Polymers with alternating anthracene fluorophore and biphenyl groups and methods of making the same

Abstract

The application discloses an anthracene fluorescent group and biphenyl group alternately arranged polymer and a preparation method thereof, and the preparation method of the polymer comprises the following steps: S1, sodium octynyl alcohol is treated with sodium hydride to prepare sodium octynyl acid, and then the mixture is stirred with tetrabutylammonium iodide and 9,10-bis(chloromethyl)anthracene in a tetrahydrofuran (THF) solution at 40 DEG C for 24 h to obtain an anthracene monomer; S2, 9,10-bisphenyl anthracene, dicyclohexyl carbodiimide (DCC), 4-dimethylaminopyridine (DMAP) and p-toluenesulfonic acid (TsOH) are mixed and stirred in an ice water bath, and then 10-undecynoic acid is dropped into a bottle and reacts at room temperature for 12 h to obtain a bisphenyl anthracene monomer. The anthracene fluorescent group and biphenyl group alternately arranged polymer and the preparation method thereof have alternately arranged 9,10-substituted anthracene groups and biphenyl groups, the liquid crystal structure is regulated by connecting different structural substituents at the 9,10 positions of anthracene, and the morphology and fluorescent performance changes of polymer thin film self-assembly are regulated through a series of subsequent environmental stimuli.

Description

Technical Field

[0001] This invention relates to the field of alternating polymer preparation technology, specifically to polymers with alternating anthracene fluorescent groups and biphenyl groups, and their preparation methods. Background Technology

[0002] Stimulus-responsive organic light-emitting materials have broad application prospects in sensors, pH indicators, material damage indicators, gas encryption and decryption, and safety dyes. Recently, researchers have focused on developing stimulus-responsive organic light-emitting materials, whose fluorescence properties can undergo reversible conversion under external stimuli (mechanical, thermal, light, acid-base, ionic, etc.).

[0003] Among luminescent materials, anthracene derivatives have attracted considerable attention. Anthracene is a blue fluorescent material, but its planar molecular structure makes it prone to aggregation and crystallization, which limits its application in organic luminescent materials. To reduce the aggregation of anthracene molecules, groups are introduced at the 9 and 10 positions of the anthracene molecule, forming anthracene derivatives with better photoelectric properties. This has resulted in a series of high-performance luminescent materials with significant application value.

[0004] The inherent phase transitions of thermotropic liquid crystal polymers under thermal stimulation can lead to significant changes in material properties, thus making them widely applicable in the construction of stimulus-responsive materials. For thermotropic liquid crystals, the structure of the liquid crystal nucleus has a significant impact on their liquid crystallization properties. The rigidity of the biphenyl group, when used as a liquid crystal nucleus, contributes to good physicochemical properties, increases the clearing point and phase transition temperatures, and also exhibits lower voltage and more stable chemical properties. The length of the flexible chains, however, affects the type of liquid crystal phase; generally, long carbon chains tend to exhibit smectic phases, while short carbon chains tend to exhibit nematic phases.

[0005] By alternating the main chain of anthracene monomers with blue fluorescence at the 9 and 10 positions and biphenyl monomers with liquid crystal properties, fluorescent liquid crystal polymer materials can be obtained for the development of novel stimuli-responsive devices. To this end, we propose polymers with alternating anthracene fluorescent groups and biphenyl groups and their preparation methods. Summary of the Invention

[0006] The purpose of this invention is to provide a polymer of anthracene fluorescent groups and biphenyl groups arranged alternately, and a method for preparing the same, in order to solve the problems mentioned in the background art.

[0007] To achieve the above objectives, the present invention provides the following technical solution: a polymer of anthracene fluorescent groups and biphenyl groups arranged alternately, wherein the polymer has the structural formula shown in any one of formulas I to V:

[0008]

[0009] Furthermore, a method for preparing a polymer with alternating anthracene fluorescent groups and biphenyl groups, applied to the aforementioned polymer with alternating anthracene fluorescent groups and biphenyl groups, includes the following steps:

[0010] S1, sodium octynoside was prepared by treating 7-octyno-1-ol with sodium hydride, and then the mixture was stirred with tetrabutylammonium iodide and 9,10-dichloromethylanthracene in a tetrahydrofuran (THF) solution at 40°C for 24 h to obtain...

[0011] Anthracene monomers;

[0012] S2, 9,10-Biphenylanthracene, dicyclohexylcarbodiimide (DCC), and 4-dimethylaminopyridine (DMAP).

[0013] Mix with p-toluenesulfonic acid (TsOH) and stir in an ice-water bath, then add 10-undecyneic acid dropwise.

[0014] In a flask, the reaction was carried out at room temperature for 12 hours to obtain the diphenyl anthracene monomer;

[0015] S3, 6-bromohexanoic acid, 4,4'-dihydroxybiphenyl, dicyclohexylcarbodiimide (DCC), 4-dimethylaminopyridine (DMAP), and p-toluenesulfonic acid (TsOH) are mixed and placed in tetrahydrofuran (THF) at 40°C.

[0016] The solution was stirred for 24 hours to obtain the biphenyl intermediate.

[0017] S4. The biphenyl intermediate, trimethylsilane azido, and tetrabutylammonium fluoride (TBAF) were mixed and refluxed in a tetrahydrofuran (THF) solution at 80°C for 24 h to obtain the biphenyl monomer.

[0018] S5, under the catalysis of cuprous bromide and pentamethyldiethylenetriamine, was polymerized in anhydrous N,N-dimethylformamide (DMF) solution using anthracene-containing monomers and biphenyl monomers with different structures to obtain polymers with alternating structures containing 9,10-substituted anthracene groups and biphenyl groups.

[0019] Furthermore, in step S1, 7-octyne-1-ol is added dropwise to a sodium hydride solution at 0°C and then heated to room temperature within 1 hour.

[0020] Furthermore, in step S1, 7-octyne-1-ol, sodium hydride, tetrabutylammonium iodide, and 9,

[0021] The molar ratio of 10-dichloromethylanthracene is 2:2.2:0.1:1.

[0022] Furthermore, in step S2, the molar ratio of 10-undecyneic acid, 9,10-bisphenylanthracene, DCC, DMAP, and TsOH is 2.5:1:3:0.4:0.4.

[0023] Furthermore, in step S3, the molar ratio of bromine-terminated alkane acid, 4,4'-dihydroxybiphenyl, DCC, DMAP, and TsOH is 2.5:1:3:0.4:0.4.

[0024] Furthermore, in step S4, the molar ratio of the biphenyl intermediate, trimethyl azidosilane, and TBAF is 1:4:2.

[0025] Furthermore, in step S5, the molar ratio of anthracene monomer, biphenyl monomer, pentamethyldiethylenetriamine, and cuprous bromide is 1:1:0.1:0.05.

[0026] Furthermore, the polymerization reaction temperature in step S5 is 40°C, the reaction environment requires anhydrous and oxygen-free conditions, nitrogen protection, and the reaction time is 24 hours.

[0027] Furthermore, the polymerization product in step S5 needs to be precipitated and centrifuged. The precipitation solvent is diethyl ether. The number average molecular weight of the alternating main-chain polymer containing anthracene groups and biphenyl groups is 5550, with a molecular weight distribution of 1.61. The number average molecular weight of the alternating main-chain polymer containing diphenyl anthracene groups and biphenyl groups is 18147, with a molecular weight distribution of 1.36.

[0028] Compared with existing technologies, the beneficial effects of this invention are as follows: the polymer with alternating anthracene fluorescent groups and biphenyl groups, and its preparation method, effectively utilize the advantages of the alternating biphenyl liquid crystal backbone and the 9, 10-position substituted anthracene and its derivatives in the polymer chain. The liquid crystal structure is controlled by connecting different structural substituents at the 9 and 10 positions of the anthracene. Based on the polymer structural design, the ratio of the two rigid units is strictly controlled to 1:1. Furthermore, environmental conditions are used to control the assembly morphology during subsequent polymer coating, providing a new approach for the research and development of intelligent stimuli-responsive soft materials. Attached Figure Description

[0029] Figure 1 This is the 1H NMR spectrum of A-6 in this invention;

[0030] Figure 2 This is the 1H NMR spectrum of E-9 in this invention;

[0031] Figure 3 This is the 1H NMR spectrum of D-6-1 in this invention;

[0032] Figure 4 This is the 1H NMR spectrum of D-6-2 in this invention;

[0033] Figure 5 This is the 1H NMR spectrum of P(A-6+D-6) in this invention;

[0034] Figure 6 This is the 1H NMR spectrum of P(E-9+D-6) in this invention;

[0035] Figure 7 This is the GPC map of P(A-6+D-6) in this invention;

[0036] Figure 8 This is the GPC map of P(E-9+D-6) in this invention;

[0037] Figure 9 This is the POM diagram of P(A-6+D-6) in this invention;

[0038] Figure 10 This is the POM diagram of P(E-9+D-6) in this invention. Detailed Implementation

[0039] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention.

[0040] like Figures 1-10 As shown, the polymer has the following structural formula: (Formula I to V)

[0041]

[0042] A method for preparing a polymer of anthracene fluorescent groups and biphenyl groups with alternating arrangements includes the following steps:

[0043] S1, sodium octynoside was prepared by treating 7-octyno-1-ol with sodium hydride, and then the mixture was stirred with tetrabutylammonium iodide and 9,10-dichloromethylanthracene in a tetrahydrofuran (THF) solution at 40°C for 24 h to obtain anthracene monomer.

[0044] S2, 9,10-Biphenylanthracene, dicyclohexylcarbodiimide (DCC), 4-dimethylaminopyridine (DMAP) and p-toluenesulfonic acid (TsOH) were mixed and stirred in an ice-water bath, and then 10-undecyneic acid was added dropwise to the flask. The mixture was reacted at room temperature for 12 h to obtain the bisphenylanthracene monomer.

[0045] S3, 6-bromohexanoic acid, 4,4'-dihydroxybiphenyl, dicyclohexylcarbodiimide (DCC), 4-dimethylaminopyridine (DMAP), and p-toluenesulfonic acid (TsOH) were mixed and stirred in a tetrahydrofuran (THF) solution at 40°C for 24 h to obtain the biphenyl intermediate;

[0046] S4. The biphenyl intermediate, trimethylsilane azido, and tetrabutylammonium fluoride (TBAF) were mixed and refluxed in a tetrahydrofuran (THF) solution at 80°C for 24 h to obtain the biphenyl monomer.

[0047] S5, under the catalysis of cuprous bromide and pentamethyldiethylenetriamine, was polymerized in anhydrous N,N-dimethylformamide (DMF) solution using anthracene-containing monomers and biphenyl monomers with different structures to obtain polymers with alternating structures containing 9,10-substituted anthracene groups and biphenyl groups.

[0048] In step S1, 7-octyne-1-ol was added dropwise to a sodium hydride solution at 0°C and then heated to room temperature within 1 hour.

[0049] The molar ratio of 7-octyne-1-ol, sodium hydride, tetrabutylammonium iodide and 9,10-dichloromethylanthracene in step S1 is 2:2.2:0.1:1.

[0050] The molar ratio of 10-undecyneic acid, 9,10-bisphenylanthracene, DCC, DMAP, and TsOH in step S2 is 2.5:1:3:0.4:0.4.

[0051] The molar ratio of bromine-terminated alkane acid, 4,4'-dihydroxybiphenyl, DCC, DMAP, and TsOH in step S3 is 2.5:1:3:0.4:0.4.

[0052] The molar ratio of the biphenyl intermediate, trimethylsilane azido, and TBAF in step S4 is 1:4:2.

[0053] In step S5, the molar ratio of anthracene monomer, biphenyl monomer, pentamethyldiethylenetriamine, and cuprous bromide is 1:1:0.1:0.05.

[0054] The polymerization reaction temperature in step S5 is 40℃, and the reaction environment requires anhydrous and oxygen-free conditions, nitrogen protection, and a reaction time of 24 hours.

[0055] The polymerization product from step S5 needs to be precipitated and centrifuged. The precipitating solvent is diethyl ether. The number average molecular weight of the alternating main-chain polymer containing anthracene groups and biphenyl groups is 5550, with a molecular weight distribution of 1.61. The number average molecular weight of the alternating main-chain polymer containing diphenyl anthracene groups and biphenyl groups is 18147, with a molecular weight distribution of 1.36.

[0056] In the following examples, the polymer 1H NMR spectra were measured on an AVANCE 400 (400MHz) NMR spectrometer, using CDCl3 as the solvent and at a temperature of 25°C.

[0057] Polymer molecules (Mw, Mn) and molecular weight distribution (Mw / Mn) were determined using gel permeation chromatography (GPC) (which consisted of a Waters 1515-grade HPLC pump and a Waters 214 refractometer, and the system was composed of three parts) under the following conditions: THF eluent, 1.0 mL / min, 100 μL injection volume, and 40 min injection time. The standard was linear polystyrene with a narrow molecular weight distribution.

[0058] Example 1

[0059] A method for preparing a main-chain alternating liquid crystal polymer containing anthracene groups and biphenyl groups includes the following steps:

[0060] (1) Preparation of monomer A-6

[0061] A solution of octyne alcohol (20 mmol) in THF (3 mL) was added dropwise to a suspension of sodium hydride (22 mmol) in THF (20 mL) at 0 °C, and the reaction mixture was allowed to warm to room temperature over 1 h. Tetrabutylammonium iodide (1 mmol) and benzylammonium bromide (10 mmol) were added sequentially to THF (5 mL), and the mixture was stirred at room temperature for 24 h. After the reaction was complete, the mixture was concentrated and extracted with ethyl acetate and saturated NHCl4 solution. The organic layer was dried over MgSO4, filtered, and concentrated. The mixture was recrystallized twice with ethanol. NMR characterization of the product is shown in [reference needed]. Figure 1 Its structural formula is as follows:

[0062]

[0063] (2) Preparation of monomer E-9

[0064] 9,10-Biphenylanthracene (5.5 mmol), DCC (28 mmol), DMAP (28 mmol), and TsOH (6 mmol) were added to 20 mL of DCM in a round-bottom flask equipped with a magnetic stir bar and placed in an ice-water bath. Under vigorous stirring, 1.1 mL (16.5 mmol) of 10-undecyneic acid from 20 mL of DCM was added dropwise to the system. The reaction was carried out at room temperature for 12 h. The resulting mixture was extracted by filtration with DCM. The organic layer was dried on MgSO4, and the solvent was removed by rotary evaporation. The product was then recrystallized twice with ethanol. NMR characterization of the product is shown below. Figure 2 Its structural formula is as follows:

[0065]

[0066] (3) Preparation of intermediate D-6-1

[0067] 25 mmol of bromoterminated alkyl acid, 10 mmol of dihydroxybiphenyl, 30 mmol of DCC, 4 mmol of DMAP, and 4 mmol of TsOH were placed in separate 250 mL round-bottom flasks, and THF was added. The resulting mixture was stirred at 40 °C for 24 hours. After filtering to form urea, the solid was washed with tetrahydrofuran, and the filtrate was concentrated using a rotary evaporator. The product was recrystallized from ethanol. NMR characterization of the product is shown below. Figure 3 Its structural formula is as follows:

[0068]

[0069] (4) Preparation of monomer D-6-2

[0070] Weigh 5 mmol of biphenyl derivative and 20 mmol of azidotrimethylsilane into a 250 mL flask, add 10 mL of 1 mol / L TBAF in THF solution and 40 mL of THF solvent. Heat the reaction mixture under reflux at 80 °C for 24 h. After the reaction is complete, remove the solvent by rotary evaporation, dilute with deionized water, and extract with DCM several times, collecting the lower organic phase. Dry the organic phase with anhydrous Mg2SO4. Concentrate by rotary evaporation and recrystallize twice with anhydrous ethanol. See below for NMR characterization of the product. Figure 4 Its structural formula is as follows:

[0071]

[0072] (5) Preparation of polymer P(A-6+D-6)

[0073] Cuprous bromide (0.05 mmol, 0.05 equiv.) was weighed and placed in a Schrank tube, sealed with a rubber stopper, and nitrogen gas was continuously introduced. Then, anthracene monomer (1 mmol, 1.0 equiv.) and biphenyl monomer (1 mmol, 1.0 equiv.) were weighed and dissolved in 1 mL of DMF, respectively, and added to the reaction tube using a syringe. A liquid nitrogen freezing-vacuuming-nitrogen purging process was used to ensure an anhydrous and oxygen-free environment in the system, repeated three times. After the second cycle, pentamethyldiethylenetriamine (0.10 mmol, 0.1 equiv.) was weighed, dissolved in 1 mL of DMF, and injected into the reaction tube using a microsyringe. The final freezing-vacuuming and nitrogen purging process was repeated, and the reaction tube was placed in a 40°C oil bath for 24 h. After the reaction was stopped, the Cu(I) catalyst was removed using 60-mesh neutral alumina, the solution was concentrated, precipitated in a large amount of ice-cold diethyl ether, dissolved in DMF, and precipitated again, repeated three times. The NMR characterization of the product is shown below. Figure 5 GPC characterization see Figure 6 POM characterization can be found in Figure 9 Its structural formula is as follows:

[0074]

[0075] (6) Preparation of polymer P(E-9+D-6)

[0076] Cuprous bromide (0.05 mmol, 0.05 equiv.) was weighed and placed in a Schrank tube, sealed with a rubber stopper, and nitrogen gas was continuously introduced. Then, anthracene monomer (1 mmol, 1.0 equiv.) and biphenyl monomer (1 mmol, 1.0 equiv.) were weighed and dissolved in 1 mL of DMF, respectively, and added to the reaction tube using a syringe. A liquid nitrogen freezing-vacuuming-nitrogen purging process was used to ensure an anhydrous and oxygen-free environment in the system, repeated three times. After the second cycle, pentamethyldiethylenetriamine (0.10 mmol, 0.1 equiv.) was weighed, dissolved in 1 mL of DMF, and injected into the reaction tube using a microsyringe. The final freezing-vacuuming and nitrogen purging process was repeated, and the reaction tube was placed in a 40°C oil bath for 24 h. After the reaction was stopped, the Cu(I) catalyst was removed using 60-mesh neutral alumina, the solution was concentrated, precipitated in a large amount of ice-cold diethyl ether, dissolved in DMF, and precipitated again, repeated three times. The NMR characterization of the product is shown below. Figure 7 GPC characterization see Figure 8 POM characterization can be found in Figure 10 Its structural formula is as follows:

[0077]

[0078] 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. A polymer of anthracene fluorescent groups and biphenyl groups arranged alternately, characterized in that, The polymer has the following structural formula as shown in Formula V: 。 2. The method for preparing the polymer with alternating anthracene fluorescent groups and biphenyl groups as described in claim 1, characterized in that: Includes the following steps: S2, 9,10-Biphenylanthracene, dicyclohexylcarbodiimide (DCC), 4-dimethylaminopyridine (DMAP) and p-toluenesulfonic acid (TsOH) were mixed and stirred in an ice-water bath, and then 10-undecyneic acid was added dropwise to the flask. The mixture was reacted at room temperature for 12 h to obtain the bisphenylanthracene monomer. S3, 6-bromohexanoic acid, 4,4'-dihydroxybiphenyl, dicyclohexylcarbodiimide (DCC), 4-dimethylaminopyridine (DMAP), and p-toluenesulfonic acid (TsOH) were mixed and stirred in a tetrahydrofuran (THF) solution at 40°C for 24 h to obtain the biphenyl intermediate; S4. The biphenyl intermediate, trimethylsilane azido, and tetrabutylammonium fluoride (TBAF) were mixed and refluxed in a tetrahydrofuran (THF) solution at 80°C for 24 h to obtain the biphenyl monomer. S5, under the catalysis of cuprous bromide and pentamethyldiethylenetriamine, was polymerized with diphenyl anthracene monomer and biphenyl monomer in anhydrous N,N-dimethylformamide (DMF) solution to obtain a polymer with alternating structures containing 9,10-substituted anthracene groups and biphenyl groups.

3. The method for preparing the polymer with alternating anthracene fluorescent groups and biphenyl groups according to claim 2, characterized in that: The molar ratio of 10-undecyneic acid, 9,10-bisphenylanthracene, DCC, DMAP, and TsOH in step S2 is 2.5:1:3:0.4:0.

4.

4. The method for preparing the polymer with alternating anthracene fluorescent groups and biphenyl groups according to claim 2, characterized in that: The molar ratio of 6-bromohexanoic acid, 4,4'-dihydroxybiphenyl, DCC, DMAP, and TsOH in step S3 is 2.5:1:3:0.4:0.

4.

5. The method for preparing the polymer with alternating anthracene fluorescent groups and biphenyl groups according to claim 2, characterized in that: The molar ratio of biphenyl intermediate, trimethylsilane azido, and TBAF in step S4 is 1:4:

2.

6. The method for preparing the polymer with alternating anthracene fluorescent groups and biphenyl groups according to claim 2, characterized in that: In step S5, the molar ratio of anthracene monomer, biphenyl monomer, pentamethyldiethylenetriamine, and cuprous bromide is 1:1:0.1:0.

05.

7. The method for preparing the polymer of alternating anthracene fluorescent groups and biphenyl groups according to claim 2, characterized in that: The polymerization reaction temperature in step S5 is 40°C, and the reaction environment requires anhydrous and oxygen-free conditions, nitrogen protection, and a reaction time of 24 hours.

8. The method for preparing the polymer with alternating anthracene fluorescent groups and biphenyl groups according to claim 2, characterized in that: The polymerization product from step S5 needs to be precipitated and centrifuged. The precipitating solvent is diethyl ether. The number average molecular weight of the main-chain alternating polymer containing diphenyl anthracene groups and biphenyl groups is 18147, with a molecular weight distribution of 1.36.

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