Preparation of anthracene-containing alternating polymer by phenol-alkyne click reaction and method thereof

Abstract

The application discloses a phenol-alkynyl click reaction preparation method of an anthracene group-containing alternating polymer, and the rigid chain segment of the polymer is 9.10-bis(4-hydroxyphenyl)anthracene (AN), the flexible chain segment is hexaethylene glycol propargylate long chain (EG6), and the anthracene group-containing alternating polymer P(AN-alt-EG6) is obtained through a phenol-alkynyl click chemical reaction under the catalysis of a catalyst 4-dimethylaminopyridine (DMAP), and the structural formula is as follows: the phenol-alkynyl click reaction preparation method of the anthracene group-containing alternating polymer and the preparation method form a novel anthracene group-containing alternating polymer through the click reaction of alkynyl and phenolic hydroxyl, the polymer has the characteristics of fast crystallization speed and photo-crosslinking, the fast formation of spherulites can be quickly observed by using a polarizing microscope (POM) under the simple condition of natural air drying of a polymer solution, and the liquid region is completely crystallized.

Description

Technical Field

[0001] This invention relates to the field of alternating polymer preparation technology, specifically to the preparation of anthracene-containing alternating polymers by phenol-alkynyl click reaction and the preparation method thereof. Background Technology

[0002] Anthracyclines and their derivatives, as an important class of fused-ring aromatic hydrocarbons, possess greater rigidity, larger conjugated systems, and more reactive chemical properties compared to naphthalene rings. Furthermore, they exhibit unique properties such as ultraviolet fluorescence and photodimerization, attracting widespread attention in recent years. Research on anthracene rings has been limited to the small molecule level for many years; therefore, introducing anthracene rings into polymer systems is a promising approach. To this end, we propose a method for preparing alternating polymers containing anthracene groups using a phenol-alkynyl click reaction. Summary of the Invention

[0003] The purpose of this invention is to provide a method for preparing anthracene-containing alternating polymers via phenol-alkynyl click reaction, thereby addressing the problems mentioned in the background art.

[0004] To achieve the above objectives, the present invention provides the following technical solution: a method for preparing an anthracene-containing alternating polymer via a phenol-alkynyl click reaction, wherein the rigid segment of the polymer is 9,10-bis(4-hydroxyphenyl)anthracene (AN), and the flexible segment is a long chain of hexaethylene glycol propynate (EG6). Under the catalysis of 4-dimethylaminopyridine (DMAP), an anthracene-containing alternating polymer P (AN-alt-EG6) is obtained via a phenol-alkynyl click reaction, with the following structural formula:

[0005]

[0006] Furthermore, a method for preparing an anthracene-containing alternating polymer via a phenol-alkynyl click reaction is characterized by: generating hexaethylene glycol propynyl ester via an esterification reaction of hexaethylene glycol and propynic acid, comprising the following steps:

[0007] S1, using toluene as the reaction solvent, at a reaction temperature of 110℃, using hexaethylene glycol and propynyl acid as raw material monomers, and p-toluenesulfonic acid monohydrate (P-TsOH) as the catalyst, after reacting for 24 hours, yielded crude hexaethylene glycol propynyl ester.

[0008] S2, purified hexaethylene glycol propynate was obtained by column chromatography with a column chromatography ratio of dichloromethane:ethyl acetate = 5:1.

[0009] Furthermore, 9,10-bis(4-hydroxyphenyl)anthracene is obtained by converting the methoxy group on the benzene ring of 9,10-bis(4-methoxyphenyl)anthracene to a hydroxyl group via boron tribromide reaction, including the following steps:

[0010] S1, using anhydrous dichloromethane as the reaction solvent, was placed in a low-temperature environment of an ice-salt bath, and 9,10-bis(4-methoxyphenyl)anthracene and boron tribromide were added. Under nitrogen protection, the reaction was carried out at low temperature for 12 hours. After the reaction was completed, the mixture was quenched with water, and a solid was precipitated. Sodium hydroxide solution was added dropwise to neutralize the solid, and finally the solid was filtered and dried to obtain 9,10-bis(4-hydroxyphenyl)anthracene.

[0011] Furthermore, the number-average molecular weight of the polymer is 9.0 × 10⁻⁶. 3 ~1.8×10 4 The molecular weight distribution is 1.3-1.8, which can be controlled within the range of g / mol.

[0012] Furthermore, the reaction organic solution for synthesizing this alternating polymer is anhydrous tetrahydrofuran (THF).

[0013] Furthermore, the reaction temperature for synthesizing this alternating polymer is 50℃~60℃, and the reaction time is 4~24h.

[0014] Furthermore, the catalyst used to synthesize this alternating polymer is 4-dimethylaminopyridine (DMAP).

[0015] Furthermore, the molar ratio of the alkynyl-terminated hexaethylene glycol propargyl ester of claim 2 to the hydroxyl-terminated 9,10-bis(4-hydroxyphenyl)anthracene of claim 3 used in the synthesis of this alternating polymer is 1:1.2.

[0016] Furthermore, the products of phenol-alkynyl click polymerization need to be precipitated and centrifuged, with anhydrous diethyl ether as the precipitating solvent.

[0017] Compared with the prior art, the beneficial effects of the present invention are: the preparation of alternating polymers containing anthracene groups by the phenol-alkynyl click reaction and the preparation method thereof, the rigid anthracene segments of the prepared alternating polymers have strong π-π stacking effects, and they also have anthracene groups that can be photocrosslinked, providing new ideas for the research and development of crystalline materials and photocrosslinked smart materials. Attached Figure Description

[0018] Figure 1 It is EG6 in this invention 1 H NMR spectrum;

[0019] Figure 2 It is AN in this invention 1 H NMR spectrum;

[0020] Figure 3 It is P(AN-alt-EG6) in this invention. 1 H NMR spectrum;

[0021] Figure 4This is the GPC curve of P(AN-alt-EG6) in this invention. Detailed Implementation

[0022] The rigid segment of this polymer is 9,10-bis(4-hydroxyphenyl)anthracene (AN), and the flexible segment is a long chain of hexaethylene glycol propynate (EG6). Under the catalysis of 4-dimethylaminopyridine (DMAP), a phenol-alkynyl click chemistry reaction yields an alternating polymer P (AN-alt-EG6) containing anthracene groups, with the following structural formula:

[0023]

[0024] A method for preparing an anthracene-containing alternating polymer via a phenol-alkynyl click reaction, characterized by: generating hexaethylene glycol propynyl ester via an esterification reaction of hexaethylene glycol and propynic acid, comprising the following steps:

[0025] S1, using toluene as the reaction solvent, at a reaction temperature of 110℃, using hexaethylene glycol and propynyl acid as raw material monomers, and p-toluenesulfonic acid monohydrate (P-TsOH) as the catalyst, after reacting for 24 hours, yielded crude hexaethylene glycol propynyl ester.

[0026] S2, purified hexaethylene glycol propynate was obtained by column chromatography with a column chromatography ratio of dichloromethane:ethyl acetate = 5:1.

[0027] The methoxy group on the benzene ring of 9,10-bis(4-methoxyphenyl)anthracene is converted to a hydroxyl group via boron tribromide reaction to obtain 9,10-bis(4-hydroxyphenyl)anthracene, comprising the following steps:

[0028] S1, using anhydrous dichloromethane as the reaction solvent, was placed in a low-temperature environment of an ice-salt bath, and 9,10-bis(4-methoxyphenyl)anthracene and boron tribromide were added. Under nitrogen protection, the reaction was carried out at low temperature for 12 hours. After the reaction was completed, the mixture was quenched with water, and a solid was precipitated. Sodium hydroxide solution was added dropwise to neutralize the solid, and finally the solid was filtered and dried to obtain 9,10-bis(4-hydroxyphenyl)anthracene.

[0029] The number-average molecular weight of the polymer is 9.0 × 10⁻⁶. 3 ~1.8×10 4 The molecular weight distribution of the alternating polymer was controlled within the range of g / mol, exhibiting a molecular weight distribution of 1.3-1.8. The organic solution used for the synthesis of this alternating polymer was anhydrous tetrahydrofuran (THF). The reaction temperature for the synthesis of this alternating polymer was 50℃~60℃, and the reaction time was 4~

[0030] The catalyst used to synthesize the alternating polymer was 4-dimethylaminopyridine (DMAP) for 24 hours. The molar ratio of the alkynyl-terminated hexaethylene glycol propargyl ester of claim 2 to the hydroxyl-terminated 9,10-bis(4-hydroxyphenyl)anthracene of claim 3 was 1:1.2. Phenol

[0031] The products of -alkynyl click chemical polymerization need to be precipitated and centrifuged, and the precipitating solvent is anhydrous diethyl ether.

[0032] In the following embodiments, the polymer's 1 The H NMR spectra were measured on an AVANCE 400 (400MHz) NMR spectrometer in CDCl3 solvent at 25℃.

[0033] Polymer molecules (Mw, Mn) and their molecular weight distribution (Mw / Mn) were determined using gel permeation chromatography (GPC) (the system consisted of three parts, including a Waters 1515-grade HPLC pump and a Waters 214 refractometer) with THF as the eluent, a flow rate of 1.0 mL / min, an injection volume of 100 μL, and an injection time of 40 min. The standard was linear polystyrene with a narrow molecular weight distribution.

[0034] Example 1

[0035] A method for preparing an alternating polymer containing anthracene groups includes the following steps:

[0036] (1) Preparation of alkynyl-terminated hexaethylene glycol propargyl ester (EG6):

[0037] In a 250 mL round-bottom beaker, hexaethylene glycol (4.23 g, 15 mmol), propargyl acid (2.45 g, 35 mmol), and p-toluenesulfonic acid monohydrate (P-TsOH, 0.76 g, 4 mmol) were added and dissolved in 50 mL of toluene. The reaction was carried out under nitrogen protection at 110 °C for 24 h. After the reaction, the mixture was cooled to room temperature, and the toluene in the mixed solvent was evaporated by rotary evaporation. The mixture was then redissolved in dichloromethane (DCM), extracted three times with 25% NaOH solution and saturated brine, dried overnight in anhydrous magnesium sulfate (MgSO4), filtered using a Buchner funnel, and the mixed solution was mixed with a suitable amount of silica gel powder and evaporated to dryness to obtain the crude product. The crude product was extracted by column chromatography (eluent: dichloromethane: ethyl acetate = 5:1). The product was characterized by 1H NMR spectroscopy. Figure 1 Its structural formula is as follows:

[0038]

[0039] (2) Preparation of hydroxyl-terminated 9,10-bis(4-hydroxyphenyl)anthracene (AN):

[0040] Under ice-salt bath (0°C) and nitrogen protection, 0.391 g (1 mmol) of 9,10-bis(4-methoxyphenyl)anthracene was added to a 125 mL Shrek flask and dissolved in 20 mL of anhydrous dichloromethane. 8 mL of boron tribromide solution (2.0 mol / L, dissolved in dichloromethane) was slowly injected into the Shrek flask using a syringe. After cooling to room temperature, the reaction was continued for 12 h. After the reaction was complete, the mixture was slowly quenched dropwise in ice water, neutralized with NaOH solution to pH ≈ 7, filtered through a Buchner funnel to obtain a solid, and dried under vacuum to obtain the product. The product was characterized by 1H NMR spectroscopy. Figure 2 Its structural formula is as follows:

[0041]

[0042] (3) Preparation of P(AN-alt-EG6)

[0043] In a 50 mL round-bottom flask, EG6 monomer (618 mg, 1.6 mmol), AN monomer (571 mg, 1.58 mmol), catalyst DMAP, and 16 mL of anhydrous tetrahydrofuran were added. The mixture was heated and stirred at 55 °C until the monomers were completely dissolved, and the reaction was allowed to proceed for 12 h. After the reaction was complete, 3 mL of anhydrous tetrahydrofuran was added to dilute the mixture and the temperature was lowered to room temperature. The polymer solution was then added dropwise to ice-cold diethyl ether at a ratio of 1:20 to precipitate the precipitate. The mixture was then centrifuged at 8000 rpm for 5 min, and the supernatant was removed. This process was repeated until all the mixture was centrifuged. The solid precipitate was placed in a cold trap for 2 days to remove residual solvent. Polymer P (AN-alt-EG6) was obtained, and its 1H NMR characterization is shown below. Figure 3 GPC characterization see Figure 4 Its structure is as follows:

[0044]

[0045] The polymer segments include 9,10-bis(4-hydroxyphenyl)anthracene and hydrophilic segments of polyhexanediol. Through a click reaction of alkynyl and phenolic hydroxyl groups, a novel anthracene-containing alternating polymer is formed. This polymer exhibits rapid crystallization and photocrosslinking capabilities. Under simple conditions of natural air drying of the polymer solution, the rapid formation of spherulites can be quickly observed using a polarizing microscope (POM), and the entire liquid region is crystallized. This invention relates to the study of the crystallization properties and crystallization rate of a novel alternating polymer, which contributes to the potential research and development of rapidly crystallizing materials in semiconductors and electronic devices.

[0046] The embodiments of the present invention are given for illustrative and descriptive purposes only, and are not intended to be exhaustive or to limit the invention to the forms disclosed. Many modifications and variations will be apparent to those skilled in the art. The embodiments were chosen and described in order to better illustrate the principles and practical application of the invention, and to enable those skilled in the art to understand the invention and to design various embodiments with various modifications suitable for a particular purpose.

Claims

1. An alternating polymer containing anthracene groups prepared by a phenol-alkynyl click reaction, characterized in that, The rigid segment of this polymer is 9,10-bis(4-hydroxyphenyl)anthracene (AN), and the flexible segment is a long chain of hexaethylene glycol propynate (EG6). Under the catalysis of 4-dimethylaminopyridine (DMAP), a phenol-alkynyl click chemistry reaction yields an alternating polymer P (AN-alt-EG6) containing anthracene groups, with the following structural formula: 。 2. A method for preparing an anthracene-containing alternating polymer prepared by the phenol-alkynyl click reaction according to claim 1, characterized in that: Hexaethylene glycol propargyl ester is produced by esterification of hexaethylene glycol and propargyl acid. Includes the following steps: S1, using toluene as the reaction solvent, at a reaction temperature of 110 °C, using hexaethylene glycol and propynyl acid as raw material monomers, and p-toluenesulfonic acid monohydrate (P-TsOH) as the catalyst, after 24 h of reaction, crude hexaethylene glycol propynyl ester was obtained. S2, purified hexaethylene glycol propynyl ester was obtained by column chromatography with a column chromatography ratio of dichloromethane:ethyl acetate = 5:

1.

3. The method for preparing the anthracene-containing alternating polymer prepared by the phenol-alkynyl click reaction according to claim 2, characterized in that, The methoxy group on the benzene ring of 9,10-bis(4-methoxyphenyl)anthracene is converted to a hydroxyl group via boron tribromide reaction to obtain 9,10-bis(4-hydroxyphenyl)anthracene, comprising the following steps: S1, using anhydrous dichloromethane as the reaction solvent, was placed in a low-temperature environment of an ice-salt bath, and 9,10-bis(4-methoxyphenyl)anthracene and boron tribromide were added. Under nitrogen protection, the reaction was carried out at low temperature for 12 h. After the reaction was completed, the mixture was quenched with water, and a solid was precipitated. Sodium hydroxide solution was added dropwise to neutralize the solid, and finally the solid was filtered and dried to obtain 9,10-bis(4-hydroxyphenyl)anthracene.

4. The method for preparing the anthracene-containing alternating polymer prepared by the phenol-alkynyl click reaction according to claim 3, characterized in that: The number-average molecular weight of the polymer is 9.0 × 10⁻⁶. 3 ~1.8×10 4 The molecular weight distribution is 1.3-1.8, which can be controlled within the range of g / mol.

5. The method for preparing the anthracene-containing alternating polymer prepared by the phenol-alkynyl click reaction according to claim 4, characterized in that: The organic solution used in the synthesis of this alternating polymer is anhydrous tetrahydrofuran (THF).

6. The method for preparing the anthracene-containing alternating polymer prepared by the phenol-alkynyl click reaction according to claim 5, characterized in that: The reaction temperature for synthesizing this alternating polymer is 50℃~60℃, and the reaction time is 4~24 h.

7. The method for preparing the anthracene-containing alternating polymer prepared by the phenol-alkynyl click reaction according to claim 6, characterized in that: The catalyst used to synthesize this alternating polymer is 4-dimethylaminopyridine (DMAP).

8. The method for preparing the anthracene-containing alternating polymer prepared by the phenol-alkynyl click reaction according to claim 7, characterized in that: The molar ratio of the alkynyl-terminated hexaethylene glycol propargyl ester as described in claim 2 to the hydroxyl-terminated 9,10-bis(4-hydroxyphenyl)anthracene as described in claim 3 is 1:1.2 in the synthesis of this alternating polymer.

9. The method for preparing the anthracene-containing alternating polymer prepared by the phenol-alkynyl click reaction according to claim 8, characterized in that: The product of the phenol-alkynyl click chemical polymerization reaction needs to be precipitated and centrifuged, and the precipitation solvent is anhydrous diethyl ether.

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