CN113372532A - Preparation method of heatable and near-infrared light-controlled self-healing polyurethane elastomer - Google Patents
Preparation method of heatable and near-infrared light-controlled self-healing polyurethane elastomer Download PDFInfo
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- 229920003225 polyurethane elastomer Polymers 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 32
- JGUQDUKBUKFFRO-CIIODKQPSA-N dimethylglyoxime Chemical compound O/N=C(/C)\C(\C)=N\O JGUQDUKBUKFFRO-CIIODKQPSA-N 0.000 claims abstract description 23
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229920000909 polytetrahydrofuran Polymers 0.000 claims abstract description 17
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 11
- 229920000642 polymer Polymers 0.000 claims description 40
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- 238000004132 cross linking Methods 0.000 claims description 9
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- 239000007795 chemical reaction product Substances 0.000 claims description 7
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- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 239000011259 mixed solution Substances 0.000 abstract 2
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 abstract 1
- 239000000463 material Substances 0.000 description 33
- 229920002939 poly(N,N-dimethylacrylamides) Polymers 0.000 description 18
- 229920006311 Urethane elastomer Polymers 0.000 description 8
- 238000012512 characterization method Methods 0.000 description 8
- 239000004020 conductor Substances 0.000 description 7
- 239000002861 polymer material Substances 0.000 description 6
- 229920002635 polyurethane Polymers 0.000 description 5
- 239000004814 polyurethane Substances 0.000 description 5
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 4
- 230000033228 biological regulation Effects 0.000 description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
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- AJUHJMMNWVKCER-UHFFFAOYSA-N 2-(2-phenylphenyl)aniline Chemical compound NC1=CC=CC=C1C1=CC=CC=C1C1=CC=CC=C1 AJUHJMMNWVKCER-UHFFFAOYSA-N 0.000 description 1
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
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- 150000002513 isocyanates Chemical class 0.000 description 1
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- 229910001338 liquidmetal Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
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- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
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- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
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Abstract
The invention discloses a preparation method of a heatable and near-infrared light-controlled self-healing polyurethane elastomer, which takes dimethylglyoxime, polytetrahydrofuran ether glycol and diphenylmethane diisocyanate as raw materials to carry out prepolymerization reaction to obtain a prepolymer mixed solution. Then, triphenylamine (ACAT) is added to the prepolymer mixed solution, and photo-thermal active groups are efficiently introduced through a repolymerization reaction. Meanwhile, the relation among the mechanical property, the photothermal effect and the healing property of the elastomer is explored by regulating and controlling the monomer structure and the component proportion, so that the novel intelligent polyurethane elastomer is prepared, and the specific application of the elastomer as a stretchable and light-controlled healing electronic conductor is shown.
Description
Technical Field
The invention belongs to the field of light-operated self-healing elastomers, and particularly relates to a preparation method of a heating and near-infrared light-operated self-healing polyurethane elastomer.
Background
In the use process of the polyurethane elastomer, the service life of the polyurethane elastomer is shortened due to the damage of environmental factors (such as abrasion, tearing, scratching and the like), the maintenance cost is increased, and the application range is limited. Damaged polymers have traditionally been repaired by welding or repair methods, but these methods are limited to repairing macroscopic damage and are not immediate and rely on human inspection. Therefore, with the demands of people on improving the reliability and resource utilization efficiency of materials and prolonging the service life of materials, self-healing polymer materials imitating the capability of life systems become an important research field in recent years. The self-healing polymer material can be self-diagnosed and repaired after being damaged, so that the service life and the safety of the material are improved, the cost of maintaining the material is reduced, the generation of wastes is reduced, and the sustainable development is reflected. Therefore, after decades of development, self-healing materials have been widely applied in the fields of artificial muscles, energy storage devices, self-healing coatings, wearable electronic devices, and the like.
There are two main methods for obtaining self-healing polymers. According to the repair mechanism of the polymer, the method can be divided into two methods of external self-repair and intrinsic self-repair. First, the self-healing type of external application disperses microcapsules or microfluids capable of storing and releasing healing agents into a polymeric material through a network to repair damaged cracks. Secondly, the intrinsic self-repairing realizes self-healing through the reconstruction of chemical bonds of the material, and theoretically can realize the repeatable chemical structure reconstruction of the same damaged part. Reversible covalent bonds or non-covalent bonds are introduced into the high molecular material to form the intrinsic self-healing polymer. Of these two approaches, intrinsic self-healing polymers are receiving increasing attention due to the lack of introduction of external materials and the ease with which multiple repairs can be achieved.
Diels-Alder dynamic bonds were first introduced into polyurethane systems to achieve self-healing, but generally require temperatures above 100 ℃. In addition to thermal initiation, photo-initiation is also an effective means of constructing self-healing polyurethane materials. Heating the material in space and time, light is the most popular way and the photo-induced temperature rise can be adjusted by adjusting the light intensity. At present, the development of novel materials based on the dynamics of the intrinsic photo-healing polyurethane elastomer, particularly the urethane bond based on the polyurethane core structure, has important practical significance.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: how to provide a preparation method of a self-healing polyoxime urethane elastomer capable of being heated and controlled by near infrared light.
The technical scheme of the invention is as follows: a preparation method of a heatable and near-infrared light-controlled self-healing polyurethane elastomer is characterized in that triphanylamine, dimethylglyoxime, polytetrahydrofuran ether glycol and diphenylmethane diisocyanate are used as raw materials, and the preparation method is obtained through polymerization reaction under the protection of nitrogen.
Further, the molar ratio of the polyaniline, the dimethylglyoxime, the polytetrahydrofuran ether glycol and the diphenylmethane diisocyanate is as follows: (0.2-1): 3-3.8): 4: 9. The preferred molar ratio is: 0.8: 3.2: 4: 9.
Further, the steps are as follows:
(1) adding polytetrahydrofuran ether glycol into a reaction vessel, heating to (100-;
(2) cooling the reaction system to 65-75 ℃, removing vacuum under the condition of ensuring nitrogen atmosphere, inserting a nitrogen balloon, dissolving dimethylglyoxime by using an organic solvent, adding the dissolved dimethylglyoxime into a reaction container, slowly adding diphenylmethane diisocyanate into the reaction container, adding the raw materials, uniformly mixing the whole reaction system, and prepolymerizing the whole reaction system for 2-3 hours at the temperature of 65-75 ℃ under the stable condition of nitrogen atmosphere;
(3) dissolving monomer polyaniline with organic solvent, adding into reaction system, and reacting at 65-75 deg.C under nitrogen atmosphere for 20-24 h;
(4) dropwise adding the reaction product solution into a container containing excessive ethyl ether, and continuously stirring to obtain a black polymer;
(5) and (3) putting the polymer in a vacuum drying oven, and performing vacuum crosslinking for 20-24 h at the temperature of 45-55 ℃ to obtain the polymer.
Further, the steps are as follows:
(1) adding polytetrahydrofuran ether glycol into a reaction container, heating to 110 ℃, vacuumizing and stirring to ensure that a reaction system is at 110 ℃ and in a vacuum state for 2 hours;
(2) cooling the reaction system to 70 ℃, removing vacuum under the condition of ensuring nitrogen atmosphere, inserting a nitrogen balloon, dissolving dimethylglyoxime by using an organic solvent, adding the dissolved dimethylglyoxime into a reaction container, slowly adding diphenylmethane diisocyanate into the reaction container, adding the raw materials, uniformly mixing the whole reaction system, and prepolymerizing the whole reaction system for 2 hours under the stable condition of 70 ℃ and the nitrogen atmosphere;
(3) dissolving a monomer of polyaniline in an organic solvent, adding the solution into a reaction system, and reacting the whole reaction system at 70 ℃ for 24 hours in a nitrogen atmosphere;
(4) dropwise adding the reaction product solution into a container containing excessive ethyl ether, and continuously stirring to obtain a black polymer;
(5) and (3) putting the polymer in a vacuum drying oven, and vacuumizing and crosslinking for 24 hours at the temperature of 50 ℃ to obtain the polymer.
Further, the organic solvent in the step (1) is N, N-dimethylformamide.
The invention introduces the trimeric aniline (ACAT) with the photothermal effect into a polyurethane system containing dimethylglyoxime, and prepares a series of different light healing polyurethane elastomers by regulating and controlling the component proportion. The system forms a cross-linked Polymer (PDMA), which improves the mechanical properties of the polymer material. The PDMA-2 polymer is healed for 2 h at 100 ℃, and the tensile strength and the elongation at break of the material are respectively recovered to the initial 40.71 +/-1.60 percent and 25.60 +/-8.91 percent. The light-operated self-healing performance of the PDMA is studied, and after the fracture of the material is irradiated by near infrared light for 3 min, the tensile strength is recovered to 56.36 +/-2.25%, and the elongation at break is recovered to 83.34 +/-2.10%. Comparing the heating and light-operated self-healing results, the polymer PDMA-2 can be clearly found to have better healing performance under the irradiation of near infrared light for 3 min. Through comparing high temperature heating material and light-operated promotion material intensification, light-operated self-healing need not heat the material is whole, because high temperature heating time is too long, this can reduce the wholeness ability of material. Based on the advantages of photo-controlled self-healing, stretchable and photo-controlled healing electronic conductors were prepared for specific applications as polymers.
Compared with the prior art, the invention has the following beneficial effects:
the invention develops the photo-healing dynamic oxime urethane elastomer with near-infrared thermal effect by reacting the polyaniline, the dimethylglyoxime, the polytetrahydrofuran diol and the diphenylmethane diisocyanate. Meanwhile, the relation among the mechanical property, the photothermal effect and the healing property of the elastomer is explored by regulating and controlling the monomer structure and the component proportion, so that the novel intelligent polyurethane elastomer is prepared.
Drawings
FIG. 1 is a graph of attenuated Total reflectance-Fourier Infrared Spectroscopy (ATR-FTIR) characterization of PDMA polymers at various ratios;
FIG. 2 is a photo-thermal property characterization of a polyurethane-oxime elastomer;
FIG. 3 is a mechanical property characterization of PDMA polymers in different proportions;
FIG. 4 is a representation of healing of a polyurethane elastomer under different temperature conditions;
FIG. 5 is a representation of the healing of the polyurethane elastomers under different light conditions.
Detailed Description
The experimental procedures in the following examples are conventional unless otherwise specified. The test materials used in the following examples were all commercially available unless otherwise specified.
(1) Synthesis of Polyoxime urethane Elastomers
Example 1
Polytetrahydrofuran ether glycol (PTMG) was added to a three-neck flask, the temperature was raised to 110 ℃, vacuum was started, and the stirrer was started. The whole system is kept at 110 ℃ and in a vacuum state for 2 h, and the absorbed water in the polytetrahydrofuran ether glycol can be fully removed. The reaction system was cooled to 70 ℃, the vacuum was removed and a nitrogen balloon was inserted while maintaining the nitrogen atmosphere. The dimethylglyoxime was dissolved in N, N-Dimethylformamide (DMF) as a solvent, and then added to a three-necked flask, followed by slowly dropping diphenylmethane diisocyanate (MDI) in the three-necked flask. After the raw materials are added and the whole system is uniformly mixed, the whole system is prepolymerized for 2 h under the stable condition of 70 ℃ and nitrogen atmosphere. Finally, monomer triamiline (ACAT) is dissolved in N, N-Dimethylformamide (DMF) and then added into a three-neck flask, so that the whole system reacts for 24 hours at 70 ℃ under the nitrogen atmosphere. The reaction product solution was added dropwise to a beaker containing an excess of diethyl ether, and stirred continuously to obtain a large amount of black polymer. And (3) putting the polymer in a vacuum drying oven, and vacuumizing and crosslinking for 24 hours at the temperature of 50 ℃. The reaction formula is as follows:
example 2
Polytetrahydrofuran ether glycol (PTMG) was added to a three-neck flask, the temperature was raised to 100 ℃, vacuum was started, and the stirrer was started. The whole system is kept at 100 ℃ and in a vacuum state for 3 hours, and the absorbed water in the polytetrahydrofuran ether glycol can be fully removed. The reaction system was cooled to 65 ℃, the vacuum was removed and a nitrogen balloon was inserted while maintaining the nitrogen atmosphere. The dimethylglyoxime was dissolved in N, N-Dimethylformamide (DMF) as a solvent, and then added to a three-necked flask, followed by slowly dropping diphenylmethane diisocyanate (MDI) in the three-necked flask. After the raw materials are added and the whole system is uniformly mixed, the whole system is prepolymerized for 3 hours under the stable condition of 65 ℃ and nitrogen atmosphere. Finally, monomer triamiline (ACAT) is dissolved in N, N-Dimethylformamide (DMF) and then added into a three-neck flask, so that the whole system reacts for 22 hours at the temperature of 65 ℃ under the nitrogen atmosphere. The reaction product solution was added dropwise to a beaker containing an excess of diethyl ether, and stirred continuously to obtain a large amount of black polymer. And (3) putting the polymer in a vacuum drying oven, and vacuumizing and crosslinking for 20 hours at the temperature of 45 ℃.
Example 3
Polytetrahydrofuran ether glycol (PTMG) was added to a three-neck flask, the temperature was raised to 120 ℃, vacuum was started, and the stirrer was started. The whole system is kept at 120 ℃ and in a vacuum state for 1.5 h, and the absorbed water in the polytetrahydrofuran ether glycol can be fully removed. The reaction system was cooled to 75 ℃, the vacuum was removed and a nitrogen balloon was inserted while maintaining the nitrogen atmosphere. The dimethylglyoxime was dissolved in N, N-Dimethylformamide (DMF) as a solvent, and then added to a three-necked flask, followed by slowly dropping diphenylmethane diisocyanate (MDI) in the three-necked flask. After the raw materials are added and the whole system is uniformly mixed, the whole system is prepolymerized for 2.5 h under the stable condition of 75 ℃ and nitrogen atmosphere. Finally, monomer triamiline (ACAT) is dissolved in N, N-Dimethylformamide (DMF) and then added into a three-neck flask, so that the whole system reacts for 24 hours at the temperature of 75 ℃ under the nitrogen atmosphere. The reaction product solution was added dropwise to a beaker containing an excess of diethyl ether, and stirred continuously to obtain a large amount of black polymer. And (3) putting the polymer in a vacuum drying oven, and vacuumizing and crosslinking for 23 h at the temperature of 48 ℃.
(2) The polyurethane elastomers with different raw material ratios are as follows:
the preparation of the polyurethane elastomer was carried out as in example 1. The dimethylglyoxime and the monomer ACAT are added into corresponding polyurethane system according to different proportions (shown in table 1) for polymerization to obtain a reacted polyurethane elastomer solution. The solution is firstly dripped into a tetrafluoro beaker filled with anhydrous ether, black polyurethane elastomer is arranged at the bottom of the tetrafluoro beaker, and the tetrafluoro beaker is washed for several times by using the anhydrous ether. The polymer was placed in a vacuum oven at 50 ℃ and crosslinked under vacuum (degree of vacuum: 1 Torr) for 24 hours, and then taken out.
Table 1 raw materials in different proportions
a=PTMG:DMG:MDI:ACAT
(3) Structural characterization results of the polyoxime urethane elastomers:
FIG. 1 shows attenuated Total reflectance-Fourier Infrared Spectroscopy (ATR-FTIR) characterization results of different proportions of a polyurethane elastomer. Typically in the infra-red spectrum, 2270 cm-1The signal peak at (a) is an asymmetric stretching vibration peak of-N = C = O in isocyanate. In the final product, the peak of-N = C = O in the polymer infrared spectrum disappeared and newly occurred at 3513 cm-1And 1673 cm-1Are the stretching vibration peaks of N-H and C = O in the urethane group, respectively. In addition, 1092cm in the product-1The absorption peak is N-O, which indicates that Dimethylglyoxime (DMG) is successfully introduced and oxime carbamate bonds are effectively formed. The structure in the infrared spectrum is consistent with the designed polymer molecular structure, which indicates that the PDMA is successfully synthesized.
(4) Characterization of photothermal properties of the polyoxime urethane elastomers:
the irradiation intensity of near infrared light at 808 nm is 0.5, 0.75, 1.0, 1.25, 1.5, 1.75W/cm2In the time, the PDMA polymer chain segment contains a photothermal effect unit ACAT, and the temperature of the polymer is rapidly increased from 21 ℃ to 40 ℃, 60 ℃, 80 ℃, 100 ℃ and 110 ℃ respectively in 10 s. After the irradiation time was prolonged to more than 50 s, the surface temperatures each tended to stabilize (fig. 2). The Polymer (PDMA) is sensitive to temperature change under the irradiation of near infrared light with wavelength of 808 nm, and has good light absorption efficiency. Therefore, in the following experiment, the selected light was 1.25W/cm2The intensity of the light irradiates the material to promote the healing of the material. The operation is convenient and the time is short through the regulation and control of near infrared light, the whole performance of the material is not reduced during the light-operated healing, and the service life of the material can be prolonged.
(5) Characterization of mechanical properties of the polyoxime urethane elastomer:
the mechanical properties of PDMA at different ratios were characterized by uniaxial tensile test mode using a universal tensile machine (table 2, fig. 3). The results show that the stress-strain curve is similar to that of a rubber-based elastomer. Under small strain conditions, PDMA exhibits elastic deformation with a gradually increasing ratio of stress to strain. From the stress-strain curve, it can be seen that when the amount of the monomeric ACAT added is small, the material is plastically deformed at this time, exhibiting strain softening. Finally at higher strains, the curves exhibit strain hardening behavior due to the orientation of the molecular chains.
As can be seen from fig. 3, the elongation at break of polymer PDMA decreases with increasing amount of melamine added. The tensile strength of PDMA increased from 8.05 MPa to 12.53 MPa when the ACAT addition in PDMA increased from 0.059 g to 0.23 g. This is probably because the added monomer ACAT cross-links in the system, with moderate cross-linking increasing the intermolecular interactions. However, too much crosslinking (e.g., PDMA-1) may adversely degrade the mechanical properties of the system.
TABLE 2 mechanical properties of PDMA obtained by reactions at different ratios
(6) Characterization of self-healing performance of the polyoxime urethane elastomer:
as shown in fig. 4, the polymer PDMA-2 exhibited some room temperature self-healing properties. After healing for 2 hours at room temperature of 25 ℃, the breaking elongation of the healed sample strip reaches 44.21 +/-3.10 percent, and the tensile strength reaches 18.11 +/-2.80 percent. The reason that the self-healing at room temperature is only partially recovered is that the polymer is added with the terphenylamine (ACAT) to be crosslinked with the diphenylmethane diisocyanate in the system, so that a space-network chain structure is formed, the mobility of the chain is reduced, the polymer chain of the section is difficult to move fully, enough oxime urethane bonds cannot be formed in time, and the elongation at break and the tensile strength are difficult to recover to the initial level.
The kinetic capacity of the polymer chain and the dynamic exchange rate of the oxime urethane bond can be improved by heating, so that the healing effect of the material is effectively improved. As shown in figure 4, after the heating and healing are carried out for 2 hours at 100 ℃, the tensile strength of the healed sample strip is recovered to 40.71 +/-1.60 percent, the elongation at break is recovered to 25.60 +/-8.90 percent, and the experimental result shows that the PDMA has self-healing performance under the heating condition.
The light intensity used was 1.25W/cm2Irradiating the splicing opening of the fracture surface by near infrared light (808 nm), respectively irradiating for 2 min and 3 min, waiting for the irradiated sample strip to be cooled to room temperature, and comparing the mechanical properties of the cut-light self-healing sample strip and the uncut sample strip. As shown in fig. 5, the PDMA showed a certain self-healing property under irradiation of near infrared light for two minutes. The illumination intensity in use is 1.25W/cm2After the healing sample band is irradiated by near infrared light for healing for 2 min, the recovery rate of the elongation at break of the healed sample band reaches 48.07 +/-2.70 percent, and the recovery rate of the tensile strength reaches 34.40 +/-2.55 percent. As shown in FIG. 5, after the material is irradiated with near infrared light at the breaking point for 3 min, the tensile strength is recovered to 56.36 + -2.25%, and the elongation at break is recovered to 83.34 + -2.10%. Experimental results show that the PDMA has self-healing performance under heating condition and near infrared light irradiation. Comparing the heating and light-operated self-healing results, the polymer PDMA-2 can be clearly found to have better healing performance under the irradiation of near infrared light for 3 min. This indicates that light can be localizedThe healing of the material is controlled remotely, so that the self-healing is realized through near infrared light regulation after the material is damaged and fails in the using process, the operation is simple, and the time is short. The mode does not reduce the overall performance of the material, and the service life of the material can be prolonged.
(7) Applications of the polyoxime urethane elastomers demonstrate:
scalable and self-healing electronic conductor materials are ideal materials for emerging bio-integrated electronics, but are still a great challenge. The healing process of electronic conductors usually requires an external energy input, such as heat or laser, which is not friendly to the human body. By way of illustration, we prepared a stretchable and photo-healing PDMA/liquid metal composite conductor sensor. The PDMA polymer is hot pressed into film, rolled into small cylinder, added with Ga-in-Sn eutectic alloy, connected with battery, lead, bulb, etc. After the power is turned on, the bulb becomes bright. After the conductor formed by the polymer coating is cut from the middle, the lamp is extinguished. Lightly butt-jointing the conductors formed by the polymers together, and the passing strength is 1.25W/cm2The fracture surface of the polymer material is irradiated by near infrared light (808 nm), the polymer material is quickly self-healed, and the bulb becomes bright again. After irradiating the fracture surface for 3 min, the conductor was stretched and the bulb was still lit. The self-healing of the conductor is realized through near infrared light regulation, and the polymer material conductor subjected to the light-operated self-healing is stretched, so that the elongation of the conductor in the above example can reach 240%. The excellent performance provides convenience for healing of damaged critical materials of the biological integrated circuit, and widens the application of the biological integrated circuit in some special environments.
Claims (6)
1. The preparation method of the heatable and near-infrared light-controlled self-healing polyurethane elastomer is characterized in that the polyurethane elastomer is prepared by taking polyaniline, dimethylglyoxime, polytetrahydrofuran ether glycol and diphenylmethane diisocyanate as raw materials and carrying out polymerization reaction under the protection of nitrogen.
2. The method according to claim 1, wherein the molar ratio of the polyaniline, the dimethylglyoxime, the polytetrahydrofuran ether glycol and the diphenylmethane diisocyanate is as follows: (0.2-1): 3-3.8): 4: 9.
3. The method according to claim 1, wherein the preferred molar ratio of the polyaniline, dimethylglyoxime, polytetrahydrofuran ether glycol and diphenylmethane diisocyanate is: 0.8: 3.2: 4: 9.
4. The preparation method according to any one of claims 1to 3, characterized by comprising the following specific steps:
(1) adding polytetrahydrofuran ether glycol into a reaction vessel, heating to (100-;
(2) cooling the reaction system to 65-75 ℃, removing vacuum under the condition of ensuring nitrogen atmosphere, inserting a nitrogen balloon, dissolving dimethylglyoxime by using an organic solvent, adding the dissolved dimethylglyoxime into a reaction container, slowly adding diphenylmethane diisocyanate into the reaction container, adding the raw materials, uniformly mixing the whole reaction system, and prepolymerizing the whole reaction system for 2-3 hours at the temperature of 65-75 ℃ under the stable condition of nitrogen atmosphere;
(3) dissolving monomer polyaniline with organic solvent, adding into reaction system, and reacting at 65-75 deg.C under nitrogen atmosphere for 20-24 h;
(4) dropwise adding the reaction product solution into a container containing excessive ethyl ether, and continuously stirring to obtain a black polymer;
(5) and (3) putting the polymer in a vacuum drying oven, and performing vacuum crosslinking for 20-24 h at the temperature of 45-55 ℃ to obtain the polymer.
5. The preparation method according to claim 4, comprising the following steps:
(1) adding polytetrahydrofuran ether glycol into a reaction container, heating to 110 ℃, vacuumizing and stirring to ensure that a reaction system is at 110 ℃ and in a vacuum state for 2 hours;
(2) cooling the reaction system to 70 ℃, removing vacuum under the condition of ensuring nitrogen atmosphere, inserting a nitrogen balloon, dissolving dimethylglyoxime by using an organic solvent, adding the dissolved dimethylglyoxime into a reaction container, slowly adding diphenylmethane diisocyanate into the reaction container, adding the raw materials, uniformly mixing the whole reaction system, and prepolymerizing the whole reaction system for 2 hours under the stable condition of 70 ℃ and the nitrogen atmosphere;
(3) dissolving a monomer of polyaniline in an organic solvent, adding the solution into a reaction system, and reacting the whole reaction system at 70 ℃ for 24 hours in a nitrogen atmosphere;
(4) dropwise adding the reaction product solution into a container containing excessive ethyl ether, and continuously stirring to obtain a black polymer;
(5) and (3) putting the polymer in a vacuum drying oven, and vacuumizing and crosslinking for 24 hours at the temperature of 50 ℃ to obtain the polymer.
6. The method according to claim 5, wherein the organic solvent in the step (1) is N, N-dimethylformamide.
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