CN113061263B - Preparation method of photocrosslinking dynamic reversible supramolecular polymer adhesive based on lipoic acid micromolecular compound - Google Patents
Preparation method of photocrosslinking dynamic reversible supramolecular polymer adhesive based on lipoic acid micromolecular compound Download PDFInfo
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Abstract
The invention discloses a preparation method of a photocrosslinking dynamic reversible supramolecular polymer adhesive based on a lipoic acid micromolecular compound, which comprises the following steps: heating, stirring and melting lipoic acid or lipoic acid derivatives, adding a cross-linking agent, stirring, adding a metal ion source, stirring, stopping heating after the reaction is finished, transferring the molten liquid to a substrate while the molten liquid is hot, carrying out hot pressing on the other substrate to obtain a yellow transparent supramolecular polymer, and irradiating the yellow transparent supramolecular polymer by using an ultraviolet-visible light source to obtain the photocrosslinking dynamic reversible supramolecular polymer adhesive based on the lipoic acid micromolecular compounds; the supermolecule polymer adhesive prepared by the invention mainly carries out cross-linking self-assembly by dynamic disulfide bonds, hydrogen bonds and metal coordination bonds; has good biocompatibility, higher stability, good uniformity, optical transparency, excellent mechanical properties, adhesion properties and reversible recycling.
Description
Technical Field
The invention belongs to the technical field of material chemistry, and particularly relates to a preparation method of a photocrosslinking dynamic reversible supramolecular polymer adhesive based on a lipoic acid micromolecular compound.
Background
The development of high-performance adhesive materials not only meets the industrial and social requirements, but also has important significance for understanding the chemical factors of biological adhesion. Traditional polymeric binders often rely on covalent polymeric backbones and have difficulty achieving dynamic properties such as on-demand adhesion, reversible adhesion, and the like. Due to the extensive development of supramolecular chemistry, many supramolecular tools have been developed and reversible non-covalent or dynamic covalent materials are expected to replace traditional covalent materials. The supermolecule intelligent adhesive material is emerging by utilizing the existing supermolecule tool kit, has the main advantages of being capable of adhering/desorbing according to needs according to external stimulation and has wide application prospect in the fields of reversible wound dressing, semiconductor adhesion and the like.
Many strategies use temperature and chemical stimuli to adjust adhesion strength, while the non-contact remote stimulation, spatiotemporal controllability, wavelength tunability and non-polluting nature of light make it an ideal stimulus, and these unique advantages have prompted the study of photoresponsive adhesive materials. It is a common strategy to introduce photoresponsive elements (such as azobenzene, stilbene, spiropyran, diarylethene, and derivatives thereof) into molecular networks to construct photocontrol dynamic systems. A typical example is the incorporation of a spiropyran/diarylethene photochromic agent into a polystyrene network that can induce UV-induced adhesion enhancement without altering covalent cross-linking (Noncovent photochromic polymer adhesion. macromolecules. 2018; 51: 2388-. However, adhesion reversibility is limited by the permanent change in the internal polymer structure. Thus, high molecular weight polymeric binders tend to be difficult to achieve complete de-bonding and recycling due to their high viscosity. Compared with polymer adhesives, the micromolecule adhesives have the advantages of precise chemical structure, easy molecular engineering design, high reproducibility and the like, and have great potential in basic research and industrial application.
Disclosure of Invention
The invention aims to provide a preparation method of a photocrosslinking dynamic reversible supramolecular polymer adhesive based on a lipoic acid micromolecular compound.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides a preparation method of a photocrosslinking dynamic reversible supramolecular polymer adhesive based on a lipoic acid micromolecular compound, which comprises the following steps:
heating lipoic acid or lipoic acid derivatives to 70-200 ℃, stirring for 2-10 min for melting, then adding a cross-linking agent, stirring for 2-10 min, finally adding a metal ion source, stirring for 2-10 min, wherein the molar ratio of the lipoic acid or the lipoic acid derivatives to the cross-linking agent to the metal ion source is 1 (0.01-1.5): 0.01-1), the molar number of the metal ion source is calculated by the molar number of the metal ions, stopping heating after the reaction is finished, moving 30-100 mu L of molten liquid to a substrate while the molten liquid is hot, performing hot pressing on the substrate to obtain a thermopolymer with the thickness of 45-55 mu m, and irradiating the thermopolymer with an ultraviolet-visible light source with the wavelength of 300-450nm for 20-60 min to obtain the photocrosslinking dynamic reversible supramolecular polymer adhesive based on the lipoic acid micromolecular compounds;
the metal ion source is composed of metal inorganic salt and an organic solvent capable of dissolving the metal inorganic salt, wherein the metal inorganic salt is at least one of ferric chloride, copper sulfate, zinc chloride, vanadium chloride, titanium chloride, cobalt chloride and nickel chloride, and the organic solvent is at least one of acetone, tetrahydrofuran, ethanol or methanol.
The structure of the lipoic acid or the lipoic acid derivatives is shown as a formula I:
in the formula I, R1Is hydrogen or C1-C4 straight chain or branched chain alkyl, R2Is hydrogen or carboxyl (-COOH), and n is an integer of 1-5.
The lipoic acid or lipoic acid derivatives are preferably lipoic acid or lipoic acid diacid, wherein the lipoic acid has a structural formula I, R1Is hydrogen, R2Is hydrogen, n is 3; in the structural formula I of the thioctic acid, R1Is hydrogen, R2Is carboxyl, and n is 2.
Preferably, the molar ratio of the lipoic acid or the lipoic acid derivatives, the cross-linking agent and the metal ion source is 1 (0.15-1.45) to 0.01-0.15.
The crosslinking agent is styrene, divinylbenzene or 1, 3-bis (1-methylvinyl) benzene.
The concentration of the metal ion source is 0.01-1 g/mL, preferably 0.1 g/mL.
The substrate is at least one of glass, iron, copper, wood, polymethyl methacrylate and polytetrafluoroethylene.
The area of the substrate is 1cm × 1 cm.
The thickness of the thermopolymer was 50 μm.
Due to the adoption of the technical scheme, the invention has the following advantages and beneficial effects:
the invention adopts micromolecular lipoic acid or lipoic acid derivatives as monomers, or is matched with specific types and specific amounts of cross-linking agents and metal ion sources, a yellow transparent thermopolymer can be obtained by a hot melting method under the condition of no addition of solvents, and a colorless transparent supramolecular adhesive is obtained by further irradiating with ultraviolet-visible light. The detection shows that the obtained supermolecule adhesive has better adhesive property on the surfaces of different materials, and the adhesion on the surface of glass can reach 11.691MPa, which is superior to most of commercial adhesives.
The preparation method of the photocrosslinking dynamic reversible supramolecular polymer adhesive based on the lipoic acid micromolecular compound has the advantages that the used raw materials are biocompatible, the source is wide, the price is low, the acquirement is easy, and the industrial feasibility is realized; the related solvent-free heating and ultraviolet-visible light process has the advantages of quick reaction, simple and safe process, no industrial pollution such as waste water, waste residue and the like, and the atom utilization rate reaches 100 percent; the whole preparation process is simple, the production cost is low, the yield is quantitative, and the requirements of green chemistry are met.
The supermolecule polymer adhesive prepared by the invention mainly carries out cross-linking self-assembly by dynamic disulfide bonds, hydrogen bonds and metal coordination bonds; excellent adhesion on different substrates; the composite material has good biocompatibility, high stability, good uniformity and optical transparency, excellent mechanical property, adhesion property and reversible recovery; the method has wide application prospect in the fields of flexible electronic screens, wearable equipment, soft robots, aerospace and the like.
The thermopolymer network in the supermolecule polymer adhesive prepared by the invention is mainly connected by supermolecule bonding force, and the disulfide five-membered ring and the hydrogen bond of the lipoic acid have reversible photo-thermal response dynamic polymerization/depolymerization characteristics, so that the adhesive has good reversible heating desorption-photo-polymerization adhesion performance, and can successfully realize adhesion and recycling as required.
The raw materials used in the preparation method of the invention are biocompatible, cheap and easily available, and have industrial feasibility. The preparation process is simple, the yield is quantitative, and the requirements of green chemistry are met.
Description of the drawings:
fig. 1 is a schematic view showing the polymerization mechanism and appearance of the supramolecular polymer adhesive prepared in example 2 of the present invention.
FIG. 2 is a schematic representation of the structural characterization of the supramolecular polymer adhesive prepared in example 2 of the present invention; wherein, A is a schematic diagram of an ultraviolet-visible absorption spectrum of the supramolecular polymer adhesive, B is a schematic diagram of a nuclear magnetic resonance hydrogen spectrum of the supramolecular polymer adhesive, C is a schematic diagram of an infrared spectrum of the supramolecular polymer adhesive, and D is a schematic diagram of a Raman spectrum of the supramolecular polymer adhesive.
Fig. 3 is an X-ray diffraction pattern and a Polarizing Optical Microscope (POM) of the supramolecular polymer adhesive prepared in example 2 of the invention.
Figure 4 is a graphical representation of the rheological and thermal performance curves of the supramolecular polymer adhesive prepared in example 2 of the invention. Wherein, A is a schematic diagram of a frequency conversion curve, B is a schematic diagram of a temperature change curve, C is a schematic diagram of a thermogravimetric curve, and D is a schematic diagram of a differential scanning calorimetry curve.
FIG. 5 is a schematic view of the UV-VIS absorption spectrum of the supramolecular polymer adhesive prepared in examples 2-5 of the present invention.
Fig. 6 is a schematic drawing of the stretching of supramolecular polymer adhesives prepared in examples 1 and 2 of the present invention. Wherein A is a schematic drawing of a tensile property curve of the supramolecular polymer adhesive, and B is a schematic drawing of the supramolecular polymer adhesive.
Fig. 7 is a schematic representation of the adhesion properties of the supramolecular polymer adhesive prepared in example 6 of the invention. Wherein, A is a graph comparing the adhesion performance of the supramolecular polymer adhesive and the commercial adhesive on different surfaces, and B is a schematic drawing of a substrate lifting weight adhered by the supramolecular polymer adhesive.
Fig. 8 is a schematic diagram of the water resistance of the supramolecular polymer adhesive prepared in example 7 of the invention. Wherein, A is a schematic diagram for comparing the adhesive strength of the supramolecular polymer adhesive after being soaked in air, deionized water, a hydrochloric acid aqueous solution and a sodium chloride aqueous solution for 10 days, and B is a schematic diagram for a time-dependent adhesive strength curve of the supramolecular polymer adhesive after being soaked in the deionized water for 10 days.
Fig. 9 is a schematic diagram of the recycling performance of the supramolecular polymer adhesive prepared in example 8 of the present invention. Wherein, A is a schematic diagram of a self-repairing image of the supramolecular polymer adhesive, B is a columnar schematic diagram of 10 times of reversible adhesion performance of the supramolecular polymer adhesive, C is a schematic diagram of an ultraviolet visible absorption spectrum of 5 times of cyclic photopolymerization-thermal depolymerization of the supramolecular polymer adhesive, and D is a schematic diagram of a nuclear magnetic resonance hydrogen spectrum of 5 times of cyclic photopolymerization-thermal depolymerization of the supramolecular polymer adhesive.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
The lipoic acid used in the examples was purchased from the manufacturer as Aladdin (Alladdin), all known as DL-lipoic acid, CAS number 1077-28-7, 500g standard, 99% purity, and Reagent Grade (RG).
The iron chloride used in the examples was purchased from Hadamard (adamas-beta), CAS number 7705-08-0, 500g, 99% purity, and Reagent Grade (RG).
The crosslinker 1, 3-bis (1-methylvinyl) benzene (DIB) used in the examples was purchased from TCI, CAS number 3748-13-8, 500mL, 97% purity, and chromatographic Grade (GC).
The acetone used in the examples was purchased from Hadamard (adamas-beta), CAS number 67-64-1, 500mL, purity ≥ 99.7%, and grade analytical grade (AR).
Example 1
The structure of the lipoic acid powder used in this example is shown in formula I:
in the formula I, R1Is hydrogen, R2Is hydrogen and n is 3.
10g of lipoic acid powder is placed in a reactor with a stirring device, heated to 120 ℃ in an oil bath and stirred for 10min until the lipoic acid powder is molten, then 6g of 1, 3-bis (1-methylvinyl) benzene (DIB) is added into the reactor, and the heating and stirring are continued for 5 min. And then adding 1mL of 0.1g/mL ferric chloride acetone solution into the reactor, wherein the molar ratio of the lipoic acid or the lipoic acid derivatives, the cross-linking agent and the metal ion source is 1:0.78:0.01, the mole number of the metal ion source is calculated by the mole number of the metal ions, continuously heating and stirring for 3 minutes, stopping heating, using a liquid transfer gun to transfer 50 mu L of molten liquid onto glass with the size of 1cm multiplied by 1cm when the molten liquid is hot, and using another piece of glass with the same size to carry out hot pressing to obtain a yellow transparent lipoic acid thermopolymer with the thickness of 50 mu m. The lipoic acid thermopolymer was irradiated with 365nm ultraviolet light for about 30 minutes to obtain colorless and transparent supramolecular polymer binder-1.
The structure of the liponic acid used in the following examples is shown in formula I:
in the formula I, R1Is hydrogen, R2Is carboxyl, and n is 2.
Examples 2 to 8
The procedure and conditions were the same as in example 1 except that the kinds of the monomeric lipoic acid or lipoic acid derivative and the crosslinking agent, and the molar ratio of the monomeric lipoic acid or lipoic acid derivative, the crosslinking agent and the metal inorganic salt in the metal ion source were changed, to obtain different supramolecular polymers, respectively, as detailed in table 1.
In example 2, the molar ratio of the lipoic acid or lipoic acid derivative, the cross-linking agent and the metal ion source is 1:0.65:0.04, and the mole number of the metal ion source is calculated by the mole number of the metal ions. The concentration of the metal ion source is 0.1 g/mL.
In example 3, the molar ratio of the lipoic acid or lipoic acid derivative, the cross-linking agent and the metal ion source is 1:0.78:0.03, and the mole number of the metal ion source is calculated by the mole number of the metal ions. The concentration of the metal ion source is 0.1 g/mL.
In example 4, the molar ratio of the lipoic acid or lipoic acid derivative, the cross-linking agent and the metal ion source is 1:1.39:0.05, and the mole number of the metal ion source is calculated by the mole number of the metal ions. The concentration of the metal ion source is 0.1 g/mL.
In example 5, the molar ratio of the lipoic acid or lipoic acid derivative, the cross-linking agent and the metal ion source is 1:1.45:0.01, and the mole number of the metal ion source is calculated by the mole number of the metal ions. The concentration of the metal ion source is 0.1 g/mL.
In example 6, the molar ratio of the lipoic acid or lipoic acid derivative, the cross-linking agent and the metal ion source is 1:0.15:0.15, and the mole number of the metal ion source is calculated by the mole number of the metal ions. The concentration of the metal ion source is 0.1 g/mL.
In example 7, the molar ratio of the lipoic acid or lipoic acid derivative, the cross-linking agent and the metal ion source is 1:0.45:0.09, and the mole number of the metal ion source is calculated by the mole number of the metal ions. The concentration of the metal ion source is 0.1 g/mL.
In example 8, the molar ratio of the lipoic acid or lipoic acid derivative, the cross-linking agent and the metal ion source is 1:0.54:0.15, and the mole number of the metal ion source is calculated by the mole number of the metal ions. The concentration of the metal ion source is 0.1 g/mL.
TABLE 1
The polymerization mechanism and appearance diagram of the supramolecular polymer adhesive provided by the invention are shown in fig. 1, and fig. 1 is a schematic view of the polymerization mechanism and appearance diagram of the supramolecular polymer adhesive prepared in example 2 of the invention. The figure shows that the lipoic acid monomer powder is heated to open the ring and carry out free radical polymerization to obtain the lipoic acid thermopolymer powder containing partial monomers and polymers. The thioctic acid thermopolymer is further subjected to ring-opening polymerization under the irradiation of 300-450nm ultraviolet-visible light to obtain a colorless and transparent thioctic acid photopolymer.
The structural representation diagram of the supramolecular polymer adhesive provided by the invention is shown in fig. 2, and fig. 2 is the structural representation diagram of the supramolecular polymer adhesive prepared in example 2 of the invention; wherein, A is the ultraviolet-visible absorption spectrum schematic diagram of the supramolecular polymer adhesive, and as can be seen from the diagram, the absorption wavelength of the disulfide five-membered ring of the lipoic acid monomer and the monomer in the thermopolymer is 330nm, and the absorption wavelength of the disulfide polymer in the photopolymer is 240nm, which proves that the lipoic acid is completely polymerized by illumination. B is a diagram of the hydrogen nuclear magnetic resonance spectrum of the supramolecular polymer adhesive, and as can be seen from the diagram, the nuclear magnetic peak of the polymer is obviously broadened and shifted compared with that of the monomer. C is the infrared spectrum schematic diagram of the supramolecular polymer adhesive, and as can be seen from the diagram, the peak of the polymer is obviously broadened, which proves the generation of a large number of hydrogen bonds. D is a Raman spectrum of the supramolecular polymer binder, which can be seen at 510 and 525cm-1The peaks at (A) represent disulfide bonds in monomers and polymers, respectivelyThe stretching vibration of (2) proves the polymerization structure of the photopolymer.
The X-ray diffraction pattern and the polarization optical micrograph of the supramolecular polymer adhesive provided by the invention are shown in fig. 3, and fig. 3 is the X-ray diffraction pattern and the Polarization Optical Micrograph (POM) of the supramolecular polymer adhesive prepared in example 2 of the invention. As can be seen from the figure, the lipoic acid monomer is crystal form powder, the thermopolymer forms a large amount of ordered crystal phase-spherulites, the diffraction peak of the photopolymer disappears, and the amorphous characteristic is shown without polarized light.
The rheological and thermal performance curves of the supramolecular polymer adhesive provided by the present invention are shown in fig. 4, and fig. 4 is a schematic diagram of the rheological and thermal performance curves of the supramolecular polymer adhesive prepared in example 2 of the present invention. Wherein A is a schematic diagram of a frequency conversion curve, and as can be seen from the diagram, the modulus change along with the frequency proves the high dynamic property of the supermolecular network. B is a schematic diagram of a temperature-change curve, and it can be seen from the diagram that the modulus is continuously reduced along with the increase of the temperature, the temperature responsiveness of the polymer is proved, and the supermolecular bonds are broken at high temperature, thereby leading to the depolymerization of the polymer. C is a schematic diagram of a thermogravimetric curve, the decomposition temperatures of monomer lipoic acid or lipoic acid derivatives, lipoic acid or lipoic acid derivative thermopolymer and supramolecular polymer adhesive are gradually increased and respectively reach 247.9 ℃, 281.4 ℃ and 306.8 ℃, and the continuous improvement of the crosslinking degree of the supramolecular polymer adhesive network is proved. D is a differential scanning calorimetry curve diagram, and it can be seen from the diagram that the glass transition temperature of the monomeric lipoic acid or lipoic acid derivatives and the thermal polymers of the lipoic acid or lipoic acid derivatives are both lower than-50 ℃, the melting point is about 60 ℃, but the lipoic acid or lipoic acid derivatives thermal polymers have a small broad peak, which indicates that the monomeric and polymeric lipoic acid or lipoic acid derivatives exist in the lipoic acid or lipoic acid derivatives thermal polymers at the same time. The glass transition temperature of the supramolecular polymer adhesive was 13 ℃ without a fixed melting point, demonstrating the formation of amorphous supramolecular polymer adhesive.
The ultraviolet-visible absorption spectrum of the supramolecular polymer adhesive provided by the invention is shown in fig. 5, and fig. 5 is a schematic view of the ultraviolet-visible absorption spectrum of the supramolecular polymer adhesive prepared in the embodiments 2 to 5 of the invention. The supramolecular polymer adhesive prepared in the embodiment 2-5 is polymerized under the irradiation of light with different wavelengths of 365, 380, 400 and 420nm to form an ultraviolet-visible absorption spectrum. The above shows that 300-450nm light can initiate ring-opening polymerization of disulfide bonds, proving the mild and universal preparation conditions of the supramolecular polymer adhesive.
Example 9
And (3) testing mechanical properties: a piece of the supramolecular polymer adhesive prepared in example 1 of the invention (taking polymer adhesive-1 as an example) in a strip shape was taken, both ends of the polymer were placed on a tensile machine jig, and the tensile properties were observed by stretching at a speed of 50 mm/min.
A piece of the supramolecular polymer adhesive prepared in example 2 of the invention (taking polymer adhesive-2 as an example) in a strip shape was taken, both ends of the polymer were placed on a tensile machine fixture, and the tensile property was observed by stretching at a speed of 50 mm/min.
A section of the hot polymer of lipoic acid prepared in example 1 of the present invention (which was a product of example 1 before being irradiated with light) was taken in the form of a bar, and both ends of the hot polymer were placed on a jig of a drawing machine, and drawn at a speed of 50mm/min, and the drawing properties thereof were observed, as shown in FIG. 6. Fig. 6 is a schematic drawing of the stretching of supramolecular polymer adhesives prepared in examples 1 and 2 of the present invention. Wherein A is a schematic drawing of a tensile property curve of the supramolecular polymer adhesive, and B is a schematic drawing of the supramolecular polymer adhesive. As can be seen from the figure, the supramolecular polymer adhesive prepared in example 1 of the present invention has a young's modulus increased 243 times and a tensile rate of 300% compared to the lipoic acid thermopolymer prepared in example 1 (which is a product before the illumination of example 1); the supramolecular polymer adhesive prepared in example 2 of the present invention has young's modulus improved 960 times and elongation 670% compared to the lipoic acid thermopolymer prepared in example 2 (which is a product before the illumination of example 2). The above shows that the supramolecular polymer adhesive prepared by the invention has high strength and excellent extensibility.
Adhesion performance test:
the two ends of the substrate of the prepared supramolecular polymer adhesive are placed on a tension machine clamp, and are sheared and stretched at the speed of 100mm/min to obtain the shearing strength, namely the adhesive strength, as shown in fig. 7, and fig. 7 is a schematic diagram of the adhesive performance of the supramolecular polymer adhesive prepared in the embodiment 6 of the invention. Wherein, A is a graph comparing the adhesion performance of the supramolecular polymer adhesive and commercial adhesives (acrylic resin, silica gel, polyurethane, polyvinyl acetate, epoxy resin, cyanoacrylate) on different surfaces, and B is a schematic diagram of a substrate lifting weight adhered by the supramolecular polymer adhesive. As can be seen from the figure, the supramolecular polymer adhesive of the present invention has higher adhesive strength on different surfaces compared to commercial adhesives (acrylic, silicone, polyurethane, polyvinyl acetate, epoxy, cyanoacrylate), which has adhesive strength as high as 11.691MPa on glass surface. Whereas commercial adhesives (e.g., polyvinyl acetate) have good adhesion only on certain surfaces (iron) or generally on all surfaces. The polymer adhesive of the invention can be used for adhering surfaces (1 cm multiplied by 1cm) of glass, iron, copper, wood and polymethyl methacrylate to lift 20kg of weights without breaking and separating, and shows excellent adhesion performance.
Fig. 8 is a schematic diagram of the water resistance of the supramolecular polymer adhesive prepared in example 7 of the invention. Wherein, A is a schematic diagram for comparing the adhesive strength of the supramolecular polymer adhesive after being soaked in air, deionized water, a hydrochloric acid aqueous solution and a sodium chloride aqueous solution for 10 days, and B is a schematic diagram for a time-dependent adhesive strength curve of the supramolecular polymer adhesive after being soaked in the deionized water for 10 days. As can be seen from the figure, the supramolecular polymer adhesive disclosed by the invention has stronger adhesive property after being soaked in deionized water, a hydrochloric acid aqueous solution and a sodium chloride aqueous solution for 10 days, and the adhesive strength is reduced from 12MPa to 3 MPa. The B picture shows that the adhesive strength is gradually reduced along with the soaking time, and is stabilized at 3MPa after soaking for 5 days, thereby proving that the adhesive strength is more stable in water resistance.
And (3) testing the recovery performance:
the surface of the supermolecule polymer adhesive is scratched by a blade, and the supermolecule polymer adhesive is placed at room temperature and 80 ℃ to observe the self-repairing condition of the supermolecule polymer adhesive. The adhered polymer adhesive is heated and depolymerized on a heating plate at 100 ℃, and after being cooled to 20 ℃, the polymer adhesive is irradiated with a visible light source with the wavelength of 420nm for 20min for photopolymerization again to test the adhesive strength of the polymer adhesive, and 10 times of repeated experiments are carried out to test the reversible adhesive property of the polymer adhesive, as shown in fig. 9, and fig. 9 is a schematic diagram of the recycling property of the supramolecular polymer adhesive prepared in the embodiment 8 of the invention. Wherein, A is a schematic diagram of a self-repairing image of the supramolecular polymer adhesive, B is a columnar schematic diagram of 10 times of reversible adhesion performance of the supramolecular polymer adhesive, C is a schematic diagram of an ultraviolet visible absorption spectrum of 5 times of cyclic photopolymerization-thermal depolymerization of the supramolecular polymer adhesive, and D is a schematic diagram of a nuclear magnetic resonance hydrogen spectrum of 5 times of cyclic photopolymerization-thermal depolymerization of the supramolecular polymer adhesive. As can be seen from the figure, the supramolecular polymer adhesive of the invention has good self-repairing performance, and the damage can be basically repaired after being placed for 48 hours at room temperature. The temperature was raised to 80 ℃ and the repair time was 12 hours. Due to the high dynamic and reversibility of the network, the supramolecular polymer adhesive is partially depolymerized at high temperatures, and the adhesion properties are significantly reduced. And (5) illuminating again, carrying out ring opening polymerization again on the dynamic disulfide bond, and recovering the initial value of the adhesion performance. After the supramolecular polymer adhesive is heated and irradiated for 10 times in a circulating manner, the adhesive strength is basically consistent with the initial value, and the reversibility of the polymerization process is proved by an ultraviolet visible absorption spectrum and a nuclear magnetic resonance hydrogen spectrum, so that the supramolecular polymer adhesive prepared by the invention can be recycled without loss of performance.
The invention constructs a high-strength supramolecular polymer adhesive by utilizing natural micromolecular lipoic acid through mild heating and green pollution-free visible light, and the adhesive property of the supramolecular polymer adhesive is superior to that of most commercially available adhesives. In addition, the hydrogen bond network with compact high dynamic property of the sulfur main chain endows the adhesive with ideal mechanical property, adhesion property and recovery property, so that the adhesive has the basic conditions of an intelligent adhesive and is expected to be applied to the fields of reversible wound dressing, flexible actuators, aerospace and the like.
Comparative example 1
Preparation of the product: heating 2g of lipoic acid to 120 ℃, stirring for 5min for melting, then adding 1g of a cross-linking agent DIB, stirring for 5min, finally adding 5mL of an acetone solution of 0.1g/mL of ferric chloride serving as a metal ion source, stirring for 5min, stopping heating after the reaction is finished, using a liquid-moving gun to move 50 mu L of molten liquid while the molten liquid is hot, moving the molten liquid to a glass substrate with the adhesive area of 1cm x 1cm, and using another glass substrate to carry out hot pressing on the lipoic acid thermopolymer adhesive with the thickness of 50 mu m.
The performance test data is shown in table 2:
table 2: adhesive strength (MPa) of example 1 and comparative example 1 on different surfaces
| Glass | Iron | Copper (Cu) | Polymethyl methacrylate | Wood (Woods) | Polytetrafluoroethylene | |
| Example 1 | 19.486 | 8.764 | 6.461 | 2.106 | 1.534 | 0.848 |
| Comparative example 1 | 0.193 | 0.191 | 0.030 | 0.069 | 0.079 | 0.012 |
The product of the application has the advantages that: the product preparation of the application only needs one more step of photopolymerization with the wavelength of 300-450nm, and the adhesive strength on different surfaces can be greatly improved (compared with the product prepared by the comparative example 1, the adhesive strength is improved by 19-215 times).
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (7)
1. A preparation method of a photocrosslinking dynamic reversible supramolecular polymer adhesive based on a lipoic acid micromolecular compound is characterized by comprising the following steps:
heating lipoic acid or lipoic acid derivatives to 70-200 ℃, stirring for 2-10 min to melt, adding a cross-linking agent, stirring for 2-10 min, finally adding a metal ion source, stirring for 2-10 min, wherein the molar ratio of the lipoic acid or the lipoic acid derivatives to the cross-linking agent to the metal ion source is 1 (0.01-1.5) to (0.01-1), the molar number of the metal ion source is calculated by the molar number of the metal ions, stopping heating after the reaction is finished, moving 30-100 mu L of molten liquid to a substrate while the molten liquid is hot, performing hot pressing on the substrate to obtain a thermopolymer with the thickness of 45-55 mu m, and irradiating the thermopolymer for 20-60 min by using an ultraviolet-visible light source with the wavelength of 300-450nm to obtain a target object;
the metal ion source consists of metal inorganic salt and an organic solvent capable of dissolving the metal inorganic salt, wherein the metal inorganic salt is at least one of ferric chloride, copper sulfate, zinc chloride, vanadium chloride, titanium chloride, cobalt chloride and nickel chloride, and the organic solvent is at least one of acetone, tetrahydrofuran, ethanol or methanol;
the crosslinking agent is styrene, divinyl benzene or 1, 3-di (1-methylvinyl) benzene;
the structure of the lipoic acid or the lipoic acid derivatives is shown as a formula I:
in the formula I, R1Is hydrogen or C1-C4 straight chain or branched chain alkyl, R2Is hydrogen or carboxyl, and n is an integer of 1 to 5.
2. The method of claim 1, wherein said lipoic acid or lipoic acid derivative is lipoic acid or lipoic acid.
3. The method of claim 1 or 2, wherein the molar ratio of the lipoic acid or lipoic acid derivatives, the cross-linking agent and the metal ion source is 1 (0.15-1.45) to 0.01-0.15.
4. The method according to claim 1, wherein the concentration of the metal ion source is 0.01g/mL to 1 g/mL.
5. The method of claim 1, wherein the substrate is at least one of glass, iron, copper, wood, polymethyl methacrylate, and polytetrafluoroethylene.
6. The method of claim 1, wherein the substrate has an area of 1cm x 1 cm.
7. The method of claim 1, wherein the thickness of the thermopolymer is 50 μm.
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| CN113501967B (en) * | 2021-08-06 | 2022-02-15 | 湖南大学 | Supermolecule polymer and preparation method and application thereof |
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| CN114605960B (en) * | 2022-03-23 | 2023-07-28 | 东南大学 | Reversible photothermal response adhesive, preparation method and application thereof |
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| CN115581808B (en) * | 2022-11-29 | 2023-08-18 | 郑州大学 | Method for preparing copper poly-lipoic acid coating on surface of cardiovascular and cerebrovascular stent material and cardiovascular and cerebrovascular stent material containing same |
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