CN113980208B - Multi-arm block type polycaprolactone color-changing polymer, light-operated color-changing sponge and preparation method thereof - Google Patents
Multi-arm block type polycaprolactone color-changing polymer, light-operated color-changing sponge and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a multi-arm block-type polycaprolactone color-changing polymer, a light-operated color-changing sponge and a preparation method thereof, wherein the polymer is formed by grafting a donor-acceptor Steinhaos adduct onto multi-arm polycaprolactone, exciting light for color change is visible light with the wavelength of 520nm, irreversible damage to a molecular structure by traditional ultraviolet light is avoided, the theoretically longer service life is obtained, the color-changing speed is high, the color-changing sponge prepared by the polymer has the advantages of uniform dispersion and stability of a color-changing phase, difficulty in elution and reutilization, and the span of a color change range is larger.
Description
Technical Field
The invention relates to the technical field of preparation of color-changing sponges, and particularly relates to a multi-arm block type polycaprolactone color-changing polymer, a light-operated color-changing sponge and a preparation method thereof.
Background
At present, most methods for preparing color-changing sponges are dipping methods, wherein the methods are also divided into a pre-dipping method and a post-dipping method. The pre-impregnation method is to mix the molecule with color-changing performance into the precursor prepared by the sponge in advance, and then to foam to prepare the color-changing sponge, and the post-impregnation method is to impregnate the existing sponge into the solution containing the surfactant, the adhesive and the molecule with color-changing performance, and to stabilize the molecule with color-changing performance on the inner surface of the sponge hole through physical or chemical adsorption to prepare the color-changing sponge.
Although the preparation method is simple, the prepared color-changing sponge has a certain color-changing capability, the dispersion is uneven due to the difficulty in coordinating the water/oil solubility, electronegativity and surface energy difference among various substances, the color-changing phase is easy to agglomerate along with the prolonging of the service time, and the color-changing capability is increasingly poor; in addition, the principle of the immersion method for stabilizing the discoloration phase is chemical and physical adsorption, the weak chemical acting force of the immersion method causes the discoloration sponge to have poor stability, the immersion method is difficult to adapt to the fluctuation of environmental conditions such as large temperature and pH change during actual use, and the unfixed discoloration phase is easy to elute by a mobile phase particularly during liquid suction/discharge. In addition, ultraviolet light triggers discolour sponge, inevitably can bring irreversible molecular structure to destroy, and ultraviolet light is difficult for obtaining at civilian within range, and the process of discolouring of traditional sponge is a forward color development's process usually, and outer molecule accomplishes the process of discolouring earlier, and it can produce the barrier effect to ultraviolet light, because ultraviolet light does not possess stronger penetrability, and the inner molecule is difficult to take place the discoloration reaction. Therefore, it is necessary to find a color-changing sponge with a wide range of application scenes.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a multi-arm block type polycaprolactone color-changing polymer, a light-operated color-changing sponge and a preparation method thereof, so as to solve the problem that the color-changing phase of the existing color-changing sponge is easy to elute.
The technical scheme for solving the technical problems is as follows: a multi-arm segmented polycaprolactone color-changing polymer is provided which is formed by grafting a donor-acceptor Stanhaus adduct onto a multi-arm polycaprolactone.
On the basis of the technical scheme, the invention can be further improved as follows:
further, the donor-acceptor Steinhaos adduct was prepared by the following preparation method: stirring the Meldrum's acid and furfural for 4-5h at 30-40 ℃, and then washing with water, removing impurities, removing water and purifying to obtain the donor-acceptor Steinhaos adduct.
Further, the molar ratio of the Meldrum's acid to the furfural is (1-3): 1.
further, the multi-arm polycaprolactone is prepared by the following preparation method: adding epsilon-caprolactone into a reactor, then adding a catalyst and kernel molecules, carrying out polymerization reaction for 10-15h at 120-150 ℃, cooling to room temperature, and then sequentially carrying out dissolution, precipitation and drying to obtain the multi-arm polycaprolactone; wherein the volume mass ratio of epsilon-caprolactone to kernel molecules is 1:8-10ml/mg.
Further, the core molecule is dissolved in N, N-dimethylformamide before being added; wherein the concentration of the core molecule in the N, N-dimethylformamide is 1.6-1.9g/L.
Further, the inner core molecule is phloroglucinol, pentaerythritol or beta-cyclodextrin.
Further, the core molecule and epsilon-caprolactone are dried before the reaction, and the polymerization is carried out under anhydrous conditions.
The invention also provides a preparation method of the multi-arm block type polycaprolactone color-changing polymer, which comprises the following steps:
(1) Adding 3- [ [ (benzylthio) thiocarbonyl ] thio ] propionic acid and multi-arm polycaprolactone into a reactor, adding a catalyst and a solvent, carrying out esterification reaction at 28-32 ℃ for 10-15h, collecting a liquid phase after cooling to room temperature, precipitating in cold methanol, and then drying to obtain an intermediate product I; wherein the mass ratio of the 3- [ [ (benzylthio) thiocarbonyl ] thio ] propionic acid to the multi-arm polycaprolactone is 1: (2-16);
(2) Adding N-methyl allyl amine and the intermediate product I into a reactor, adding an inner core molecule and a solvent, carrying out RAFT reaction for 10-15h at 65-75 ℃, collecting a liquid phase after cooling to room temperature, precipitating in cold methanol, and drying to obtain an intermediate product II; wherein the mass ratio of the N-methyl allyl amine to the intermediate product I is 1: (4-27);
(3) Adding a donor-acceptor Steinhaos adduct and an intermediate product II into a reactor, adding a solvent, carrying out ring-opening reaction at 28-32 ℃ for 45-50h, cooling to room temperature, collecting a liquid phase, precipitating in cold methanol, and drying to obtain the multi-arm block type polycaprolactone color-changing polymer; wherein the mass ratio of the donor-acceptor Steinhaos adduct to the intermediate product II is 1: (1-8).
Further, in the step (1), the catalyst is N, N-dicyclohexyl carbodiimide and 4-dimethyl aminopyridine, and the solvent is dichloromethane.
Further, in the step (2), the inner core molecule is azodiisobutyronitrile, and the solvent is N, N-dimethylformamide.
The invention also provides a preparation method of the light-operated color-changing sponge, which comprises the following steps: the multi-arm block-type polycaprolactone color-changing polymer prepared by the method is foamed, dried and polished to obtain the light-control color-changing multi-arm block-type polycaprolactone sponge.
The invention also provides the light-operated color-changing sponge prepared by the preparation method.
The invention has the following beneficial effects: the light-operated color-changing sponge is prepared by grafting a color-changing molecular donor-acceptor Steinhaos adduct to the tail end of multi-arm polycaprolactone to form a multi-arm block-type polycaprolactone color-changing polymer, and carrying out foaming, molding and polishing treatment.
The color change principle is as follows: after the color-changing molecular donor-acceptor Steinhaos adduct is grafted on the multi-arm polycaprolactone, the multi-arm block-type polycaprolactone color-changing polymer is formed. When the polymer is irradiated with light at 520nm wavelength, the donor-acceptor Steinhaos adduct attached to the polymer block by grafting isomerizes from a colored linear form to a colorless cyclic form, and the colorless cyclic donor-acceptor Steinhaos adduct at the end of the polymer can return to a colored linear form again after heat treatment in the dark.
(1) Compared with the traditional impregnation method, the method has the advantages that the color-changing molecules are grafted to the multi-arm block-type polycaprolactone, and the problems of easy elution, instability, low efficiency, uneven dispersion and the like of the color-changing phase caused by the impregnation method can be perfectly solved.
(2) The excitation light used by the light-operated color-changing sponge is visible light with the wavelength of 520nm, the irreversible damage of the molecular structure by the traditional ultraviolet light is avoided, the theoretically longer service life is obtained, in addition, the visible light with the wavelength of 520nm is easy to obtain in the civil range, the energy consumption is lower, and the application range of the sponge is greatly expanded.
(3) Compared with the traditional photo-induced color development process, the negative color development process of the invention can not generate light ray blocking because the molecules on the outer layer complete color change firstly, and in addition, compared with ultraviolet light, the visible light has stronger penetrating power, and the molecules on the inner layer can also easily generate color change reaction.
(4) Compared with the traditional photochromic sponge, which has slow color change time, the photochromic sponge prepared by the method has rich ester functional groups on a polycaprolactone block due to the fact that polycaprolactone is used as a main body, and the stable and abundant functional groups can serve as an electron transfer intermediate in the process of isomerizing color-changing molecules, so that a catalytic effect is achieved, isomerization can be rapidly and stably carried out under low illumination energy, and the purpose of high-efficiency and rapid overall color change is achieved.
The light-operated color-changing sponge has the advantages of high visible light induced color-changing speed (the stimulation time is less than 10 s), high conversion rate (100%), reusability and large color change range span, and the reflectivity span of the light-operated color-changing sponge is over 50% through ultraviolet-visible spectrum determination.
Drawings
FIG. 1 is a color change process of the photo-chromic sponge prepared in example 1;
FIG. 2 is a heat recovery process for the light-operated color-changing sponge prepared in example 1;
FIG. 3 is a photo-chromic sponge of different substrate colors;
FIG. 4 is a differential scanning calorimetry exotherm plot for the three-arm star-shaped polycaprolactone prepared in example 1;
FIG. 5 is a differential scanning calorimetry exotherm plot for the four-arm star-shaped polycaprolactone prepared in example 2;
FIG. 6 is a differential scanning calorimetry exotherm plot for the multi-arm star-shaped polycaprolactone prepared in example 3.
Detailed Description
The principles and features of this invention are described below in conjunction with the following drawings, which are set forth to illustrate, but are not to be construed to limit the scope of the invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used are conventional products available from commercial sources, not indicated by the manufacturer.
Example 1:
a preparation method of a light-operated color-changing sponge comprises the following steps:
(1) Preparation of three-arm polycaprolactone by using phloroglucinol as core molecule
The reaction principle is as follows: the three-arm star-shaped polycaprolactone is synthesized by controlling ring-opening polymerization by taking phloroglucinol as a core molecule and stannous octoate as a catalyst. For efficient initiation and homogeneous polymerization, phloroglucinol is dissolved using DMF as a solvent. All polymerizations were carried out under strictly anhydrous conditions to avoid initiation by water. By varying the concentration or temperature of stannous octoate, three samples of different molecular weights were synthesized. The higher the catalyst concentration, the higher the temperature, the faster the polymerization rate, and the more complete the monomer conversion reaction.
The specific polymerization process is as follows: connecting a double-mouth bottle to a double-calandria pipe, performing air pumping and inflating for three times through the double-calandria pipe to remove air and moisture in the double-mouth bottle, adding 10mL of epsilon-caprolactone dried in nitrogen atmosphere into the double-mouth bottle, adding 40mg of stannous octoate serving as a catalyst and 90mg of phloroglucinol serving as a dried kernel dissolved by N, N-dimethylformamide, immersing the double-mouth bottle into an oil bath kettle at 130 ℃, performing polymerization for 12 hours, cooling to room temperature, dissolving a crude product by using chloroform, precipitating for three times in cold methanol, and drying in a vacuum oven to obtain 8g of white purified three-arm polycaprolactone; wherein the concentration of the inner core molecule phloroglucinol in the N, N-dimethylformamide is 1.8g/L;
(2) Esterification reaction of 3- [ [ (benzylthio) thiocarbonyl ] thio ] propionic acid and three-arm polycaprolactone
Connecting a double-mouth bottle to a double-calandria, performing air suction and inflation for three times through the double-calandria to remove air and water in the double-mouth bottle, adding 318mg of 3- [ [ (benzylthio) thiocarbonyl ] thio ] propionic acid and 4g of three-arm polycaprolactone into the double-mouth bottle, adding 372mg of catalyst DCC (N, N-dicyclohexylcarbodiimide) and 144mg of catalyst DMAP (4-dimethylaminopyridine), adding 30mL of solvent dichloromethane, immersing the double-mouth bottle into an oil bath kettle at 30 ℃, performing esterification for 12 hours, cooling to room temperature, collecting a light yellow liquid phase, precipitating the light yellow liquid in cold methanol for three times, and drying in an air oven to obtain 1.4g of a light yellow purified intermediate product I;
(3) RAFT reaction of N-methylallylamine with intermediate one
Connecting a double-mouth bottle to a double-row pipe, performing air suction and inflation for three times through the double-row pipe to remove air and moisture in the double-mouth bottle, adding 4g of N-methyl allylamine and 1g of an intermediate product I into the double-mouth bottle, adding 50mg of kernel molecule Azobisisobutyronitrile (AIBN) and 50mL of solvent N, N-dimethylformamide into the double-mouth bottle, immersing the double-mouth bottle into an oil bath kettle at 70 ℃, stirring at 350rpm, performing RAFT reaction for 12 hours, collecting a dark yellow liquid phase after cooling to room temperature, precipitating the dark yellow liquid in cold methanol for three times, and drying in an air oven to obtain 800mg of a purified intermediate product II;
(4) Preparation of donor-acceptor Steiner adducts
Stirring the Meldrum's acid and furfural at 35 ℃ for 4.5h, washing the obtained product with water, performing suction filtration to remove water, then sequentially extracting with saturated sodium bisulfite and saturated sodium chloride aqueous solution to remove impurities, further removing water with anhydrous magnesium sulfate, performing suction filtration to remove anhydrous magnesium sulfate, finally purifying with a chromatographic column, and eluting with dichloromethane to obtain a yellow solid donor-acceptor Steinhaos adduct; wherein the molar ratio of the Meldrum's acid to the furfural is 1:1.
(5) Ring opening reaction of intermediate product two and donor-acceptor Steinhaos adduct
Connecting a double-mouth bottle to a double-row pipe, performing air suction and inflation for three times through the double-row pipe to remove air and water in the double-mouth bottle, adding 100mg of donor-acceptor Steiner adduct and 800mg of intermediate product II into the double-mouth bottle, adding 30mL of solvent dichloromethane, immersing the double-mouth bottle into an oil bath kettle at 30 ℃, stirring at 350rpm simultaneously, performing ring-opening reaction for 2 days, cooling to room temperature, collecting a purple liquid phase, precipitating the purple liquid phase in cold methanol for three times, and drying in an air oven to obtain the multi-arm block type polycaprolactone color-changing polymer;
(6) Preparation of light-operated color-changing sponge
Putting the multi-arm block-type polycaprolactone color-changing polymer into supercritical carbon dioxide foaming equipment, fully swelling the multi-arm block-type polycaprolactone color-changing polymer by using a carbon dioxide supercritical fluid at 60 ℃ and under the pressure of 13.75MPa, then quickly cooling and relieving pressure, and drying and polishing to obtain the light-operated color-changing sponge.
Example 2:
a preparation method of a light-operated color-changing sponge comprises the following steps:
(1) Preparation of four-arm polycaprolactone by using pentaerythritol as core molecule
The reaction principle is as follows, pentaerythritol is used as a core molecule, stannous octoate is used as a catalyst, and the four-arm star-shaped polycaprolactone is synthesized by controlling ring-opening polymerization. For efficient initiation and homogeneous polymerization, pentaerythritol was dissolved using DMF as a solvent. All polymerizations were carried out under strictly anhydrous conditions to avoid initiation by water. By varying the concentration or temperature of stannous octoate, three samples of different molecular weights were synthesized. The higher the catalyst concentration, the higher the temperature, the faster the polymerization rate, and the more complete the monomer conversion reaction.
The specific polymerization process is as follows: connecting a double-mouth bottle to a double-calandria pipe, performing air pumping and inflating for three times through the double-calandria pipe to remove air and moisture in the double-mouth bottle, adding 10mL of epsilon-caprolactone dried in nitrogen atmosphere into the double-mouth bottle, adding 40mg of stannous octoate catalyst and 90mg of pentaerythritol serving as a dry kernel molecule dissolved by N, N-dimethylformamide, immersing the double-mouth bottle into an oil bath kettle at 120 ℃, performing polymerization for 15 hours, cooling to room temperature, dissolving a crude product by using chloroform, precipitating in cold methanol for three times, and drying in a vacuum oven to obtain 10g of white purified four-arm polycaprolactone; wherein the concentration of the core molecule pentaerythritol in the N, N-dimethylformamide is 1.6g/L;
(2) Esterification reaction of 3- [ [ (benzylthio) thiocarbonyl ] thio ] propionic acid and four-arm polycaprolactone
Connecting a double-mouth bottle to a double-calandria, performing air suction and inflation for three times through the double-calandria to remove air and water in the double-mouth bottle, adding 318mg of 3- [ [ (benzylthio) thiocarbonyl ] thio ] propionic acid and 5g of four-arm polycaprolactone into the double-mouth bottle, adding 382mg of catalyst DCC (N, N-dicyclohexylcarbodiimide) and 154mg of catalyst DMAP (4-dimethylaminopyridine), adding 30mL of solvent dichloromethane, immersing the double-mouth bottle into a 28 ℃ oil bath kettle, stirring at 350rpm, performing esterification for 15 hours, cooling to room temperature, collecting a light yellow liquid phase, precipitating the light yellow liquid in cold methanol for three times, and drying in an air oven to obtain 4.4g of light yellow purified intermediate product I;
(3) RAFT reaction of N-methyl allylamine and intermediate one
Connecting a double-mouth bottle to a double-row pipe, performing air suction and inflation for three times through the double-row pipe to remove air and water in the double-mouth bottle, adding 16g of N-methyl allylamine and 4g of an intermediate product I into the double-mouth bottle, adding 200mg of core molecule Azodiisobutyronitrile (AIBN) and 100mL of solvent N, N-dimethyl formamide, immersing the double-mouth bottle into an oil bath kettle at 65 ℃, stirring at 350rpm, performing RAFT reaction for 15 hours, collecting a dark yellow liquid phase after cooling to room temperature, precipitating the dark yellow liquid in cold methanol for three times, and drying in an air oven to obtain 3.56g of a purified intermediate product II;
(4) Preparation of donor-acceptor Steiner adducts
Stirring the Meldrum's acid and furfural at 30 ℃ for 5 hours, washing the obtained product with water, performing suction filtration to remove water, then sequentially extracting with saturated sodium bisulfite and saturated sodium chloride aqueous solution to remove impurities, further removing water with anhydrous magnesium sulfate, performing suction filtration to remove anhydrous magnesium sulfate, finally purifying with a chromatographic column, and eluting with dichloromethane to obtain a yellow solid donor-acceptor Steinhaos adduct; wherein the mol ratio of the Meldrum's acid to the furfural is 2:1.
(5) Ring opening reaction of intermediate product two and donor-acceptor Steinhaos adduct
Connecting a double-mouth bottle to a double-row pipe, performing air suction and inflation for three times through the double-row pipe to remove air and moisture in the double-mouth bottle, adding 400mg of donor-acceptor Steiner adduct and 3.2g of intermediate product II into the double-mouth bottle, adding 100mL of solvent dichloromethane, immersing the double-mouth bottle into an oil bath kettle at 28 ℃, stirring at 350rpm simultaneously, performing ring-opening reaction for 50 hours, cooling to room temperature, collecting a purple liquid phase, precipitating the purple liquid phase in cold methanol for three times, and drying in an air oven to obtain the multi-arm block-type polycaprolactone color-changing polymer;
(6) Preparation of light-operated color-changing sponge
The multi-arm block-type polycaprolactone color-changing polymer is placed in supercritical carbon dioxide foaming equipment, the carbon dioxide supercritical fluid fully swells the multi-arm block-type polycaprolactone color-changing polymer at 60 ℃ and under the pressure of 13.75MPa, then the multi-arm block-type polycaprolactone color-changing polymer is rapidly cooled and decompressed, and then the light-operated color-changing sponge is obtained through drying and polishing.
Example 3:
a preparation method of a light-operated color-changing sponge comprises the following steps:
(1) Preparation of multi-arm polycaprolactone by taking beta-cyclodextrin as core molecule
The reaction principle is as follows, the multi-arm star-shaped polycaprolactone is synthesized by controlling ring-opening polymerization by taking beta-cyclodextrin as an inner core molecule and stannous octoate as a catalyst. For efficient initiation and homogeneous polymerization, DMF was used as a solvent to dissolve the β -cyclodextrin. All polymerizations were carried out under strictly anhydrous conditions to avoid initiation by water. By varying the concentration or temperature of stannous octoate, three samples of different molecular weights were synthesized. The higher the catalyst concentration, the higher the temperature, the faster the polymerization rate, and the more complete the monomer conversion reaction.
The specific polymerization process is as follows: connecting a double-mouth bottle to a double-calandria, performing air pumping and inflation for three times through the double-calandria to remove air and water in the double-mouth bottle, adding 10mL of epsilon-caprolactone dried in nitrogen atmosphere into the double-mouth bottle, adding 40mg of stannous octoate serving as a catalyst and 90mg of beta-cyclodextrin serving as a dry inner nuclear molecule dissolved by N, N-dimethylformamide, immersing the double-mouth bottle into an oil bath kettle at 150 ℃, performing polymerization for 10 hours, cooling to room temperature, dissolving a crude product by using chloroform, precipitating for three times in cold methanol, and drying in a vacuum oven to obtain 12g of brown purified multi-arm polycaprolactone; wherein the concentration of the core molecule beta-cyclodextrin in the N, N-dimethylformamide is 1.9g/L;
(2) Esterification reaction of 3- [ [ (benzylthio) thiocarbonyl ] thio ] propionic acid and multi-arm polycaprolactone
Connecting a double-mouth bottle to a double-row pipe, performing air suction and inflation for three times through the double-row pipe to remove air and water in the double-mouth bottle, adding 2.9g of 3- [ [ (benzylthio) thiocarbonyl ] thio ] propionic acid and 6g of multi-arm polycaprolactone into the double-mouth bottle, adding 382mg of catalyst DCC (N, N-dicyclohexylcarbodiimide) and 154mg of catalyst DMAP (4-dimethylaminopyridine), adding 50mL of solvent dichloromethane, immersing the double-mouth bottle into an oil bath kettle at 32 ℃, performing esterification reaction for 10 hours, cooling to room temperature, collecting a light yellow liquid phase, precipitating the light yellow liquid in cold methanol for three times, and drying in an air oven to obtain 5.6g of a dark yellow purified intermediate product I;
(3) RAFT reaction of N-methylallylamine with intermediate one
Connecting a double-mouth bottle to a double-row pipe, performing air suction and inflation for three times through the double-row pipe to remove air and water in the double-mouth bottle, adding 130g of N-methyl allylamine and 5g of an intermediate product I into the double-mouth bottle, adding 200mg of core molecule Azodiisobutyronitrile (AIBN) and 100mL of solvent N, N-dimethyl formamide, immersing the double-mouth bottle into an oil bath kettle at 75 ℃, stirring at 350rpm, performing RAFT reaction for 10 hours, collecting a dark yellow liquid phase after cooling to room temperature, precipitating the dark yellow liquid in cold methanol for three times, and drying in an air oven to obtain 4.25g of a purified intermediate product II;
(4) Preparation of donor-acceptor Steiner adducts
Stirring the Meldrum's acid and furfural at 40 ℃ for 4h, washing the obtained product, performing suction filtration to remove moisture, sequentially extracting with saturated sodium bisulfite and saturated sodium chloride aqueous solution to remove impurities, further removing moisture with anhydrous magnesium sulfate, performing suction filtration to remove anhydrous magnesium sulfate, purifying with a chromatographic column, and eluting with dichloromethane to obtain a yellow solid donor-acceptor Steinhaos adduct; wherein the molar ratio of the Meldrum's acid to the furfural is 3:1.
(5) Ring opening reaction of intermediate product two and donor-acceptor Steinhaos adduct
Connecting a double-mouth bottle to a double-row pipe, performing air suction and inflation for three times through the double-row pipe to remove air and moisture in the double-mouth bottle, adding 3.47g of donor-acceptor Steiner adduct and 4g of intermediate product II into the double-mouth bottle, adding 200mL of solvent dichloromethane, immersing the double-mouth bottle into an oil bath kettle at 32 ℃, stirring at 350rpm simultaneously, performing ring-opening reaction for 45 hours, cooling to room temperature, collecting a purple liquid phase, precipitating the purple liquid phase in cold methanol for three times, and drying in an air oven to obtain the multi-arm block-type polycaprolactone color-changing polymer;
(6) Preparation of light-operated color-changing sponge
The multi-arm block-type polycaprolactone color-changing polymer is placed in supercritical carbon dioxide foaming equipment, the carbon dioxide supercritical fluid fully swells the multi-arm block-type polycaprolactone color-changing polymer at 60 ℃ and under the pressure of 13.75MPa, then the multi-arm block-type polycaprolactone color-changing polymer is rapidly cooled and decompressed, and then the light-operated color-changing sponge is obtained through drying and polishing.
And (4) detecting a result:
1. the light-operated color-changing sponge prepared in example 1 was placed in a petri dish and irradiated with 520nm light for 10 seconds, and the experimental result is shown in fig. 1, as can be seen from fig. 1, the light-operated color-changing sponge rapidly changes from purple to white, then the white light is removed, and the sponge is heated, as can be seen from fig. 2, and as can be seen from fig. 2, the light-operated color-changing sponge is restored from white to purple. The light-operated color-changing sponge prepared by the invention has high color-changing speed and good color-changing effect.
2. On the basis of the light-operated color-changing sponge, the color-changing sponge with different substrate colors can be prepared by soaking other color dyes, and the second dye comprises but is not limited to Sudan red, golden lotus orange, dimethyl yellow, fast green or methylene blue, and the result is shown in figure 3, and as can be seen from figure 3, the light-operated color-changing sponge prepared by the invention can realize the switching among various colors, and has wide application range. The original color of the light-operated color-changing sponge prepared by the invention is purple, after the second dye is loaded, the light-operated color-changing result is shown in table 1, as can be seen from table 1, after Sudan red is loaded, the color of the sponge is changed into orange, after 520nm illumination treatment, the color of the sponge is changed into red, and after dark and 30 ℃ heating treatment, the color of the sponge is changed into orange; after loading the globeflower orange, the color of the sponge is changed into dark red, the color of the sponge is changed into orange after being treated by illumination of 520nm, and the color of the sponge is changed into dark red again after being treated by darkness and heating at 30 ℃; after the dimethyl yellow is loaded, the sponge becomes dark red, the color of the sponge becomes yellow after 520nm illumination treatment, and the color of the sponge becomes dark red after dark and 30 ℃ heating treatment; after the load is fast green, the color of the sponge is changed into dark green, the color of the sponge is changed into green after the sponge is irradiated by 520nm light, and the color of the sponge is changed into dark green after the sponge is heated at 30 ℃; after the methylene blue is loaded, the color of the sponge is changed into blue-purple, the color of the sponge is changed into blue after the sponge is illuminated by 520nm light, and the color of the sponge is changed into blue-purple after the sponge is heated by dark at 30 ℃;
TABLE 1 light-controlled discoloration and restoration of color-changing sponges of different substrate colors
3. FIG. 4 is a Differential Scanning Calorimetry (DSC) endothermic/exothermic curve of the three-arm star-shaped polycaprolactone prepared in example 1, wherein the melting curve in FIG. 4 shows that the melting peak temperature is 55.01 ℃, the peak shape is Gaussian single peak, the melting peak is typical of polymer, the crystallization temperature is 29.31 ℃, the peak shape is Gaussian single peak, and the crystallization peak is typical pure substance crystallization peak; FIG. 5 is a graph of the differential scanning calorimetry plot of the four-arm star-shaped polycaprolactone prepared in example 2, wherein the melting curve in FIG. 5 shows that the melting peak temperature is 53.29 ℃, the peak shape is Gaussian single peak, the melting peak is typical polymer melting peak type, the crystallization temperature is 23.16 ℃, the peak shape is Gaussian single peak, and the crystallization peak is typical pure substance crystallization peak; FIG. 6 is a differential scanning calorimetry endothermic heat release curve of the multi-arm star polycaprolactone prepared in example 3, as seen by the melting curve in FIG. 6, having a melting peak temperature of 56.12 ℃, a Gaussian single peak shape, a typical polymer melting peak shape, a crystallization temperature of 29.88 ℃, a Gaussian single peak shape, and a typical pure material crystallization peak.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (7)
1. A multi-arm block-type polycaprolactone color-changing polymer is characterized in that the polymer is formed by grafting a donor-acceptor Steinhaos adduct to multi-arm polycaprolactone;
the preparation method of the multi-arm block type polycaprolactone color-changing polymer comprises the following steps:
(1) Adding 3- [ [ (benzylthio) thiocarbonyl ] thio ] propionic acid and multi-arm polycaprolactone into a reactor, adding a catalyst and a solvent, carrying out esterification reaction at 28-32 ℃ for 10-15h, collecting a liquid phase after cooling to room temperature, precipitating in cold methanol, and drying to obtain an intermediate product I; wherein the mass ratio of the 3- [ [ (benzylthio) thiocarbonyl ] thio ] propionic acid to the multi-arm polycaprolactone is 1: (2-16);
(2) Adding N-methyl allyl amine and the intermediate product I into a reactor, adding an inner core molecule and a solvent, carrying out RAFT reaction for 10-15h at 65-75 ℃, collecting a liquid phase after cooling to room temperature, precipitating in cold methanol, and drying to obtain an intermediate product II; wherein the mass ratio of the intermediate product I to the N-methyl allyl amine is 1: (4-27);
(3) Adding a donor-acceptor Steinhaos adduct and an intermediate product II into a reactor, adding a solvent, performing ring-opening reaction at 28-32 ℃ for 45-50h, cooling to room temperature, collecting a liquid phase, precipitating in cold methanol, and drying to obtain the multi-arm block-type polycaprolactone color-changing polymer; wherein the mass ratio of the donor-acceptor Steinhaos adduct to the intermediate product II is 1: (1-8);
wherein, in the step (2), the inner core molecule is azodiisobutyronitrile, and the solvent is N, N-dimethylformamide.
2. The multi-arm block-type polycaprolactone color-changing polymer of claim 1, wherein the donor-acceptor Steinhaos adduct is prepared by the following method: stirring the Meldrum's acid and furfural for 4-5h at 30-40 ℃, and then washing with water, removing impurities, removing water and purifying to obtain the donor-acceptor Steinhaos adduct.
3. The multi-arm block-type polycaprolactone color-changing polymer according to claim 1, characterized in that the multi-arm polycaprolactone is prepared by the following preparation method: adding epsilon-caprolactone into a reactor, then adding a catalyst and kernel molecules, carrying out polymerization reaction for 10-15h at 120-150 ℃, and after cooling to room temperature, sequentially carrying out dissolution, precipitation and drying to obtain the multi-arm polycaprolactone; in the preparation method of the multi-arm polycaprolactone, the volume-mass ratio of epsilon-caprolactone to inner core molecules is 1:8-10ml/mg; the inner core molecule is phloroglucinol, pentaerythritol or beta-cyclodextrin.
4. The multi-arm block-type polycaprolactone color-changing polymer of claim 3, characterized in that, in the preparation method of the multi-arm polycaprolactone, the core molecule and the epsilon-caprolactone are dried before the reaction, and the polymerization reaction is carried out under anhydrous condition.
5. The multi-arm block-type polycaprolactone color-changing polymer according to claim 1, wherein in step (1), the catalyst is N, N' -dicyclohexylcarbodiimide and 4-dimethylamine pyridine, and the solvent is dichloromethane.
6. The preparation method of the light-operated color-changing sponge is characterized by comprising the following steps of: foaming, drying and polishing the multi-arm block-type polycaprolactone color-changing polymer of any one of claims 1-5 to obtain the light-controlled color-changing multi-arm block-type polycaprolactone sponge.
7. The light-operated color-changing sponge prepared by the preparation method of the light-operated color-changing sponge of claim 6.
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