A photoinduced reversible color-changing polymer material and its preparation method

Abstract

The present invention belongs to the field of polymer materials, and particularly relates to a photoinduced reversible color-changing polymer material and a preparation method thereof. First, a functional hyperbranched polyether is prepared by hybrid copolymerization using glycidol, diene and amine as monomers, and then a small molecule receptor of a thiophene derivative is doped therein, and a photoinduced reversible color-changing polymer is obtained after heat treatment. The photoinduced reversible color-changing polymer material provided by the present invention will rapidly turn blue under the irradiation of ultraviolet light, and can be restored to light yellow transparency after avoiding light or heat treatment. The reversible color-changing polymer material prepared by the present invention has the advantages of fast response, good stability, simple and efficient preparation method, low raw material price, etc., and can be widely applied to the fields of information storage, optical devices, sensors and anti-counterfeiting, etc.

Description

Technical Field

[0001] The present invention belongs to the field of polymer materials, and particularly relates to a photo-induced reversible color-changing polymer material and a preparation method thereof. Background Art

[0002] The reversible photochromic phenomenon refers to that a compound undergoes a specific chemical or physical reaction under the irradiation of light with a certain wavelength, forming a new structure that causes a significant change in the absorption spectrum of its visible part. And it returns to the original structural form under the irradiation of light with another wavelength or the action of heat. Due to its unique properties, it has been attracting great attention from research scholars for many years and has been widely applied in photochromic camouflage, color-changing coatings, optical devices, anti-counterfeiting, intelligent switches, sensors, writable information storage media, etc.

[0003] Due to the drastic structural changes or the photochromic phenomenon caused by free radicals generated by light in traditional photochromic materials, it is easy to damage the morphology of the materials. Therefore, they usually have disadvantages such as short lifespan, poor cyclicity, and insufficient material stability, which greatly limit the application of photochromic materials. Therefore, designing and synthesizing color-changing materials with obvious color change, good cyclic performance, and environmental friendliness can reduce the use and recycling of materials, which is of great significance for promoting environmental protection and resource conservation. Summary of the Invention

[0004] The purpose of the present invention is to provide a polymer material with reversible photochromism and a preparation method thereof. A reversible photochromic polymer material with fast response, reversible recovery, and good stability is prepared.

[0005] To achieve the above purpose, the present invention first prepares a functional hyperbranched polyether by one-step hybrid copolymerization using glycidol, diene, and amine as monomers, and then dopes a small molecule receptor of thiophene derivatives therein, and obtains a photo-induced reversible color-changing polymer thin film material after heat treatment. The specific preparation method steps are as follows:

[0006] (1) Glycidol reacts with diene monomers and amine monomers under the action of a catalyst to undergo a hybrid copolymerization reaction to prepare a functional hyperbranched polyether in one step;

[0007] Among them, the diene monomers are: one or several of 1,4-butanediol diacrylate (BDDA), 1,6-hexanediol diacrylate (HDDA), neopentyl glycol diacrylate (NPGDA), and ethylene glycol diacrylate (EGDA).

[0008] The amine is: one or more of N,N-dimethyl-p-phenylenediamine (NNDMP), 4-isopropylaniline (IPA), diphenylamine (DPA), and N,N'-diphenyl-p-phenylenediamine (DPPD).

[0009] During the synthesis of hyperbranched polyethers, the molar ratio of glycidyl to diene monomers is 1000:10 to 200;

[0010] The molar ratio of glycidyl to amine monomers is 1000:1 to 100;

[0011] The catalyst is one or more of t-BuP1, t-BuP2, and t-BuP4.

[0012] The molar ratio of glycidyl to the catalyst is 1000:1 to 10.

[0013] The hybrid copolymerization reaction can be carried out by bulk polymerization or solution polymerization. The solvent used in solution polymerization is any one or a mixture of several organic solvents such as tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), N,N'-dimethylformamide (DMF), and dioxane (DD). The mass of the solvent used in solution polymerization is 0.1 to 5 times the mass of the monomers.

[0014] In the polymerization reaction stage, the reaction temperature range is 25 to 100 °C.

[0015] (2) The generated hyperbranched polyethers are blended with small molecule acceptors of thiophene derivatives and heat-treated to prepare a photoinduced reversible color-changing polymer thin film material.

[0016] The small molecule acceptors of thiophene derivatives are: 2-dibenzothienyl diphenylphosphine oxide (2-DBS), 2-dibenzothienyl diphenylphosphine oxide S,S-dioxide (2-DBSOSPO), 3-dibenzothienyl diphenylphosphine oxide S,S-dioxide (3-DBSOSPO), 4-dibenzothienyl diphenylphosphine oxide S,S-dioxide (4-DBSOSPO).

[0017] The molar ratio of amine monomers to thiophene derivatives is 1 to 100:1000.

[0018] The heat treatment temperature is in the range of 25 to 100 °C or a larger range, and the heat treatment time is 0.5 to 24 h.

[0019] The present invention has the following beneficial effects:

[0020] (1) The present invention uses non-toxic glycidyl, common diene monomers, and amine monomers as raw materials, and the raw materials are cheap and widely available.

[0021] (2) In the heat treatment stage, the temperature range is 25 to 100 °C or a larger range, and the heat treatment time is 0.5 to 24 h.

[0022] (3) The process is simple and controllable. Under the action of a simple organic catalyst, the polymer can be prepared by a one-step method, and the polymer thin film material can be made by simple heat treatment. The reversible recovery rate is controllable.

[0023] (4) The polymer film prepared by the present invention has a rapid response, good repeatability, good film-forming properties and excellent stability, and has good application prospects. Description of the Drawings

[0024] Figure 1 Practical pictures of the products obtained in Example 1, Example 2 and Example 9.

[0025] Figure 2 Ultraviolet absorption spectrum of the product obtained in Example 1.

[0026] Figure 3 Practical picture of the thermal recovery of the product obtained in Example 1.

[0027] Figure 4 Ultraviolet absorption spectra of the thermal recovery of the product obtained in Example 1 at different temperatures.

[0028] Figure 5 Practical picture of the repeatability of the product obtained in Example 4.

[0029] Figure 6 Ultraviolet absorption spectra of the product obtained in Example 13 at different times.

[0030] Figure 7 Ultraviolet absorption spectrum of the product obtained in Example 14. Detailed Embodiments

[0031] The present invention will be further described below in conjunction with embodiments, but not limited to the following embodiments. For process parameters not specifically noted, conventional techniques can be referred to.

[0032] Example 1

[0033] The experiment was carried out in a glove box filled with an argon atmosphere. 1 g (13.50 mmol) of glycidol, 0.054 g (0.27 mol) of 1,4-butanediol diacrylate and 0.018 g (0.13 mmol) of N,N-dimethyl-p-phenylenediamine were added to a 5 mL round-bottom flask with a magnetic rotor, and 6.7 μl (0.01 mmol) of t-BuP2 was added. It was taken out and placed in an oil bath at 60 °C for 12 h. After the reaction, it was dissolved with a small amount of tetrahydrofuran and precipitated in n-hexane to obtain a pale yellow product. It was dried overnight in a vacuum oven. 0.012 g of the polymer product was taken, 0.020 g (0.052 mmol) of 2-DBS was added thereto, dissolved with an appropriate amount of dimethyl sulfoxide and heat-treated in an oven at 100 °C for 30 min to obtain a pale yellow transparent polymer film.

[0034] The obtained polymer film has good film-forming property and stability. It can quickly turn blue under ultraviolet light irradiation for 2 s and reach the maximum ultraviolet absorption at 20 s. As Figure 4 shown, after heat treatment at 100 °C, it can return to its original state within 30 min and has different recovery rates at different heat treatment temperatures. The physical picture and ultraviolet absorption spectrum of this polymer film are as Figure 1 , Figure 2 shown.

[0035] Example 2

[0036] The experiment was carried out in a glove box filled with argon atmosphere. 1 g (13.50 mmol) of glycidol, 0.054 g (0.27 mol) of 1,4-butanediol diacrylate and 0.002 g (0.01 mmol) of N,N-dimethyl-p-phenylenediamine were added to a 5 mL round-bottom flask with a magnetic rotor, and 6.7 μL (0.01 mmol) of t-BuP2 was added. It was taken out and placed in an oil bath at 60 °C for reaction for 12 h. After the reaction, it was dissolved with a small amount of tetrahydrofuran and precipitated in n-hexane to obtain a pale yellow product. It was dried overnight in a vacuum oven. 0.012 g of the polymer product was taken, 0.02 g (0.052 mmol) of 2-DBS was added thereto, and it was dissolved with an appropriate amount of dimethyl sulfoxide and heat-treated in an oven at 100 °C for 30 min to obtain a pale yellow transparent polymer film.

[0037] As Figure 1 shown, due to the relatively small addition ratio of the donor amine monomer, the polymer film is basically colorless and transparent and has no obvious color change under ultraviolet light irradiation.

[0038] Example 3

[0039] The experiment was carried out in a glove box filled with argon atmosphere. 1 g (13.50 mmol) of glycidol, 0.535 g (2.70 mol) of 1,4-butanediol diacrylate and 0.184 g (1.35 mmol) of N,N-dimethyl-p-phenylenediamine were added to a 5 mL round-bottom flask with a magnetic rotor, and 6.7 μL (0.01 mmol) of t-BuP2 was added. It was taken out and placed in an oil bath at 60 °C for reaction for 12 h. After the reaction, it was dissolved with a small amount of tetrahydrofuran and precipitated in n-hexane to obtain a pale yellow product. It was dried overnight in a vacuum oven. 0.019 g of the polymer product was taken, 0.02 g (0.052 mmol) of 2-DBS was added thereto, and it was dissolved with an appropriate amount of dimethyl sulfoxide and heat-treated in an oven at 50 °C for 12 h to obtain a pale yellow transparent polymer film.

[0040] The obtained polymer film has good film-forming property and stability. It will quickly turn blue under ultraviolet light irradiation and can return to colorless and transparent after being protected from light or heat-treated.

[0041] Example 4

[0042] The experimental operation was carried out in a glove box filled with an argon atmosphere. 1 g (13.50 mmol) of glycidol, 0.268 g (1.35 mmol) of 1,4-butanediol diacrylate and 0.092 g (0.67 mmol) of N,N-dimethyl-p-phenylenediamine were added to a 5 mL round-bottom flask equipped with a magnetic rotor, and 6.7 μL (0.01 mmol) of t-BuP2 was added. It was taken out and placed in an oil bath at 60 °C for reaction for 12 h. After the reaction was completed, it was dissolved with a small amount of tetrahydrofuran and precipitated in n-hexane to obtain a pale yellow product. It was dried overnight in a vacuum oven. 0.015 g of the polymerization product was taken, 0.02 g (0.052 mmol) of 2-DBS was added thereto, dissolved with an appropriate amount of dimethyl sulfoxide and heat-treated in an oven at 100 °C for 30 min to obtain a pale yellow transparent polymer film.

[0043] The obtained polymer film had good film-forming property and stability, and would rapidly turn blue under ultraviolet light irradiation, and could be restored to colorless and transparent after being shielded from light or heat-treated.

[0044] Example 5

[0045] The experimental operation was carried out in a glove box filled with an argon atmosphere. 1 g (13.50 mmol) of glycidol, 0.153 g (0.67 mmol) of 1,6-hexanediol diacrylate and 0.018 g (0.13 mmol) of N,N-dimethyl-p-phenylenediamine were added to a 5 mL round-bottom flask equipped with a magnetic rotor, and 6.7 μL (0.01 mmol) of t-BuP2 was added. It was taken out and placed in an oil bath at 60 °C for reaction for 12 h. After the reaction was completed, it was dissolved with a small amount of tetrahydrofuran and precipitated in n-hexane to obtain a pale yellow product. It was dried overnight in a vacuum oven. 0.013 g of the polymerization product was taken, 0.02 g (0.052 mmol) of 2-DBS was added thereto, dissolved with an appropriate amount of dimethyl sulfoxide and heat-treated in an oven at 50 °C for 12 h to obtain a pale yellow transparent polymer film.

[0046] The obtained polymer film had good film-forming property and stability, and would rapidly turn blue under ultraviolet light irradiation, and could be restored to colorless and transparent after being shielded from light or heat-treated.

[0047] Example 6

[0048] The experiment was carried out in a glove box filled with an argon atmosphere. 1 g (13.50 mmol) of glycidol, 0.430 g (2.02 mol) of neopentyl glycol diacrylate and 0.092 g (0.67 mmol) of N,N-dimethyl-p-phenylenediamine were added to a 5 mL round-bottom flask equipped with a magnetic rotor, and 6.7 μL (0.01 mmol) of t-BuP2 was added. It was taken out and placed in an oil bath at 60 °C for reaction for 12 h. After the reaction was completed, it was dissolved with a small amount of tetrahydrofuran and precipitated in n-hexane to obtain a pale yellow product. It was dried overnight in a vacuum oven. 0.017 g of the polymerization product was taken, 0.02 g (0.052 mmol) of 2-DBS was added thereto, and it was dissolved with an appropriate amount of dimethyl sulfoxide and heat-treated in an oven at 100 °C for 30 min to obtain a pale yellow transparent polymer film.

[0049] The obtained polymer film has good film-forming property and stability. It will quickly turn blue under ultraviolet light irradiation and can be restored to colorless and transparent after avoiding light or heat treatment.

[0050] Example 7

[0051] The experiment was carried out in a glove box filled with an argon atmosphere. 1 g (13.50 mmol) of glycidol, 0.578 g (2.70 mol) of ethylene glycol diacrylate and 0.002 g (0.01 mmol) of N,N-dimethyl-p-phenylenediamine were added to a 5 mL round-bottom flask equipped with a magnetic rotor, and 6.7 μL (0.01 mmol) of t-BuP2 was added. It was taken out and placed in an oil bath at 60 °C for reaction for 12 h. After the reaction was completed, it was dissolved with a small amount of tetrahydrofuran and precipitated in n-hexane to obtain a pale yellow product. It was dried overnight in a vacuum oven. 0.017 g of the polymerization product was taken, 0.02 g (0.052 mmol) of 2-DBS was added thereto, and it was dissolved with an appropriate amount of dimethyl sulfoxide and heat-treated in an oven at 100 °C for 30 min to obtain a pale yellow transparent polymer film.

[0052] The obtained polymer film has good film-forming property and stability. It will quickly turn blue under ultraviolet light irradiation and can be restored to colorless and transparent after avoiding light or heat treatment.

[0053] Example 8

[0054] The experiment was carried out in a glove box filled with an argon atmosphere. 1 g (13.50 mmol) of glycidol, 0.027 g (0.13 mol) of 1,4-butanediol diacrylate and 0.183 g (1.35 mmol) of 4-isopropyl aniline were added to a 5 mL round-bottom flask equipped with a magnetic rotor, and 6.7 μL (0.01 mmol) of t-BuP2 was added. It was taken out and placed in an oil bath at 60 °C for reaction for 12 h. After the reaction was completed, it was dissolved with a small amount of tetrahydrofuran and precipitated in n-hexane to obtain a pale yellow product. It was dried overnight in a vacuum oven. 0.013 g of the polymer product was taken, 0.02 g (0.052 mmol) of 2-DBS was added thereto, dissolved with an appropriate amount of dimethyl sulfoxide and heat-treated in an oven at 50 °C for 12 h to obtain a pale yellow transparent polymer film.

[0055] The obtained polymer film has good film-forming property and stability. It will quickly turn blue under ultraviolet light irradiation and can be restored to colorless and transparent after avoiding light or heat treatment.

[0056] Example 9

[0057] The experiment was carried out in a glove box filled with an argon atmosphere. 1 g (13.50 mmol) of glycidol, 0.489 g (2.16 mol) of 1,6-hexanediol diacrylate and 0.183 g (1.08 mmol) of diphenylamine were added to a 5 mL round-bottom flask equipped with a magnetic rotor, and 6.7 μL (0.01 mmol) of t-BuP2 was added. It was taken out and placed in an oil bath at 60 °C for reaction for 12 h. After the reaction was completed, it was dissolved with a small amount of tetrahydrofuran and precipitated in n-hexane to obtain a pale yellow product. It was dried overnight in a vacuum oven. 0.015 g of the polymer product was taken, 0.02 g (0.052 mmol) of 2-DBS was added thereto, dissolved with an appropriate amount of dimethyl sulfoxide and heat-treated in an oven at 100 °C for 30 min to obtain a yellow transparent polymer film.

[0058] The obtained polymer film has good film-forming property and stability. It turns gray under ultraviolet light irradiation. The physical picture of the polymer film is as Figure 1 shown.

[0059] Example 10

[0060] The experiment was conducted in a glove box filled with an argon atmosphere. 1 g (13.50 mmol) of glycidol, 0.116 g (0.54 mol) of ethylene glycol diacrylate, and 0.070 g (0.27 mmol) of N,N'-diphenyl-p-phenylenediamine were added to a 5 mL round-bottom flask equipped with a magnetic rotor, and 6.7 μL (0.01 mmol) of t-BuP2 was added. It was taken out and placed in an oil bath at 60 °C for reaction for 12 h. After the reaction, it was dissolved in a small amount of tetrahydrofuran and precipitated in n-hexane to obtain a pale yellow product. It was dried overnight in a vacuum oven. 0.007 g of the polymer product was taken, 0.02 g (0.052 mmol) of 2-DBS was added thereto, and it was dissolved in an appropriate amount of dimethyl sulfoxide and heat-treated in an oven at 25 °C for 12 h to obtain a pale yellow transparent polymer film.

[0061] The obtained polymer film has good film-forming property and stability. It will quickly turn blue under ultraviolet light irradiation and can be restored to colorless and transparent after avoiding light or heat treatment.

[0062] Example 11

[0063] The experiment was conducted in a glove box filled with an argon atmosphere. 1 g (13.50 mmol) of glycidol, 0.054 g (0.27 mol) of 1,4-butanediol diacrylate, and 0.018 g (0.13 mmol) of N,N-dimethyl-p-phenylenediamine were added to a 5 mL round-bottom flask equipped with a magnetic rotor, and 6.7 μL (0.01 mmol) of t-BuP2 was added. It was taken out and placed in an oil bath at 60 °C for reaction for 12 h. After the reaction, it was dissolved in a small amount of tetrahydrofuran and precipitated in n-hexane to obtain a pale yellow product. It was dried overnight in a vacuum oven. 0.012 g of the polymer product was taken, 0.02 g (0.052 mmol) of 2-DBSOSPO was added thereto, and it was dissolved in an appropriate amount of dimethyl sulfoxide and heat-treated in an oven at 60 °C for 8 h to obtain a pale yellow transparent polymer film.

[0064] The obtained polymer film has good film-forming property and stability. It will quickly turn blue under ultraviolet light irradiation and can be restored to colorless and transparent after avoiding light or heat treatment.

[0065] Example 12

[0066] The experiment was conducted in a glove box filled with an argon atmosphere. 1 g (13.50 mmol) of glycidol, 0.054 g (0.27 mol) of 1,4-butanediol diacrylate, and 0.018 g (0.13 mmol) of N,N-dimethyl-p-phenylenediamine were added to a 5 mL round-bottom flask equipped with a magnetic rotor, and 6.7 μL (0.01 mmol) of t-BuP2 was added. It was taken out and placed in an oil bath at 60 °C for reaction for 12 h. After the reaction, it was dissolved with a small amount of tetrahydrofuran and precipitated in n-hexane to obtain a pale yellow product. It was dried overnight in a vacuum oven. 0.012 g of the polymerization product was taken, 0.02 g (0.052 mmol) of 3-DBSOSPO was added thereto, dissolved with an appropriate amount of dimethyl sulfoxide, and heat-treated in an oven at 25 °C for 12 h to obtain a pale yellow transparent polymer film.

[0067] The obtained polymer film has good film-forming property and stability, and will quickly turn blue under ultraviolet light irradiation, and can be restored to colorless and transparent after avoiding light or heat treatment.

[0068] Example 13

[0069] The experiment was conducted in a glove box filled with an argon atmosphere. 1 g (13.50 mmol) of glycidol, 0.054 g (0.27 mol) of 1,4-butanediol diacrylate, and 0.018 g (0.13 mmol) of N,N-dimethyl-p-phenylenediamine were added to a 5 mL round-bottom flask equipped with a magnetic rotor, and 6.7 μL (0.01 mmol) of t-BuP2 was added. It was taken out and placed in an oil bath at 60 °C for reaction for 12 h. After the reaction, it was dissolved with a small amount of tetrahydrofuran and precipitated in n-hexane to obtain a pale yellow product. It was dried overnight in a vacuum oven. 0.012 g of the polymerization product was taken, 0.02 g (0.052 mmol) of 4-DBSOSPO was added thereto, dissolved with an appropriate amount of dimethyl sulfoxide, and heat-treated in an oven at 100 °C for 30 min to obtain a pale yellow transparent polymer film.

[0070] The obtained polymer film will quickly turn blue under ultraviolet light irradiation, and can be restored to colorless and transparent after avoiding light or heat treatment. The ultraviolet absorption of the prepared polymer film did not change significantly after being placed in a room temperature environment for seven days, and it has good film-forming property and stability.

[0071] Example 14

[0072] The experiment was carried out in a glove box filled with an argon atmosphere. 1 g (13.50 mmol) of glycidol, 0.054 g (0.27 mol) of 1,4-butanediol diacrylate and 0.023 g (0.13 mmol) of diphenylamine were added to a 5 mL round-bottom flask equipped with a magnetic rotor, and 6.7 μL (0.01 mmol) of t-BuP2 was added. It was taken out and placed in an oil bath at 60 °C for reaction for 12 h. After the reaction, it was dissolved with a small amount of tetrahydrofuran and precipitated in n-hexane to obtain a pale yellow product. It was dried overnight in a vacuum oven. 0.012 g of the polymerization product was taken, 0.02 g (0.052 mmol) of 4-DBSOSPO was added thereto, dissolved with an appropriate amount of dimethyl sulfoxide and heat-treated in an oven at 100 °C for 30 min to obtain a pale yellow transparent polymer film.

[0073] The obtained polymer film has good film-forming property and stability. It will quickly turn blue under ultraviolet light irradiation and can be restored to colorless and transparent after being shielded from light or heat-treated. This polymer film can quickly turn dark blue under ultraviolet light irradiation for 20 s and reach the maximum ultraviolet absorption at 80 s. The ultraviolet absorption spectrum and the physical picture of this polymer film are as Figure 7 shown.

[0074] Example 15

[0075] The experiment was carried out in a glove box filled with an argon atmosphere. 1 g (13.50 mmol) of glycidol, 0.0611 g (0.27 mol) of 1,6-hexanediol diacrylate and 0.018 g (0.13 mmol) of N,N-dimethyl-p-phenylenediamine were added to a 5 mL round-bottom flask equipped with a magnetic rotor, and 6.7 μL (0.01 mmol) of t-BuP2 was added. It was taken out and placed in an oil bath at 60 °C for reaction for 12 h. After the reaction, it was dissolved with a small amount of tetrahydrofuran and precipitated in n-hexane to obtain a pale yellow product. It was dried overnight in a vacuum oven. 0.012 g of the polymerization product was taken, 0.020 g (0.052 mmol) of 2-DBS was added thereto, dissolved with an appropriate amount of dimethyl sulfoxide and heat-treated in an oven at 100 °C for 30 min to obtain a pale yellow transparent polymer film.

[0076] The obtained polymer film has good film-forming property and stability. It will quickly turn blue under ultraviolet light irradiation and can be restored to colorless and transparent after being shielded from light or heat-treated.

[0077] Example 16

[0078] The experiment was conducted in a glove box filled with an argon atmosphere. 1 g (13.50 mmol) of glycidol, 0.054 g (0.27 mol) of 1,4-butanediol diacrylate, and 0.035 g (0.13 mmol) of N,N'-diphenyl-p-phenylenediamine were added to a 5 mL round-bottom flask equipped with a magnetic rotor, and 6.7 μL (0.01 mmol) of t-BuP2 was added. It was taken out and placed in an oil bath at 60 °C for reaction for 12 h. After the reaction was completed, it was dissolved with a small amount of tetrahydrofuran and precipitated in n-hexane to obtain a pale yellow product. It was dried overnight in a vacuum oven. 0.012 g of the polymer product was taken, 0.020 g (0.052 mmol) of 2-DBS was added thereto, dissolved with an appropriate amount of dimethyl sulfoxide, and heat-treated in an oven at 100 °C for 30 min to obtain a pale yellow transparent polymer film.

[0079] The obtained polymer film has good film-forming property and stability. It will quickly turn blue under ultraviolet light irradiation and can be restored to colorless and transparent after avoiding light or heat treatment.

[0080] Example 17

[0081] The experiment was conducted in a glove box filled with an argon atmosphere. 1 g (13.50 mmol) of glycidol, 0.0611 g (0.27 mol) of 1,6-hexanediol diacrylate, and 0.018 g (0.13 mmol) of N,N-dimethyl-p-phenylenediamine were added to a 5 mL round-bottom flask equipped with a magnetic rotor, and 6.7 μL (0.01 mmol) of t-BuP2 was added. It was taken out and placed in an oil bath at 60 °C for reaction for 12 h. After the reaction was completed, it was dissolved with a small amount of tetrahydrofuran and precipitated in n-hexane to obtain a pale yellow product. It was dried overnight in a vacuum oven. 0.012 g of the polymer product was taken, 0.020 g (0.052 mmol) of 3-DBSOSPO was added thereto, dissolved with an appropriate amount of dimethyl sulfoxide, and heat-treated in an oven at 100 °C for 30 min to obtain a pale yellow transparent polymer film.

[0082] The obtained polymer film has good film-forming property and stability. It will quickly turn blue under ultraviolet light irradiation and can be restored to colorless and transparent after avoiding light or heat treatment.

Claims

1. A preparation method of a photo-induced reversible color-changing polymer material, characterized in that, The preparation method is as follows: (1) Glycidol undergoes a hybrid copolymerization reaction with diene monomers and amine monomers under the action of a catalyst to prepare a functional hyperbranched polyether in one step; The diene monomers are one or more of: 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, or ethylene glycol diacrylate; The amine monomers are one or more of: N,N-dimethyl-p-phenylenediamine, 4-isopropylaniline, diphenylamine, or N,N'-diphenyl-p-phenylenediamine, and their structural formulas are: The molar ratio of glycidol to diene monomers is 1000:10 - 200; the molar ratio of glycidol to amine monomers is 1000:1 - 100; (2) The generated hyperbranched polyether is blended with a small molecule receptor of a thiophene derivative and heat-treated to form a photoinduced reversible color-changing polymer material; The small molecule receptor of a thiophene derivative is: 2-dibenzothienyl diphenylphosphine oxide 2-DBS, 2-dibenzothienyl diphenylphosphine oxide S,S-dioxide 2-DBSOSPO, 3-dibenzothienyl diphenylphosphine oxide S,S-dioxide 3-DBSOSPO, or 4-dibenzothienyl diphenylphosphine oxide S,S-dioxide 4-DBSOSPO, and their structural formulas are:

2. The preparation method of the photo-induced reversible color-changing polymer material according to claim 1, characterized in that, The catalyst is one or more of t-BuP1, t-BuP2, t-BuP4, and the molar ratio of glycidol to the catalyst is 1000:1 - 10.

3. The preparation method of the photo-induced reversible color-changing polymer material according to claim 1, characterized in that, The hybrid copolymerization reaction is bulk polymerization or solution polymerization. The solvent used in solution polymerization is any one or a mixture of several of the organic solvents of tetrahydrofuran, dimethyl sulfoxide, N,N'-dimethylformamide, and dioxane. The mass of the solvent used in solution polymerization is 0.1 - 5 times the mass of the monomers.

4. The preparation method of the photo-induced reversible color-changing polymer material according to claim 1, characterized in that, The molar ratio of the amine monomers to the small molecule receptor of a thiophene derivative is 1 - 100:1000.

5. The preparation method of the photo-induced reversible color-changing polymer material according to claim 1, characterized in that, The temperature for the hybrid copolymerization reaction is 25 - 100 °C, the heat treatment temperature is 25 - 100 °C, and the heat treatment time is 0.5 - 24 h.

6. A photoinduced reversible color-changing polymer material prepared by the method according to any one of claims 1 - 5.

Images