CN115058111A - Force-induced color-changing porous particle polyurethane elastomer material and preparation method thereof - Google Patents
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Abstract
The invention discloses a force-induced color-changing porous particle polyurethane elastomer material and a preparation method thereof, belonging to the technical field of mechanochemical conductive materials. The invention discloses a method for preparing a mechanochromic porous particle polyurethane elastomer, which comprises the following steps: (1) adding a catalyst dibutyl tin dilaurate into polytetrahydrofuran, heating, and refluxing in an inert gas atmosphere; adding isophorone diisocyanate solution and silica dispersion liquid to perform prepolymerization reaction; (2) after the prepolymerization reaction is finished, adding trihydroxy rhodamine derivative solution for reaction; (3) and after the reaction is finished, adding a cross-linking agent triethanolamine solution, uniformly mixing, and replacing the solvent in the system with water to obtain the porous particle polyurethane elastomer. The tensile strength of the force-induced color-changing porous particle polyurethane elastomer can reach 4.5 Mpa; the elongation at break can reach more than 1750 percent; and meanwhile, the stable reversible force-induced discoloration characteristic is shown, and the recovery performance is good.
Description
Technical Field
The invention relates to a mechanochromic porous particle polyurethane elastomer material and a preparation method thereof, belonging to the technical field of mechanochemical conductive materials.
Background
The mechanochromic material is a functional material which can obviously change the optical behavior (such as absorption, reflection, fluorescence, phosphorescence and the like) of the material when being stimulated by external force, and can also be reversibly returned to the initial state when the external force is removed. The mechanochromic material can be used in the fields of color-changing fibers, anti-counterfeiting devices, stress sensors, intelligent wearable equipment and the like.
The realization of the mechano-chromic function usually depends on micromolecule mechano-chromic groups, and the common mechano-chromic groups are spiropyran derivatives and rhodamine derivatives. Wherein, the ring opening of the spiropyran group is easy, the force for causing the force to discolor is 2.6nN, and the ring opening is easily influenced by external stimuli such as temperature, illumination and the like, so the spiropyran group is not suitable for stress sensing; rhodamine is stable, and a single molecule can be subjected to ring opening only by a force not less than 4.6nN, so that the rhodamine functionalized polyurethane material has the problem of insensitive response to force, and the extensive application is limited.
Disclosure of Invention
[ problem ] to
The existing mechanochromic material prepared by using rhodamine groups has the problems of poor mechanical property and insufficient sensitivity. The rhodamine is adopted to prepare the mechanochromic polyurethane, so that the mechanical property of the mechanochromic polyurethane is improved to a certain extent, but the problem of insufficient mechanical property still exists.
[ solution ]
In order to solve the problems, the invention prepares hybrid polyurethane by adding nano particles on the basis of trihydroxy rhodamine mechanochromic polyurethane, and then prepares porous polyurethane by a solvent exchange method. The porous polyurethane has a hierarchical structure, and the mechanical property is greatly improved.
It is a first object of the present invention to provide a process for preparing a mechanochromic cellular particulate polyurethane elastomer, comprising the steps of:
(1) adding a catalyst of dibutyltin dilaurate into polytetrahydrofuran, heating, and refluxing in an inert gas atmosphere; adding isophorone diisocyanate solution and silica dispersion liquid to perform prepolymerization reaction;
(2) after the prepolymerization reaction is finished, adding trihydroxy rhodamine derivative solution for reaction;
(3) and after the reaction is finished, adding a cross-linking agent triethanolamine solution, uniformly mixing, and replacing the solvent in the system with water to obtain the porous particle polyurethane elastomer.
In one embodiment of the invention, the molar ratio of the trihydroxyrhodamine derivative, the isophorone diisocyanate, the polytetrahydrofuran and the triethanolamine is 1 (100-200): 10-100.
In one embodiment of the present invention, the amount of dibutyl tin dilaurate used as the catalyst in step (1) is 3-5 wt% of polytetrahydrofuran.
In one embodiment of the present invention, the heating in step (1) is performed to 65 to 75 ℃, and more preferably to 70 ℃.
In one embodiment of the present invention, the inert gas in step (1) is nitrogen.
In one embodiment of the invention, the concentration of the isophorone diisocyanate solution in step (1) is 0.3-0.4 g/mL, and the solvent is acetone.
In one embodiment of the present invention, the silica dispersion liquid in step (1) is prepared by dispersing nano silica particles in acetone, wherein the ratio of the nano silica to the acetone is 0.01 to 2 g: 10mL, the particle size of the nano silicon dioxide is 100-300 nm, and the silicon dioxide is hydrophilic.
In one embodiment of the present invention, the amount (by mass) of silica added in step (1) is 1 to 2% of polytetrahydrofuran.
In one embodiment of the present invention, the prepolymerization reaction in step (1) is carried out at 65-75 ℃ for 4-8 h.
In one embodiment of the invention, the structural color of the trihydroxy rhodamine derivative in the step (2) is as shown in formula I:
in one embodiment of the invention, the trihydroxy rhodamine derivative solution in the step (2) is trihydroxy rhodamine derivative acetone solution, and the dosage ratio of the trihydroxy rhodamine derivative to the acetone is 0.06-0.07 g: 10 mL.
In one embodiment of the present invention, the reaction in step (2) is carried out at 65-75 ℃ for 4-8 h.
In one embodiment of the present invention, the triethanolamine solution in step (3) is an acetone solution of triethanolamine, and the ratio of the amounts of triethanolamine and acetone is 0.3 to 0.4 g: 10 mL.
The second object of the invention is the mechanochromic cellular particulate polyurethane elastomer prepared by the process of the invention.
The third purpose of the invention is the application of the force-induced color-changing porous particle polyurethane elastomer in color-changing fibers, anti-counterfeiting devices, stress sensors and intelligent wearable equipment.
[ advantageous effects ]
(1) According to the invention, by adding the nano silicon dioxide particles and adopting a solvent replacement method, the structure of the polyurethane base material is changed, so that the mechanical property and the color-changing property of the polyurethane are improved, and the optimal preparation of the polyurethane elastomer with the force-induced color-changing porous particles is determined.
(2) The color change of the force-induced color-changing porous particle polyurethane elastomer is quick and reversible, and the force-induced color-changing porous particle polyurethane elastomer is excellent in recovery and can be repeatedly used. Specifically, the color of the force-induced color-changing porous particle polyurethane elastomer changes from colorless to red after being stressed, the color of the polyurethane can be recovered to a colorless state before being stressed after the polyurethane elastomer is placed for 5 minutes at room temperature, and the color-changing performance is not obviously reduced after the polyurethane elastomer is repeated for 5 times.
(3) The force-induced color-changing porous particle polyurethane elastomer has lower glass transition temperature and high elasticity, and is easy to combine with fabrics. These make the material useful in smart apparel, strain sensors, and color changing decorative products.
(4) The tensile strength of the force-induced color-changing porous particle polyurethane elastomer can reach 4.5 Mpa; the elongation at break can reach over 1750 percent; and meanwhile, the stable reversible force-induced discoloration characteristic is shown, and the recovery performance is good.
(5) According to the force-induced discoloration porous particle polyurethane elastomer disclosed by the invention, through a tensile test, on the premise of ensuring that the material is not broken, the strain height reaches 1750%, and the released stress is recovered to the initial length, so that the force-induced discoloration porous particle polyurethane elastomer has excellent tensile strength and resilience.
Drawings
FIG. 1 is an SEM of the cellular polyurethane elastomer of example 2.
FIG. 2 shows the results of the discoloration property test of the cellular polyurethane elastomer (1: 2) of example 2.
FIG. 3 is an SEM of the particulate polyurethane elastomer of example 3 wherein (a) is 0.014 g; (b) 0.14 g; (c)1.4 g.
FIG. 4 shows the results of the discoloration property test of the granular polyurethane elastomer of example 3.
FIG. 5 shows the results of the discoloration property test at primary pressure for the granular polyurethane elastomer prepared by adding 0.14g of nano silica particles.
FIG. 6 shows the results of 5 cycles of discoloration tests of a granular polyurethane elastomer prepared by adding 0.14g of nano silica particles.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of better illustrating the invention and is not intended to limit the invention thereto.
The test method comprises the following steps:
and (4) SEM test: and (3) observing the microporous particle modified polyurethane by using an SU1510 scanning electron microscope, and observing the pore diameter of micropores and the dispersion condition of nanoparticles.
Testing of tensile strength and elongation at break: and testing the mechanical property of the mechanochromic polyurethane by using a universal testing machine. And (3) testing conditions are as follows: the tensile rate was 250mm/min and the test temperature was 25 ℃.
Testing of color change: applying different pressures of 0-1000 Mpa to the sample by using a hydraulic press, taking a picture by using a Canon EOS 70D camera under a D65 light source, and reading RGB values representing color characteristics in a color changing process and a color fading process by using a color picker tool of Photoshop mapping software.
Example 1
A method of preparing a mechanochromic cellular particulate polyurethane elastomer comprising the steps of:
(1) to 10g of polytetrahydrofuran (11.8mmol), dibutyltin dilaurate, a catalyst, 0.4g, was added, the mixture was heated to 70 ℃ and refluxed under a nitrogen atmosphere; adding isophorone diisocyanate acetone solution (10mL acetone +3.5g 15.7mol isophorone diisocyanate) and 300nm hydrophilic silica acetone dispersion liquid (0.14g silica +10mL acetone), and performing prepolymerization reaction at 70 ℃ for 6 h;
(2) after the prepolymerization reaction is finished, adding a trihydroxy rhodamine derivative acetone (0.067g of 0.1mol trihydroxy rhodamine derivative +10mL acetone) solution, and reacting for 6h at 70 ℃;
(3) after the reaction is finished, adding a cross-linking agent triethanolamine acetone (0.399g of 2.7mmol triethanolamine +10mL acetone) solution, uniformly mixing, and replacing solvent acetone in a system with water (the volume ratio of acetone to water is 1: 2) to obtain the porous particle polyurethane elastomer.
The obtained porous particle polyurethane elastomer is subjected to performance test, and the test result is as follows:
the SEM results show that: the nanoparticles are dispersed on the surface of the polyurethane and modified on the inner surface of the micropores, and the successful synthesis of the force-induced discoloration polyurethane with the particle-micropore structure is proved.
The mechanical property results show that: the breaking strength of the porous particle polyurethane elastomer can reach 4.5Mpa, and the breaking elongation can reach 1750%.
Results of color change performance: by fitting to the red component it can be seen that: when the pressure reaches about 100Mpa, the color of the porous particle polyurethane elastomer is changed, the color is gradually deepened along with the increase of the pressure, and the color reaches the deepest when the pressure reaches 700 Mpa; applying 1000Mpa pressure to the porous particle polyurethane elastomer, and after the pressure is removed, recovering the saturated color to the initial color after 5 minutes; the fitting result of the stressed color change and the faded red light component of the experimental material is obtained through five times of repeated experiments: the porous particle polyurethane elastomer has good repeated color change performance for many times, and the color change performance is not obviously reduced.
Comparative example 1
A polyurethane elastomer was obtained in the same manner as in example 1 except that the 300nm hydrophilic silica acetone dispersion obtained in step (1) of example 1 and the "substitution of acetone as a solvent in a water substitution system (the volume ratio of acetone to water: 1: 2)" obtained in step (3) were omitted.
Comparative example 2
A polyurethane elastomer was obtained in the same manner as in example 1 except that the 300nm hydrophilic silica acetone dispersion obtained in step (1) of example 1 was omitted.
Comparative example 3
A polyurethane elastomer was obtained by omitting the step (3) of example 1 in which the solvent acetone in the system was replaced with water (the volume ratio of acetone to water was 1: 2), and keeping the same as in example 1.
Comparative example 4
The hydrophilic silica used in the step (1) of example 1 was oleophilic silica, and a polyurethane elastomer was obtained in the same manner as in example 1.
Comparative example 5
A polyurethane elastomer was obtained in the same manner as in example 1 except that the 300nm hydrophilic silica acetone dispersion obtained in step (1) in example 1 was changed to 300nm hydrophilic silica.
The obtained polyurethane elastomer is subjected to performance test, and the test result is as follows:
TABLE 1
Example 2 optimization of the volume ratio of acetone to water
The volume ratio of acetone to water in step (3) of example 1 was adjusted to 1: 1. 1: 2. 1: 3, while omitting "300 nm hydrophilic silica acetone dispersion (0.14g silica +10mL acetone)"; the rest was the same as in example 1, and a cellular polyurethane elastomer was obtained.
The obtained porous polyurethane elastomer is subjected to performance test, and the test result is as follows:
fig. 1 is an SEM image, as can be seen from fig. 1: porous polyurethane elastomers are synthesized.
Table 2 shows the mechanical property test results, and it can be seen from table 2 that: the volume ratio of acetone to water is 1: 1, the tensile strength of the prepared porous polyurethane elastomer can reach 1.3Mpa, and the elongation at break is 800%; the volume ratio of acetone to water is 1: 2, the tensile strength of the prepared porous polyurethane elastomer can reach 1.5Mpa, and the elongation at break is 500 percent; the volume ratio of acetone to water is 1: 3, the tensile strength of the prepared porous polyurethane elastomer can reach 1.0Mpa, and the elongation at break is 350 percent.
TABLE 2
| Ratio of | Tensile strength (Mpa) | Elongation at Break (%) |
| 1：1 | 1.3 | 800 |
| 1: 2 (comparative example 2) | 1.5 | 500 |
| 1：3 | 1.0 | 350 |
FIG. 2 shows the result of a test for discoloration properties; as can be seen from fig. 2: applying 1000Mpa pressure to a porous polyurethane elastomer (the volume ratio of acetone to water is 1: 2), releasing strain, and recovering the color to the original color after 10 minutes; the fitting result of the stressed color change and the faded red light component of the experimental material is obtained through five times of repeated experiments: the porous polyurethane elastomer has good repeated color change performance for many times, and the color change performance is reduced by 20 percent.
Example 3 optimization of the amount of nanoparticles used
The amounts of the hydrophilic silica used in step (1) of example 1 were adjusted to 0.014, 0.14g and 1.4g, and the "replacement of acetone as a solvent in the system with water (the volume ratio of acetone to water was 1: 2)" in step (3) was omitted, and the rest was the same as in example 1, to obtain a granular polyurethane elastomer.
The obtained polyurethane elastomer is subjected to performance test, and the test result is as follows:
FIG. 3 is an SEM image, as can be seen from FIG. 3: the nano particles are uniformly dispersed in the polyurethane matrix, and the successful synthesis of the polyurethane particles is proved.
Table 3 shows the mechanical property test results, and it can be seen from table 3 that: with the increase of the addition amount of the silicon dioxide, the tensile strength of the polyurethane is increased from 2.0MPa to 2.5MPa and then is reduced to 2.2 MPa; the elongation at break of the polyurethane is slightly improved, and the elongation at break of the mechanochromic polyurethane added with 0.14g of nano silicon dioxide particles reaches 1300 percent.
TABLE 3
| Amount of silica used (g) | Tensile strength (Mpa) | Elongation at Break (%) |
| 0.014 | 2.0 | 1100 |
| 0.14 (comparative example 3) | 2.5 | 1300 |
| 1.4 | 2.2 | 1250 |
Fig. 4 shows the result of the discoloration property test, and it can be seen from fig. 4 that: the addition of 0.14g of nano silicon dioxide particles has two turning points, the color of the polyurethane is rapidly deepened after 300MPa, and the color of 700MPa can reach the deepest; the color of the added nano silicon dioxide particles of 0.014 and 1.4g is changed under 200Mpa, the color is gradually deepened along with the increase of force, the color change performance of the polyurethane added with 0.14g of nano particles is slightly better than that of the polyurethane added with 0.014g of nano particles, and the color change performance is relatively similar.
FIGS. 5 and 6 are results of discoloration property test of polyurethane elastomer prepared by adding 0.14g of nano silica particles; as can be seen from fig. 5: applying 1000Mpa pressure to the polyurethane film by using a hydraulic press, and completely fading the color of the polyurethane film after the stressed polyurethane film is kept stand for 20 minutes under the natural condition; the same film was subjected to the pressure-recovery test 5 times to examine the repeatable property of the material discoloration due to force. As can be seen from fig. 6: the fitting of the stressed color change and the faded red light component of the material in the five-time repeated experiment can show that the material has good repeated color change performance for multiple times, and the color change performance is reduced by 20 percent.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A method for preparing a mechanochromic cellular particulate polyurethane elastomer, comprising the steps of:
(1) adding a catalyst of dibutyltin dilaurate into polytetrahydrofuran, heating, and refluxing in an inert gas atmosphere; adding isophorone diisocyanate solution and silica dispersion liquid to perform prepolymerization reaction;
(2) after the prepolymerization reaction is finished, adding trihydroxy rhodamine derivative solution for reaction;
(3) and after the reaction is finished, adding a cross-linking agent triethanolamine solution, uniformly mixing, and replacing the solvent in the system with water to obtain the porous particle polyurethane elastomer.
2. The method of claim 1, wherein the molar ratio of trihydroxyrhodamine derivative, isophorone diisocyanate, polytetrahydrofuran and triethanolamine is 1 (100-200): 100-200: 10-100.
3. The method according to claim 1, wherein the silica dispersion liquid in the step (1) is prepared by dispersing nano silica particles in acetone, and the using ratio of the nano silica to the acetone is 0.01-2 g: 10mL, the particle size of the nano silicon dioxide is 100-300 nm, and the silicon dioxide is hydrophilic.
4. The method of claim 1, wherein the prepolymerization reaction in step (1) is carried out at 65-75 ℃ for 4-8 h.
5. The method of claim 1, wherein the reaction in step (2) is carried out at 65-75 ℃ for 4-8 h.
6. The method according to claim 1, wherein the catalyst dibutyl tin dilaurate in step (1) is added in an amount of 3-5 wt% of polytetrahydrofuran.
7. The method as claimed in claim 1, wherein the trihydroxyrhodamine derivative of step (2) has a structural color of formula I:
8. the method as claimed in claim 1, wherein the trihydroxyrhodamine derivative solution in the step (2) is trihydroxyrhodamine derivative acetone solution, and the dosage ratio of the trihydroxyrhodamine derivative to the acetone is 0.06-0.07 g: 10 mL.
9. A mechanochromic cellular particulate polyurethane elastomer prepared by the process of any one of claims 1 to 8.
10. Use of the mechanochromic porous particulate polyurethane elastomer of claim 9 in color shifting fibers, security devices, stress sensors, and smart wearable devices.
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