White fluorescent hyperbranched polyether and preparation method thereof

Abstract

The invention belongs to the field of polymer luminescent materials, and particularly relates to white fluorescent hyperbranched polyether and a preparation method thereof. The hyperbranched polyether is prepared through autocatalysis of ring opening and oxygen-Michael addition reaction of a monomer containing an alcoholic hydroxyl group and an epoxy structure and various amide-containing vinyl monomers in a solvent under the condition of tertiary amine on the epoxy monomer and the vinyl monomers. White fluorescence emission in a room temperature environment can be realized by changing various terminal amide structures of hyperbranched polyether, and the material can be applied to the fields of life illumination, optical devices, anti-counterfeiting and the like. The preparation method has the advantages of simplicity, low price, environmental friendliness and the like, is suitable for large-scale production and has a good application prospect.

Description

Technical Field

[0001] The invention belongs to the field of polymer luminescent materials, and particularly relates to a white fluorescent hyperbranched polyether and a preparation method thereof. Background Art

[0002] In recent years, white fluorescent polymers have been shining in the fields of solid light sources and full-information display screen backlight sources. Compared with traditional small molecule systems, polymer white light materials have the advantages of simple process, low cost, and easy large-scale manufacturing. However, because white fluorescence needs to cover the emission of the entire visible light region, it is difficult to achieve it through a single molecule, which makes it difficult to achieve such a span of visible light emission in the same polymer.

[0003] In the process of the scientific community's research to find alternatives to dendritic polymers, hyperbranched polymers stand out. Due to their unique topological structure and convenient synthesis advantages, they have aroused widespread interest among researchers. Among them, hyperbranched polyethers are one of the most common and interesting hyperbranched polymers. Usually, the structure of hyperbranched polyethers contains 50-60% branched structures. Due to its simple synthesis, special structure and unique properties, its large number of terminal groups can easily be introduced into terminal functional groups as needed through chemical or physical modification methods to enhance or add special properties. Since the main chain structure of hyperbranched polyethers is single, their modification is usually concentrated on the terminal groups, and their ends are modified into functional groups through chemical bond reactions to give them special functions. Functionalized hyperbranched polyethers have been widely used in many applications that are inseparable from people's production and life, such as biomedicine, nanotechnology, marine antifouling, surface modification and polyelectrolytes. However, hyperbranched polyethers with a variety of terminal amide structures as white fluorescent emission materials have not been reported. Summary of the invention

[0004] The purpose of the present invention is to provide a hyperbranched polyether polymer material with white fluorescence emission and a preparation method thereof. A polymer material with advantages of white fluorescence emission, good stability, wide monomer adaptability and low cost is prepared.

[0005] To achieve the above object, the present invention prepares hyperbranched polyether by one-step method under autocatalytic conditions from monomers containing alcoholic hydroxyl groups and epoxy structures and multiple vinyl monomers containing amides. The specific preparation method is: monomers containing alcoholic hydroxyl groups and epoxy structures and multiple vinyl monomers containing amides are in a solvent, and one-step method is used to prepare hyperbranched polyether under autocatalytic conditions;

[0006] The monomer containing alcoholic hydroxyl group and epoxy structure is one or more of glycidol, glycidyl methacrylate or allyl glycidyl ether.

[0007] The vinyl monomer is one or more of dimethylaminopropyl acrylamide, acrylamide, N,N-dimethylacrylamide or N-phenylmaleimide.

[0008] The molar ratio of the monomer containing alcoholic hydroxyl group and epoxy structure to the vinyl monomer is 1000:10-200.

[0009] The solvent used is one or a mixture of tetrahydrofuran, dimethyl sulfoxide, N,N'-dimethylformamide and dioxane organic solvents, and the mass of the solvent used is 0.1 to 5 times the mass of the monomer.

[0010] The reaction temperature used in the polymerization reaction stage is ≥25°C; the reaction time range is: 8 to 48 hours.

[0011] The generated hyperbranched polyether polymer is dissolved in any one or a mixture of two of tetrahydrofuran, dimethyl sulfoxide, N,N'-dimethylformamide and dioxane to prepare a 5 mg / ml solution, and can emit white fluorescence visible to the naked eye under the excitation irradiation of a point light source of 365 nm. Therefore, the white fluorescent hyperbranched polyether prepared by the present invention can be used in the fields of life lighting, optical devices or anti-counterfeiting.

[0012] Beneficial effects:

[0013] (1) The raw materials of the present invention are cheap and industrially available, the material has good performance, a wide range of applications, and is suitable for mass production.

[0014] (2) The polymerization reaction conditions of the present invention are mild, the reaction temperature ranges from 25 to 100° C., and the self-catalytic method is adopted. The hyperbranched polyether product does not need to remove the catalyst and the presence of the catalyst will not affect the properties of the polymer.

[0015] (3) The polymer can be prepared in one step using simple compounds under autocatalytic conditions, and white fluorescence emission can be achieved by simply preparing it into a solution after simple precipitation. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 These are actual photos of Example 2, Example 3 and Example 6 under the excitation of 365nm ultraviolet lamp.

[0017] Figure 2 This is the HNHR test of the white fluorescent hyperbranched polyether polymer of Example 3.

[0018] Figure 3 This is the FT-IR spectrum of the white fluorescent hyperbranched polyether polymer of Example 3.

[0019] Figure 4 This is the fluorescence spectrum of the white fluorescent hyperbranched polyether polymer of Example 4.

[0020] Figure 5 This is the ultraviolet absorption diagram of the white fluorescent hyperbranched polyether polymer of Example 5.

[0021] Figure 6 This is a diagram of the quantum yield of the white fluorescent hyperbranched polyether polymer of Example 7.

[0022] Figure 7 This is the lifetime decay curve of the white fluorescent hyperbranched polyether polymer of Example 8.

[0023] Figure 8 The normalized fluorescence spectra of the white fluorescent hyperbranched polyether polymers of Comparative Examples 1 and 3 are shown. DETAILED DESCRIPTION

[0024] The present invention is further described below in conjunction with the embodiments, but is not limited to the following embodiments. For process parameters not particularly noted, conventional techniques may be used.

[0025] Example 1

[0026] A dry 100 mL round-bottom flask with a rotor was placed in a glove box filled with argon atmosphere, and 2 g (26.9 mmol) of glycidol, 1.15 g (6.7 mmol) of dimethylaminopropyl acrylamide, 0.24 g (3.4 mmol) of acrylamide and 3.55 g of tetrahydrofuran were added thereto, and the rubber stopper was covered, and the mixture was placed in a 40°C oil bath pot for reaction for 6 hours. After the reaction, a light yellow viscous liquid was obtained, which was precipitated and dried in 100 ml of n-hexane, and then prepared into a 5 mg / ml polymer solution with dimethyl sulfoxide, which emitted white fluorescence under excitation at a wavelength of 365 nm.

[0027] Example 2

[0028] A dry 100 mL oil round-bottom flask with a rotor was placed in a glove box filled with argon atmosphere, and 2 g (26.9 mmol) of glycidol, 1.15 g (6.7 mmol) of dimethylaminopropyl acrylamide, 0.34 g (3.4 mmol) of N, N-dimethyl acrylamide and 3.55 g of tetrahydrofuran were added thereto, and the rubber stopper was covered, and the mixture was placed in a 40°C oil bath pot for reaction for 6 hours. After the reaction, a white viscous liquid was obtained, which was precipitated and dried in 100 ml of n-hexane, and then prepared into a 5 mg / ml polymer solution with dimethyl sulfoxide, which could emit blue fluorescence under excitation at a wavelength of 365 nm.

[0029] Example 3

[0030] A dry 100 mL round-bottom flask with a rotor was placed in a glove box filled with argon atmosphere, and 3.83 g (51.7 mmol) of glycidol, 0.91 g (12.9 mmol) of acrylamide, 0.64 g (6.5 mmol) of N, N-dimethylacrylamide and 196 g of tetrahydrofuran were added thereto, and the rubber stopper was covered, and the mixture was placed in a 40°C oil bath pot for reaction for 12 hours. After the reaction, a colorless viscous liquid was obtained, which was precipitated and dried in 150 ml of n-hexane, and then prepared into a 5 mg / ml polymer solution with tetrahydrofuran, which emitted white fluorescence under excitation at a wavelength of 365 nm.

[0031] Example 4

[0032] A dry 100 mL round-bottom flask with a rotor was placed in a glove box filled with argon atmosphere, and 3.80 g (51.3 mmol) of glycidol, 1.27 g (12.8 mmol) of N, N-dimethylacrylamide, 1.11 g (6.4 mmol) of N-phenylmaleimide and 10 g of N, N-dimethylformamide were added thereto, and the rubber stopper was covered, and the mixture was placed in an 80°C oil bath pot for reaction for 48 hours. After the reaction, a white viscous liquid was obtained, which was precipitated and dried in 50 ml of n-hexane, and then prepared into a 5 mg / ml polymer solution with dimethyl sulfoxide, which emitted white fluorescence under excitation at a wavelength of 365 nm.

[0033] Example 5

[0034] A dry 100 mL round-bottom flask with a rotor was placed in a glove box filled with argon atmosphere, and 4.53 g (31.9 mmol) of glycidyl methacrylate, 10.2 g (8 mmol) of dimethylaminopropyl acrylamide, 1.04 g (4 mmol) of acrylamide and 20 g of N,N-dimethylformamide were added thereto, covered with a rubber stopper, and placed in a 100°C oil bath for 24 hours. After the reaction, a yellow viscous liquid was obtained, which was precipitated and dried in 100 ml of n-hexane, and then prepared into a 5 mg / ml polymer solution with dimethyl sulfoxide, which emitted white fluorescence under excitation at a wavelength of 365 nm.

[0035] Example 6

[0036] A dry 100 mL round-bottom flask with a rotor was placed in a glove box filled with argon atmosphere, and 2 g (26.9 mmol) of glycidol, 0.48 g (6.7 mmol) of acrylamide, 0.59 g (3.4 mmol) of N-phenylmaleimide and 3.55 g of tetrahydrofuran were added thereto, and the rubber stopper was covered, and the mixture was placed in a 40°C oil bath pot for reaction for 6 hours. After the reaction, a light yellow viscous liquid was obtained, which was precipitated and dried in 100 ml of n-hexane, and then prepared into a 5 mg / ml polymer solution with dimethyl sulfoxide, which emitted red fluorescence under excitation at a wavelength of 365 nm.

[0037] Example 7

[0038] A dry 100 mL round-bottom flask with a rotor was placed in a glove box filled with argon atmosphere, and 3.55 g (25 mmol) of glycidyl methacrylate, 0.44 g (6.25 mmol) of acrylamide, 0.31 g (3.13 mmol) of N, N-dimethylacrylamide and 20 g of N, N-dimethylformamide were added thereto, and the rubber stopper was covered, and the mixture was placed in a 60°C oil bath pot for reaction for 2 hours. After the reaction, a light yellow viscous liquid was obtained, which was precipitated and dried in 150 ml of n-hexane, and then prepared into a 5 mg / ml polymer solution with tetrahydrofuran, which emitted white fluorescence under excitation at a wavelength of 365 nm.

[0039] Example 8

[0040] A dry 100 mL round-bottom flask with a rotor was placed in a glove box filled with argon atmosphere, and 3.27 g (20.4 mmol) of glycidyl methacrylate, 6.63 g (10.2 mmol) of N, N-dimethylacrylamide, 1.56 g (10.2 mmol) of N-phenylmaleimide and 50 g of dimethyl sulfoxide were added thereto, and the rubber stopper was covered, and the mixture was placed in a 50°C oil bath pot for reaction for 6 hours. After the reaction, a light yellow viscous liquid was obtained, which was precipitated and dried in 150 ml of n-hexane, and then prepared into a 5 mg / ml polymer solution with tetrahydrofuran, which emitted white fluorescence under excitation at a wavelength of 365 nm.

[0041] Example 9

[0042] A dry 100 mL round-bottom flask with a rotor was placed in a glove box filled with argon atmosphere, and 3.39 g (29.7 mmol) of allyl glycidyl ether, 0.63 (7.4 mmol) of dimethylaminopropyl acrylamide, 1.49 g (3.7 mmol) of acrylamide and 30 g of dioxane were added thereto, and the rubber stopper was covered, and the mixture was placed in a 40°C oil bath pot for reaction for 6 hours. After the reaction, a light yellow viscous liquid was obtained, which was precipitated and dried in 100 ml of n-hexane, and then prepared into a 5 mg / ml polymer solution with tetrahydrofuran, which emitted white fluorescence under excitation at a wavelength of 365 nm.

[0043] Example 10

[0044] A dry 100 mL round-bottom flask with a rotor was placed in a glove box filled with argon atmosphere, and 3.07 g (26.9 mmol) of allyl glycidyl ether, 0.48 g (6.7 mmol) of acrylamide, 0.59 g (3.4 mmol) of N-phenylmaleimide and 3.55 g of tetrahydrofuran were added thereto, and the rubber stopper was covered, and the mixture was placed in a 40°C oil bath pot for reaction for 6 hours. After the reaction, a light yellow viscous liquid was obtained, which was precipitated and dried in 100 ml of n-hexane, and then prepared into a 5 mg / ml polymer solution with dimethyl sulfoxide, which emitted red fluorescence under excitation at a wavelength of 365 nm.

[0045] Embodiment 11

[0046] A dry 100 mL round-bottom flask with a rotor was placed in a glove box filled with argon atmosphere, and 5.00 g (43.8 mmol) of allyl glycidyl ether, 0.78 g (10.9 mmol) of acrylamide, 0.44 g (5.5 mmol) of N, N-dimethylacrylamide and 30 g of N, N-dimethylformamide were added thereto, and the mixture was covered with a rubber stopper and placed in a 50°C oil bath for reaction for 6 h. After the reaction, a light yellow viscous liquid was obtained, which was precipitated and dried in 100 ml of n-hexane, and then prepared into a 5 mg / ml polymer solution with dioxane, which emitted white fluorescence under excitation at a wavelength of 365 nm.

[0047] Example 12

[0048] A dry 100 mL round-bottom flask with a rotor was placed in a glove box filled with argon atmosphere, and 3.84 g (27.2 mmol) of allyl glycidyl ether, 0.67 g (6.8 mmol) of N, N-dimethylacrylamide, 0.72 g (3.4 mmol) of N-phenylmaleimide and 20 g of tetrahydrofuran were added thereto, and the rubber stopper was covered, and the mixture was placed in an oil bath at 25°C for 2 h to react. After the reaction, a light yellow viscous liquid was obtained, which was precipitated and dried in 150 ml of n-hexane, and then prepared into a 5 mg / ml polymer solution with dioxane, which emitted white fluorescence under excitation at a wavelength of 365 nm.

[0049] Comparative Example 1

[0050] A dry 100 mL round-bottom flask with a rotor was placed in a glove box filled with argon atmosphere, and 0.2 g (2.7 mmol) of glycidol, 0.28 g (0.14 mmol) of dimethylaminopropyl acrylamide and 3 g of N,N-dimethylformamide were added, and the mixture was covered with a rubber stopper and placed in a 40°C oil bath for 6 hours. After the reaction, a white viscous liquid was obtained, which was precipitated and dried in 150 ml of n-hexane, and then prepared into a 5 mg / ml polymer solution with dioxane, which emitted blue fluorescence under excitation at a wavelength of 365 nm.

[0051] Comparative Example 2

[0052] A dry 100 mL round-bottom flask with a rotor was placed in a glove box filled with argon atmosphere, and 1 g (13.5 mmol) of glycidol, 0.24 g (3.37 mmol) of acrylamide and 3 g of N,N-dimethylformamide were added, and the mixture was covered with a rubber stopper and placed in an 80°C oil bath for reaction for 6 h. After the reaction, a light yellow viscous liquid was obtained, which was precipitated and dried in 150 ml of n-hexane, and then prepared into a 5 mg / ml polymer solution with N,N-dimethylformamide, which emitted red fluorescence under excitation at a wavelength of 365 nm.

[0053] Comparative Example 3

[0054] A dry 100 mL round-bottom flask with a rotor was placed in a glove box filled with argon atmosphere, and 1 g (13.5 mmol) of glycidol, 0.58 g (3.37 mmol) of N-phenylmaleimide and 3 g of dimethyl sulfoxide were added, covered with a rubber stopper, and placed in a 50°C oil bath for reaction for 12 hours. After the reaction, a light yellow viscous liquid was obtained, which was precipitated and dried in 100 ml of n-hexane, and then prepared into a 5 mg / ml polymer solution with N,N-dimethylformamide, which emitted red fluorescence under excitation at a wavelength of 365 nm.

[0055] Comparative Example 4

[0056] A dry 100 mL round-bottom flask with a rotor was placed in a glove box filled with argon atmosphere, and 1 g (13.5 mmol) of glycidol, 0.28 g (0.14 mmol) of N, N-dimethylacrylamide and 3 g of tetrahydrofuran were added, and the mixture was covered with a rubber stopper and placed in a 40°C oil bath for reaction for 8 hours. After the reaction, a colorless viscous liquid was obtained, which was precipitated and dried in 100 ml of n-hexane, and then prepared into a 5 mg / ml polymer solution with N, N-dimethylformamide, which emitted blue fluorescence under excitation at a wavelength of 365 nm.

Claims

1. A method for preparing a white fluorescent hyperbranched polyether, characterized in that: The preparation method comprises the following steps: monomers containing alcoholic hydroxyl groups and epoxy structures and a plurality of vinyl monomers containing amides are placed in a solvent, and the ring-opening and oxygen-Michael addition reactions of the epoxy monomers and the vinyl monomers are carried out under tertiary amine conditions to prepare hyperbranched polyethers by self-catalysis.

2. The method for preparing a white fluorescent hyperbranched polyether according to claim 1, wherein The monomer containing alcoholic hydroxyl group and epoxy structure is: glycidol, glycidyl methacrylate or allyl glycidyl ether.

3. The method for preparing a white fluorescent hyperbranched polyether according to claim 1, characterized in that: The amide-containing vinyl monomer is: dimethylaminopropyl acrylamide, acrylamide, N,N-dimethylacrylamide or N-phenylmaleimide.

4. The method for preparing a white fluorescent hyperbranched polyether according to claim 1, wherein The molar ratio of the monomer containing alcoholic hydroxyl group and epoxy structure to the amide-containing vinyl monomer is 1000:10-200.

5. The method for preparing a white fluorescent hyperbranched polyether according to claim 1, wherein The solvent is one or a mixture of tetrahydrofuran, dimethyl sulfoxide, N,N'-dimethylformamide and dioxane organic solvents, and the mass of the solvent used is 0.1 to 5 times the total mass of the monomers.

6. The method for preparing a white fluorescent hyperbranched polyether according to claim 1, characterized in that: The reaction temperature for preparing the hyperbranched polyether is ≥25° C., and the reaction time is 8 to 48 hours.

7. A white fluorescent hyperbranched polyether prepared according to the method according to any one of claims 1 to 6.

8. The white fluorescent hyperbranched polyether according to claim 7, characterized in that The hyperbranched polyether is dissolved in an organic solvent to prepare a 5 mg / ml solution, and emits white fluorescence visible to the naked eye under the excitation of a point light source at 365 nm.

9. The white fluorescent hyperbranched polyether according to claim 8, characterized in that The organic solvent is one or a mixture of tetrahydrofuran, dimethyl sulfoxide, N,N'-dimethylformamide and dioxane organic solvents.

10. An application of the white fluorescent hyperbranched polyether according to claim 7, characterized in that: The white fluorescent hyperbranched polyether is used in the fields of living lighting, optical devices or anti-counterfeiting.

Images