A side chain containing photoelectric group polyaryletherketone polymer and a preparation method thereof

Abstract

The application discloses a kind of side chain containing photoelectric group polyaryletherketone polymer and its preparation method, wherein the method comprises: the side chain containing carboxyl polyaryletherketone, amino monomer, calcium chloride, triphenyl phosphate, pyridine are mixed in organic solvent, in protective atmosphere, sufficient reaction is stirred and heated;The reaction is added to methanol to terminate reaction, the product is washed with hot water and methanol multiple times, vacuum dried until mass is unchanged, to obtain the side chain containing photoelectric group polyaryletherketone polymer.The polyaryletherketone synthesized in the application not only has typical photoelectric activity, but also simple synthesis, has good solubility.Polyaryletherketone polymer preparation uses amino monomer phosphoracylation and is grafted on the side chain containing carboxyl polyaryletherketone, and has higher reactivity, higher grafting rate, is easy to commercial production, and has practical value;And polyaryletherketone polymer material not only has good photoelectric property, also has polyaryletherketone material good thermal stability, solubility, mechanical property etc.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, specifically to a polyaryletherketone polymer with photoelectric groups in its side chains and its preparation method. Background Technology

[0002] The widespread application of information system transmission and display technologies marked the beginning of the "information age" in the early 21st century, revolutionizing human lifestyles and bringing immense benefits. The rapid development of information industry technologies necessitates continuous improvement in technology and processes, as well as innovation in theoretical knowledge. The development of new materials not only provides a basis for theoretical research but also better meets the requirements of production processes and promotes their improvement. Therefore, the development of new functional materials has become crucial in this field, with the development of novel organic polymer optoelectronic functional materials being of paramount importance.

[0003] Polyaryletherketones (PAGEs) are a class of high-performance engineering plastics with excellent mechanical properties and thermal stability. Materials with PAGEs as the polymer backbone have been applied in many fields. However, because the ether bonds in the backbone can hinder charge transport, PAGEs are rarely reported for use in optoelectronic materials.

[0004] Carbazole, triphenylamine, anthraquinone, and azobenzene are several common compounds with excellent photoelectric properties. Due to their inherent good photoelectric activity, small-molecule and high-molecular-weight photoelectric functional materials constructed from them have been widely used in photoelectric fields such as hole transport, electrochromism, electroluminescence, information storage, and solar cells, exhibiting excellent performance. Regardless of the method used to introduce these functional structural units, the key to obtaining high-performance photoelectric materials and corresponding functional devices lies in how to effectively form a controllable and ordered stacking and arrangement among them. Combining these photoelectric active groups with polyaryletherketones (PAEs) suggests that such materials will possess unique and novel functional properties, high scientific research value, and broad application prospects. Summary of the Invention

[0005] The purpose of this invention is to provide a series of novel polyaryletherketone polymer materials with excellent photoelectric activity, solubility, and thermal stability, and containing multiple photoelectric functional groups in their side chains. Based on this, this invention provides a polyaryletherketone polymer with photoelectric functional groups in its side chains and its preparation method, thereby solving the technical problem of combining polyaryletherketones with photoelectric functional units such as carbazole, triphenylamine, anthraquinone, and azobenzene in the prior art.

[0006] To achieve the above objectives, the present invention provides a polyaryletherketone polymer with photoelectric groups in its side chains, the structural formula of which is shown below:

[0007]

[0008] Where n is the degree of polymerization, taking the integer value between 30 and 50; m is the copolymerization ratio, 0 < m ≤ 1; X is selected from one of the following four structures:

[0009]

[0010] Where R is -H, -t-Bu, or -OCH3.

[0011] Depending on the selection of X and R, the polyaryletherketone polymers with photoelectric groups in the side chains of the present invention have the following structures P1-P8:

[0012]

[0013] According to another aspect of the present invention, the present invention also provides a method for preparing a polyaryletherketone polymer with photoelectric groups on the side chain, specifically comprising the following steps:

[0014] A polyaryletherketone with carboxyl-containing side chains, an amino-containing monomer, calcium chloride, triphenyl phosphate (TPP), pyridine, and N-methylpyrrolidone (NMP) were added to a three-necked flask equipped with a nitrogen inlet, an oil-water separator, and a mechanical stirrer. The mixture was stirred and heated to 100-110°C under a nitrogen atmosphere and maintained for 2-3 hours. The reaction was terminated by adding methanol. The resulting product was washed 4-5 times with hot water and methanol and dried under vacuum at 150°C until its mass remained unchanged, yielding a polyaryletherketone polymer with photoelectric groups on its side chains.

[0015] The reaction formula for synthesizing polyaryletherketone polymers with photoelectric groups in the side chains is as follows:

[0016]

[0017] Where n represents the degree of polymerization, approximately equal to an integer between 30 and 50; m is the copolymerization ratio, 0 < m ≤ 1; X is selected from one of the following four structures:

[0018]

[0019] Where R is -H, -t-Bu, or -OCH3.

[0020] Preferably, the reaction feed amount of the amino monomer is 2.5-5 times the mass of the polyarylether ketone with carboxyl groups in the side chain.

[0021] This invention, from a molecular design perspective, introduces carbazole, triphenylamine, anthraquinone, or azobenzene containing conjugated photoactive groups as photoactive units into polyaryletherketones (PAEs). This allows PAEs to retain their excellent engineering plastic properties while introducing photoelectric functionality. The introduced photoactive units, acting as electron donors, can form intermolecular donor-acceptor structures with electron-withdrawing ketone groups in the PAE backbone, facilitating charge migration. Although the ether bonds in the backbone structure still hinder charge migration, charge can be transferred through the donor-acceptor structures of the side chains, effectively reducing the driving potential. Simultaneously, by grafting relatively rigid photoactive groups into the polymer instead of synthesizing monomers first and then performing the polymerization reaction, this method effectively avoids the difficulties of anionic polymerization caused by steric hindrance, helping to maintain the high molecular weight of PAEs and thus possessing great potential for practical applications.

[0022] Polyaryletherketone (PLEK) polymers with photoelectric groups in their side chains combine the photoelectric properties of the corresponding photoelectric active units with the advantages of high mechanical strength, good thermal stability, and good solubility of PLEK polymers. Building upon this achievement, by introducing other photoelectric functional groups into the polymer side chains according to specific needs, a series of functional PLEK polymer materials meeting different photoelectric performance requirements can be prepared, giving them a very broad range of applications and practical value. Based on their structure and photoelectric properties, these materials will have broad development prospects and enormous application potential in the optoelectronic field, especially in electrochromic and information storage.

[0023] The polyaryletherketone polymer with photoelectric groups in its side chain and its preparation method of the present invention, by adopting the above technical solution, can achieve the following beneficial effects:

[0024] The polyaryletherketone synthesized in this invention not only exhibits typical photoelectric activity but also boasts a simple synthesis and good solubility. The preparation of the polyaryletherketone polymer involves phosphorylating an amino monomer and grafting it onto a polyaryletherketone containing a carboxyl group in its side chain. This method demonstrates high reactivity, a high grafting rate, and ease of commercial production, making it practically valuable.

[0025] The prepared polyaryletherketone polymer materials not only possess excellent optoelectronic properties but also exhibit the good thermal stability, solubility, and mechanical properties of polyaryletherketone materials, effectively addressing some of the shortcomings of existing optoelectronic materials. Importantly, these materials retain the optoelectronic functional characteristics of their side-chain functional groups, thus giving them a very broad range of applications and practical value. Based on their structural characteristics and optoelectronic properties, it is foreseeable that such materials will have broad development prospects and enormous application potential in the optoelectronic field, particularly in electrochromic and information storage. Attached Figure Description

[0026] The present invention will now be described in further detail with reference to the accompanying drawings and specific embodiments.

[0027] Figure 1 1H NMR spectra of the polyaryletherketone polymers prepared in Examples 1, 2, 3 and 4, at 20% P1, 40% P4, 80% P5 and 50% P7.

[0028] Figure 2 Differential scanning calorimetry (DSC) spectra of the polyaryletherketone polymers 20% P1, 40% P4, and 80% P5 prepared in Examples 1, 2, and 3.

[0029] Figure 3 Thermogravimetric spectra of polyaryletherketone polymers 20% P1, 40% P4 and 80% P5 prepared in Examples 1, 2 and 3 under nitrogen protection.

[0030] Figure 4 UV absorption spectrum of the polyaryletherketone polymer 80% P5 film prepared in Example 3.

[0031] Figure 5 Fluorescence emission spectrum of the 20% P1 polyaryletherketone polymer film prepared in Example 1.

[0032] Figure 6 Cyclic voltammetry curve of the polyaryletherketone polymer 80% P5 prepared in Example 3.

[0033] The objectives, features, and advantages of this invention will be further explained in conjunction with the embodiments and with reference to the accompanying drawings. Detailed Implementation

[0034] The specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are for illustration and explanation only and are not intended to limit the present invention.

[0035] Unless otherwise defined, the technical terms used in the following embodiments have the same meanings as commonly understood by those skilled in the art to which this invention pertains. Unless otherwise specified, the experimental reagents used in the following embodiments are conventional biochemical reagents; and the experimental methods described are conventional methods.

[0036] This invention proposes a polyaryletherketone polymer with photoelectric groups in the side chain, the structural formula of which is shown below:

[0037]

[0038] Where n is the degree of polymerization, taking the integer value between 30 and 50; m is the copolymerization ratio, 0 < m ≤ 1; X is selected from one of the following four structures:

[0039]

[0040] Where R is -H, -t-Bu, or -OCH3.

[0041] Depending on the selection of X and R, the polyaryletherketone polymers with photoelectric groups in the side chains of the present invention have the following structures P1-P8:

[0042]

[0043] The difference between polymers P1, P2, and P3 lies in the different R groups. These different R groups are mainly used to control the absorption spectrum of the material. Moreover, the reactivity of the amino-containing monomers grafted onto each polymer P1, P2, and P3 is not significantly different during their preparation. Similarly, the difference between polymers P4, P5, and P6 also lies in the different R groups. These different R groups are mainly used to control the absorption spectrum of the material. Moreover, the reactivity of the amino-containing monomers grafted onto each polymer P4, P5, and P6 is not significantly different during their preparation.

[0044] To enable those skilled in the art to better understand and implement the technical solutions of the present invention, the present invention will be further described in detail below through specific embodiments.

[0045] Example 1: Preparation of 20% P1 of polyaryletherketone polymer

[0046] 1g of 20% polyarylether ketone with carboxyl-containing side chains (number average molecular weight 4.07 × 10⁻⁶) 5 N-(4-aminophenyl)-carbazole (0.3 g, 1.16 mmol), calcium chloride (0.2 g, 1.80 mmol), triphenyl phosphate (0.7 ml, 2.67 mmol), pyridine (1 ml, 12.4 mmol), and N-methylpyrrolidone (7 ml, 20% solids content) were added to a 25 ml three-necked flask equipped with a nitrogen inlet, an oil-water separator, and a mechanical stirrer. The mixture was stirred and heated to 105 °C for 3 h under a nitrogen atmosphere. The reaction was terminated by adding 100 ml of methanol. The mixture was ground into powder using a tissue homogenizer, filtered under reduced pressure, and the solid precipitate was collected. The precipitate was then washed by boiling with water (5 times, 200 mL each time) and methanol (3 times, 100 mL each time), filtered, and dried in an oven at 150 °C for 10 h to obtain a light yellow polymer powder (1.11 g, 100% grafting rate), which is the polyaryletherketone polymer with structural formula P1.

[0047] The polyaryletherketone polymer obtained in this embodiment was subjected to structural analysis, and the 1H NMR spectrum of the product is shown in the attached figure. Figure 1 As shown. Its number-average molecular weight is 4.21 × 10⁻⁶. 5The molecular weight distribution is 1.28. Furthermore, the differential scanning calorimetry (DSC) spectrum of the obtained product is as follows: Figure 2 As shown, the thermogravimetric spectrum under nitrogen protection is as follows: Figure 3 As shown, the fluorescence emission spectrum of the thin film formed by the polyaryletherketone polymer material is as follows: Figure 5 As shown.

[0048] Example 2: Preparation of 40% P4 polyaryletherketone polymer

[0049] 1g of polyarylether ketone with 40% carboxyl-containing side chains (number average molecular weight 3.58 × 10⁻⁶) 5 N-4-amino-triphenylamine (0.3 g, 1.15 mmol), calcium chloride (0.2 g, 1.80 mmol), triphenyl phosphate (0.7 ml, 2.67 mmol), pyridine (1 ml, 12.4 mmol), and N-methylpyrrolidone (7 ml, 20% solids content) were added to a 25 ml three-necked flask equipped with a nitrogen inlet, an oil-water separator, and a mechanical stirrer. The mixture was stirred and heated to 105 °C for 3 h under a nitrogen atmosphere. The reaction was terminated by adding 100 ml of methanol. The mixture was ground into powder using a tissue homogenizer, filtered under reduced pressure, and the solid precipitate was collected. The precipitate was then washed by boiling with water (5 times, 200 mL each time) and methanol (3 times, 100 mL each time), filtered, and dried in an oven at 150 °C for 10 h to obtain a white polymer powder (1.12 g, 100% grafting rate), which is the polyaryletherketone polymer with structural formula P4.

[0050] The polymer obtained in this embodiment was subjected to structural analysis, and the 1H NMR spectrum of the product is shown in the attached figure. Figure 1 As shown. Its number-average molecular weight is 3.78 × 10⁻⁶. 5 The molecular weight distribution is 1.31. Furthermore, the differential scanning calorimetry (DSC) spectrum of the obtained product is as follows: Figure 2 As shown, the thermogravimetric spectrum under nitrogen protection is as follows: Figure 3 As shown.

[0051] Example 3: Preparation method of polyaryletherketone polymer 80% P5

[0052] 1g of polyarylether ketone with 80% carboxyl-containing side chains (number average molecular weight 2.01×10⁻⁶) was used. 54-Amino-4',4”-bis-tert-butyltriphenylamine (0.6 g, 1.61 mmol), calcium chloride (0.2 g, 1.80 mmol), triphenyl phosphate (0.7 ml, 2.67 mmol), pyridine (1 ml, 12.4 mmol), and N-methylpyrrolidone (7 ml, 20% solids content) were added to a 25 ml three-necked flask equipped with a nitrogen inlet, an oil-water separator, and a mechanical stirrer. The mixture was stirred and heated to 110 °C for 3 h under a nitrogen atmosphere. The reaction was terminated by adding 100 ml of methanol. The mixture was ground into powder using a tissue homogenizer, filtered under reduced pressure, and the solid precipitate was collected. The precipitate was then washed by boiling with water (5 times, 200 mL each time) and methanol (3 times, 100 mL each time), filtered, and dried in an oven at 150 °C for 10 h to obtain a white polymer powder (1.12 g, 100% grafting rate), which is the polyaryletherketone polymer with structural formula P5.

[0053] The polyaryletherketone polymer obtained in this embodiment was subjected to structural analysis, and the 1H NMR spectrum of the product is shown in the attached figure. Figure 1 As shown. Its number-average molecular weight is 2.22 × 10⁻⁶. 5 The molecular weight distribution is 1.32. Furthermore, the differential scanning calorimetry (DSC) spectrum of the obtained product is as follows: Figure 2 As shown, the thermogravimetric spectrum under nitrogen protection is as follows: Figure 3 As shown, the UV absorption spectrum of the thin film formed by the polyaryletherketone polymer material is as follows: Figure 4 As shown, the cyclic voltammetry curve is as follows: Figure 6 As shown.

[0054] Example 4: Preparation method of polyaryletherketone polymer 50% P7

[0055] 1g of 50% polyarylether ketone with carboxyl-containing side chains (number average molecular weight 3.12 × 10⁻⁶) 5 2-Aminoanthraquinone (0.4 g, 1.79 mmol), calcium chloride (0.2 g, 1.80 mmol), triphenyl phosphate (0.7 ml, 2.67 mmol), pyridine (1 ml, 12.4 mmol), and N-methylpyrrolidone (7 ml, 20% solids content) were added to a 25 ml three-necked flask equipped with a nitrogen inlet, an oil-water separator, and a mechanical stirrer. The mixture was heated to 110 °C under a nitrogen atmosphere and maintained for 3 h. The reaction was terminated by adding 100 ml of methanol. The mixture was ground into powder using a tissue homogenizer, filtered under reduced pressure, and the solid precipitate was collected. The precipitate was then washed by boiling with water (5 times, 200 mL each time) and methanol (3 times, 100 mL each time), filtered, and dried in an oven at 150 °C for 10 h. A red polymer powder (1.09 g, 100% grafting rate) was obtained, which is the polyaryletherketone polymer with structural formula P7.

[0056] The polymer obtained in this embodiment was subjected to structural analysis, and the 1H NMR spectrum of the product is shown in the attached figure. Figure 1 As shown. Its number-average molecular weight is 3.22 × 10⁻⁶. 5 The molecular weight distribution is 1.25.

[0057] exist Figure 1 The chemical shift distributions of the 20% P1, 40% P4, 80% P5 and 50% P7 NMR spectra of the polyaryletherketone polymer are clear. In particular, the peaks on all carboxyl groups have disappeared, which proves the successful preparation of the polymer and that it has a relatively complete grafting success rate.

[0058] exist Figure 2 As can be seen, the glass transition temperatures of the three polyaryletherketone polymers are all above 170℃. Furthermore, with the increase in the proportion of bulk side chains, the material's rigidity increases, leading to a higher glass transition temperature for materials with a larger grafting ratio. This demonstrates that these polymers not only retain the good thermal stability of engineering plastics but also offer some improvement in thermal stability.

[0059] exist Figure 3 As can be seen, the thermal decomposition temperatures of polyaryletherketone polymers 20% P1, 40% P4, and 80% P5 under nitrogen protection all exceed 350℃, which fully meets the requirements for the use of optoelectronic materials in most environments.

[0060] exist Figure 4 The UV absorption spectrum of the polyaryletherketone polymer 80% P5 shows a broad peak in the 310nm-350nm range, proving that the grafting of the polyaryletherketone polymer was successful and that there is a donor-acceptor effect in the polymer.

[0061] exist Figure 5 The study observed that the polyaryletherketone polymer 20%P1 exhibits strong blue fluorescence emission at 450 nm, indicating that carbazole in the polymer film does not undergo fluorescence aggregation quenching like smaller molecules. The polymer backbone restricts the free movement and π-π stacking of the side chains, which is beneficial to the fluorescence emission of the side chain photoelectric structure, demonstrating the significant application potential of this type of material in the optoelectronic field.

[0062] exist Figure 6 As can be seen from the curves, the polyaryletherketone polymer 80% P5 has symmetrical cyclic voltammetry curves, which proves that the material has good electrochemical stability and low driving potential, indicating good electrochemical performance.

[0063] Solubility test

[0064] The solubility of a series of polyaryletherketone polymers prepared in this invention was tested. The solvents used and the results are shown in Table 1.

[0065] Table 1 Solubility Test Table

[0066]

[0067] Experimental results show that the polyaryletherketone polymer provided by this invention is soluble in organic solvents such as tetrahydrofuran, dichloromethane, chloroform, N,N'-dimethylformamide (DMF), N-methylpyrrolidone (NMP), and dimethyl sulfoxide (DMSO). This demonstrates that all the polyaryletherketone polymers in the examples exhibit good solubility, indicating a wide range of solvent choices during processing. Furthermore, better solubility means that the material is less prone to precipitation during film formation, which is beneficial for forming a smoother surface morphology and improving the material's performance.

[0068] Mechanical performance testing

[0069] The mechanical properties of a series of polymer films prepared according to this invention were tested, and the results are shown in Table 2:

[0070] Table 2 Mechanical Performance Test Table

[0071]

[0072] Mechanical property tests demonstrated that the polyaryletherketone polymer materials prepared in all the above embodiments possessed good mechanical properties, indicating that this grafting method had little impact on the mechanical properties of the polyaryletherketone backbone structure. These good mechanical properties allow the materials to be suitable for a wider range of applications.

[0073] While specific embodiments of the present invention have been described above, those skilled in the art should understand that these are merely illustrative examples, and various changes or modifications can be made to these embodiments without departing from the principles and essence of the present invention. The scope of protection of the present invention is defined only by the appended claims.

Claims

1. A polyaryletherketone polymer with photoelectric groups in its side chains, characterized in that, The structural formula of the polyaryletherketone polymer is shown below: ； Where n is the degree of polymerization, an integer between 30 and 50; m is the copolymerization ratio, 0 < m < 1; X is the photoelectric functional group, selected from one of the following four structures: ； Where R is -H, -t-Bu, or -OCH3.

2. A method for preparing the polyaryletherketone polymer with photoelectric groups in the side chain as described in claim 1, characterized in that, Includes the following steps: A polyarylether ketone with carboxyl groups in the side chain, an amino monomer, calcium chloride, triphenyl phosphate, and pyridine were mixed in an organic solvent and stirred and heated to react fully under a protective atmosphere. The reaction was terminated by adding methanol to the reactants. The resulting product was washed several times with water and methanol and dried under vacuum until its mass remained unchanged to obtain a polyarylether ketone polymer with photoelectric groups in the side chain. The amino-containing monomer has the structural formula H2N—X, where X is selected from one of the following four structures: ； Where R is -H, -t-Bu, or -OCH3.

3. The method for preparing the polyaryletherketone polymer with photoelectric groups in the side chain according to claim 2, characterized in that, The specific steps for the stirring and heating to ensure a full reaction are as follows: stir and heat to 100-110℃ and maintain for 2-3 hours.

4. The method for preparing the polyaryletherketone polymer with photoelectric groups in the side chain according to claim 2, characterized in that, The reaction vessel used for the stirring and heating to ensure a complete reaction is a three-necked flask equipped with a nitrogen inlet, an oil-water separator, and a mechanical stirrer.

5. The method for preparing the polyaryletherketone polymer with photoelectro-optic groups in the side chain according to claim 2, characterized in that, The reaction feed amount of the amino monomer is 2.5-5 times the mass of the polyarylether ketone with carboxyl groups in the side chain.

6. The method for preparing the polyaryletherketone polymer with photoelectro-optic groups in the side chain according to claim 2, characterized in that, The organic solvent is N-methylpyrrolidone.

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