A poly(arylene ether ketone) oligomer having pendant carboxyl groups, a thermoset shape memory poly(arylene ether ketone), and a method of making the same

Abstract

The application provides a polyaryletherketone oligomer with side groups containing carboxyl, a thermosetting shape memory polyaryletherketone and a preparation method thereof, and belongs to the technical field of high molecular polymers. The application uses 4,4-difluorobenzophenone, hexafluorobisphenol A and bisphenol acid as reaction monomers, can introduce carboxyl into the structure of the polyaryletherketone oligomer, and obtains the polyaryletherketone oligomer with side groups containing carboxyl. The obtained polyaryletherketone oligomer has good solubility in a polar solvent, can realize simple and rapid forming of the polyaryletherketone, overcomes the defects existing in the forming and manufacturing of the existing polyaryletherketone, and expands the application range of the polyaryletherketone. The application uses the above-mentioned polyaryletherketone oligomer with side groups containing carboxyl as raw material, and matches cyanate as a crosslinking agent, can realize simple and rapid curing forming of the polyaryletherketone, and the obtained thermosetting shape memory polyaryletherketone has good mechanical properties and excellent shape memory performance.

Description

Technical Field

[0001] This invention relates to the field of polymer technology, and in particular to a polyaryletherketone oligomer with carboxyl groups on its side groups, a thermosetting shape memory polyaryletherketone and its preparation method. Background Technology

[0002] Polyaryletherketone (PAGE) is a high-performance specialty plastic. Its unique molecular structure endows it with excellent comprehensive properties, such as superior high-temperature performance, mechanical properties, electrical insulation, radiation resistance, chemical resistance, and self-lubrication. Since its successful development in the 1960s, PAGE has been widely used in industrial, transportation, aerospace, electronics, and medical fields, becoming one of the most popular specialty plastics today.

[0003] Polyaryletherketones (PAGEs) are crystalline aromatic thermoplastic polymers formed by the linkage of phenylene rings with carbonyl (ketone) groups via ether bonds. PAGEs are primarily produced through nucleophilic substitution reactions, undergoing condensation polymerization at high temperatures to obtain high molecular weight PAGEs. Due to their rigid molecular chains and high molecular weight, they are difficult to dissolve in commonly used polar solvents. Therefore, current molding methods for PAGEs mainly involve high-temperature melt extrusion, injection molding, and compression molding. These methods not only require high temperatures but also place high demands on the molding dies, hindering rapid molding and limiting the applications of PAGEs.

[0004] With technological advancements, the development of polyaryletherketone (PAEK) materials with good solubility and excellent mechanical properties is imperative. If rapid and simple preparation and molding of PAEK can be achieved, it will greatly overcome the shortcomings of existing molding processes and expand the application areas of PAEK in real life. Summary of the Invention

[0005] In view of this, the present invention aims to provide a polyaryletherketone oligomer with carboxyl groups on its side groups, a thermosetting shape memory polyaryletherketone, and a method for preparing the same. Using the polyaryletherketone oligomer with carboxyl groups on its side groups provided by the present invention as a raw material, simple and rapid curing of polyaryletherketone can be achieved, and the resulting thermosetting shape memory polyaryletherketone exhibits good mechanical properties and excellent shape memory properties.

[0006] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0007] This invention provides a method for preparing polyaryletherketone oligomers with carboxyl groups as side groups, comprising the following steps:

[0008] 4,4-Difluorobenzophenone, hexafluorobisphenol A, bisphenol acid, basic carbonate, and a first polar solvent were mixed and subjected to a polycondensation reaction to obtain a polyarylether ketone oligomer with carboxyl groups on the side groups.

[0009] Preferably, the molar ratio of 4,4-difluorobenzophenone, hexafluorobisphenol A, and bisphenolic acid is 1:0.25-0.75:0.25-0.75.

[0010] Preferably, the polycondensation reaction is carried out at a temperature of 180–200°C for 8–10 hours.

[0011] Preferably, the first organic solvent is one or more of N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, toluene, tetrahydrofuran, and sulfolane.

[0012] The present invention provides polyaryletherketone oligomers with carboxyl groups on the side groups prepared by the above preparation method.

[0013] This invention provides a method for preparing thermosetting shape memory polyaryletherketone, comprising the following steps:

[0014] The above-mentioned polyarylether ketone oligomer with carboxyl groups on its side groups is mixed with cyanate ester and a second polar solvent to obtain oligomer ink;

[0015] The oligomer ink is applied to the substrate surface and then thermosetting to obtain thermosetting shape memory polyaryletherketone.

[0016] Preferably, the oligomer ink comprises, by weight percentage:

[0017] 70-80 parts of polyaryletherketone oligomers with carboxyl groups on the side groups;

[0018] 20-30 parts of cyanate.

[0019] Preferably, the second polar solvent is one or more of N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and chloroform.

[0020] Preferably, the thermosetting temperature is 70–100°C and the time is 12–36 h.

[0021] This invention provides a thermosetting shape memory polyaryletherketone prepared by the above preparation method.

[0022] This invention provides a method for preparing polyaryletherketone oligomers with carboxyl groups on the side chains, comprising the following steps: mixing 4,4-difluorobenzophenone, hexafluorobisphenol A, bisphenolic acid, and basic carbonate with a first polar solvent, and carrying out a polycondensation reaction to obtain polyaryletherketone oligomers with carboxyl groups on the side chains. This invention uses 4,4-difluorobenzophenone, hexafluorobisphenol A, and bisphenolic acid as reactant monomers, which can introduce carboxyl groups into the structure of polyaryletherketone oligomers, resulting in polyaryletherketone oligomers with carboxyl groups on the side chains. The carboxyl groups on the side chains can disrupt the regularity of the molecular chains, making them more soluble in polar solvents. The resulting polyaryletherketone oligomers have good solubility in polar solvents, enabling simple and rapid molding of polyaryletherketones, overcoming the defects of existing polyaryletherketone molding and manufacturing methods, and expanding the application range of polyaryletherketones.

[0023] This invention provides a method for preparing thermosetting shape memory polyaryletherketone (PAEK), comprising the following steps: mixing the above-mentioned PAEK oligomer containing carboxyl groups on its side groups, cyanate ester, and a second polar solvent to obtain an oligomer ink; applying the oligomer ink to a substrate surface and performing thermosetting to obtain the thermosetting shape memory PAEK. This invention uses the above-mentioned PAEK oligomer containing carboxyl groups on its side groups as a raw material, combined with cyanate ester as a crosslinking agent, to achieve simple and rapid curing of PAEK. The resulting thermosetting shape memory PAEK exhibits good mechanical properties and excellent shape memory performance. Example results show that the thermosetting shape memory PAEK provided by this invention has a tensile strength ≥45 MPa, a transition temperature ≥80℃, a shape fixation rate of 98%, and a shape recovery rate of 83%, exhibiting excellent shape memory performance. Attached Figure Description

[0024] Figure 1 Synthetic routes for polyaryletherketone oligomers with carboxyl groups on the side groups;

[0025] Figure 2 The infrared spectrum of the polyaryletherketone oligomer obtained in Example 1 is shown below.

[0026] Figure 3 The molecular weight GPC diagram of the polyaryletherketone oligomer obtained in Example 1 is shown below.

[0027] Figure 4 The stress-strain curve diagram is shown in the example.

[0028] Figure 5 This is a shape memory curve diagram of Example 1. Detailed Implementation

[0029] This invention provides a method for preparing polyaryletherketone oligomers with carboxyl groups as side groups, comprising the following steps:

[0030] 4,4-Difluorobenzophenone, hexafluorobisphenol A, bisphenol acid, basic carbonate, and a first polar solvent were mixed and subjected to a polycondensation reaction to obtain a polyarylether ketone oligomer with carboxyl groups on the side groups.

[0031] In this invention, the molar ratio of 4,4-difluorobenzophenone, hexafluorobisphenol A, and bisphenolic acid is preferably 1:0.25-0.75:0.25-0.75, more preferably 1:0.3-0.6:0.3-0.6, and even more preferably 1:0.4-0.5:0.4-0.5.

[0032] In this invention, the alkaline carbonate is preferably potassium carbonate and / or sodium carbonate.

[0033] In this invention, the molar ratio of 4,4-difluorobenzophenone to potassium carbonate is preferably 1:1 to 2, more preferably 1:1 to 1.5, and even more preferably 1:1 to 1.1.

[0034] In this invention, the first organic solvent is preferably one or more of N,N-dimethylacetamide, N,N-dimethylacetamide, dimethyl sulfoxide, toluene, tetrahydrofuran, and sulfolane, more preferably sulfolane and / or N,N-dimethylformamide.

[0035] In this invention, the mixing is preferably carried out under a protective atmosphere, preferably argon. This invention does not have any special requirements for the mixing method; any mixing method known to those skilled in the art can be used, such as stirring.

[0036] In this invention, before the polycondensation reaction, the resulting mixture is preferably heated to 120-145°C for dehydration, preferably 135°C, and the dehydration time is preferably 2-4 hours, more preferably 3 hours.

[0037] In this invention, the temperature of the polycondensation reaction is preferably 180-200°C, more preferably 190°C; the time is preferably 8-10 hours, more preferably 9 hours.

[0038] Following the polycondensation reaction, the present invention preferably performs post-processing on the obtained polycondensation product, the post-processing preferably including the following steps:

[0039] The polycondensation product was poured into water, and the pH was adjusted to neutral to obtain a precipitate.

[0040] The precipitate was washed and dried to obtain a solid polyarylether ketone oligomer with carboxyl groups on the side.

[0041] In this invention, hydrochloric acid is preferably used as the reagent to adjust the pH value.

[0042] In this invention, the detergent used for washing is preferably methanol and deionized water; the drying temperature is preferably 80°C and the time is 24 hours.

[0043] In this invention, the preferred synthetic route for the polyarylether ketone oligomer with carboxyl groups as described above is as follows: Figure 1 As shown.

[0044] This invention provides polyaryletherketone oligomers with carboxyl groups on the side groups prepared by the above-described method. In this invention, the number-average molecular weight of the polyaryletherketone oligomer is preferably Mn = 6000–10000, more preferably 8800. The polyaryletherketone oligomers obtained by this invention have small molecular weight deviations and good solubility in organic solvents.

[0045] This invention provides a method for preparing thermosetting shape memory polyaryletherketone, comprising the following steps:

[0046] The above-mentioned polyarylether ketone oligomer with carboxyl groups on its side groups is mixed with cyanate ester and a second polar solvent to obtain oligomer ink;

[0047] The oligomer ink is applied to the substrate surface and then thermosetting to obtain thermosetting shape memory polyaryletherketone.

[0048] This invention involves mixing the aforementioned polyaryletherketone oligomer with carboxyl groups on its side groups, a cyanate ester, and a second polar solvent to obtain an oligomer ink. In this invention, the oligomer ink comprises, by weight percentage: 70-80 parts of the polyaryletherketone oligomer with carboxyl groups on its side groups; preferably 72-78 parts, more preferably 75 parts; and 20-30 parts of the cyanate ester, preferably 22-28 parts, more preferably 25 parts.

[0049] In this invention, the second polar solvent is preferably N,N-dimethylformamide. In this invention, the mass ratio of the polyarylether ketone oligomer with carboxyl groups on its side groups to the second polar solvent is preferably 1:3 to 10, more preferably 1:3 to 5.

[0050] The present invention does not have any special requirements for the mixing method; any mixing method known to those skilled in the art can be used, such as stirring.

[0051] This invention involves applying the oligomer ink to a substrate surface and then thermally curing it to obtain a thermosetting shape memory polyaryletherketone. In this invention, the substrate is preferably a glass plate.

[0052] In this invention, the thermosetting temperature is preferably 70–100°C, more preferably 90°C, and the time is preferably 12–36 h, more preferably 24 h. In this invention, the thermosetting process is also a process of removing organic solvents.

[0053] This invention provides a thermosetting shape memory polyaryletherketone prepared by the above-described preparation method. In this invention, the thermosetting shape memory polyaryletherketone is preferably a thin film material, and the thickness of the thin film material is preferably 0.8–2 mm, more preferably 1 mm.

[0054] In this invention, the thermosetting shape memory polyaryletherketone is preferably used in the fields of actuators, robots or responders.

[0055] The following detailed description, in conjunction with embodiments, illustrates a polyaryletherketone oligomer with carboxyl groups on its side groups, a thermosetting shape memory polyaryletherketone, and its preparation method, but these should not be construed as limiting the scope of protection of this invention.

[0056] Example 1

[0057] Under argon protection, 16.15 g of 4,4-difluorobenzophenone, 13.45 g of hexafluorobisphenol A, 11.45 g of bisphenol A, and 11.89 g of anhydrous potassium carbonate were dissolved in a mixture of 80 mL of sulfolane and 25 mL of toluene solution. The solution was first heated to 135 °C for dehydration for 2 h, then heated to 190 °C for polycondensation reaction for 6 h. The stirred solution was poured into 2 L of water, and hydrochloric acid was added dropwise to adjust the pH to neutral for precipitation. The precipitate was repeatedly washed with methanol and deionized water, and finally dried in an oven at 80 °C for 24 h to obtain a polyaryletherketone oligomer (PAEK-COOH) with carboxyl-modifiable side groups. 2.38 g of the polyaryletherketone oligomer, 0.35 g of cyanate ester, and 7 g of N,N-dimethylformamide were mixed. The mixture was spread evenly on a glass plate and dried in a forced-air oven at 90 °C for 24 h to remove the solvent, yielding the polyaryletherketone material.

[0058] The infrared spectrum of the polyaryletherketone oligomer obtained in Example 1 is shown below. Figure 2 As shown, it can be observed at 3100cm -1 Up to 3700cm -1 The broad peak at 2274 cm⁻¹ is related to the characteristic peak of the hydroxyl group in the carboxyl group of PAEKP. -1 and 2236cm -1 The strong tensile vibration at the point is attributed to the -OCN group.

[0059] The molecular weight GPC diagram of the polyaryletherketone oligomer obtained in Example 1 is shown below. Figure 3 As shown.

[0060] Example 2

[0061] Under argon protection, 16.15 g of 4,4-difluorobenzophenone, 13.45 g of hexafluorobisphenol A, 11.45 g of bisphenol A, and 11.89 g of anhydrous potassium carbonate were dissolved in a mixture of 80 mL of sulfolane and 25 mL of toluene solution. The solution was first heated to 135 °C for dehydration for 2 h, then heated to 190 °C for polycondensation reaction for 6 h. The stirred solution was poured into 2 L of water, and hydrochloric acid was added dropwise to adjust the pH to neutral for precipitation. The precipitate was repeatedly washed with methanol and deionized water, and finally dried in an oven at 80 °C for 24 h to obtain a polyaryletherketone oligomer (PAEK-COOH) with carboxyl-modifiable side groups. 2.38 g of the polyaryletherketone oligomer, 0.4375 g of cyanate ester, and 7 g of N,N-dimethylformamide were mixed. The mixture was spread evenly on a glass plate and dried in a forced-air oven at 90 °C for 24 h to remove the solvent, yielding the polyaryletherketone material.

[0062] Example 3

[0063] Under argon protection, 16.15 g of 4,4-difluorobenzophenone, 13.45 g of hexafluorobisphenol A, 11.45 g of bisphenol A, and 11.89 g of anhydrous potassium carbonate were dissolved in a mixture of 80 mL of sulfolane and 25 mL of toluene solution. The solution was first heated to 135 °C for dehydration for 2 h, then heated to 190 °C for polycondensation reaction for 6 h. The stirred solution was poured into 2 L of water, and hydrochloric acid was added dropwise to adjust the pH to neutral for precipitation. The precipitate was repeatedly washed with methanol and deionized water, and finally dried in an oven at 80 °C for 24 h to obtain a polyaryletherketone oligomer (PAEK-COOH) with carboxyl-modifiable side groups. 2.38 g of the polyaryletherketone oligomer, 0.525 g of cyanate ester, and 7 g of N,N-dimethylformamide were mixed. The mixture was spread evenly on a glass plate and dried in a forced-air oven at 90 °C for 24 h to remove the solvent, yielding the polyaryletherketone material.

[0064] Example 4

[0065] Under argon protection, 16.15 g of 4,4-difluorobenzophenone, 13.45 g of hexafluorobisphenol A, 11.45 g of bisphenol A, and 11.89 g of anhydrous potassium carbonate were dissolved in a mixture of 80 mL of sulfolane and 25 mL of toluene solution. The solution was first heated to 135 °C for dehydration for 2 h, then heated to 190 °C for polycondensation reaction for 6 h. The stirred solution was poured into 2 L of water, and hydrochloric acid was added dropwise to adjust the pH to neutral for precipitation. The precipitate was repeatedly washed with methanol and deionized water, and finally dried in an oven at 80 °C for 24 h to obtain a polyaryletherketone oligomer (PAEK-COOH) with carboxyl-modifiable side groups. 2.38 g of the polyaryletherketone oligomer, 0.6125 g of cyanate ester, and 7 g of N,N-dimethylformamide were mixed. The mixture was spread evenly on a glass plate and dried in a forced-air oven at 90 °C for 24 h to remove the solvent, yielding the polyaryletherketone material.

[0066] Example 5

[0067] Under argon protection, 16.15 g of 4,4-difluorobenzophenone, 13.45 g of hexafluorobisphenol A, 11.45 g of bisphenol A, and 11.89 g of anhydrous potassium carbonate were dissolved in a mixture of 80 mL of sulfolane and 25 mL of toluene solution. The solution was first heated to 135 °C for dehydration for 2 h, then heated to 190 °C for polycondensation reaction for 6 h. The stirred solution was poured into 2 L of water, and hydrochloric acid was added dropwise to adjust the pH to neutral for precipitation. The precipitate was repeatedly washed with methanol and deionized water, and finally dried in an oven at 80 °C for 24 h to obtain a polyaryletherketone oligomer (PAEK-COOH) with carboxyl-modifiable side groups. 2.38 g of the polyaryletherketone oligomer, 0.7 g of cyanate ester, and 7 g of N,N-dimethylformamide were mixed. The mixture was spread evenly on a glass plate and dried in a forced-air oven at 90 °C for 24 h to remove the solvent, yielding the polyaryletherketone material.

[0068] Comparative Example 1

[0069] Mix 2.38 g of polyaryletherketone oligomer, 0.2625 g of cyanate ester, and 7 g of N,N-dimethylformamide. Spread the mixture evenly on a glass plate and remove the solvent in a 90°C forced-air oven for 24 hours.

[0070] Comparative Example 2

[0071] Mix 2.38 g of polyaryletherketone oligomer, 0.35 g of cyanate ester, and 7 g of N,N-dimethylformamide. Spread the mixture evenly on a glass plate and remove the solvent in a 90°C forced-air oven for 24 hours, then heat at 180°C for 3 hours.

[0072] Comparative Example 3

[0073] Mix 2.38 g of polyaryletherketone oligomer, 0.525 g of cyanate ester, and 7 g of N,N-dimethylformamide. Spread the mixture evenly on a glass plate and remove the solvent in a 90°C forced-air oven for 24 hours, then heat at 180°C for 3 hours.

[0074] Comparative Example 4

[0075] Mix 2.38 g of polyaryletherketone oligomer, 0.219 g of toluene diisocyanate, and 7 g of N,N-dimethylformamide. Heat in an oil bath at 80°C for 6 hours. Spread the mixture evenly on a glass plate and remove the solvent in a forced-air drying oven for 24 hours.

[0076] Comparative Examples 1 to 4 can all form films, but the film-formed products are relatively brittle and cannot be used to prepare standard specimens for mechanical property testing.

[0077] Performance testing

[0078] The mechanical properties of the thermosetting shape memory polyaryletherketones obtained in Examples 1-5 were tested at room temperature using a universal testing machine. The tensile speed was 1 mm / min, and the sample shape was prepared into a dumbbell shape according to the international standard ISO-527-2 / 5A. The shape memory properties of the materials were tested using a dynamic thermomechanical analyzer, with a temperature range of 25℃ to 120℃. Figure 4 and Figure 5 All tests were plotted using Origin software. Figure 4 The stress-strain curve is shown in the example diagram. Figure 5 This is a shape memory curve diagram of Example 1.

[0079] Table 1 shows the thermal performance test results of the thermosetting shape memory polyaryletherketones obtained in Examples 1-5.

[0080] Table 1 Thermal properties of thermosetting shape memory polyaryletherketone

[0081]

[0082] As can be seen from the thermal properties of thermosetting shape memory polyaryletherketone in Table 1, the polyaryletherketone obtained by the method of the present invention has good thermal stability, and its transition temperature can be controlled by adjusting the ratio of the two components.

[0083] Table 1 and Figure 5 This demonstrates that the thermosetting polyaryletherketone obtained by the method of the present invention has a high transition temperature, and that the transition temperature can be controlled by adjusting the ratio of the two components. Table 1 shows that the addition of different proportions of cyanate ester has an effect on adjusting the transition temperature. A clear difference of 10°C is observed between the transition temperatures of Examples 1 and 5.

[0084] Figure 5 Example 1, the shape memory curve, illustrates that the thermosetting shape memory obtained by the method of the present invention has a high shape fixation rate and shape recovery rate, and can be used as an excellent shape memory material.

[0085] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A method for preparing thermosetting shape memory polyaryletherketone, comprising the following steps: A polyaryletherketone oligomer with carboxyl groups on its side groups is mixed with a cyanate ester and a second polar solvent to obtain an oligomer ink. The oligomer ink is applied to the substrate surface and then thermosetting to obtain thermosetting shape memory polyaryletherketone. The method for preparing the polyaryletherketone oligomer with carboxyl groups on its side groups includes the following steps: 4,4-Difluorobenzophenone, hexafluorobisphenol A, bisphenol acid, basic carbonate, and a first polar solvent were mixed and subjected to a polycondensation reaction to obtain a polyarylether ketone oligomer with carboxyl groups on the side groups.

2. The preparation method according to claim 1, characterized in that, The oligomer ink comprises, by weight percentage: 70-80 parts of polyaryletherketone oligomers with carboxyl groups on the side groups; 20-30 parts of cyanate.

3. The preparation method according to claim 1, characterized in that, The second polar solvent is one or more of N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and chloroform.

4. The preparation method according to claim 1, characterized in that, The thermosetting temperature is 70–100°C, and the time is 12–36 hours.

5. The preparation method according to claim 1, characterized in that, The molar ratio of 4,4-difluorobenzophenone, hexafluorobisphenol A, and bisphenolic acid is 1:0.25-0.75:0.25-0.

75.

6. The preparation method according to claim 1, characterized in that, The polycondensation reaction is carried out at a temperature of 180–200°C for 8–10 hours.

7. The preparation method according to claim 1, characterized in that, The first polar solvent is one or more of N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, toluene, tetrahydrofuran, and sulfolane.

8. The thermosetting shape memory polyaryletherketone prepared by the preparation method according to any one of claims 1 to 7.

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