C 3 、C 4 、C 5 、C 6 、C 7 、C 8 、C 9 、C 10 、C 11 Or C 12 Is a hydrocarbon group of (a).
The preparation method of the azobenzene polyimide film material with reversible photoinduced deformation performance comprises the following steps:
1) Dissolving diamine monomer containing azobenzene unit and dianhydride monomer containing X in polar aprotic solvent, and performing condensation polymerization reaction to obtain polyamic acid solution;
2) Coating the polyamic acid solution on a substrate, and performing thermal imidization to obtain a polyimide film material;
3) The polyimide film material is subjected to hot stretching.
Further, in the step 1), the molar ratio of the dianhydride monomer to the diamine monomer is 1 (1-1.01), the polar aprotic solvent comprises one or more of N, N-dimethylacetamide, N-dimethylformamide or 1-methylpyrrolidone, and the solid content in the polyamic acid solution is 3-15 wt%.
Further, in the step 1), the reaction temperature is 25-90 ℃ and the reaction time is 6-24 hours in the condensation polymerization reaction process.
Further, in step 2), the thermal imidization process includes the steps of:
2-1) heating to 75-85 ℃ and reacting for 0.5-1.5h;
2-2) heating to 95-105 ℃ and reacting for 0.5-1.5h;
2-3) heating to 145-155 ℃ and reacting for 0.5-1.5h;
2-4) heating to 195-205 ℃ and reacting for 0.5-1.5h;
2-5) heating to 245-255 ℃ and reacting for 0.5-1.5h.
The thermal imidization method is firstly carried out by keeping the temperature of the polyamide acid solution at a lower temperature (75-85 ℃, 95-105 ℃ and 145-155 ℃) for about 1h to enable the polyamide acid solution to be fully desolvated, and the gradient heating is also carried out to prevent foaming, then keeping the temperature at 195-205 ℃ for about 1h and then keeping the temperature at 245-255 ℃ for about 1h to carry out imidization.
Further, in the step 3), the temperature of hot stretching is 20-50 ℃ above the glass transition temperature of the polyimide film material, the time of hot stretching is 2-6h, and the stretching ratio is 30-200%.
The application of the azobenzene polyimide film material with reversible photoinduced deformation performance adopts ultraviolet light and visible light as driving sources of photoinduced deformation.
Compared with the prior art, the invention has the following characteristics:
the invention uses ultraviolet light and visible light (green light) as the driving source of the photo-deformable polyimide, and the material can be deformed rapidly and reversibly. Ultraviolet-visible light driven photoinduced deformation and reversion are realized by utilizing azobenzene molecules to generate trans-cis isomerization reaction under ultraviolet light, because trans (trans) azobenzene is in a long rod shape, and cis (cis) azobenzene is in a bending structure, the conformational change of the azobenzene molecules is amplified by the action of a polymer network, and macroscopic deformation of a polymer can be generated. The cis-azobenzene configuration is in an unstable state in thermodynamics, and can return to a trans state through irradiation of visible light, so that the film can return to an initial state.
Compared with the linear polarized light used as a driving source, the method provided by the invention uses the ultraviolet-visible light to drive the photoinduced deformation of the material, so that the problem that the material can not realize rapid reversible deformation under ultraviolet/visible light is solved. According to the invention, by introducing the chain segment (flexible chain segment) of the-O-R-O-part, on one hand, the movement capability of the high molecular chain segment can be changed, the photoisomerization speed of the azo phenyl group is improved, and on the other hand, the stretchability of the polymer material is improved, so that the material is easy to stretch, the polymer is stretched to generate ordered arrangement of the molecular chain segments, the deformation caused by the isomerization of the azo phenyl group element is amplified, and the photoresponse deformation amplitude of the polymer is enhanced.
Drawings
FIG. 1 is a polyimide D (AC) of example 1 n AB) -6FDA infrared spectrum;
FIG. 2 is a schematic illustration of the hot stretching of the film in example 1;
FIG. 3 is a schematic representation of the photodeformation of the stretched film of example 2.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples. The present embodiment is implemented on the premise of the technical scheme of the present invention, and a detailed implementation manner and a specific operation process are given, but the protection scope of the present invention is not limited to the following examples.
Example 1:
azobenzene polyimide D (AC) n The synthesis method of AB) -6FDA is as follows:
1) Using monomer D (AC) n AB) and 4,4' - (hexafluoroisopropenyl) diphthalic anhydride (6 FDA) to prepare azobenzene polyamic acid:
a100 mL Xiding bottle was charged with 1mmol D (AC n AB), under the protection of argon, anhydrous dimethylacetamide is added until D (AC) n AB), 1mmol of 6FDA was added thereto and reacted at 90℃for 24 hours to obtain a polyamic acid (PAA) solution. Wherein the solid content of PAA is controlled to be about 5wt%.
2) Preparation of azobenzene polyimide film:
the polyamic acid was filtered and then uniformly applied dropwise to a clean glass plate, and the temperature was raised according to the following procedure: heating to 80 ℃, reacting for 1h, then heating to 100 ℃, reacting for 1h, then heating to 150 ℃, reacting for 1h, then heating to 200 ℃, reacting for 1h, and finally heating to 250 ℃, and reacting for 1h. Then the heating is turned off, the glass plate containing the film is placed in water or dilute hydrofluoric acid solution after being cooled, and after the film is separated from the glass plate, the film is cleaned and bakedAnd (5) drying. Polyimide D (AC) n The infrared spectrum of AB) -6FDA (n=3, 4,6, 8) is shown in fig. 1:
3) Preparation of oriented film:
as shown in FIG. 2, the azobenzene polyimide obtained above was clamped up and down by a clamp, and a weight was hung at the bottom and suspended in an oven at 120-250℃for 2-6 hours. And slowly cooling to obtain polyimide films with different stretching ratios (30-200%).
Example 2:
stretched azobenzene polyimide D (AC) having different values of n (3, 12, 8) was prepared in the same manner as in example 1 n AB) -6FDA and tested for photo-deformation properties as shown in fig. 3.
1) 50% draw ratio D (AC 3 Photo deformation behavior of AB) -6FDA film:
the stretched film was cut into a size of 5 mm. Times.1 mm. Times.20. Mu.m, at 70mW/cm 2 Under 365nm ultraviolet light, the spline is bent towards the light source to reach a maximum bending angle of 110 degrees, and the bending time is 13s. Thereafter, 80mW/cm was used 2 The film was irradiated with the 530nm visible light, and the film was returned to its original state for 11s. Meanwhile, the photoinduced deformation behavior of the film has good repeatability.
2) 100% draw ratio D (AC 3 Photo deformation behavior of AB) -6FDA film:
the stretched film was cut into a size of 5 mm. Times.1 mm. Times.20. Mu.m, at 70mW/cm 2 Under 365nm ultraviolet irradiation, the spline is bent towards the light source to reach a maximum bending angle of 110 degrees, and the bending time is 8s. Thereafter, 80mW/cm was used 2 The film was irradiated with the 530nm visible light, and the film was returned to its original state for 10s. Meanwhile, the photoinduced deformation behavior of the film has good repeatability.
3) 50% draw ratio D (AC 12 Photo deformation behavior of AB) -6FDA film:
the stretched film was cut into a size of 5 mm. Times.1 mm. Times.20. Mu.m, at 40mW/cm 2 Under 365nm ultraviolet irradiation, bending the spline toward the light source to reach a maximum bending angle of 103 deg. for 14s, and then using 80mW/cm 2 Is irradiated by 530nm visible lightThe film was returned to the original state for 15s. Meanwhile, the photoinduced deformation behavior of the film has good repeatability.
4) 100% draw ratio D (AC 12 Photo deformation behavior of AB) -6FDA film:
the stretched film was cut into a size of 5 mm. Times.1 mm. Times.20. Mu.m, at 40mW/cm 2 Under 365nm ultraviolet light, the spline was bent toward the light source to reach a maximum bending angle of 112 ° and a bending time of 6s. Thereafter, 80mW/cm was used 2 The film was irradiated with the 530nm visible light, and the film was returned to its original state for 15s. Meanwhile, the photoinduced deformation behavior of the film has good repeatability.
5) 50% draw ratio D (AC 8 Photo deformation behavior of AB) -6FDA film:
the stretched film was cut into a size of 5 mm. Times.1 mm. Times.20. Mu.m, at 70mW/cm 2 Under 365nm ultraviolet irradiation, bending the spline toward the light source to reach a maximum bending angle of 99 deg. for 5s, and then using 80mW/cm 2 The film was irradiated with the 530nm visible light, and the film was returned to its original state for 14s. Meanwhile, the photoinduced deformation behavior of the film has good repeatability.
6) 100% draw ratio D (AC 8 Photo deformation behavior of AB) -6FDA film:
the stretched film was cut into a size of 5 mm. Times.1 mm. Times.20. Mu.m, at 70mW/cm 2 Under 365nm ultraviolet irradiation, the spline was bent toward the light source to reach a maximum bending angle of 98 deg. and a bending time of 2s. Thereafter, 80mW/cm was used 2 The film was irradiated with the 530nm visible light, and the film was returned to its original state for 14s. Meanwhile, the photoinduced deformation behavior of the film has good repeatability.
Example 3:
the preparation method of the azobenzene polyimide film material with reversible photoinduced deformation performance comprises the following steps:
firstly synthesizing diamine monomer containing azobenzene units, then placing the monomer into a reactor, deoxidizing, adding a proper amount of polar aprotic solvent by using a syringe, and dissolving the monomer at 25-80 ℃. Then the dianhydride monomer is dissolved in the polar aprotic solvent, after the monomer is completely dissolved, the solution containing the dianhydride monomer is injected into a reactor by using a syringe, and the polyamide acid (PAA) solution is generated through condensation polymerization. After the reaction is completed, the PAA solution is coated on a substrate, and the substrate is placed in an oven for thermal imidization, so that the polyimide film material is obtained.
And carrying out hot stretching on the prepared azobenzene-containing polyimide film. The film was clamped at both ends, one end was suspended in an oven, and stress was applied at the other end. The temperature of the oven is kept 20-50 ℃ above the glass transition temperature, the film is stretched, and the film is slowly cooled after heat preservation for a certain time.
The molar ratio of dianhydride monomer to diamine monomer in the polyimide film material is 1 (1-1.01). The polar aprotic solvent is any one of N, N-dimethylacetamide (DMAc), N-Dimethylformamide (DMF) or 1-methylpyrrolidone (NMP). The solid content of the polyamic acid solution is 3 to 15wt%. The reaction temperature is 25-90 ℃, and the polymerization time is 6-24 hours, preferably 6-8 hours.
The procedure temperature for thermal imidization was: heating to 80 ℃, reacting for 1h, then heating to 100 ℃, reacting for 1h, then heating to 150 ℃, reacting for 1h, then heating to 200 ℃, reacting for 1h, and finally heating to 250 ℃, and reacting for 1h.
The polyimide film material has a hot stretching time of 2-6h and a stretching ratio of 30-200%.
Example 4:
the azobenzene polyimide film material with reversible photoinduced deformation performance has the chemical structural formula:
wherein m represents the degree of polymerization, X is a tetravalent aromatic or aliphatic hydrocarbon group, and Y is a diamine residue containing an azobenzene moiety.
According to actual requirements, controlling m to be more than or equal to 10.
X may be selected from the following groups, each of which is capable of imparting to the corresponding material reversible photoinduced deformation properties according to the invention:
the chemical structural formula of Y is as follows:
wherein R is selected from C 1 、C 2 、C 3 、C 4 、C 5 、C 6 、C 7 、C 8 、C 9 、C 10 、C 11 Or C 12 Is a hydrocarbon group of (a).
The preparation method of the material comprises the following steps:
1) Dissolving diamine monomer containing azobenzene unit and dianhydride monomer containing X in polar aprotic solvent, and performing condensation polymerization reaction to obtain polyamic acid solution;
2) Coating the polyamic acid solution on a substrate, and performing thermal imidization to obtain a polyimide film material;
3) The polyimide film material is subjected to hot stretching.
In step 1), the molar ratio of dianhydride monomer to diamine monomer is 1 (1-1.01), the polar aprotic solvent comprises one or more of N, N-dimethylacetamide, N-dimethylformamide or 1-methylpyrrolidone, and the solid content in the polyamic acid solution is 3-15 wt%. In the condensation polymerization reaction process, the reaction temperature is 25-90 ℃ and the reaction time is 6-24 h.
In step 2), the thermal imidization process comprises the steps of:
2-1) heating to 75-85 ℃ and reacting for 0.5-1.5h;
2-2) heating to 95-105 ℃ and reacting for 0.5-1.5h;
2-3) heating to 145-155 ℃ and reacting for 0.5-1.5h;
2-4) heating to 195-205 ℃ and reacting for 0.5-1.5h;
2-5) heating to 245-255 ℃ and reacting for 0.5-1.5h.
In the step 3), the temperature of hot stretching is 20-50 ℃ above the glass transition temperature of the polyimide film material, the time of hot stretching is 2-6h, and the stretching ratio is 30-200%.
All the technological parameters in the preparation process can be adjusted according to actual needs.
When the material is applied, ultraviolet light and visible light are used as driving sources for photoinduced deformation.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (8)
1. The azobenzene polyimide film material with reversible photoinduced deformation performance is characterized by comprising the following chemical structural formula:
wherein m represents the degree of polymerization, X is a tetravalent aromatic or aliphatic hydrocarbon group, Y is a diamine residue containing an azobenzene moiety;
the chemical structural formula of Y is as follows:
wherein R is selected from C 1 、C 2 、C 3 、C 4 、C 5 、C 6 、C 7 、C 8 、C 9 、C 10 、C 11 Or C 12 Is a hydrocarbon group of (2);
ultraviolet light and visible light are used as a driving source of the azobenzene polyimide film material with reversible photoinduced deformation performance, and the material can generate rapid and reversible deformation;
ultraviolet-visible light driving photoinduced deformation and recovery are realized by utilizing azobenzene molecules to generate trans-cis isomerization reaction under ultraviolet light, and the conformational change of the azobenzene molecules is amplified by the action of a polymer network, so that macroscopic deformation of the polymer can be generated; the cis-azobenzene configuration is in an unstable state in thermodynamics, and can return to a trans state through irradiation of visible light, so that the film material can return to an initial state.
2. The azobenzene polyimide film material with reversible photoinduced deformation property as claimed in claim 1, wherein m is more than or equal to 10.
3. The azobenzene polyimide film material with reversible photoinduced deformation property as claimed in claim 1, wherein X is selected from one of the following groups:
4. a method for producing an azobenzene polyimide film material having reversible photoinduced deformation property as claimed in any one of claims 1 to 3, which comprises the steps of:
1) Dissolving diamine monomer containing azobenzene unit and dianhydride monomer containing X in polar aprotic solvent, and performing condensation polymerization reaction to obtain polyamic acid solution;
2) Coating the polyamic acid solution on a substrate, and performing thermal imidization to obtain a polyimide film material;
3) The polyimide film material is subjected to hot stretching.
5. The method for preparing an azobenzene polyimide film material with reversible photoinduced deformation property as claimed in claim 4, wherein in the step 1), the mole ratio of dianhydride monomer to diamine monomer is 1 (1-1.01), the polar aprotic solvent comprises one or more of N, N-dimethylacetamide, N-dimethylformamide or 1-methylpyrrolidone, and the solid content in the polyamic acid solution is 3wt% to 15wt%.
6. The method for preparing an azobenzene polyimide film material with reversible photoinduced deformation property as claimed in claim 4, wherein in the step 1), the reaction temperature is 25-90 ℃ and the reaction time is 6-24h in the condensation polymerization process.
7. The method for preparing an azobenzene polyimide film material with reversible photoinduced deformation property as claimed in claim 4, wherein in the step 2), the thermal imidization process comprises the following steps:
2-1) heating to 75-85 ℃ and reacting for 0.5-1.5h;
2-2) heating to 95-105 ℃ and reacting for 0.5-1.5h;
2-3) heating to 145-155 ℃ and reacting for 0.5-1.5h;
2-4) heating to 195-205 ℃ and reacting for 0.5-1.5h;
2-5) heating to 245-255 ℃ and reacting for 0.5-1.5h.
8. The method for preparing an azobenzene polyimide film material with reversible photoinduced deformation property as claimed in claim 4, wherein in the step 3), the temperature of hot stretching is 20-50 ℃ above the glass transition temperature of the polyimide film material, the time of hot stretching is 2-6h, and the stretching ratio is 30-200%.
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| US9644071B1 (en) * | 2014-09-05 | 2017-05-09 | The United States Of America As Represented By The Secretary Of The Air Force | Bis(azobenzene) diamines and photomechanical polymers made therefrom |
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