Purification method of phthalazinone polyarylether material

Abstract

The invention relates to a purification method of a phthalazinone polyarylether material. According to the method, a chloroform-acetone mixed solution with the volume ratio of (1: 1)-(4: 1) is adopted as a purification solvent, a crude phthalazinone polyarylether product synthesized through nucleophilic polycondensation reaction with K2CO3 and / or Na2CO3 as a catalyst is purified under the Soxhlet extraction or ultrasonic-assisted condition, and inorganic salts (such as KF, KCl, K2CO3 and the like) in the crude phthalazinone polyarylether product are effectively removed. Chloroform serving as a good solvent promotes polymer chain swelling, acetone serving as a poor solvent inhibits dissolution and promotes impurity diffusion, and efficient purification is achieved through the synergistic effect of chloroform and acetone. The method is mild in process and simple and convenient to operate, the solvent can be recycled, and the content of metal ions in the final product can be reduced to 30 ppm or below. The used solvent is stable in component and clear in boiling point difference, and can be recycled and reused through simple distillation, so that the solvent consumption and the environmental protection cost are greatly reduced.

Description

Technical Field

[0001] This invention belongs to the field of purification of polyarylene ether materials, and relates to a purification method for polyarylene ether ketone materials of naphthalene-biphenyl. Background Technology

[0002] Polyaryletherketones (PAEKs) are high-performance engineering plastics whose main chain consists of alternating aromatic ether and ketone bonds. They possess excellent thermal stability, mechanical properties, and chemical inertness, and are widely used in high-end fields such as aerospace, precision electronics, and implantable medical devices. PAEK synthesis typically utilizes catalysts or auxiliaries containing metal elements, often leaving trace amounts of metal ions in the product after the reaction. The presence of metal ions affects the polymer's molecular weight distribution and thermal decomposition temperature, reduces its chemical stability, and may induce cytotoxicity or inflammatory reactions in medical applications, and cause fluctuations in electrical properties in the electronics field. To ensure that PAEK meets the purity requirements of high-end applications, purification treatment is necessary after polymer preparation. This reduces the metal ion content, improves material purity and structural uniformity, and thus guarantees its performance reliability and biosafety during long-term use.

[0003] Traditional purification methods for PAEK materials typically involve first grinding the crude polymerization product into a finer powder, followed by multiple rounds of washing with dilute hydrochloric acid solution, deionized water, and ethanol. The hydrochloric acid removes residual metal catalyst ions, the deionized water rinses away acidic substances and some soluble impurities, and the ethanol dissolves unreacted monomers and oligomers. However, this method has significant drawbacks: multiple washing cycles result in low purification efficiency, and switching washing media requires strict control of pH and temperature, making the process cumbersome. Furthermore, the large amounts of acids, alkalis, and organic solvents generate industrial wastewater and organic waste liquid, polluting the environment and requiring additional treatment costs. In addition, organic solvents such as ethanol present challenges in recovery and residue management: recovery requires specialized equipment such as distillation columns, significantly increasing equipment and energy costs. Summary of the Invention

[0004] To address the aforementioned technical problems, this invention provides a purification method for heteronaphthyl biphenyl polyarylene ether materials. This method employs Soxhlet extraction or ultrasound-assisted treatment, followed by washing and purification in a chloroform-acetone mixed solvent system with a volume ratio of 1:1 to 4:1. This method is simple, requires fewer washing cycles, and the solvent can be efficiently recovered and reused through distillation, offering both environmental friendliness and economic benefits. The purification process is mild, with no significant adverse effects on the biosafety and biocompatibility of the material. It effectively removes inorganic salts and other impurities from the crude heteronaphthyl biphenyl polyarylene ether synthesized via nucleophilic polycondensation using K₂CO₃ / Na₂CO₃ as a catalyst, significantly reducing residual metal ions.

[0005] The technical solution of the present invention is as follows: A method for purifying a naphthalene-biphenyl polyaryl ether material includes placing the crude naphthalene-biphenyl polyaryl ether product in a chloroform-acetone mixed solvent, washing and purifying it under Soxhlet extraction or ultrasonic-assisted conditions, and drying it after purification to obtain a high-purity naphthalene-biphenyl polyaryl ether material; the volume ratio of chloroform to acetone is 1:1-4:1; the heating temperature in the Soxhlet extraction purification method is 70-85℃, the reflux temperature is 50-65℃, and the washing and purification time is 3-8 hours.

[0006] The molecular chain of the aforementioned naphthalene-biphenyl polyarylene contains a diazonanone-biphenyl structure, and its structural expression is shown in Formula I: (I) Ar1 is the main structure of the dihalogenated monomer, which is one or more of the following structures:

[0007] Ar2 is the main structure of the bisphenol monomer, and it is one or more of the following structures:

[0008] Among them, R1, R2, R3, and R4 are hydrogen, halogen substituents, phenyl, phenoxy, straight-chain alkyl containing at least one carbon atom, branched alkyl containing at least one carbon atom, or branched alkoxy containing at least one carbon atom. The structures of R1, R2, R3, and R4 are the same or different. m is a positive integer; n is 0 or a positive integer.

[0009] The crude product of the heteronaphthyl biphenyl polyarylene was synthesized by nucleophilic polycondensation reaction under the action of catalysts K2CO3 and / or Na2CO3.

[0010] The particle size of the crude product of the heteronaphthalene biphenyl polyarylene is 200-800 μm.

[0011] The volume ratio of chloroform to acetone is 3:1.

[0012] In the ultrasound-assisted purification method, the ultrasound frequency is 20-60 kHz and the power is 140-200 W.

[0013] The mass-to-volume ratio of the crude naphthalene-biphenyl polyarylene ether to the solvent is 1 g: 30-60 mL.

[0014] The drying method includes vacuum drying. The vacuum drying temperature is 65-100 ℃, and the time is 6-12 hours.

[0015] The beneficial effects of this invention are as follows: This invention provides a purification method for heteronaphthyl biphenyl polyaryl ether materials, which is a highly efficient purification method based on the polymer swelling-impurity diffusion mechanism. By employing a chloroform-acetone mixed solvent system, combined with Soxhlet extraction or ultrasonic-assisted treatment, efficient removal of metal ions from crude polyaryl ether products synthesized using K₂CO₃ / Na₂CO₃ as a catalyst is achieved. The heteronaphthyl biphenyl polyaryl ether molecular chain contains rigid heteronaphthyl and biphenyl structural units. The molecular chain is regularly arranged and contains numerous polar ether bonds and ketone sites. This molecular structure endows the polymer with good swelling properties, facilitating the formation of impurity diffusion channels, and through the interaction of polar groups with metal ions, makes them more easily carried out by the solvent during the swelling process. Chloroform, as a good solvent, promotes polymer chain swelling, increasing the impurity diffusion channels; acetone, as a poor solvent, inhibits polymer dissolution and promotes the migration of impurities from the polymer interior into the solvent. The synergistic effect of both significantly improves the extraction efficiency of impurities. Detailed Implementation

[0016] The following specific embodiments further illustrate the essential features and significant advancements of the present invention. However, the content of the present invention is not limited to the following embodiments and can be adjusted according to actual circumstances.

[0017] The structural formula of the example naphthalene-biphenyl polyarylether sulfone ketone is as follows:

[0018] Example 1 The heteronaphthyl biphenyl polyarylene sulfone ketone synthesized via nucleophilic condensation polymerization (using K₂CO₃ and Na₂CO₃ as catalysts and sulfolane as the reaction solvent) was mechanically pulverized and sieved. 5g of the powder with a particle size of 300-500μm was placed in a filter paper packet and placed in the extraction tube of a Soxhlet extractor. 300mL of a mixed solvent of chloroform and acetone (chloroform:acetone volume ratio = 3:1) was added to the extraction flask. The solvent was refluxed (temperature approximately 50-65℃), and the heating temperature was controlled at 85℃ to stabilize the extraction cycle. Extraction and purification were carried out continuously for 8 hours. After extraction, the solid material was removed, dried at 40℃ for 1 hour under ventilation, and then transferred to a vacuum drying oven and dried under reduced pressure at 70℃ and -0.09MPa for 6 hours to obtain the purified product. The residual metal ions in the product were detected by inductively coupled plasma optical emission spectrometry (ICP-OES).

[0019] Example 2 Take 5g of the powdered material described in Example 1 with a particle size of 300-500μm and place it in a polytetrafluoroethylene beaker. Add 300mL of a mixed solvent of chloroform and acetone, where the volume ratio of chloroform to acetone is 3:1. Sonicate at 40kHz and 160W for 8 hours. After purification, transfer the mixture to a centrifuge for solid-liquid separation and collect the solid material. After extraction, remove the solid material, first air-dry it at 40℃ for 1 hour, then transfer it to a vacuum drying oven and dry it under reduced pressure at 70℃ and -0.09MPa for 6 hours to obtain the purified product. Inductively coupled plasma optical emission spectrometry (ICP-OES) was used to detect the residual metal ions in the product.

[0020] Example 3 The purification of the naphthalene-biphenyl polyarylether sulfone ketone material was carried out according to the method of Example 1, except that the mixed solvent was changed to chloroform:acetone volume ratio = 1:1.

[0021] Example 4 The purification of the naphthalene-biphenyl polyarylether sulfone ketone material was carried out according to the method of Example 1, except that the mixed solvent was changed to chloroform:acetone volume ratio = 2:1.

[0022] Example 5 The purification of the naphthalene-biphenyl polyarylether sulfone ketone material was carried out according to the method of Example 1, except that the mixed solvent was changed to chloroform:acetone volume ratio = 4:1.

[0023] Example 6 The purification of the naphthalene-biphenyl polyarylether sulfone ketone material was carried out according to the method of Example 1, except that the purification time was 6 hours.

[0024] Example 7 The purification of the naphthalene-biphenyl polyarylether sulfone ketone material was carried out according to the method of Example 1, except that the amount of solvent added was 150 ml.

[0025] Example 8 The purification of the naphthalene-biphenyl polyarylether sulfone ketone material was carried out according to the method of Example 1, except that the heating temperature was 70°C.

[0026] Example 9 The purification of the naphthalene-biphenyl polyarylether sulfone ketone material was carried out according to the method of Example 1, but the particle size was 600 μm.

[0027] Comparative Example 1 The purification of the naphthalene-biphenyl polyarylether sulfone ketone material was carried out according to the method of Example 1, except that the solvent was acetone.

[0028] Comparative Example 2 The purification of the naphthalene-biphenyl polyarylether sulfone ketone material was carried out according to the method of Example 1, except that the purification time was 2 hours.

[0029] Comparative Example 3 The purification of the naphthalene-biphenyl polyarylether sulfone ketone material was carried out according to the method of Example 2, except that the solvent was acetone.

[0030] Comparative Example 4 The purification of the naphthalene-biphenyl polyarylether sulfone ketone material was carried out according to the method of Example 2, except that the purification time was 2 hours.

[0031] Comparative Example 5 The polyarylene ether sulfone ketone material was purified according to the method in Example 2, but the difference was that it was only soaked and not subjected to ultrasonic treatment.

[0032] Comparative Example 6 The purification of the naphthalene-biphenyl polyarylether sulfone ketone material was carried out according to the method of Example 2, but the difference was that mechanical stirring was turned on and ultrasonic treatment was not performed.

[0033] Comparative Example 7 The purification of the naphthalene-biphenyl polyarylether sulfone ketone material was carried out according to the method of Example 1, but the apparatus did not include a Soxhlet extractor.

[0034] Table 1. Test results of the examples and comparative examples

[0035] Calcium ions mainly originate from organic solvents, while iron ions mainly originate from raw materials participating in nucleophilic condensation reactions.

Claims

1. A method for purifying a heteronaphthyl biphenyl polyarylether material, characterized in that: Including the polymerization of naphthalene biphenyl The crude aromatic ether product is placed in a chloroform-acetone mixed solvent and washed and purified under Soxhlet extraction or ultrasonic-assisted conditions. After purification, it is dried to obtain high-purity heteronaphthyl biphenyl polyarylene ether material. The volume ratio of chloroform to acetone is 1:1-4:

1. The heating temperature in the Soxhlet extraction purification method is 70-85℃, and the reflux temperature is 50-65℃. The washing and purification time is 3-8 hours.

2. The purification method according to claim 1, characterized in that: The crude product of the heteronaphthyl biphenyl polyarylene was obtained by nucleophilic condensation polymerization under the action of catalysts K2CO3 and / or Na2CO3.

3. The purification method according to claim 1, characterized in that: The molecular chain of the aforementioned naphthalene-biphenyl polyarylene contains a diazonanone-biphenyl structure, and its structural expression is shown in Formula I: （I） Ar1 is the main structure of the dihalogenated monomer, which is one or more of the following structures: Ar2 is the main structure of the bisphenol monomer, and it is one or more of the following structures: Among them, R1, R2, R3, and R4 are hydrogen, halogen substituents, phenyl, phenoxy, straight-chain alkyl containing at least one carbon atom, branched alkyl containing at least one carbon atom, or branched alkoxy containing at least one carbon atom. The structures of R1, R2, R3, and R4 are the same or different. m is a positive integer; n is 0 or a positive integer.

4. The purification method according to claim 1, characterized in that: The particle size of the crude product of the heteronaphthalene biphenyl polyarylene is 200-800 μm.

5. The purification method according to claim 1, wherein the ultrasonic-assisted purification method has an ultrasonic frequency of 20-60 kHz and a power of 140-200 W.

6. The purification method according to claim 1, characterized in that: The mass-to-volume ratio of the crude naphthalene-biphenyl polyarylene ether to the solvent is 1 g: 30-60 mL.

7. The purification method according to claim 1, characterized in that: The drying process includes vacuum drying.

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