Method of Preparing Electric and Temperature Dual-control Bi-stable Color-changing Dyes and Microcapsules

Abstract

The disclosure discloses a method of preparing electric and temperature dual-control bi-stable color-changing dyes and microcapsules, belonging to the technical fields of fine chemicals and materials science. According to the disclosure, after an electrolyte, a leuco dye and an organic solid material are mixed according to 1:(2-10):(15-50), a series of electric and temperature dual-control bi-stable color-changing dye compounds having a color change temperature range of −5° C. to +80° C. can be prepared. The dye compounds change color under cooperative control of electricity and temperature, and can be continuously stable at a certain color change state according to different conditions, and finally achieve controllable color change conditions and controllable color change stable states. When being driven by voltage and temperature, the dual-control bi-stable color-changing microcapsules prepared according to the disclosure achieve controllable color change performance and color change stable states, and have the driving voltage being lower than 10 V (much lower than the human body safety voltage 36 V).

Claims

1. An electric and temperature dual-control bi-stable color-changing dye, comprising a leuco dye, an electrolyte and an organic solid material, wherein the leuco dye is 2′-chloro-6′-(diethylamino)fluoran; the electrolyte is tetrabutylammonium perchlorate; the organic solid material is selected from one or more of stearyl alcohol, cetyl alcohol, myristyl alcohol, myristic acid, palmitic acid, stearic acid, glyceryl monostearate, glycerin monostearate, glyceryl laurate, p-azoxyanisole, diphenyl carbonate, phenyl salicylate, phenyl stearate and benzyl benzoate; and a ratio of the leuco dye to the electrolyte to the organic solid material is 1:(2-10):(15-50).

2. The electric and temperature dual-control bi-stable color-changing dye according to claim 1, wherein the leuco dye is 1,3-dimethyl-6-diethylaminofluoran, 2′-chloro-6′-(diethylamino)-3′-methylfluoran, 2′-chloro-6′-(diethylamino) fluoran, 6′-(diethylamino)-1′,3′-dimethylfluoran, crystal violet lactone or screw pyran class.

3. The electric and temperature dual-control bi-stable color-changing dye according to claim 1, wherein the electrolyte is tetrabutylammonium perchlorate, tetraethylammonium perchlorate, ferric nitrate, barium sulfate, calcium carbonate, mercuric chloride or lead acetate.

4. The electric and temperature dual-control bi-stable color-changing dye according to claim 1, wherein the organic solid material is one or more of small molecular organic alkyl alcohols and alkyl acids, and macromolecular ethers and esters, and the organic solid material is selected from one or more of stearyl alcohol, cetyl alcohol, myristyl alcohol, myristic acid, palmitic acid, stearic acid, glyceryl monostearate, glycerin monostearate, glyceryl laurate, p-azoxyanisole, diphenyl carbonate, phenyl salicylate, phenyl stearate and benzyl benzoate.

5. An electric and temperature dual-control bi-stable color-changing microcapsule, comprising the dual-control color-changing dye according to claim 1 as a core material.

6. A method of preparing the electric and temperature dual-control bi-stable color-changing microcapsules of claim 6, comprising the following steps: (1) preparing dual-control compound: heating and stirring the dual-control bi-stable color-changing dye according to claim 1 to form a uniform mixed solution, namely, a dual-control compound; and (2) preparation of dual-control bi-stable microcapsules: dropwise adding the dual-control compound obtained in step (1) to an aqueous solution containing an emulsifier, the emulsifier accounting for 25-100% by mass of the dual-control compound, and carrying out high-speed emulsification to form a uniform dye dispersion; dropwise adding monomers accounting for 20-100% by mass of the dye compound to the dye dispersion, and continuing emulsification for 10-20 minutes; and then, transferring the emulsified dispersion into a four-neck flask with a reflux condenser and a stirring device, after introducing nitrogen for 5-30 minutes, raising a temperature to 55-75° C. at a stirring speed of 250-500 r/min, after reaching a reaction temperature, dropwise adding an initiator accounting for 0.1-1% of a total amount of the monomers, keeping the temperature to react for 2-6 hours, and after the completion of the reaction, washing a product with water and drying the product to obtain the dual-control bi-stable microcapsules.

7. The method according to claim 6, wherein the monomers are selected from one or two of methyl methacrylate, styrene, ethyl methacrylate, butyl methacrylate, vinyl acetate, methyl vinyl ether, acrylonitrile, acrylamide, isoprene and dicyclopentadiene.

8. The method according to claim 6, wherein the initiator is selected from one of potassium persulfate, ammonium persulfate and azobisisobutylamidine hydrochloride.

9. The method according to claim 6, wherein the emulsifier is selected from one or more of nonionic surfactants, anionic surfactants and polymeric surfactants.

10. The method according to claim 6, wherein the emulsifier is selected from gum arabic, sodium dodecylbenzenesulfonate, styrene-maleic anhydride copolymer, Tween and Span.

Description

DETAILED DESCRIPTION

[0022] Preferred examples of the disclosure will be described below. It should be understood that the examples are intended to better explain the disclosure and are not intended to limit the disclosure.

[0023] A rigid substrate with an electrode is coated with color-changing microcapsules. After the coating is completely dried, the film is covered with another rigid electrode, the upper and lower electrodes are bonded by a colloid, and a display device is obtained by packaging. The device is respectively driven by a DC stable-state power supply, and the driving voltage of the color-changing microcapsules is verified according to the color change phenomenon.

Example 1

[0024] 0.1 g of 2′-chloro-6′-(diethylamino) fluoran, 0.8 g of tetrabutylammonium perchlorate (TBAP) and 5 g of diphenyl carbonate were magnetically stirred at 80° C. for 1 hour to obtain a uniform mixed solution. 1.8 g of sodium dodecylbenzenesulfonate and 95.2 g of water were emulsified under conditions of 70° C. and 6000 r/min for 20 minutes while an oil phase (2 g of uniform compound and 1 g of polymethyl methacrylate) was added dropwise. Then 0.01 g of ammonium persulfate was added, mechanical stirring (500 r/min) was carried out at 80° C. for 3 hours, and finally, the mixture was washed with water and dried to obtain a microcapsule product. 0.2 g of the product was weighed and pressed into a tablet to be used as a research object. When a voltage was applied and the temperature was lower than 31° C., the sample was colorless; when the temperature was higher than 31° C., the sample became orange-red from colorless; when the temperature was lowered to 31° C. or below and the voltage was removed, the sample still remained orange-red and had an energy-saving effect; and when the temperature was raised, the sample became colorless again. When no voltage was applied, the sample was colorless under any conditions.

Example 2

[0025] 0.1 g of 2′-chloro-6′-(diethylamino) fluoran, 0.8 g of tetrabutylammonium perchlorate (TBAP) and 5 g of phenyl salicylate were magnetically stirred at 80° C. for 1 hour to obtain a uniform mixed solution. 1.8 g of sodium dodecylbenzenesulfonate and 95.2 g of water were emulsified under conditions of 70° C. and 6000 r/min for 20 minutes while an oil phase (2 g of uniform compound and 1 g of polymethyl methacrylate) was added dropwise. Then 0.01 g of ammonium persulfate was added, mechanical stirring (500 r/min) was carried out at 80° C. for 3 hours, and finally, the mixture was washed with water and dried to obtain a microcapsule product. 0.2 g of the product was weighed and pressed into a tablet to be used as a research object. When a voltage was applied and the temperature was lower than 25° C., the sample was colorless; when the temperature was higher than 25° C., the sample became orange-red from colorless; when the temperature was lowered to 25° C. or below and then the voltage was removed, the sample still remained orange-red; and when the temperature was raised, the sample became colorless again. When no voltage was applied, the sample was colorless under any conditions.

Example 3

[0026] 0.1 g of 2′-chloro-6′-(diethylamino) fluoran, 0.8 g of tetrabutylammonium perchlorate (TBAP) and 5 g of phenyl stearate were magnetically stirred at 80° C. for 1 hour to obtain a uniform mixed solution. 1.8 g of sodium dodecylbenzenesulfonate and 95.2 g of water were emulsified under conditions of 70° C. and 6000 r/min for 20 minutes while an oil phase (2 g of uniform compound and 1 g of polymethyl methacrylate) was added dropwise. Then 0.01 g of ammonium persulfate was added, mechanical stirring (500 r/min) was carried out at 80° C. for 3 hours, and finally, the mixture was washed with water and dried to obtain a microcapsule product. 0.2 g of the product was weighed and pressed into a tablet to be used as a research object. When a voltage was applied and the temperature was lower than 31° C., the sample was colorless; when the temperature was higher than 31° C., the sample became orange-red from colorless; when the temperature was lowered to 31° C. or below and then the voltage was removed, the sample still remained orange-red; and when the temperature was raised, the sample became colorless again. When no voltage was applied, the sample was colorless under any conditions.

Example 4

[0027] 0.1 g of 2′-chloro-6′-(diethylamino) fluoran, 0.8 g of tetrabutylammonium perchlorate (TBAP) and 5 g of benzyl benzoate were magnetically stirred at 80° C. for 1 hour to obtain a uniform mixed solution. 1.8 g of sodium dodecylbenzenesulfonate and 95.2 g of water were emulsified under conditions of 70° C. and 6000 r/min for 20 minutes while an oil phase (2 g of uniform compound and 1 g of polymethyl methacrylate) was added dropwise. Then 0.01 g of ammonium persulfate was added, mechanical stirring (500 r/min) was carried out at 80° C. for 3 hours, and finally, the mixture was washed with water and dried to obtain a microcapsule product. 0.2 g of the product was weighed and pressed into a tablet to be used as a research object. When a voltage was applied and the temperature was lower than 5° C., the sample was colorless; when the temperature was higher than 5° C., the sample became orange-red from colorless; when the temperature was lowered to 5° C. or below and then the voltage was removed, the sample still remained orange-red; and when the temperature was raised, the sample became colorless again. When no voltage was applied, the sample was colorless under any conditions.

Example 5

[0028] 0.1 g of 2′-chloro-6′-(diethylamino) fluoran, 0.8 g of tetrabutylammonium perchlorate (TBAP) and 5 g of glycerin monostearate were magnetically stirred at 80° C. for 1 hour to obtain a uniform mixed solution. 1.8 g of sodium dodecylbenzenesulfonate and 95.2 g of water were emulsified under conditions of 70° C. and 6000 r/min for 20 minutes while an oil phase (2 g of uniform compound and 1 g of polymethyl methacrylate) was added dropwise. Then 0.01 g of ammonium persulfate was added, mechanical stirring (500 r/min) was carried out at 80° C. for 3 hours, and finally, the mixture was washed with water and dried to obtain a microcapsule product. 0.2 g of the product was weighed and pressed into a tablet to be used as a research object. When a voltage was applied and the temperature was lower than 80° C., the sample was colorless; when the temperature was higher than 80° C., the sample became orange-red from colorless; when the temperature was lowered to 80° C. or below and then the voltage was removed, the sample still remained orange-red; and when the temperature was raised, the sample became colorless again. When no voltage was applied, the sample was colorless under any conditions.

Example 6

[0029] 0.1 g of 2′-chloro-6′-(diethylamino) fluoran, 0.8 g of tetrabutylammonium perchlorate (TBAP), 2.7 g of cetyl alcohol and 2.3 g of glycerin monostearate were magnetically stirred at 80° C. for 1 hour to obtain a uniform mixed solution. 1.8 g of sodium dodecylbenzenesulfonate and 95.2 g of water were emulsified under conditions of 70° C. and 6000 r/min for 20 minutes while an oil phase (2 g of uniform compound and 1 g of polymethyl methacrylate) was added dropwise. Then 0.01 g of ammonium persulfate was added, mechanical stirring (500 r/min) was carried out at 80° C. for 3 hours, and finally, the mixture was washed with water and dried to obtain a microcapsule product. 0.2 g of the product was weighed and pressed into a tablet to be used as a research object. When a voltage was applied and the temperature was lower than 60° C., the sample was colorless; when the temperature was higher than 60° C., the sample became orange-red from colorless; when the temperature was lowered to 60° C. or below and then the voltage was removed, the sample still remained orange-red; and when the temperature was raised, the sample became colorless again. When no voltage was applied, the sample was colorless under any conditions. Compared with Example 5, the cetyl alcohol and the glycerin monostearate were compounded, and the color change temperature was lowered from 80° C. to 60° C.; and when the glycerin monostearate was used alone, the color change temperature was 80° C., indicating that the compounding of the cetyl alcohol and the glycerin monostearate could significantly lower the color change temperature by 20° C.

Comparative Example 1

[0030] The 0.8 g of tetrabutylammonium perchlorate (TBAP) in Example 1 was omitted, other conditions or parameters were the same as those in Example 1, and a microcapsule product was obtained. 0.2 g of the product was weighed and pressed into a tablet to be used as a research object. The sample was colorless under any conditions, and thus, could not achieve electric and temperature dual-control color change.

Comparative Example 2

[0031] The diphenyl carbonate in Example 1 was replaced with cetyl alcohol, other conditions or parameters were the same as those in Example 1, and a microcapsule product was obtained. 0.2 g of the product was weighed and pressed into a tablet to be used as a research object. When a voltage was applied and the temperature was lower than 28° C., the sample was colorless; when the temperature was higher than 28° C., the sample became orange-red from colorless; when the temperature was lowered to 28° C. or below and the voltage was removed, the sample still remained orange-red, and had an energy-saving effect; and when the temperature was raised, the sample became colorless again. When no voltage was applied, the sample was colorless under any conditions. However, the color change of the sample was uneven, the color was lighter, and the driving voltage was larger.

Comparative Example 3

[0032] The 0.1 g of 2′-chloro-6′-(diethylamino) fluoran in Example 1 was replaced with 0.1 g of N-[4-[2-(4-methoxyphenyl) diazenyl]phenyl]-2-nitroaniline, other conditions or parameters were the same as those in Example 1, and a microcapsule product was obtained. 0.2 g of the product was weighed and pressed into a tablet to be used as a research object. The sample was colorless under any conditions, and thus, could not achieve electric and temperature dual-control color change. The inventors found after many experiments that fluoran dyes, such as 1,3-dimethyl-6-diethylaminofluoran, 2′-chloro-6′-(diethylamino)-3′-methylfluoran, 2′-chloro-6′-(diethylamino)fluoran and 6′-(diethylamino)-1′,3′-dimethylfluoran, or crystal violet lactone or spiropyran leuco dyes could better achieve electric and temperature dual-control color change.

TABLE-US-00001 TABLE 1 Color change performance of electric and temperature dual-control color-changing dye microcapsules Voltage Compound Driving Applied (1/8/50) Voltage or Not Color Change Status Example 1 Fluoran dye + 2.0 V Yes When the temperature was lower than 31° C., TBAP + diphenyl the sample was colorless; when the carbonate temperature was higher than 31° C., the sample became orange-red from colorless; when the temperature was lowered to 31° C. or below and then the voltage was removed, the sample still remained orange-red; and when the temperature was raised, the sample became colorless again No The sample was colorless under any conditions Example 2 Fluoran dye + 3.6 V Yes When the temperature was lower than 25° C., TBAP + phenyl the sample was colorless; when the salicylate temperature was higher than 25° C., the sample became orange-red from colorless; when the temperature was lowered to 25° C. or below and then the voltage was removed, the sample still remained orange-red; and when the temperature was raised, the sample became colorless again No The sample was colorless under any conditions Example 3 Fluoran dye + 5.7 V Yes When the temperature was lower than 31° C., TBAP + phenyl the sample was colorless; when the stearate temperature was higher than 31° C., the sample became orange-red from colorless; when the temperature was lowered to 31° C. or below and then the voltage was removed, the sample still remained orange-red; and when the temperature was raised, the sample became colorless again No The sample was colorless under any conditions Example 4 Fluoran dye +   4 V Yes When the temperature was lower than 5° C., TBAP + benzyl the sample was colorless; when the benzoate temperature was higher than 5° C., the sample became orange-red from colorless; when the temperature was lowered to 5° C. or below and then the voltage was removed, the sample still remained orange-red; and when the temperature was raised, the sample became colorless again No The sample was colorless under any conditions Example 5 Fluoran dye +   2 V Yes When the temperature was lower than 80° C., TBAP + glycerin the sample was colorless; when the monostearate temperature was higher than 80° C., the sample became orange-red from colorless; when the temperature was lowered to 80° C. or below and then the voltage was removed, the sample still remained orange-red; and when the temperature was raised to 80° C., the sample became colorless again No The sample was colorless under any conditions Example 6 Fluoran dye +   2 V Yes When the temperature was lower than 60° C., TBAP + cetyl the sample was colorless; when the alcohol + glycerin temperature was higher than 60° C., the sample monostearate became orange-red from colorless; when the temperature was lowered to 60° C. or below and then the voltage was removed, the sample still remained orange-red; and when the temperature was raised to 60° C., the sample became colorless again No The sample was colorless under any conditions Comparative Fluoran dye + Arbitrary Yes/No The sample was colorless under any conditions Example 1 diphenyl carbonate Comparative Fluoran dye +  11 V Yes When the temperature was lower than 28° C., Example 2 TBAP + cetyl the sample was colorless; when the alcohol temperature was higher than 28° C., the sample became orange-red from colorless (the color change was uneven and the color was lighter); when the temperature was lowered to 28° C. or below and then the voltage was removed, the sample still remained orange-red; and when the temperature was raised, the sample became colorless again No The sample was colorless under any conditions Comparative Fluoran dye + Arbitrary Yes/No The sample was colorless under any conditions Example 3 TBAP + diphenyl carbonate

[0033] The inventors have found after many experiments that when the selected organic solid material is one or more of macromolecular ethers and esters, including glyceryl monostearate, glycerin monostearate, phenyl salicylate, glyceryl laurate, p-azoxyanisole, diphenyl carbonate, phenyl salicylate, phenyl stearate and benzyl benzoate, the obtained microcapsule product can achieve electric and temperature dual-control color change and a driving voltage being lower than 10 V. When other types of organic solid materials (such as small molecular organic alkyl alcohols and alkyl acids, including stearyl alcohol, cetyl alcohol, myristyl alcohol, myristic acid, palmitic acid, stearic acid and the like) are used alone, electric and temperature dual-control color change cannot be achieved, or the driving voltage is too high, or the color development effect is not good. However, when the small molecular organic alkyl alcohols and alkyl acids, such as stearyl alcohol, cetyl alcohol, myristyl alcohol, myristic acid, palmitic acid, stearic acid and the like, are compounded with ethers and esters, such as glyceryl monostearate, glycerin monostearate, phenyl salicylate, glyceryl laurate, p-azoxyanisole, diphenyl carbonate, phenyl salicylate, phenyl stearate, benzyl benzoate and the like, the color change temperature can be significantly lowered.

[0034] The inventors have found after many experiments that when the ratio of the leuco dye to the electrolyte to the organic solid material is 1:(2-10):(15-50), the electric and temperature dual-control bi-stable color-changing microcapsules prepared from the selected electrolyte, leuco dye and ester organic solid material have good color change performance and a driving voltage of less than 10 V, which is lower than the human body safety voltage. After the microcapsules change color and then the power is cut off, the stable time can reach 5 days.