CN117903478A - Shape memory polymer with photoinduced complex three-dimensional deformation and preparation method thereof - Google Patents
Shape memory polymer with photoinduced complex three-dimensional deformation and preparation method thereof Download PDFInfo
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- CN117903478A CN117903478A CN202410061941.XA CN202410061941A CN117903478A CN 117903478 A CN117903478 A CN 117903478A CN 202410061941 A CN202410061941 A CN 202410061941A CN 117903478 A CN117903478 A CN 117903478A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 38
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- 238000000034 method Methods 0.000 claims abstract description 25
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229920000642 polymer Polymers 0.000 claims abstract description 23
- -1 acrylic ester Chemical group 0.000 claims abstract description 16
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- 238000010438 heat treatment Methods 0.000 claims abstract description 10
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- 238000002156 mixing Methods 0.000 claims description 35
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
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- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 14
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- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 5
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- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 5
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 5
- MZRQZJOUYWKDNH-UHFFFAOYSA-N diphenylphosphoryl-(2,3,4-trimethylphenyl)methanone Chemical compound CC1=C(C)C(C)=CC=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MZRQZJOUYWKDNH-UHFFFAOYSA-N 0.000 claims description 5
- HCZMHWVFVZAHCR-UHFFFAOYSA-N 2-[2-(2-sulfanylethoxy)ethoxy]ethanethiol Chemical compound SCCOCCOCCS HCZMHWVFVZAHCR-UHFFFAOYSA-N 0.000 claims description 4
- 244000028419 Styrax benzoin Species 0.000 claims description 4
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 4
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 4
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- JOBBTVPTPXRUBP-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS JOBBTVPTPXRUBP-UHFFFAOYSA-N 0.000 claims 1
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- YIIPOGLCNUDSBG-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;3-sulfanylpropanoic acid Chemical compound OC(=O)CCS.OC(=O)CCS.OC(=O)CCS.OC(=O)CCS.OCC(CO)(CO)CO YIIPOGLCNUDSBG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
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- Treatments Of Macromolecular Shaped Articles (AREA)
Abstract
The invention discloses a shape memory polymer with photoinduced complex three-dimensional deformation and a preparation method thereof, wherein a terminal acrylic ester functionalized prepolymer is prepared, and the double bond of the terminal of Polycaprolactone (PCL) glycol is functionalized in the presence of acryloyl chloride under the condition that triethylamine is used as a catalyst; preparing a single-layer polymer elastomer, and constructing a chemical cross-linked network structure through sulfhydryl-alkene clicking; preparing a PCL/PDA double-layer shape memory polymer elastomer, and coating the full area or partial area of the blank PCL film with (polydopamine) PDA by a full coating or template method; preparing a three-dimensional complex deformed shape memory polymer: and heating and melting the elastomer, stretching to constant strain, and performing laser three-dimensional forming to enable the irradiated part to bend and deform. The invention effectively solves the problem that nano particles are easy to agglomerate in a polymer matrix, realizes remote programming of the three-dimensional deformation behavior of the shape memory polymer material, and has important application prospect in the fields of flexible robots and biomedicine.
Description
Technical Field
The invention relates to the technical field of manufacturing of three-dimensional structures of photoresponsive high polymer materials, in particular to a method for preparing a shape memory polymer with photoinduced complex three-dimensional deformation through regionalization response and a preparation method thereof.
Background
Shape Memory Polymers (SMP) are a typical class of stimuli-responsive deformable materials that are capable of sensing stimuli of changes in the external environment and responding to such changes, and returning from a temporary state to their original form, and in recent years have shown attractive application prospects in the fields of aerospace, flexible electronics, smart wearable, flexible drives, biomedical, and the like.
The most common trigger mode for shape memory polymer materials is thermal stimulation, but in many cases, thermally induced shape memory materials are difficult to meet when the shape memory material is applied to biomedical devices or to bulk materials where the local need for stimulated deformation is present while the rest is still present. In recent years, light-responsive shape memory materials have been a hotspot in research in the biomedical field. However, the current study on the photoresponse of shape memory materials is mostly focused on the introduction of photoisomerization groups (azo phenyl groups, anthracene groups, cinnamoyl groups and derivatives thereof) or the penetration of light absorbing additives (carbon black, carbon nanotubes, gold nanoparticles, etc.) on polymer segments, and the photoresponsive properties of the materials are largely dependent on their chemical structures and material compositions. For example, the Jiang group in 2019 caused anthracene-based polymer segments to assume two different configurations by introducing anthracene groups into the polymer network, by modulating the wavelength of ultraviolet light: dimerization and decrosslinking behavior; thereby achieving a deformation behaviour of the polymer material (Jiang et al, angel. Chem. Int. Ed.2019, 16:5332-5337); the Zhou group of topics achieved the photospiral deformation of composite materials by means of asymmetric shrinkage vector summation by adding a light absorber W 18O49 to the polymer matrix in 2019 et al (Zhou et al adv. Funct. Mater.2019,29,1901202). Second, it is often desirable for the polymer elastomer to have a three-dimensional complex structure after exposure to light. However, in the above methods, either the isomerisable group or the light absorber needs to be added during the initial preparation process of the material, and both methods have certain limitations, and the isomerisable group has a plurality of synthesis steps, high cost and can only absorb specific wavelength; while inorganic fillers generally have poor interfacial properties when used as light absorbers in polymer matrices, inorganic nanoparticles tend to have a tendency to aggregate severely in polymer matrices, which can significantly alter the mechanical properties of the material and adversely affect its photo-driven behavior, which severely limits the range of applications for photo-induced three-dimensional shape memory polymers.
Disclosure of Invention
In order to solve the above-mentioned defects existing in the prior art, the present invention aims to provide a shape memory polymer with photoinduced complex three-dimensional deformation and a preparation method thereof. The invention is based on active groups on the surface of PDA, adopts a soaking spin coating method to adsorb PDA nano particles on the surface of PCL matrix, and utilizes laser to induce anisotropic structures of upper and lower layers of PCL/PDA crosslinked network to construct a light response complex three-dimensional structure.
The invention is realized by the following technical scheme.
According to one aspect of the present invention, there is provided a method for preparing a shape memory polymer having a photoinduced complex three-dimensional deformation, comprising the steps of:
(1) Preparation of acrylate functionalized double bond-terminated PCL prepolymers
According to the mass ratio (5-20): (40-180) mixing PCL glycol with an organic solvent to obtain PCL glycol mixed solution; according to the mass ratio (1-5): (0.5-5): (10-30) mixing and reacting the mixed solution of the triethylamine, the acrylic chloride and the PCL diol; according to the mass ratio (60-100): (150-300) mixing the mixed reaction product with an extracting agent, standing, filtering the precipitate, and drying to obtain an acrylic ester functionalized double-bond-terminated PCL prepolymer;
(2) Preparation of shape memory PCL elastomer
According to the mass ratio of 100: (4-7): 2: (0.5-5) mixing an acrylic ester functionalized double-bond-terminated PCL prepolymer, an organic solvent, a crosslinking agent and a photoinitiator, performing ultrasonic vibration, injecting the vibration mixture into a mold, irradiating for a certain time under illumination, and performing vacuum drying to obtain a shape memory PCL elastomer;
(3) Preparation of PCL/PDA double-layer shape memory Polymer elastomer
According to the mass ratio (1-4): (30-60): (90-150) mixing dopamine hydrochloride monomer, ammonia water solution and absolute ethyl alcohol for self-polymerization; immersing and suspending the PCL elastomer in dopamine hydrochloride polymerization liquid, preparing a PCL/PDA double-layer structure with the surface of the PDA at different times, and washing to obtain the PCL/PDA double-layer shape memory polymer elastomer;
(4) Preparation of three-dimensional complex deformed shape memory polymers
Heating the PCL/PDA double-layer shape memory polymer elastomer, applying constant strain, and cooling to normal temperature under constant stress to obtain a PCL/PDA temporary shape; and irradiating specific areas of the pre-stretched double-layer polymer elastomer film by using multi-point laser fixed points to obtain the three-dimensional complex deformation shape memory polymer.
Preferably, the molecular weight of the PCL diol is 4000-10000 g/mol.
Preferably, the organic solvent is one or more of tetrahydrofuran, chloroform, methylene chloride and N, N-dimethylformamide.
Preferably, the cross-linking agent is one or more of pentaerythritol tetrakis (3-mercaptopropionic acid), 3, 6-dioxa-1, 8-octanedithiol and benzoyl peroxide.
Preferably, the photoinitiator is one or more of benzoin dimethyl ether, trimethylbenzoyl-diphenyl phosphine oxide and 1-hydroxycyclohexyl phenyl ketone.
Preferably, the extractant is one or more of n-hexane, n-butane and petroleum ether.
Preferably, in the step (1), the reaction is carried out for 24 to 36 hours under magnetic stirring at normal temperature; mixing the mixed reaction product with the extractant, standing for 6-12 h, and vacuum drying the precipitate at 40-50 ℃.
Preferably, in the step (2), mixing ultrasonic vibration is carried out for 0.2-1 h; the light irradiation wavelength is 254-960 nm, the light intensity is 48-96W, and the irradiation time is 30-60 min.
Preferably, in the step (3), the mass concentration of the ammonia water solution is 3-5%; PDA surfaced PCL/PDA bilayer structures were prepared at 24h, 48h, 72h different times.
Preferably, in the step (4), the PCL/PDA double-layer shape memory polymer elastomer is heated to 50-90 ℃; applying constant strain to 100% -300%;
The laser irradiation is carried out, the laser intensity is 100-1000 mW/cm 2, the laser wavelength is 254-960 nm, and the laser irradiation time is 1-10 s.
According to another aspect of the present invention, there is provided a shape memory polymer having a photoinduced complex three-dimensional deformation prepared by the method.
Due to the adoption of the technical scheme, the invention has the following beneficial effects:
(1) The shape memory polymer network constructed based on mercapto-alkene click chemistry has excellent shape memory performance, and can realize deformation behaviors such as continuous stretching, shrinkage and the like of an elastomer material.
(2) The invention realizes regional programming through coating and photo-thermal effect, can avoid the aggregation phenomenon of nano particles in a polymer matrix, and lays a good foundation for photo-thermal response performance.
(3) The method can accurately regulate the deformation behavior of the shape memory polymer elastomer under the irradiation of laser, solves the defects of multiple synthesis steps, high cost and absorption of specific wavelength only when a crosslinked network is constructed by complex isomerization groups, and has the excellent characteristic of universality.
(4) The invention can carry out three-dimensional complex shape programming on the driving behavior of the elastomer material again through heating, stretching, cooling shaping and laser irradiation by a laser-induced three-dimensional shape forming mode.
The chemical cross-linked PCL has good thermal shape memory effect, and realizes the photo-thermal conversion of the polymer material through the spin coating of the nano particles. The nano particles in the elastomer coating absorb laser photons, so that the temperature of the upper layer of the film is quickly increased to be higher than the crystallization melting temperature of the elastomer, the upper layer of the film is triggered to locally shrink due to the light response shape memory effect, the lower layer of the film is still in a prestretched glass state due to the temperature gradient, and the shrinkage force of the upper layer of the film drives the film to bend and deform out of plane towards the incidence direction of laser. Based on the above, the photoinduced complex three-dimensional deformation is finally realized by a photo-template method and multi-point laser irradiation.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and constitute a part of this specification, are incorporated in and constitute a part of this specification and do not limit the application in any way, and in which:
FIG. 1 is a graph showing the change in the photoinduced bending angle with irradiation time of examples 1, 2,3, 4, and 5.
Fig. 2 is a graph showing the variation of the photo maximum bending angle with the laser intensity of examples 6, 7, 8, 9, 10.
Fig. 3 is a two-dimensional pattern and three-dimensional structure display diagram of example sample 11.
Fig. 4 is a two-dimensional pattern and three-dimensional structure representation of example sample 12.
Detailed Description
The present invention will now be described in detail with reference to the drawings and the specific embodiments thereof, wherein the exemplary embodiments and descriptions of the present invention are provided for illustration of the invention and are not intended to be limiting.
The embodiment of the invention provides a preparation method of a shape memory polymer with photoinduced complex three-dimensional deformation, which comprises the following steps:
(1) Preparation of acrylate functionalized double bond-terminated PCL prepolymer: preparation of a terminal acrylate functionalized prepolymer, wherein the terminal of PCL diol is double bond functionalized in the presence of acryloyl chloride under the condition of using triethylamine as a catalyst.
Specifically, the mass ratio (5-20): (40-180) mixing and dissolving PCL glycol and an organic solvent (one or more of tetrahydrofuran, chloroform, methylene dichloride and N, N-dimethylformamide) and cooling; according to the mass ratio (1-5): (0.5-5): (10-30) mixing the triethylammonium, the acryloyl chloride and the PCL diol mixed solution which is dissolved in advance by tetrahydrofuran, and magnetically stirring for 24-36 hours at normal temperature, wherein the color of the liquid is changed from colorless and transparent to milky; after the reaction is finished, the mass ratio (60-100): (150-300) mixing the mixed product and normal hexane, standing for 6-12 h, filtering the precipitate, and drying the precipitate in vacuum at 40-50 ℃ to obtain an acrylic ester-terminated PCL prepolymer;
(2) Preparing a shape memory PCL elastomeric material: the monolayer polymer elastomer is prepared by constructing a chemical cross-linked network structure through sulfhydryl-alkene clicking.
Specifically, according to the mass ratio of 100: (4-7): 2: (0.5-5) ultrasonically oscillating acrylate functionalized double-bond-terminated PCL prepolymer, one or more of organic solvents (tetrahydrofuran, trichloromethane, dichloromethane and N, N-dimethylformamide), cross-linking agents (one or more of pentaerythritol tetrakis (3-mercaptopropionic acid) (cross-linking agent A), 3, 6-dioxa-1, 8-octanedithiol (cross-linking agent B) and benzoyl peroxide (cross-linking agent C), a photoinitiator (one or more of benzoin dimethyl ether (photoinitiator A), trimethylbenzoyl-diphenyl phosphine oxide (photoinitiator B) and 1-hydroxycyclohexyl phenyl ketone (photoinitiator C) in a beaker for 0.2-1 h, injecting the mixture into a mold, irradiating the mixture with light at a wavelength of 254-960 nm and a light intensity of 48-96W for 30-60 min, and vacuum drying to obtain a shape memory PCL elastomer material;
(3) Preparation of PCL/PDA double-layer shape memory Polymer elastomer: preparation of bilayer Polymer elastomer full or partial areas of blank PCL film were PDA coated by either full or template methods.
Specifically, the mass ratio (1-4): (30-60): (90-150) mixing dopamine hydrochloride monomer, 3-5% ammonia water solution and absolute ethyl alcohol for self-polymerization; on the basis, the prepared shape memory PCL elastomer material is immersed and suspended in dopamine hydrochloride polymerization liquid, and for a film with a non-full coating, a Polytetrafluoroethylene (PTFE) template with specific black and white phases is attached to the surface of the PCL, the PCL is immersed and suspended in the mixed solution, a PCL/PDA double-layer structure with the surface of the PDA is prepared at different time intervals of 24 hours, 48 hours and 72 hours, and the PCL/PDA double-layer shape memory polymer elastomer film is obtained by washing with deionized water;
(4) Preparing a three-dimensional complex deformed shape memory polymer: firstly pre-stretching, heating the elastomer to a temperature above the transformation temperature of the crystalline melt phase, stretching to constant strain, and cooling to normal temperature under constant stress to obtain a temporary stretched shape. And then performing laser three-dimensional forming: and placing the elastomer under laser irradiation, and carrying out fixed-point irradiation by a series of multi-point lasers to realize rapid molding of the three-dimensional structure.
Specifically, heating a PCL/PDA double-layer shape memory polymer elastomer to 50-90 ℃, applying constant strain to 100-300%, and cooling to 25 ℃ under constant stress of 0.5N to obtain a PCL/PDA temporary shape; secondly, irradiating a specific area of the pre-stretched double-layer polymer elastomer film with laser with the wavelength of 254-960 nm and the intensity of 100-1000 mW/cm 2 for 1-10 s, and obtaining a pre-designed complex three-dimensional shape through repeated fixed-point irradiation.
The preparation process according to the invention is further illustrated by the following examples.
Example 1
(1) Preparation of acrylate functionalized double bond-terminated PCL prepolymers
The mass ratio is 10:150, mixing PCL glycol with the molecular weight of 4000g/mol with tetrahydrofuran as an organic solvent to obtain PCL glycol mixed solution; according to the mass ratio of 3:2: stirring and reacting the mixed solution of the triethylamine, the acryloyl chloride and the PCL diol for 32 hours; according to the mass ratio of 60:180 mixing the mixed reaction product with an extracting agent (one or more of n-hexane, n-butane and petroleum ether), standing for 10 hours, filtering the precipitate, and drying the precipitate in vacuum at 40 ℃ to obtain an acrylic ester functionalized double-bond-terminated PCL prepolymer;
(2) Preparation of shape memory PCL elastomer
According to the mass ratio of 100:5:2:0.5 mixing acrylic ester functionalized double bond end-capped PCL prepolymer, organic solvent tetrahydrofuran, cross-linking agent tetra (3-mercaptopropionic acid) pentaerythritol ester (cross-linking agent A) and photoinitiator benzoin dimethyl ether (photoinitiator A), ultrasonically oscillating for 0.2-1 h, injecting the oscillating mixture into a mould, irradiating for 60min under the conditions of 254nm wavelength and 48W light intensity for ultraviolet crosslinking, and vacuum drying to obtain the shape memory PCL elastomer;
(3) Preparation of PCL/PDA double-layer shape memory Polymer elastomer
According to the mass ratio of 2:50:100, mixing dopamine hydrochloride monomer, 3% ammonia water solution and absolute ethyl alcohol for self-polymerization; immersing and suspending the PCL elastomer in dopamine hydrochloride polymerization liquid, preparing a PCL/PDA double-layer structure with the surface of the PDA at different time intervals of 24 hours, 48 hours and 72 hours, and washing to obtain the PCL/PDA double-layer shape memory polymer elastomer;
(4) Preparation of three-dimensional complex deformed shape memory polymers
Heating the PCL/PDA double-layer shape memory polymer elastomer to 50 ℃, applying 100-300% of constant strain, and cooling to normal temperature under constant stress to obtain a PCL/PDA temporary shape; the specific area of the pre-stretched double-layer polymer elastomer film is irradiated by laser, the laser intensity is 100mW/cm 2, the laser wavelength is 254-960 nm, and the laser irradiation time is 1-10 s, so that the three-dimensional complex deformation shape memory polymer is obtained.
Example 2
(1) Preparation of acrylate functionalized double bond-terminated PCL prepolymers
According to the mass ratio of 5:100, mixing PCL glycol with the molecular weight of 6000g/mol with an organic solvent chloroform to obtain PCL glycol mixed solution; according to the mass ratio of 1:5:10, mixing the mixed solution of the triethylamine, the acrylic chloride and the PCL diol to react for 36h; according to the mass ratio of 80:150 mixing the mixed reaction product with an extracting agent (one or more of n-hexane, n-butane and petroleum ether), standing for 12 hours, filtering the precipitate, and drying the precipitate in vacuum at 45 ℃ to obtain an acrylic ester functionalized double-bond-terminated PCL prepolymer;
(2) Preparation of shape memory PCL elastomer
According to the mass ratio of 100:6:2:1, mixing acrylate functionalized double bond end-capped PCL prepolymer, organic solvent chloroform, cross-linking agent 3, 6-dioxa-1, 8-octane dithiol (cross-linking agent B) and photoinitiator trimethylbenzoyl-diphenyl phosphine oxide (photoinitiator B) +1-hydroxycyclohexyl phenyl ketone (photoinitiator C), carrying out ultrasonic oscillation for 0.2-1 h, injecting the oscillation mixture into a mould, irradiating for 30min for cross-linking under the condition that the wavelength is 960nm and the light intensity is 96W, and carrying out vacuum drying to obtain a shape memory PCL elastomer;
(3) Preparation of PCL/PDA double-layer shape memory Polymer elastomer
According to the mass ratio of 4:60:150, mixing dopamine hydrochloride monomer, 5% ammonia water solution and absolute ethyl alcohol for self-polymerization; immersing and suspending the PCL elastomer in dopamine hydrochloride polymerization liquid, preparing different PCL/PDA double-layer structures with the surface of the PDA at different time intervals of 24 hours, 48 hours and 72 hours, and washing to obtain the PCL/PDA double-layer shape memory polymer elastomer;
(4) Preparation of three-dimensional complex deformed shape memory polymers
Heating the PCL/PDA double-layer shape memory polymer elastomer to 70 ℃, applying constant strain to 300%, and cooling to normal temperature under constant stress to obtain a PCL/PDA temporary shape; and irradiating a specific area of the pre-stretched double-layer polymer elastomer film by using laser, wherein the laser intensity is 200mW/cm 2, the laser wavelength is 542nm, and the laser irradiation time is 9s, so that the three-dimensional complex deformation shape memory polymer is obtained.
Example 3
(1) Preparation of acrylate functionalized double bond-terminated PCL prepolymers
According to the mass ratio of 15:40, mixing PCL glycol with molecular weight of 8000g/mol with organic solvent dichloromethane+N, N dimethylformamide to obtain PCL glycol mixed solution; according to the mass ratio of 2:0.5:30, stirring and reacting the mixed solution of the triethylamine, the acryloyl chloride and the PCL diol for 24 hours; according to the mass ratio of 90:300, mixing the mixed reaction product with an extracting agent (one or more of n-hexane, n-butane and petroleum ether), standing for 8 hours, filtering the precipitate, and drying the precipitate in vacuum at 50 ℃ to obtain an acrylic ester functionalized double-bond-terminated PCL prepolymer;
(2) Preparation of shape memory PCL elastomer
According to the mass ratio of 100:4:2:5, mixing an acrylic ester functionalized double-bond-terminated PCL prepolymer, an organic solvent methylene dichloride+N, N dimethylformamide, a cross-linking agent benzoyl peroxide (cross-linking agent C) and a photoinitiator trimethyl benzoyl-diphenyl phosphine oxide (photoinitiator B), performing ultrasonic oscillation for 0.2-1 h, injecting the oscillation mixture into a mold, irradiating for 50min at the wavelength of 254nm and the light intensity of 48W for photocrosslinking, and performing vacuum drying to obtain a shape memory PCL elastomer;
(3) Preparation of PCL/PDA double-layer shape memory Polymer elastomer
According to the mass ratio of 3:40:90, mixing dopamine hydrochloride monomer, 3% ammonia water solution and absolute ethyl alcohol for self-polymerization; immersing and suspending the PCL elastomer in dopamine hydrochloride polymerization liquid, preparing a PCL/PDA double-layer structure with the surface of the PDA at different time intervals of 24 hours, 48 hours and 72 hours, and washing to obtain the PCL/PDA double-layer shape memory polymer elastomer;
(4) Preparation of three-dimensional complex deformed shape memory polymers
Heating the PCL/PDA double-layer shape memory polymer elastomer to 90 ℃, applying constant strain of 300%, and cooling to normal temperature under constant stress to obtain a PCL/PDA temporary shape; and irradiating a specific area of the pre-stretched double-layer polymer elastomer film by using laser, wherein the laser intensity is 100mW/cm 2, the laser wavelength is 432nm, and the laser irradiation time is 9s, so that the three-dimensional complex deformation shape memory polymer is obtained.
Example 4
(1) Preparation of acrylate functionalized double bond-terminated PCL prepolymers
According to the mass ratio of 20:180, mixing PCL glycol with molecular weight of 10000g/mol with an organic solvent N, N dimethylformamide to obtain PCL glycol mixed solution; according to the mass ratio of 5:3:18, stirring the mixed solution of the triethylamine, the acryloyl chloride and the PCL diol for reaction for 30 hours; according to the mass ratio of 100:260 mixing the mixed reaction product with an extracting agent (one or more of n-hexane, n-butane and petroleum ether) and standing for 6 hours, filtering the precipitate, and drying the precipitate in vacuum at 40 ℃ to obtain an acrylic ester functionalized double bond end-capped PCL prepolymer;
(2) Preparation of shape memory PCL elastomer
According to the mass ratio of 100:7:2:4, mixing an acrylic ester functionalized double bond end-capped PCL prepolymer, an organic solvent N, N dimethylformamide, a cross-linking agent tetra (3-mercaptopropionic acid) pentaerythritol ester (cross-linking agent A) +benzoyl peroxide (cross-linking agent C) and a photoinitiator 1-hydroxycyclohexyl phenyl ketone (photoinitiator C), carrying out ultrasonic oscillation for 0.2h, injecting the oscillation mixture into a mold, carrying out photocrosslinking at the wavelength of 960nm and the light intensity of 96W for 40min, and carrying out vacuum drying to obtain a shape memory PCL elastomer;
(3) Preparation of PCL/PDA double-layer shape memory Polymer elastomer
According to the mass ratio of 1:30:130 mixing dopamine hydrochloride monomer, 4% ammonia water solution and absolute ethyl alcohol for self-polymerization; immersing and suspending the PCL elastomer in dopamine hydrochloride polymerization liquid, preparing a PCL/PDA double-layer structure with the surface of the PDA at different time intervals of 24 hours, 48 hours and 72 hours, and washing to obtain the PCL/PDA double-layer shape memory polymer elastomer;
(4) Preparation of three-dimensional complex deformed shape memory polymers
Heating the PCL/PDA double-layer shape memory polymer elastomer to 80 ℃, applying constant strain to 300%, and cooling to normal temperature under constant stress to obtain a PCL/PDA temporary shape; the specific area of the pre-stretched double-layer polymer elastomer film is irradiated by laser, the laser intensity is 100mW/cm 2, the laser wavelength is 960nm, and the laser irradiation time is 9s, so that the three-dimensional complex deformation shape memory polymer is obtained. The laser irradiation time, bend angle and programmed pattern are specifically shown in table 2.
The elastomer gel contents prepared in examples 1 to 4 of the present invention are described below by Table 1.
Table 1: the molecular weight of PCL, the cross-linking agent, the photoinitiator, the feeding ratio and the gel content of the elastomer are adopted in the preparation of the elastomer.
Gel content is one method used to test the degree of crosslinking, during which the uncrosslinked linear PCL molecules are dissolved in tetrahydrofuran, whereas the crosslinked PCL is not. The specific test method is that a small piece of crosslinked PCL is cut and weighed to obtain the initial mass (M 0), the small piece of PCL is wrapped on a copper net and placed in a Soxhlet extractor, toluene is taken as a solvent and refluxed at 80 ℃ for 96 hours, gel is taken out after cooling and washed with ethanol for several times, and then the gel is dried in an oven at 50 ℃ for 24 hours to obtain the mass (M 1), and the calculated formula of the gel content is G=M 1/M0.
The photo-induced bending deformation behavior of the double layer elastomer of step (4) is described below by table 2.
Table 2: elastomer, pretension times, laser irradiation time, bend angle and programmed pattern in samples 1-12
In the present invention, the crystalline melting behavior of the elastomer can be analyzed by differential calorimetric test (DSC) and its shape memory recovery process quantitatively analyzed by shape memory. The method specifically comprises the following steps:
DSC: the specific method is that the crosslinked PCL system sample is cut into 5-10 mg, then the PCL system sample is added into a crucible and is protected by nitrogen, and the temperature test interval is 25-120 ℃. The temperature rise rate and the temperature drop rate in the test process are 10 ℃/min. To eliminate thermal history during testing, each cycle was subjected to two cycle values.
DMA: the shape recovery process of the elastomer after the photothermal effect was quantitatively characterized by a constant stress pattern in dynamic mechanical analysis (DMA Q800). The sample bar was clamped in a stretching clamp and then stretched to 60% of original length with a constant stress of 0.5N (epsilon d), kept isothermally for 5min, cooled to 0 ℃ again, the stress was not unloaded during cooling, and equilibrated at 0 ℃ for 3min, then the loaded stress was relieved again, the strain at this time being designated epsilon dload, and when the sample was heated again to 60 ℃, the material returned to maximum strain (epsilon rec). The shape fixation ratio (R f) and the shape recovery ratio (R r) were calculated as follows:
Rf＝εdload/εd
Rr＝(εd～εrec)/εd
Analysis of experimental data:
From Table 2, it can be seen that the chemically crosslinked PDA/PCL elastomers had good photo-thermal and shape memory effects. In samples 1 to 5, the elastic body can be subjected to different degrees of bending deformation under the irradiation of laser light of 100mW/cm 2 for different times (figure 1), which shows that the elastic body has good photo-thermal conversion efficiency and shape recovery rate, and the increase of the bending angle with the irradiation time of the laser light can be explained as follows: more grain melting triggers more shape recovery force. In samples 6 to 10, as the laser intensity increases, more crystal chain breaks in the irradiated region are melted, and the temperature gradient extends in the film thickness direction, so that the elastomer generates a larger maximum bending angle (fig. 2).
Based on the different positions of the PDA coating in the PCL blank matrix, the double-layer PCL/PDA polymer elastomer can be molded under specific laser intensity to have a complex three-dimensional structure. In the elastomer samples 1 to 10, different out-of-plane bending deformation shapes were constructed due to the patterning of the full coating. In the elastomer sample 11, as the position of the PDA pattern area was changed to a diagonal form, the PCL coated with the PDA layer was subjected to shape shrinkage recovery when irradiated with laser, and the vector sum of asymmetric shrinkage forces was subjected to spiral deformation of the anisotropic film (fig. 3). In example 12, when the coating layer was coated in a specific shape on the front and back sides, respectively, different three-dimensional structures were formed (fig. 4).
When the laser-irradiated elastomer is completely melted in an environment of 60 ℃, the elastomer returns to an isotropic programmable state and can be reprogrammed and three-dimensional structure prepared.
Description of the inventive principles: the monolayer polymer elastomer in the invention is a chemical cross-linked network constructed based on mercapto-ene click chemistry. The crystalline melting temperature of the PCL prepared is controlled by the length of the molecular chain among the crosslinking nodes as a typical shape memory polymer. Wherein, the single-layer polymer elastomer with low melting temperature has low shape memory transition temperature, and the driving temperature corresponding to the system with high melting temperature is correspondingly higher. Furthermore, the molecular chain length between the crosslinking nodes affects the properties such as modulus, shape retention, and shape recovery of the polymer.
The preparation of the shape memory polymer with the photoinduced complex three-dimensional deformation in the invention is designed based on the crosslinked PCL. Based on the active groups inherent to the surface of PDA, PDA has strong adhesion to almost any substrate. When the prestretched composite film is irradiated by laser, the PDA in the irradiated area absorbs laser photons to generate photo-thermal conversion, and the upper layer and the lower layer of the film have temperature gradient and single domain orientation difference in thickness, so that the upper layer film is crystallized and melted to generate shape memory effect to shrink when being irradiated by the laser, meanwhile, the lower layer film is still in a glass state, and the shrinkage force of the upper layer film enables the PCL/PDA elastomer film to generate out-of-plane bending deformation towards the laser irradiation direction. After turning off the laser, the upper layer is recrystallized instantaneously, thereby maintaining the bending angle. While the non-irradiated film substrate does not undergo a crystallization melt-recrystallization process, it still maintains the pre-stretched shape of the pre-stretched strain.
The invention is not limited to the above embodiments, and based on the technical solution disclosed in the invention, a person skilled in the art may make some substitutions and modifications to some technical features thereof without creative effort according to the technical content disclosed, and all the substitutions and modifications are within the protection scope of the invention.
Claims (10)
1. A method for preparing a shape memory polymer with photoinduced complex three-dimensional deformation, which is characterized by comprising the following steps:
(1) Preparation of acrylate functionalized double bond-terminated PCL prepolymers
According to the mass ratio (5-20): (40-180) mixing PCL glycol with an organic solvent to obtain PCL glycol mixed solution; according to the mass ratio (1-5): (0.5-5): (10-30) mixing and reacting the mixed solution of the triethylamine, the acrylic chloride and the PCL diol; according to the mass ratio (60-100): (150-300) mixing the mixed reaction product with an extracting agent, standing, filtering the precipitate, and drying to obtain an acrylic ester functionalized double-bond-terminated PCL prepolymer;
(2) Preparation of shape memory PCL elastomer
According to the mass ratio of 100: (4-7): 2: (0.5-5) mixing an acrylic ester functionalized double-bond-terminated PCL prepolymer, an organic solvent, a crosslinking agent and a photoinitiator, performing ultrasonic vibration, injecting the vibration mixture into a mold, irradiating under illumination, and performing vacuum drying to obtain the shape memory PCL elastomer;
(3) Preparation of PCL/PDA double-layer shape memory Polymer elastomer
According to the mass ratio (1-4): (30-60): (90-150) mixing dopamine hydrochloride monomer, ammonia water solution and absolute ethyl alcohol for self-polymerization; immersing and suspending the PCL elastomer in dopamine hydrochloride polymerization liquid, preparing a PCL/PDA double-layer structure with the surface of the PDA at different times, and washing to obtain the PCL/PDA double-layer shape memory polymer elastomer;
(4) Preparation of three-dimensional complex deformed shape memory polymers
Heating the PCL/PDA double-layer shape memory polymer elastomer, applying constant strain, and cooling to normal temperature under constant stress to obtain a PCL/PDA temporary shape; and irradiating specific areas of the pre-stretched double-layer polymer elastomer film by using multi-point laser fixed points to obtain the three-dimensional complex deformation shape memory polymer.
2. The method for preparing a shape memory polymer with photoinduced complicated three-dimensional deformation according to claim 1, wherein the molecular weight of PCL diol is 4000 to 10000g/mol.
3. The method for preparing a shape memory polymer with photoinduced complex three-dimensional deformation according to claim 1, wherein the organic solvent is one or more of tetrahydrofuran, chloroform, methylene chloride and N, N-dimethylformamide;
The extractant is one or more of n-hexane, n-butane and petroleum ether.
4. The method of preparing a shape memory polymer with photoinduced complex three-dimensional deformation according to claim 1, wherein the crosslinking agent is one or more of pentaerythritol tetrakis (3-mercaptopropionate), 3, 6-dioxa-1, 8-octanedithiol, and benzoyl peroxide.
5. The method of preparing a shape memory polymer with photoinduced complex three-dimensional deformation according to claim 1, wherein the photoinitiator is one or more of benzoin dimethyl ether, trimethylbenzoyl-diphenyl phosphine oxide, and 1-hydroxycyclohexyl phenyl ketone.
6. The method for preparing a shape memory polymer with photoinduced complex three-dimensional deformation according to claim 1, wherein in the step (1), the reaction is performed under magnetic stirring at normal temperature for 24 to 36 hours; mixing the mixed reaction product with the extractant, standing for 6-12 h, and vacuum drying the precipitate at 40-50 ℃.
7. The method for preparing a shape memory polymer with photoinduced complex three-dimensional deformation according to claim 1, wherein in the step (2), mixing ultrasonic vibration is performed for 0.2-1 h; the irradiation wavelength is 254-960 nm, the light intensity is 48-96W, and the irradiation time is 30-60 min.
8. The method for preparing a shape memory polymer with photoinduced complicated three-dimensional deformation according to claim 1, wherein in the step (3), the mass concentration of the ammonia water solution is 3-5%; PDA surfaced PCL/PDA bilayer structures were prepared at 24h, 48h, 72h different times.
9. The method of preparing a shape memory polymer with photoinduced complex three-dimensional deformation according to claim 1, wherein in step (4), PCL/PDA double-layer shape memory polymer elastomer is heated to 50-90 ℃; applying constant strain to 100% -300%;
The laser irradiation is carried out, the laser intensity is 100-1000 mW/cm 2, the laser wavelength is 254-960 nm, and the laser irradiation time is 1-10 s.
10. A shape memory polymer with photoinduced complex three-dimensional deformation prepared by the method of any one of claims 1 to 9.
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