A method for preparing polyaryletherketone resin for 3D printing material

Abstract

The present invention provides a preparation method of a polyaryletherketone resin for 3D printing materials, relating to the technical field of polymer materials, the polyaryletherketone resin is prepared by using 4,4-difluorobenzophenone, hydroquinone, biphenol, and bisphenol fluorene as reaction raw materials, using diphenyl sulfone as solvent, and using alkali metal carbonate as catalyst, and carrying out nucleophilic polycondensation reaction, which has the advantages of high melting point, high glass transition temperature, high thermal decomposition temperature and low crystallization rate. The preparation method proposed by the present invention, by adding a certain amount of bisphenol fluorene in the later stage of polymerization reaction, on the one hand, the introduction of fluorenyl structure can further destroy the regularity of molecular chain, reduce crystallinity and crystallization rate; on the other hand, fluorenyl structure can be used to hinder segment motion, which is beneficial to improve the resin melting point.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, and in particular to a method for preparing a polyaryletherketone resin for 3D printing materials. Background Art

[0002] Polyaryletherketone (PAEK) resin is a class of high-performance thermoplastic polymers widely used in high-end fields such as aerospace, medical devices, and automotive manufacturing due to its excellent high-temperature resistance, mechanical strength, and chemical stability. Among them, polyetheretherketone (PEEK), as a representative material of the PAEK family, has become an important candidate material for 3D printing technologies such as fused deposition modeling (FDM) due to its high glass transition temperature (143°C) and melting point (334°C), outstanding wear resistance, and biocompatibility. For example, in the manufacture of orthopedic implants, PEEK can achieve complex structural customization through FDM technology, and its elastic modulus is similar to that of human bone, effectively reducing stress shielding effects. In the aerospace field, its lightweight and high-temperature resistance can replace metal components, significantly reducing equipment weight.

[0003] Ideal PAEK materials for 3D printing must possess the following properties: (1) a moderately low melting point to reduce equipment dependence and energy consumption; (2) a controllable crystallization rate to improve interlayer fusion and structural uniformity; and (3) maintain the excellent temperature resistance of PAEK materials. However, PEEK still faces significant challenges in melt 3D printing. First, PEEK's high melting point (334°C) requires the printing equipment to have a high-temperature heating chamber (usually >350°C) and a constant temperature environment (>120°C), which not only increases energy consumption and equipment costs, but also easily causes the printed parts to warp or crack due to temperature fluctuations. Second, PEEK's rapid crystallization characteristics make it easy to form an uneven crystal structure during the cooling process, resulting in weak interlayer bonding and internal stress concentration, thereby affecting the mechanical properties and dimensional accuracy of the part. In addition, the high crystallization rate also limits the fluidity of the melt during printing, making it difficult to achieve precise molding of complex thin-walled structures. Although existing technologies attempt to improve its performance through carbon fiber reinforcement (CFR-PEEK) or surface modification, the material's intrinsic processing properties have not yet been broken through, making it difficult to meet the requirements of industrial-grade 3D printing for high efficiency, low cost and high yield.

[0004] In view of this, it is necessary to design an improved method for preparing polyaryletherketone resin for 3D printing materials to solve the above problems. Summary of the Invention

[0005] The object of the present invention is to provide a method for preparing a polyaryletherketone resin for 3D printing materials.

[0006] To achieve the above-mentioned object of the invention, on the one hand, the present invention provides a method for preparing a polyaryletherketone resin for 3D printing materials, comprising the following steps:

[0007] Add diphenyl sulfone, 4,4'-difluorobenzophenone, biphenol, hydroquinone and a catalyst into a reaction vessel, under an argon protective atmosphere, stir and heat to 150-170°C, react for 0.5-2h, heat to 210-230°C, react for 0.5-2h, heat to 250-270°C, and react for 0.5-2h; wherein the molar amount of the 4,4'-difluorobenzophenone is 1.01-1.05 times the total molar amount of the biphenol and the hydroquinone, and the molar ratio of the biphenol to the hydroquinone is 2:8-3:7, and the molar amount of the catalyst is 1.1-1.2 times the total molar amount of the biphenol and the hydroquinone;

[0008] Under stirring and argon protective atmosphere, bisphenol fluorene is added to a reaction vessel, and the reaction is carried out at 270-300° C. for 0.5-1 hour. After the reaction is completed, a capping agent is added and the reaction is continued for 0.5-1 hour. The reaction product is collected and then subjected to impurity removal treatment to remove impurities therein to obtain a polyaryletherketone resin.

[0009] Preferably, the molar amount of the bisphenol fluorene is 0.01-1% of the total molar amount of biphenol and hydroquinone.

[0010] Preferably, the molar ratio of biphenol to hydroquinone is 1:3.

[0011] Preferably, the catalyst is an alkali metal carbonate, which is one or more of sodium carbonate and potassium carbonate.

[0012] Preferably, the end-capping agent is benzoyl chloride, and its molar amount is 3-5% of the total molar amount of hydroquinone and resorcinol.

[0013] Preferably, the delivery flow rate of argon is 50-100 mL / min.

[0014] On the other hand, the present invention also provides a polyaryletherketone resin having a glass transition temperature of 149-160°C, a melting point of 297-305°C, and a thermal decomposition temperature of 549-580°C.

[0015] The beneficial effects of the present invention are:

[0016] 1. The present invention provides a method for preparing a polyaryletherketone resin for 3D printing materials. By replacing a portion of the traditional PEEK molecular chain structure with a biphenyl structure, the regularity of the original PEEK molecular chain structure is disrupted to a certain extent, reducing the material's melting temperature and crystallization rate. However, due to the higher rigidity of the biphenyl structure itself, an excessive amount of biphenyl structure can also lead to an increase in the melting point. Therefore, the present invention selects a biphenyl group ratio in the range of 20-30%.

[0017] 2. The preparation method of the polyaryletherketone resin for 3D printing materials provided by the present invention, by adding bisphenol fluorene in the later stage of the polymerization reaction, on the one hand, the introduction of the fluorene structure can further destroy the regularity of the molecular chain, reduce the crystallinity and reduce the crystallization rate; on the other hand, the fluorene structure hinders the movement of the chain segments, which will be reflected in the increase of the melting point. At the same time, bisphenol fluorene, as a bisphenol structure monomer, has problems such as poor reactivity and prone to side reactions in the reaction, so strictly controlling the addition timing and amount is also one of the technical points.

[0018] 3. The preparation method of the polyaryletherketone resin for 3D printing materials provided by the present invention, by controlling the biphenyl structure content and introducing a small amount of bisphenolfluorene structure, achieves the goal of lowering the melting point of traditional PEEK material from 334°C to about 300°C, while slowing down the crystallization rate, making it more in line with the requirements of 3D printing materials.

[0019] 4. The preparation method of the polyaryletherketone resin for 3D printing materials provided by the present invention has significantly improved the glass transition temperature and decomposition temperature in air compared with PEEK materials due to the introduction of biphenyl and fluorene structures. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 The present invention provides a molecular structural formula for the polyaryletherketone resin prepared by the preparation method. DETAILED DESCRIPTION

[0021] In order to make the objectives, technical solutions and advantages of the present invention more clear, the present invention is described in detail below with reference to the accompanying drawings and specific embodiments.

[0022] It should also be noted here that, in order to avoid obscuring the present invention due to unnecessary details, only structures and / or processing steps closely related to the solutions of the present invention are shown in the drawings, while other details that are not closely related to the present invention are omitted.

[0023] In addition, it should be noted that the terms "comprises", "includes" or any other variations thereof are intended to cover non-exclusive inclusion, so that a process, method, article or apparatus that includes a series of elements includes not only those elements, but also includes other elements not explicitly listed, or also includes elements inherent to such process, method, article or apparatus.

[0024] The method for preparing a polyaryletherketone resin for 3D printing materials provided by the present invention comprises the following steps:

[0025] Add diphenyl sulfone, 4,4'-difluorobenzophenone, biphenol, hydroquinone and catalyst into a reaction vessel, under argon atmosphere, stir and heat to 150-170°C, react for 0.5-2h, heat to 210-230°C, react for 0.5-2h, heat to 250-270°C, react for 0.5-2h;

[0026] Under stirring and argon protective atmosphere, bisphenol fluorene is added to a reaction vessel, and the reaction is carried out at 270-300°C for 0.5-1 hour. After the reaction is completed, a capping agent is added and the reaction is continued for 0.5-1 hour. Then, the reaction product is poured into cold water, cooled and solidified, and then crushed. Impurities therein are removed by ethanol reflux treatment and water boiling treatment to obtain a polyaryletherketone resin.

[0027] The molecular structure of the polyaryletherketone resin prepared by the above method is as follows: Figure 1 As shown, n1+n2 represents the degree of polymerization of the resin, and n1:n2 represents the molar ratio of hydroquinone to biphenol.

[0028] In some embodiments, the molar amount of 4,4'-difluorobenzophenone is 1.01-1.05 times the total molar amount of biphenol and hydroquinone, the molar ratio of biphenol to hydroquinone is 2:8-3:7, and the molar amount of the catalyst is 1.1-1.2 times the total molar amount of biphenol and hydroquinone.

[0029] In some embodiments, the molar amount of bisphenol fluorene is 0.01-1% of the total molar amount of biphenol and hydroquinone. In this process, by adding bisphenol fluorene late in the polymerization reaction, the fluorenyl structure can disrupt the regularity of the molecular chain, reducing crystallinity and crystallization rate. Furthermore, the fluorenyl structure can hinder chain segment motion, which manifests as an increase in the melting point of the resin. Furthermore, because bisphenol fluorene, which has a bisphenol structure, suffers from poor reactivity and the susceptibility to side reactions during the reaction, its addition amount must be controlled within the prescribed dosage of the present invention.

[0030] In some embodiments, the molar ratio of biphenol to hydroquinone is 1:3.

[0031] In some embodiments, the catalyst is an alkali metal carbonate, specifically one or more of sodium carbonate and potassium carbonate. The amount added can be adjusted according to the actual reaction needs, and is not limited thereto.

[0032] In some embodiments, the capping agent is benzoyl chloride, and its molar amount is 3-5% of the total molar amount of hydroquinone and resorcinol.

[0033] In some embodiments, the argon gas is delivered at a flow rate of 50-100 mL / min. It should be noted that in other embodiments, other gases, such as nitrogen, may also be used as shielding gases. Furthermore, the stirring rate during the preparation process can be adjusted as needed, as long as the corresponding purpose can be achieved, and is not limited thereto.

[0034] The preparation method of the polyaryletherketone resin for 3D printing materials provided by the present invention is further described below with reference to specific examples:

[0035] Example 1

[0036] This embodiment prepares a polyaryletherketone resin for 3D printing materials, and the preparation method thereof includes the following steps:

[0037] Diphenyl sulfone, 4,4'-difluorobenzophenone, biphenol, hydroquinone and catalyst potassium carbonate were added to a reaction vessel, argon was continuously supplied to the reaction vessel at a flow rate of 90 mL / min, and the temperature was raised to 150° C. with stirring, and the reaction was carried out for 2 h, then raised to 210° C., and the reaction was carried out for 2 h, and then raised to 250° C., and the reaction was carried out for 2 h; wherein the total molar amount of biphenol and hydroquinone was 1 mol, the molar amount of 4,4'-difluorobenzophenone was 1.04 times the total molar amount of biphenol and hydroquinone, the molar ratio of biphenol and hydroquinone was 2:8, and the molar amount of potassium carbonate was 1.1 times the total molar amount of biphenol and hydroquinone;

[0038] Under stirring and an argon atmosphere, bisphenol fluorene was added to a reaction vessel and reacted at 300°C for 0.5 hours. After the reaction, a capping agent, benzoyl chloride, was added and the reaction continued for 1 hour. The reaction product was then poured into cold water, cooled and solidified, and then pulverized. Impurities were removed by ethanol reflux and boiling in water to obtain a polyaryletherketone resin. The molar amount of bisphenol fluorene was 0.02% of the total molar amount of biphenol and hydroquinone, and the molar amount of benzoyl chloride was 5% of the total molar amount of hydroquinone and resorcinol.

[0039] Example 2

[0040] This embodiment prepares a polyaryletherketone resin for 3D printing materials, and the preparation method thereof includes the following steps:

[0041] Diphenyl sulfone, 4,4'-difluorobenzophenone, biphenol, hydroquinone and catalyst sodium carbonate were added to a reaction vessel, argon was continuously supplied to the reaction vessel at a flow rate of 60 mL / min, and the temperature was raised to 160° C. with stirring, and the reaction was carried out for 1 hour, then raised to 220° C., and the reaction was carried out for 1 hour, and then raised to 260° C., and the reaction was carried out for 1 hour; wherein the total molar amount of biphenol and hydroquinone is 1 mol, the molar amount of 4,4'-difluorobenzophenone is 1.04 times the total molar amount of biphenol and hydroquinone, the molar ratio of biphenol and hydroquinone is 2.5:7.5, and the molar amount of sodium carbonate is 1.18 times the total molar amount of biphenol and hydroquinone;

[0042] Under stirring and an argon atmosphere, bisphenol fluorene was added to a reaction vessel and reacted at 270°C for 0.5 h. After the reaction, a capping agent, benzoyl chloride, was added and the reaction continued for 0.5 h. The reaction product was then poured into cold water, cooled and solidified, and then pulverized. Impurities were removed by ethanol reflux and boiling in water to obtain a polyaryletherketone resin. The molar amount of bisphenol fluorene was 0.02% of the total molar amount of biphenol and hydroquinone, and the molar amount of benzoyl chloride was 5% of the total molar amount of hydroquinone and resorcinol.

[0043] Example 3

[0044] This embodiment prepares a polyaryletherketone resin for 3D printing materials, and the preparation method thereof includes the following steps:

[0045] Diphenyl sulfone, 4,4'-difluorobenzophenone, biphenol, hydroquinone and catalyst sodium carbonate were added to a reaction vessel, argon was continuously supplied to the reaction vessel at a flow rate of 50 mL / min, and the temperature was raised to 170° C. with stirring, and the reaction was carried out for 0.6 h, then raised to 230° C., and the reaction was carried out for 0.6 h, and then raised to 270° C., and the reaction was carried out for 0.6 h; wherein the total molar amount of biphenol and hydroquinone was 1 mol, the molar amount of 4,4'-difluorobenzophenone was 1.05 times the total molar amount of biphenol and hydroquinone, the molar ratio of biphenol and hydroquinone was 3:7, and the molar amount of sodium carbonate was 1.2 times the total molar amount of biphenol and hydroquinone;

[0046] Under stirring and an argon atmosphere, bisphenol fluorene was added to a reaction vessel and reacted at 270°C for 1 hour. After the reaction, a capping agent, benzoyl chloride, was added and the reaction continued for 0.9 hours. The reaction product was then poured into cold water, cooled and solidified, and then pulverized. Impurities were removed by ethanol reflux and boiling in water to obtain a polyaryletherketone resin. The molar amount of bisphenol fluorene was 0.02% of the total molar amount of biphenol and hydroquinone, and the molar amount of benzoyl chloride was 3% of the total molar amount of hydroquinone and resorcinol.

[0047] Example 4

[0048] This embodiment prepares a polyaryletherketone resin for 3D printing materials, and the preparation method thereof includes the following steps:

[0049] Diphenyl sulfone, 4,4'-difluorobenzophenone, biphenol, hydroquinone and catalyst sodium carbonate were added to a reaction vessel, argon was continuously supplied to the reaction vessel at a flow rate of 60 mL / min, and the temperature was raised to 160° C. with stirring, and the reaction was carried out for 1 hour, then raised to 220° C., and the reaction was carried out for 1 hour, and then raised to 260° C., and the reaction was carried out for 1 hour; wherein the total molar amount of biphenol and hydroquinone was 1 mol, the molar amount of 4,4'-difluorobenzophenone was 1.04 times the total molar amount of biphenol and hydroquinone; and the molar ratio of biphenol to hydroquinone was 2.5:7.5; and the molar amount of sodium carbonate was 1.18 times the total molar amount of biphenol and hydroquinone;

[0050] Under stirring and an argon atmosphere, bisphenol fluorene was added to a reaction vessel and reacted at 270°C for 0.5 h. After the reaction, a capping agent, benzoyl chloride, was added and the reaction continued for 0.5 h. The reaction product was then poured into cold water, cooled and solidified, and then pulverized. Impurities were removed by ethanol reflux and boiling in water to obtain a polyaryletherketone resin. The molar amount of bisphenol fluorene was 1% of the total molar amount of biphenol and hydroquinone, and the molar amount of benzoyl chloride was 5% of the total molar amount of hydroquinone and resorcinol.

[0051] Comparative Example 1

[0052] This comparative example uses a traditional method to prepare a polyaryletherketone resin, and its preparation method includes the following steps:

[0053] Diphenyl sulfone, 4,4'-difluorobenzophenone, hydroquinone and catalyst sodium carbonate were added to a reaction vessel, argon was continuously supplied to the reaction vessel at a flow rate of 90 mL / min, and the temperature was raised to 170°C with stirring, and the reaction was carried out for 1 hour, then raised to 230°C, and the reaction was carried out for 1 hour, then raised to 290°C, and the reaction was carried out for 1 hour, and then raised to 310°C, and the reaction was carried out for 1 hour; wherein the molar amount of hydroquinone was 1 mol, the molar amount of 4,4'-difluorobenzophenone was 1.03 times the molar amount of hydroquinone, and the molar amount of sodium carbonate was 1.15 times the molar amount of hydroquinone;

[0054] Benzoyl chloride, a capping agent, was added to the reaction vessel under stirring and an argon atmosphere, and the reaction was continued for 0.5 h. The reaction product was then poured into cold water, cooled and solidified, and then pulverized. Impurities were removed by ethanol reflux and boiling in water to obtain a polyaryletherketone resin. The molar amount of benzoyl chloride was 3% of the total molar amount of hydroquinone and resorcinol.

[0055] Comparative Example 2

[0056] This comparative example prepares a polyaryletherketone resin, and its preparation method comprises the following steps:

[0057] Diphenyl sulfone, 4,4'-difluorobenzophenone, hydroquinone and catalyst sodium carbonate were added to a reaction vessel, argon was continuously supplied to the reaction vessel at a flow rate of 90 mL / min, and the temperature was raised to 170°C with stirring, and the reaction was carried out for 1 hour, then raised to 230°C, and the reaction was carried out for 1 hour, then raised to 290°C, and the reaction was carried out for 1 hour, and then raised to 310°C, and the reaction was carried out for 1 hour; wherein the molar amount of hydroquinone was 1 mol, the molar amount of 4,4'-difluorobenzophenone was 1.03 times the molar amount of hydroquinone, and the molar amount of sodium carbonate was 1.15 times the molar amount of hydroquinone;

[0058] Under stirring and an argon atmosphere, bisphenol fluorene was added to a reaction vessel and reacted at 310°C for 0.5 h. After the reaction, a capping agent, benzoyl chloride, was added and the reaction continued for 0.5 h. The reaction product was then poured into cold water, cooled and solidified, and then pulverized. Impurities were removed by ethanol reflux and boiling in water to obtain a polyaryletherketone resin. The molar amount of bisphenol fluorene was 0.01% of the molar amount of hydroquinone, and the molar amount of benzoyl chloride was 3% of the molar amount of hydroquinone.

[0059] The properties of the polyaryletherketone resins prepared in Examples 1 to 4 and Comparative Examples 1 to 2 are shown in Table 1, wherein the glass transition temperature and melting point were measured by differential scanning calorimetry, the thermal decomposition temperature was measured by thermogravimetric analysis, and the crystallization state of the resin was observed by fully melting at 400°C and then cooling to room temperature. As can be seen from the data in the table, in Examples 1 to 4, as the proportion of biphenyl groups increases, the glass transition temperature of the resin shows an upward trend. This is because the biphenyl structure has higher chain rigidity than hydroquinone in structure, and the melting point shows a trend of first decreasing and then increasing. This is due to the dual effects of the destruction of the biphenyl structure on the regularity of the chain segments and the rigidity of the biphenyl structure itself. The result also proves that the molar ratio of biphenyl and hydroquinone in the entire reaction system has the lowest melting point between 2:8 and 3:7, that is, the lowest processing temperature; Comparing Example 2 and Example 4, as the amount of bisphenol fluorene increases, the glass transition temperature and melting point of the obtained resin increase, which is caused by the hindrance of the fluorene group to the movement of the chain segments. At the same time, the increase in the amount of bisphenol fluorene also brings better heat resistance, and the decomposition temperature increases from 557.8°C in Example 2 to 578.2°C in Example 4. In addition, by comparing the glass transition temperature, melting point, and crystallization state of the resins in Example 1 and Example 2, it can be proved that the introduction of the fluorene group structure will increase the glass transition temperature and melting point of the resin to a certain extent, and will also delay the well-known crystallization; and the comprehensive comparison of the embodiments and the comparative examples can be proved that the introduction of the biphenyl structure and the fluorene group can effectively reduce the glass transition temperature of the material, slow down the crystallization rate of the material, and increase the thermal decomposition temperature of the material.

[0060] Table 1 Properties of polyaryletherketone resins prepared in Examples 1 to 4 and Comparative Examples 1 to 2

[0061] project Molar ratio of hydroquinone to biphenol Molar ratio of bisphenol fluorene to hydroquinone and biphenol Glass transition temperature (℃) Melting point (℃) Thermal decomposition temperature (℃) Sample state after melting at 400℃ and cooling to room temperature Example 1 80:20 0.01% 149.5 298.3 550.1 Cooling to room temperature and remaining transparent and slightly yellow Example 2 75:25 0.01% 152.1 297.5 557.8 Cooling to room temperature and remaining transparent and slightly yellow Example 3 70:30 0.01% 154.0 299.7 559.8 Cooling to room temperature and remaining transparent and slightly yellow Example 4 75:25 1% 158.0 302.2 578.2 Cooling to room temperature and remaining transparent and slightly yellow Comparative Example 1 / / 143.2 334.1 545.8 Quickly changes from transparent to off-white opaque Comparative Example 2 / 0.01% 144.1 334.6 546.1 Gradually changes from transparent to off-white opaque

[0062] In summary, the polyaryletherketone resin prepared by the preparation method proposed in the present invention has a lower melting point, a slower crystallization rate, and a higher thermal decomposition temperature than traditional PEEK materials, and has great application prospects in the field of 3D printing.

[0063] The above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solutions of the present invention may be modified or replaced by equivalents without departing from the spirit and scope of the technical solutions of the present invention.

Claims

1. A method for preparing a polyaryletherketone resin for 3D printing materials, characterized in that: The steps include: Add diphenyl sulfone, 4,4'-difluorobenzophenone, biphenol, hydroquinone and a catalyst into a reaction vessel, under an argon protective atmosphere, stir and heat to 150-170°C, react for 0.5-2h, heat to 210-230°C, react for 0.5-2h, heat to 250-270°C, and react for 0.5-2h; wherein the molar amount of the 4,4'-difluorobenzophenone is 1.01-1.05 times the total molar amount of the biphenol and the hydroquinone, and the molar ratio of the biphenol to the hydroquinone is 2:8-3:7, the molar amount of the catalyst is 1.1-1.2 times the total molar amount of the biphenol and the hydroquinone, and the molar ratio of the biphenol to the hydroquinone is 1:3; Under stirring and argon protection atmosphere, bisphenol fluorene is added to a reaction vessel, and the reaction is carried out at 270-300° C. for 0.5-1 hour. After the reaction is completed, a capping agent is added and the reaction is continued for 0.5-1 hour; the reaction product is collected and then subjected to impurity removal treatment to remove impurities therein to obtain a polyaryletherketone resin; The molar amount of the bisphenol fluorene is 0.01-1% of the total molar amount of biphenol and hydroquinone.

2. The preparation method according to claim 1, characterized in that The catalyst is an alkali metal carbonate, which is one or more of sodium carbonate and potassium carbonate.

3. The preparation method according to claim 1, characterized in that The end-capping agent is benzoyl chloride, and its molar amount is 3-5% of the total molar amount of hydroquinone and resorcinol.

4. The preparation method according to claim 1, characterized in that The delivery flow rate of argon was 50-100 mL / min.

5. A polyaryletherketone resin, characterized in that The method is prepared according to any one of claims 1 to 4.

6. The polyaryletherketone resin according to claim 5, characterized in that The polyaryletherketone resin has a glass transition temperature of 149-160°C, a melting point of 297-305°C, and a thermal decomposition temperature of 549-580°C.

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