CN109575230B - Preparation method and application of multifunctional polyurethane derivative - Google Patents
Preparation method and application of multifunctional polyurethane derivative Download PDFInfo
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Abstract
The invention relates to a preparation method and application of a multifunctional polyurethane derivative. The invention aims to solve the problem that the existing multifunctional material has few functional types. The invention firstly synthesizes two monomers of triphenylamine and tert-butyl substituted triphenylamine and 1, 2-bis (4-hydroxyphenyl) -1, 2-diphenylethene containing a hydroxyl structure, and simultaneously introduces 4, 4' -diphenylmethane diisocyanate, and the triphenylamine is prepared by means of copolymerization. The material has electrochromic and fluorescence sensing hole transmission functions, and can be used as automobile rearview mirror materials and display materials; and can be used for preparing explosive detection and memory performance devices. The invention is applied to the field of multifunctional materials.
Description
Technical Field
The invention relates to a multifunctional polyurethane derivative and a preparation method and application thereof.
Background
Polyurethanes (PU) have many desirable properties, such as better flexibility, greater tensile strength, greater hardness, greater resistance to chemical solvents and temperature conditions, greater abrasion resistance, greater oil resistance, and longer fatigue life. Polyurethanes are also potential candidates for film preparation due to good mechanical and chemical properties. Although the polyurethane has excellent comprehensive performance, the traditional PU has some defects, such as high processing difficulty, poor solubility and the like, which greatly limits the application of the polyurethane material in industry. Therefore, in recent years, more and more researchers are concerned about the research on the preparation and modification of polyurethane and the application of related materials.
Multifunctional materials are rapidly evolving by virtue of their excellent capabilities for use in sensors, actuators, memory devices and high contrast displays. External stimuli such as chemicals, acids and bases, temperature, light and electricity can change the chemical or physical properties of these materials. A common method for preparing multi-stimulus responsive materials is to introduce groups with special functions and sensitivity on the same molecular skeleton. In the last decade, despite great advances in this area, the simultaneous synthesis of polymers with more than three functions remains a challenge.
Disclosure of Invention
The invention provides a multifunctional polyurethane derivative and a preparation method and application thereof, aiming at solving the problem that the existing multifunctional material has few functional types.
The multifunctional polyurethane derivative is a multifunctional polyurethane derivative containing triphenylamine and tetraphenylethylene groups or a multifunctional polyurethane derivative containing tert-butyl substituted triphenylamine and tetraphenylethylene groups;
wherein the structural formula of the multifunctional polyurethane derivative containing triphenylamine and tetraphenylethylene groups is as follows:
the structural formula of the multifunctional polyurethane derivative containing tert-butyl substituted triphenylamine and tetraphenylethylene groups is as follows:
wherein n is an integer of 3 to 10.
The preparation method of the multifunctional polyurethane derivative comprises the following steps: mixing 1, 2-bis (4-hydroxyphenyl) -1, 2-diphenylethylene and 4, 4' -diphenylmethane diisocyanate with a solvent N, N-dimethylacetamide, and stirring and refluxing for 5-15h at the room temperature at the stirring speed of 800-900 r/min to obtain a precursor; secondly, adding a diamine monomer containing triphenylamine or tert-butyl substituted triphenylamine into the precursor prepared in the first step, heating to 70-120 ℃, stirring and refluxing for 5-15h, cooling, pouring into methanol, filtering, and vacuum-drying the obtained solid phase to obtain the multifunctional polyurethane derivative containing triphenylamine or tert-butyl substituted triphenylamine and tetraphenylethylene groups with aggregation-induced emission properties;
wherein the molar ratio of the diamine monomer containing triphenylamine or tert-butyl substituted triphenylamine, 1, 2-bis (4-hydroxyphenyl) -1, 2-diphenylethylene and 4, 4' -diphenylmethane diisocyanate is (0.5-2.5) to 1: 2;
the volume mass ratio of the N, N-dimethylacetamide solvent to the diamine monomer containing triphenylamine or tert-butyl substituted triphenylamine is (10-30) mL (0.5-2.5 g).
The invention relates to application of a multifunctional polyurethane derivative as an electrochromic material.
The invention relates to application of a multifunctional polyurethane derivative as an electroluminescent fluorescent material.
The invention relates to application of a multifunctional polyurethane derivative as an explosive detection material.
The invention has the beneficial effects that:
the triarylamine groups with destroyed accumulation performance are introduced into the polyurethane structure, so that the high thermal stability of the original polyurethane can be maintained, the solubility of the triarylamine groups can be increased, the film forming capability is enhanced, the manufacturing of a large-area thin film electrochromic device is facilitated, and an electroactive center is provided to promote the treatment and application of the electrochromic device; tetraphenylethylenes (TPEs) containing four rotatable phenyl rings have been well developed for their Aggregation Induced Emission (AIE) activity. TPE derivatives can overcome the problem of quenching (ACQ) caused by aggregation of conventional organic luminophores, which greatly facilitates their various applications in bioprobes, chemical sensing and optoelectronic devices. The polyurethane derivative prepared by the invention takes the propeller type triarylamine as a monomer, can effectively reduce the strong acting force between polymer molecular chains, increases the solubility of the polymer, and simultaneously the triarylamine is easy to form the triarylamine with cationic free radicals which are different from a neutral state. The multifunctional polyurethane derivative containing electroactive triphenylamine or tert-butyl substituted triphenylamine and tetraphenylethylene group with aggregation-induced emission performance has high-temperature resistance, is generally decomposed at a temperature of more than 350 ℃ in a nitrogen atmosphere, and is suitable for being used in devices. The multifunctional polyurethane derivative material containing triphenylamine or triphenylamine containing tert-butyl substitution and tetraphenylethylene group with aggregation-induced emission property is prepared into a film, so that the film does not have large aggregation phenomenon and breakage phenomenon on an ITO substrate, and also shows good wetting capability on the ITO substrate. This means that the multifunctional polyurethane derivative material has good film forming characteristics and can be used to make a large-area thin film. After voltage is applied, the transmittance of the film can still reach 50%, the transparency is good, and the polymer film can keep good stability of the circulating ring in the voltage application process, can be circulated for more than 20 times and has unchanged transparency.
The multifunctional polyurethane derivative containing triphenylamine or triphenylamine containing tert-butyl substitution and tetraphenylethylene group with aggregation-induced emission performance has the following advantages in practical application that (1) the multifunctional polyurethane derivative has good electrochemical redox reversibility and can still keep reversibility after dozens of redox cycles; (2) the response time of color change is fast, and the color can be changed rapidly within 2 seconds after voltage is applied; (3) the change in color is reversible; (4) the color change sensitivity is high; (5) the cycle life is longer; (6) the color-changing material has a storage memory function, can be stably kept in an original state or a state after color changing before and after response, can be maintained for months to years after color changing, and can be kept unchanged for half a year after electrochromism in the experiment; (7) the material has better color change before and afterGood chemical stability, and can exist stably in the air at normal temperature and normal pressure. (8) Has response to explosive TNT and picric acid, and has detectable concentration of 1 × 10 for both picric acid and TNT-12mol/L, good sensitivity. (9) The fluorescence switch has good electroluminescent property, the fluorescence intensity of the fluorescence switch can be quenched in the process of applying voltage, the contrast ratio of the fluorescence switch can reach more than 100, and the fluorescence switch has great application potential in the aspects of intelligent photoelectricity and sensors. (10) Has good photoelectric response capability and keeps stable in the process of 500s of circulation.
In conclusion, the multifunctional polyurethane derivative containing triphenylamine or triphenylamine with tert-butyl substitution and tetraphenylethylene has 10 functions.
Drawings
FIG. 1 is a hydrogen nuclear magnetic spectrum of a multifunctional polyurethane derivative containing triphenylamine and tetraphenylethylene groups prepared in the first example;
FIG. 2 is a cyclic voltammogram of a multifunctional polyurethane derivative containing triphenylamine and tetraphenylethylene groups prepared in example one;
FIG. 3 is a graph of the stability and transmittance of multifunctional polyurethane derivatives containing triphenylamine and tetraphenylethylene groups prepared in example one after voltage application;
FIG. 4 is an electrochromic diagram of a multifunctional polyurethane derivative containing triphenylamine and tetraphenylethylene groups prepared in the first example;
FIG. 5 is an electroluminescent diagram of a multifunctional polyurethane derivative containing triphenylamine and tetraphenylethylene groups prepared in the first example;
FIG. 6 is a graph showing the thermogravimetric curves of the multifunctional polyurethane derivative containing triphenylamine and tetraphenylethylene groups prepared in the first example;
FIG. 7 is an aggregation induction diagram of the multifunctional polyurethane derivative containing triphenylamine and tetraphenylethylene groups prepared in the first example;
FIG. 8 is a diagram showing the detection of picric acid, which is an explosive substance, of a multifunctional polyurethane derivative containing triphenylamine and tetraphenylethylene groups prepared in the first example;
FIG. 9 is a graph showing the detection of explosives TNT of multifunctional polyurethane derivatives containing triphenylamine and tetraphenylethylene groups prepared in example one;
FIG. 10 is a graph showing the memory properties of a multifunctional polyurethane derivative containing triphenylamine and tetraphenylethylene groups prepared in the first example;
FIG. 11 is a graph of the optoelectronic properties of the multifunctional polyurethane derivative containing triphenylamine and tetraphenylethylene groups prepared in the first example;
FIG. 12 is a hydrogen nuclear magnetic spectrum of the multifunctional polyurethane derivative containing tert-butyl substituted triphenylamine and tetraphenylethylene groups prepared in example two;
FIG. 13 is a cyclic voltammogram of the multifunctional polyurethane derivative containing tert-butyl substituted triphenylamine and tetraphenylethylene groups prepared in example two;
FIG. 14 is a graph of the stability and transmittance of the multifunctional polyurethane derivative containing tert-butyl substituted triphenylamine and tetraphenylethylene groups prepared in example two after voltage application;
FIG. 15 is an electrochromic diagram of the multifunctional polyurethane derivative containing tert-butyl substituted triphenylamine and tetraphenylethylene groups prepared in example two;
FIG. 16 is an electroluminescent plot of a multifunctional polyurethane derivative containing tert-butyl substituted triphenylamine and tetraphenylethylene groups prepared in example two;
FIG. 17 is a graph showing the thermogravimetric curves of the multifunctional polyurethane derivative containing tert-butyl substituted triphenylamine and tetraphenylethylene groups prepared in example two;
FIG. 18 is an aggregation induction diagram of the multifunctional polyurethane derivative containing tert-butyl substituted triphenylamine and tetraphenylethylene groups prepared in example two;
FIG. 19 is a graph showing the detection of the p-explosive picric acid of the multifunctional polyurethane derivative containing tert-butyl substituted triphenylamine and tetraphenylethylene groups prepared in example two;
FIG. 20 is a graph showing the detection of explosives TNT of multifunctional polyurethane derivatives containing tert-butyl substituted triphenylamine and tetraphenylethylene groups prepared in example two;
FIG. 21 is a graph of memory properties of a multifunctional polyurethane derivative containing tert-butyl substituted triphenylamine and tetraphenylethylene groups prepared in example two;
FIG. 22 is a graph of the optoelectronic properties of the multifunctional polyurethane derivative containing tert-butyl substituted triphenylamine and tetraphenylethylene groups prepared in example two.
Detailed Description
The technical solution of the present invention is not limited to the specific embodiments listed below, and includes any combination of the specific embodiments.
The first embodiment is as follows: the multifunctional polyurethane derivative of the embodiment is a multifunctional polyurethane derivative containing triphenylamine and tetraphenylethylene groups or a multifunctional polyurethane derivative containing tert-butyl-substituted triphenylamine and tetraphenylethylene groups;
wherein the structural formula of the multifunctional polyurethane derivative containing triphenylamine and tetraphenylethylene groups is as follows:
the structural formula of the multifunctional polyurethane derivative containing tert-butyl substituted triphenylamine and tetraphenylethylene groups is as follows:
wherein n is an integer of 3 to 10.
In the embodiment, the triarylamine groups with the destroyed accumulation performance are introduced into the polyurethane structure, so that the high thermal stability of the original polyurethane can be maintained, the solubility of the triarylamine groups can be increased, the film forming capability is enhanced, the manufacturing of a large-area thin film electrochromic device is facilitated, and an electroactive center is provided to promote the treatment and application of the electrochromic device; tetraphenylethylenes (TPEs) containing four rotatable phenyl rings have been well developed for their Aggregation Induced Emission (AIE) activity. TPE derivatives can overcome the problem of quenching (ACQ) caused by aggregation of conventional organic luminophores, which greatly facilitates their various applications in bioprobes, chemical sensing and optoelectronic devices. The polyurethane derivative prepared by the embodiment takes the propeller type triarylamine as a monomer, so that the strong acting force between polymer molecular chains can be effectively reduced, the solubility of the polymer is increased, and meanwhile, the triarylamine is easy to form the triarylamine with a cationic free radical which is different from a neutral state. The multifunctional polyurethane derivative containing triphenylamine or triphenylamine containing tert-butyl substitution and tetraphenylethylene group with aggregation-induced emission performance in the embodiment has high temperature resistance, generally has a decomposition temperature of more than 350 ℃ in a nitrogen atmosphere, and is suitable for being used in devices. The multifunctional polyurethane derivative material containing triphenylamine or triphenylamine containing tert-butyl substitution and tetraphenylethylene group with aggregation-induced emission performance is made into a thin film, so that the large aggregation phenomenon and the breakage phenomenon do not occur on an ITO substrate, and the good wetting capacity is also displayed on the ITO substrate. This means that the multifunctional polyurethane derivative material has good film forming characteristics and can be used to make a large-area thin film. After voltage is applied, the transmittance of the film can still reach 50%, the transparency is good, and the polymer film can keep good stability of the circulating ring in the voltage application process, can be circulated for more than 20 times and has unchanged transparency.
The multifunctional polyurethane derivative containing triphenylamine or triphenylamine containing tert-butyl substitution and tetraphenylethylene group with aggregation-induced emission performance has the following advantages in practical application that (1) the multifunctional polyurethane derivative has good electrochemical redox reversibility and can still keep reversibility after dozens of redox cycles; (2) the response time of color change is fast, and the color can be changed rapidly within 2 seconds after voltage is applied; (3) the change in color is reversible; (4) the color change sensitivity is high; (5) the cycle life is longer; (6) the color-changing material has a storage memory function, can be stably kept in an original state or a state after color changing before and after response, can be maintained for months to years after color changing, and can be kept unchanged for half a year after electrochromism in the experiment; (7) the material has better chemical stability before and after color change, and can stably exist in the air at normal temperature and normal pressure. (8) Has response to explosive TNT and picric acid, and has detectable concentration of 1 × 10 for both picric acid and TNT-12mol/L, good sensitivity. (9) The fluorescence switch has good electroluminescent property, the fluorescence intensity of the fluorescence switch can be quenched in the process of applying voltage, the contrast ratio of the fluorescence switch can reach more than 100, and the fluorescence switch has great application potential in the aspects of intelligent photoelectricity and sensors. (10) Has good photoelectric response capability and keeps stable in the process of 500s of circulation.
The multifunctional polyurethane derivative containing triphenylamine or triphenylamine with tert-butyl substitution and tetraphenylethylene group with aggregation-induced emission performance has ten functions.
The second embodiment is as follows: the preparation method of the multifunctional polyurethane derivative of the embodiment comprises the following steps: mixing 1, 2-bis (4-hydroxyphenyl) -1, 2-diphenylethylene and 4, 4' -diphenylmethane diisocyanate with a solvent N, N-Dimethylacetamide (DMAC), and stirring and refluxing for 5-15h at the room temperature at the stirring speed of 800-900 r/min to obtain a precursor; secondly, adding a diamine monomer containing triphenylamine or tert-butyl substituted triphenylamine into the precursor prepared in the first step, heating to 70-120 ℃, stirring and refluxing for 5-15h, cooling, pouring into methanol, filtering, and vacuum-drying the obtained solid phase to obtain the multifunctional polyurethane derivative;
wherein the molar ratio of the diamine monomer containing triphenylamine or tert-butyl substituted triphenylamine, 1, 2-bis (4-hydroxyphenyl) -1, 2-diphenylethylene and 4, 4' -diphenylmethane diisocyanate is (0.5-2.5) to 1: 2;
the volume-to-mass ratio of the solvent N, N-Dimethylacetamide (DMAC) to the diamine monomer containing triphenylamine or tert-butyl-substituted triphenylamine was (10-30) mL (0.5-2.5 g).
The third concrete implementation mode: the second embodiment is different from the first embodiment in that: in the step one, the molar ratio of the diamine monomer containing triphenylamine or tert-butyl substituted triphenylamine, 1, 2-bis (4-hydroxyphenyl) -1, 2-diphenylethylene and 4, 4' -diphenylmethane diisocyanate is 2:1: 2. The rest is the same as the second embodiment.
The fourth concrete implementation mode: the second or third embodiment is different from the first or second embodiment in that: in the second step, the molar ratio of the diamine monomer containing triphenylamine or tert-butyl substituted triphenylamine, 1, 2-bis (4-hydroxyphenyl) -1, 2-diphenylethylene, 4' -diphenylmethane diisocyanate and solvent N, N-Dimethylacetamide (DMAC) is 1: 1: 2: 20. the other embodiments are the same as the second or third embodiment.
The fifth concrete implementation mode: the multifunctional polyurethane derivative of the present embodiment is applied to electrochromic materials.
The sixth specific implementation mode: the fifth embodiment is different from the fifth embodiment in that: the application method of the multifunctional polyurethane derivative as the electrochromic material comprises the following steps: dissolving a multifunctional polyurethane derivative in an organic solvent to obtain a polyurethane derivative solution, and then coating the polyurethane derivative solution on conductive glass to obtain an electrochromic material; wherein the organic solvent is tetrahydrofuran, chloroform, N '-dimethylacetamide, N' -dimethylformamide or N-methylpyrrolidone. The rest is the same as the fifth embodiment.
The seventh embodiment: the multifunctional polyurethane derivative containing triphenylamine and tert-butyl substituted triphenylamine and tetraphenylethylene groups is applied to being used as an electroluminescent material.
The specific implementation mode is eight: the seventh embodiment is different from the seventh embodiment in that: the application method of the multifunctional polyurethane derivative as the electroluminescent fluorescent material comprises the following steps: dissolving a multifunctional polyurethane derivative in an organic solvent to obtain a polyurethane derivative solution, and then coating the polyurethane derivative solution on conductive glass to obtain an electroluminescent material; wherein the organic solvent is tetrahydrofuran, chloroform, N '-dimethylacetamide, N' -dimethylformamide or N-methylpyrrolidone. The rest is the same as the seventh embodiment.
The specific implementation method nine: the multifunctional polyurethane derivative containing triphenylamine and tert-butyl substituted triphenylamine and tetraphenylethylene groups is applied as an explosive detection material.
The detailed implementation mode is ten: the present embodiment differs from the ninth embodiment in that: the application method of the multifunctional polyurethane derivative as the explosive detection comprises the following steps: dissolving the multifunctional polyurethane derivative in an organic solvent to obtain a multifunctional polyurethane derivative solution, then dropwise adding the solution containing the explosive into the polyurethane derivative solution, and detecting whether the explosive exists in the solution by using the change of the fluorescence intensity of the solution. The rest is the same as in the ninth embodiment.
In the explosive of the embodiment, the detectable concentrations of picric acid and TNT are both 1 × 10-12mol/L, good sensitivity.
The following examples were used to demonstrate the beneficial effects of the present invention:
the first embodiment is as follows: the preparation method of the multifunctional polyurethane derivative containing triphenylamine and tetraphenylethylene groups comprises the following steps: mixing 1, 2-bis (4-hydroxyphenyl) -1, 2-diphenylethylene (5mmol,0.2g) and 4, 4' -diphenylmethane diisocyanate (10mmol,0.25g) with 10mL of N, N-Dimethylacetamide (DMAC) solvent, stirring and refluxing for 10h at room temperature at the stirring speed of 800r/min, adding a diamine monomer (10mmol,0.43g) containing triphenylamine into the prepared precursor, heating to 80 ℃, stirring and refluxing for 10h, cooling, pouring into methanol, filtering, and vacuum drying the obtained solid phase to obtain the multifunctional polyurethane derivative containing triphenylamine and tetraphenylethylene groups; the chemical structural formula is as follows:
wherein n is an integer of 3 to 10.
The preparation method of the multifunctional polyurethane derivative containing triphenylamine and tetraphenylethylene groups as the electrochromic material comprises the following steps: dissolving a multifunctional polyurethane derivative containing triphenylamine and tetraphenylethylene groups in an organic solvent to obtain a multifunctional polyurethane derivative solution, and then coating the multifunctional polyurethane derivative solution on conductive glass to obtain an electrochromic material; wherein the organic solvent is tetrahydrofuran, chloroform, N '-dimethylacetamide, N' -dimethylformamide or N-methylpyrrolidone.
The application method of the multifunctional polyurethane derivative containing triphenylamine and tetraphenylethylene groups as the electroluminescent material comprises the following steps: dissolving a multifunctional polyurethane derivative containing triphenylamine and tetraphenylethylene groups in an organic solvent to obtain a polyurethane derivative solution, and then coating the polyurethane derivative solution on conductive glass to obtain an electroluminescent material; wherein the organic solvent is tetrahydrofuran, chloroform, N '-dimethylacetamide, N' -dimethylformamide or N-methylpyrrolidone.
The application method of the multifunctional polyurethane derivative containing triphenylamine and tetraphenylethylene groups as explosives for detection comprises the following steps: dissolving a multifunctional polyurethane derivative containing triphenylamine and tetraphenylethylene groups in an organic solvent to obtain a multifunctional polyurethane derivative solution, then dropwise adding a solution containing explosives into the multifunctional polyurethane derivative solution, and detecting whether the explosives exist in the solution by using the change of the fluorescence intensity of the solution.
The multifunctional polyurethane derivative containing triphenylamine and tetraphenylethylene groups is coated into a film, and the performance of the film is tested:
FIG. 1 is a hydrogen nuclear magnetic spectrum of a multifunctional polyurethane derivative containing triphenylamine and tetraphenylethylene groups prepared in the first example; as can be seen from the figure 1 of the drawings,1H-NMR (DMSO, TMS): the peak at δ ═ 9.4ppm is the chemical shift of H on CO — NH, and δ ═ 6.4 to 7.60ppm is the chemical shift of H on the benzene ring, and it can be said that in the first example, a multifunctional polyurethane derivative containing triphenylamine and tetraphenylethylene groups was synthesized.
FIG. 2 is a cyclic voltammogram of a multifunctional polyurethane derivative containing triphenylamine and tetraphenylethylene groups prepared in example one; as can be seen from fig. 2, two oxidation peaks and two reduction peaks, respectively, appear at 0.75V and 0.55V, respectively; two oxidation peaks appear at 0.85V and two reduction peaks appear at 0.62V, respectively
FIG. 3 is a graph of the stability and transmittance of multifunctional polyurethane derivatives containing triphenylamine and tetraphenylethylene groups prepared in example one after voltage application; as can be seen from fig. 3, after a voltage is applied, the transmittance of the multifunctional polyurethane derivative film containing triphenylamine and tetraphenylethylene groups can still reach 50%, which indicates that the transparency is relatively good, and the polymer film can keep good stability of the circulation loop during the voltage application process, and can be circulated for more than 20 times without changing the transparency.
FIG. 4 is an electrochromic diagram of a multifunctional polyurethane derivative containing triphenylamine and tetraphenylethylene groups prepared in the first example; as can be seen from FIG. 4, the multifunctional polyurethane derivative containing triphenylamine and tetraphenylethylene groups prepared in example one has an absorption peak at 352nm before no voltage is applied, and when the applied voltage is from 0.0V to 1.6V, the absorption peak at 352nm gradually rises, and new absorption peaks appear and gradually rise at 560nm and 735 nm; the electrochromic colors all range from light yellow to dark blue.
FIG. 5 is an electroluminescent diagram of a multifunctional polyurethane derivative containing triphenylamine and tetraphenylethylene groups prepared in the first example; the fluorescence intensity reaches the highest level before no voltage is applied, and gradually decreases from 0.0V to 1.5V with the applied voltage, and finally approaches to zero.
FIG. 6 is a graph showing the thermogravimetric curves of the multifunctional polyurethane derivative containing triphenylamine and tetraphenylethylene groups prepared in the first example; as can be seen from fig. 6, the multifunctional polyurethane derivative containing triphenylamine and tetraphenylethylene groups prepared in example one starts to lose a large amount of weight at about 300 ℃, when the temperature is 308 ℃, the weight loss amount is 5%, and when the temperature is 330 ℃, the weight loss amount is 10%; when the temperature is 367 ℃, the weight loss is 20%, and when the temperature reaches 800 ℃, the residual carbon content of the multifunctional polyurethane derivative containing the electroactive triphenylamine and the tetraphenylethylene group with the aggregation-induced emission performance prepared in the embodiment one is 30, so that the multifunctional polyurethane derivative has better high-temperature resistance.
FIG. 7 is a graph of aggregation-induced emission effect of the multifunctional polyurethane derivative containing triphenylamine and tetraphenylethylene groups prepared in the first example; it can be seen from FIG. 7 that the fluorescence intensity of the polymer gradually increases as the mass fraction of water increases; wherein a is 80%, b is 60%, c is 40%, d is 20%, and e is 0%.
FIG. 8 is a fluorescent graph showing the response of multifunctional polyurethane derivatives containing triphenylamine and tetraphenylethylene groups to picric acid prepared in the first example; it can be seen from FIG. 8 that the fluorescence intensity of the polymer solution gradually decreased with increasing picric acid concentration.
FIG. 9 is a fluorescence plot of the TNT response of multifunctional polyurethane derivatives containing triphenylamine and tetraphenylethylene groups prepared in the first example; it can be seen from fig. 9 that the fluorescence intensity of the polymer solution gradually decreased as the concentration of TNT increased.
FIG. 10 is a graph showing the memory properties of a multifunctional polyurethane derivative containing triphenylamine and tetraphenylethylene groups prepared in the first example; it can be seen from fig. 10 that in the first voltage sweep, from 0 to-6V (sweep 1), a sharp increase in current is observed when the negative threshold voltage is-1.0 and the memory device switches from the low conductivity state (OFF) to the high conductivity state (ON). This conversion process can be used as a "write" process for ITO/PI/Al devices. During the next scan (scan 2), the current is still in the ON state and the device remains in the high ON state. In the third scan from 0 to +6V (scan 3), we observed a sudden drop in current at a threshold voltage of +3.6, indicating that the memory device underwent a transition from the ON state to the original OFF state. This transition from ON to OFF may be as an "erase" process. As forward bias is applied, the current remains in the low on state in the subsequent voltage sweep (sweep 4). Thus, the memory devices manufactured with PU are binary flash data storage devices.
FIG. 11 is a diagram of the photoelectric properties of the multifunctional polyurethane derivative containing triphenylamine and tetraphenylethylene groups prepared in the first example; it can be seen from fig. 11 that the photoelectric properties of the polymer are very stable under light and dark conditions.
Example two, a method for preparing a multifunctional polyurethane derivative containing tert-butyl substituted triphenylamine and tetraphenylethylene groups comprises: mixing 1, 2-bis (4-hydroxyphenyl) -1, 2-diphenylethylene (5mmol,0.2g) and 4, 4' -diphenylmethane diisocyanate (10mmol,0.25g) with 10mL of N, N-Dimethylacetamide (DMAC) solvent, stirring and refluxing for 10h at room temperature at the stirring speed of 800r/min, adding a diamine monomer (10mmol,0.45g) containing tert-butyl substituted triphenylamine into the prepared precursor, heating to 80 ℃, stirring and refluxing for 10h, cooling, pouring into methanol, filtering, and vacuum drying the obtained solid phase to obtain the multifunctional polyurethane derivative containing tert-butyl substituted triphenylamine and tetraphenylethylene; the chemical structural formula is as follows:
wherein n is an integer of 3 to 10.
The preparation method of the multifunctional polyurethane derivative containing tert-butyl substituted triphenylamine and tetraphenylethylene group with aggregation-induced emission performance as the electrochromic material comprises the following steps: dissolving a multifunctional polyurethane derivative containing tert-butyl substituted triphenylamine and tetraphenylethylene groups with aggregation-induced emission properties in an organic solvent to obtain a polyurethane derivative solution, and then coating the polyurethane derivative solution on conductive glass to obtain an electrochromic material; wherein the organic solvent is tetrahydrofuran, chloroform, N '-dimethylacetamide, N' -dimethylformamide or N-methylpyrrolidone.
The application method of the multifunctional polyurethane derivative containing tert-butyl substituted triphenylamine and tetraphenylethylene group with aggregation-induced emission performance as the electroluminescent material is as follows: dissolving a multifunctional polyurethane derivative containing tert-butyl substituted triphenylamine and tetraphenylethylene groups with aggregation-induced emission properties in an organic solvent to obtain a polyurethane derivative solution, and then coating the polyurethane derivative solution on conductive glass to obtain an electroluminescent material; wherein the organic solvent is tetrahydrofuran, chloroform, N '-dimethylacetamide, N' -dimethylformamide or N-methylpyrrolidone.
The application method of the multifunctional polyurethane derivative containing tert-butyl substituted triphenylamine and tetraphenylethylene group with aggregation-induced emission performance as explosives for detection comprises the following steps: dissolving a multifunctional polyurethane derivative containing tert-butyl substituted triphenylamine and tetraphenylethylene groups with aggregation-induced emission properties in an organic solvent to obtain a polyurethane derivative solution, then dropwise adding a solution containing explosives into the polyurethane derivative solution, and detecting whether the explosives exist in the solution by using the change of the fluorescence intensity of the solution.
The multifunctional polyurethane derivative containing tert-butyl substituted triphenylamine and tetraphenylethylene groups is coated into a film, and the performance of the film is tested:
FIG. 12 is a hydrogen nuclear magnetic spectrum of the multifunctional polyurethane derivative containing tert-butyl substituted triphenylamine and tetraphenylethylene groups prepared in example two; as can be seen from the figure 1 of the drawings,1H-NMR (DMSO, TMS): the peak at δ ═ 9.4ppm is the chemical shift of H on CO — NH, and δ ═ 6.4 to 7.60ppm is the chemical shift of H on the benzene ring, and it is considered that example two synthesizes a multifunctional polyurethane derivative containing tert-butyl-substituted triphenylamine and tetraphenylethylene groups having aggregation-induced emission properties.
FIG. 13 is a cyclic voltammogram of the multifunctional polyurethane derivative containing tert-butyl substituted triphenylamine and tetraphenylethylene groups prepared in example two; as can be seen from fig. 13, two oxidation peaks appear at 1.02V and two reduction peaks appear at 0.99V, respectively; two oxidation peaks appear at 1.1V and two reduction peaks appear at 0.97V, respectively
FIG. 14 is a graph of the stability and transmittance of the multifunctional polyurethane derivative containing tert-butyl substituted triphenylamine and tetraphenylethylene groups prepared in example two after voltage application; as can be seen from fig. 14, after voltage is applied, the transmittance of the multifunctional polyurethane derivative thin film containing tert-butyl-substituted triphenylamine and tetraphenylethylene groups with aggregation-induced emission properties can still reach 45%, which indicates that the transparency is good, and the polymer thin film can keep good stability of the circulation loop during the voltage application process, can be circulated for more than 20 times and has no change in transparency.
FIG. 15 is an electrochromic diagram of the multifunctional polyurethane derivative containing tert-butyl substituted triphenylamine and tetraphenylethylene groups prepared in example two; as can be seen from fig. 15, the multifunctional polyurethane derivative containing tert-butyl substituted triphenylamine and tetraphenylethylene group having aggregation-induced emission property prepared in example two had an absorption peak at 350nm before voltage application, and when the applied voltage was from 0.0V to 1.6V, the absorption peak at 350nm gradually rose, and new absorption peaks appeared and gradually rose at 520nm,640nm, and 784 nm; the electrochromic colors all range from light yellow to dark blue.
FIG. 16 is an electroluminescent plot of a multifunctional polyurethane derivative containing tert-butyl substituted triphenylamine and tetraphenylethylene groups prepared in example two; the fluorescence intensity reaches the highest level before no voltage is applied, and gradually decreases from 0.0V to 1.5V with the applied voltage, and finally approaches to zero.
FIG. 17 is a graph showing the thermogravimetric curves of the multifunctional polyurethane derivative containing tert-butyl substituted triphenylamine and tetraphenylethylene groups prepared in example two; as can be seen from fig. 17, the multifunctional polyurethane derivative containing tert-butyl substituted triphenylamine and tetraphenylethylene group prepared in example two began to lose a large amount of weight at about 300 ℃, when the temperature was 336; when the weight loss is 5 percent, and when the temperature is 351 ℃; when the weight loss is 10%, the weight loss is 10%; when the temperature reaches 800 ℃, the carbon residue of the multifunctional polyurethane derivative containing tert-butyl substituted triphenylamine and tetraphenylethylene groups with aggregation-induced emission performance prepared in the first embodiment is 30%, and the multifunctional polyurethane derivative has better high-temperature resistance.
FIG. 18 is a graph of aggregation-induced emission of multifunctional polyurethane derivatives containing tert-butyl substituted triphenylamine and tetraphenylethylene groups prepared in example two; it can be seen from fig. 18 that the fluorescence intensity of the polymer gradually increased as the mass fraction of water increased; wherein a is 80%, b is 60%, c is 40%, d is 20%, and e is 0%.
FIG. 19 is a fluorescent plot of the response of multifunctional polyurethane derivatives containing tert-butyl substituted triphenylamine and tetraphenylethylene groups to picric acid prepared in example two; it can be seen from FIG. 19 that the fluorescence intensity of the polymer solution gradually decreased with increasing picric acid concentration.
FIG. 20 is a fluorescent plot of the TNT response of a multifunctional polyurethane derivative containing tert-butyl substituted triphenylamine and tetraphenylethylene groups prepared in example two; it can be seen from fig. 20 that the fluorescence intensity of the polymer solution gradually decreased as the concentration of TNT increased.
FIG. 21 is a graph of memory properties of a multifunctional polyurethane derivative containing tert-butyl substituted triphenylamine and tetraphenylethylene groups prepared in example two; it can be seen from fig. 21 that in the first voltage sweep, from 0 to-6V (sweep 1), a sharp increase in current is observed when the negative threshold voltage is-1.2V and the memory device switches from the low conductivity state (OFF) to the high conductivity state (ON). This conversion process can be used as a "write" process for ITO/PI/Al devices. During the next scan (scan 2), the current is still in the ON state and the device remains in the high ON state. In the third scan from 0 to +6V (scan 3), we observed a sudden drop in current at a threshold voltage of +3.2V, indicating that the memory device underwent a transition from the ON state to the original OFF state. This transition from ON to OFF may be as an "erase" process. As forward bias is applied, the current remains in the low on state in the subsequent voltage sweep (sweep 4). Thus, the memory devices manufactured with PU are binary flash data storage devices.
FIG. 22 is a graph of the optoelectronic properties of the multifunctional polyurethane derivative containing tert-butyl substituted triphenylamine and tetraphenylethylene groups prepared in example two; it can be seen from fig. 22 that the photoelectric properties of the polymer are very stable under light and dark conditions.
The solubility of the multifunctional polyurethane derivative containing triphenylamine and tetraphenylethylene group having aggregation-induced emission property and the solubility of the multifunctional polyurethane derivative containing tert-butyl-substituted triphenylamine and tetraphenylethylene group were tested, and as shown in table 1, it can be seen from table 1 that the multifunctional polyurethane derivative containing triphenylamine and tetraphenylethylene group having aggregation-induced emission property and the multifunctional polyurethane derivative containing tert-butyl-substituted triphenylamine and tetraphenylethylene group of this example have good solubility.
TABLE 1
The experiments of the first and second examples show that the triarylamine groups with the stacking failure performance are introduced into the polyurethane structure, so that the high thermal stability of the original polyurethane can be maintained, the solubility of the polyurethane can be increased, the film forming capability is enhanced, the large-area thin-film electrochromic device can be manufactured, and an electroactive center is provided to promote the treatment and application of the electrochromic device; tetraphenylethylenes (TPEs) containing four rotatable phenyl rings have been well developed for their Aggregation Induced Emission (AIE) activity. TPE derivatives can overcome the problem of quenching (ACQ) caused by aggregation of conventional organic luminophores, which greatly facilitates their various applications in bioprobes, chemical sensing and optoelectronic devices. The polyurethane derivative prepared by the embodiment takes the propeller type triarylamine as a monomer, so that the strong acting force between polymer molecular chains can be effectively reduced, the solubility of the polymer is increased, and meanwhile, the triarylamine is easy to form the triarylamine with a cationic free radical which is different from a neutral state. The multifunctional polyurethane derivative containing triphenylamine or triphenylamine containing tert-butyl substitution and tetraphenylethylene group with aggregation-induced emission performance in the embodiment has high temperature resistance, generally has a decomposition temperature of more than 350 ℃ in a nitrogen atmosphere, and is suitable for being used in devices. The multifunctional polyurethane derivative material containing triphenylamine or triphenylamine containing tert-butyl substitution and tetraphenylethylene group with aggregation-induced emission performance is prepared into a thin film, so that the thin film does not have large aggregation phenomenon and breakage phenomenon on an ITO substrate, and shows good wetting capacity on the ITO substrate. This means that the multifunctional polyurethane derivative material has good film forming characteristics and can be used to make a large-area thin film. After voltage is applied, the transmittance of the film can still reach 50%, the transparency is good, and the polymer film can keep good stability of the circulating ring in the voltage application process, can be circulated for more than 20 times and has unchanged transparency.
The multifunctional polyurethane derivative containing triphenylamine and tert-butyl substituted triphenylamine and tetraphenylethylene groups has the following advantages in practical application that (1) the multifunctional polyurethane derivative has good electrochemical redox reversibility and can still keep reversibility after dozens of redox cycles; (2) the response time of color change is fast, and the color can be changed rapidly within 2 seconds after voltage is applied; (3) the change in color is reversible; (4) the color change sensitivity is high; (5) the cycle life is longer; (6) the color-changing material has a storage memory function, can be stably kept in an original state or a state after color changing before and after response, can be maintained for months to years after color changing, and can be kept unchanged for half a year after electrochromism in the experiment; (7) the material has better chemical stability before and after color change, and can stably exist in the air at normal temperature and normal pressure. (8) Picric acid responds to the explosive TNT. (9) The fluorescence switch has good electroluminescent property, the fluorescence intensity of the fluorescence switch can be quenched in the process of applying voltage, the contrast ratio of the fluorescence switch can reach more than 100, and the fluorescence switch has great application potential in the aspects of intelligent photoelectricity and sensors. (10) Has good photoelectric response capability and keeps stable in the process of 500s of circulation.
In summary, the multifunctional polyurethane derivatives prepared in the first and second embodiments have ten functions, and multifunctional materials with more functional types are prepared.
Claims (8)
1. A preparation method of a multifunctional polyurethane derivative is characterized by comprising the following steps: mixing 1, 2-bis (4-hydroxyphenyl) -1, 2-diphenylethylene, 4' -diphenylmethane diisocyanate and a solvent N, N-dimethylacetamide, and stirring and refluxing for 5-15h at the room temperature at the stirring speed of 800-900 r/min to obtain a precursor; secondly, adding a diamine monomer containing triphenylamine or tert-butyl substituted triphenylamine into the precursor prepared in the first step, heating to 70-120 ℃, stirring and refluxing for 5-15h, cooling, pouring into methanol, filtering, and vacuum-drying the obtained solid phase to obtain the multifunctional polyurethane derivative;
wherein the molar ratio of the diamine monomer containing triphenylamine or tert-butyl substituted triphenylamine, 1, 2-bis (4-hydroxyphenyl) -1, 2-diphenylethylene and 4, 4' -diphenylmethane diisocyanate is (0.5-2.5) to 1: 2;
the volume mass ratio of the solvent N, N-dimethylacetamide to the diamine monomer containing triphenylamine or tert-butyl substituted triphenylamine is (10-30) mL (0.5-2.5) g.
2. The method of claim 1, wherein the molar ratio of 1, 2-bis (4-hydroxyphenyl) -1, 2-diphenylethylene to 4, 4' -diphenylmethane diisocyanate is 2:1: 2.
3. Use of a multifunctional polyurethane derivative prepared according to claim 1, characterized by the use of the multifunctional polyurethane derivative as an electrochromic material.
4. The use of the multifunctional polyurethane derivative according to claim 3, wherein the multifunctional polyurethane derivative is applied as an electrochromic material by: dissolving a multifunctional polyurethane derivative in an organic solvent to obtain a polyurethane derivative solution, and then coating the polyurethane derivative solution on conductive glass to obtain an electrochromic material; wherein the organic solvent is tetrahydrofuran, chloroform, N-dimethylacetamide, N-dimethylformamide or N-methylpyrrolidone.
5. Use of a multifunctional polyurethane derivative prepared according to claim 4, characterized in that the multifunctional polyurethane derivative is used as an electroluminescent material.
6. The use of the multifunctional polyurethane derivative according to claim 5, wherein the multifunctional polyurethane derivative is applied as an electroluminescent material by the following method: dissolving a multifunctional polyurethane derivative in an organic solvent to obtain a polyurethane derivative solution, and then coating the polyurethane derivative solution on conductive glass to obtain an electroluminescent material; wherein the organic solvent is tetrahydrofuran, chloroform, N-dimethylacetamide, N-dimethylformamide or N-methylpyrrolidone.
7. Use of a multifunctional polyurethane derivative prepared according to claim 1, characterized by the use of the multifunctional polyurethane derivative as an explosive detection material.
8. The use of the multifunctional polyurethane derivative according to claim 7, wherein the multifunctional polyurethane derivative is used as an explosive detection material by the following method: the multifunctional polyurethane derivative is dissolved in an organic solvent to obtain a polyurethane derivative solution, then the solution containing the explosive is dripped into the polyurethane derivative solution, and the existence of the explosive in the solution is detected by utilizing the change of the fluorescence intensity of the solution.
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