A method of synthesizing a polyarene ketone compound
By using a high-boiling-point organic Lewis base solvent in the presence of a Lewis acid catalyst for Friedel-Crafts acylation, the problems of high synthesis cost and difficulty in quality control of polyarylene compounds in existing technologies have been solved, achieving efficient synthesis of high molecular weight polyarylene compounds and improving product performance.
Patent Information
- Application Number
- CN202610550633.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2026-04-24
- Publication Date
- 2026-08-04
- Estimated Expiration
- 2046-04-24
AI Technical Summary
Existing methods for synthesizing polyarylene compounds suffer from high costs, complex processes, and difficulty in controlling product quality. In particular, there are few research reports on polyphenylene ketones and polyphenylene ketones, and the synthesis methods are difficult to obtain high molecular weight products.
Polyaryl ketone compounds were synthesized at 100-350℃ via Friedel-Crafts acylation reaction using a high-boiling-point organic Lewis base as a solvent and under Lewis acid catalytic conditions. The reaction temperature and catalyst dosage were controlled to avoid complexation of the catalyst with ether bonds or carbonyl groups. A weak Lewis acid was used to regulate the reaction and increase the molecular weight.
This technology enables the efficient synthesis of high molecular weight polyaromatic ketone compounds, reducing production costs and improving product quality and performance, particularly the mechanical and heat resistance properties of polyphenylene ketone and polyphenylene ketone ketone.
Smart Images
Figure QLYQS_1 
Figure QLYQS_2 
Figure QLYQS_3
Abstract
Description
Technical Field
[0001] This invention belongs to the field of polymer material preparation and relates to a method for synthesizing polyaromatic ketone compounds. Background Technology
[0002] Polyaryl ketones are high molecular weight compounds containing phenylene and carbonyl units in their main chain. The rigid benzene ring in their molecular structure gives them excellent high-temperature performance, mechanical properties, electrical insulation, radiation resistance, and chemical resistance. They can be broadly classified into two categories: 1) polyaryl ether ketones (PAEKs) containing ether bonds, such as polyether ether ketone (PEEK), polyether ketone (PEK), and polyether ketone ketone (PEKK); 2) fully aromatic polyketones without ether bonds, such as polyphenylene ketone (PPK) and polyphenylene ketone ketone (PPKK).
[0003] Polyether ether ketone (PEEK), obtained through nucleophilic reactions, is a relatively mature product. As an engineering plastic, it is widely used in automotive, aerospace, electrical and electronic equipment, and biomedical fields, and its application areas are expanding. It holds approximately 90% of the market share of polyaryl ketones. Foreign manufacturers in this field are mainly Victrex from the UK, while domestic manufacturers are primarily Jilin Zhongyan Polymer Materials Co., Ltd. (Zhongyan Shares). Both companies use expensive 4,4'-difluorobenzophenone and p-phenol as raw materials to synthesize PEEK through nucleophilic reactions at high temperatures.
[0004] Given the high cost and expensive price of synthesized polyetheretherketones (PEEKs), developing low-cost, high-performance polyaromatic ketones such as polyetherketoneketones (PEKKs) has been a popular research focus. Compared to PEEKs, which contains two ether bonds and one carbonyl group in its repeating unit, PEKKs contains one ether bond and two carbonyl groups. The reduction in flexible ether bonds and the increase in rigid carbonyl groups structurally determine that the latter has higher mechanical properties and better heat resistance. Currently, the synthesis methods for PEKKs are mostly based on electrophilic reactions, such as DuPont's two-step process (US4816556A), Raychem's (WO1984003891A1), and Kaisheng New Materials' (CN107987272A) Lewis acid / Lewis base co-catalysis, with relatively cheaper raw materials. However, the process is complex, requires large amounts of Lewis acids such as aluminum chloride, and involves numerous side reactions, making product quality difficult to control and resulting in a high price. PEKKs hold less than 10% of the polyaromatic ketone market share. Currently, the main manufacturers are Arkema (CN119487101A, electrophilic reaction) from France and Solvay (WO2018115033A1, nucleophilic reaction) from Belgium.
[0005] Furthermore, ether bonds impart greater flexibility to polyaryl ketone materials compared to carbonyl groups, but their stability is inferior, making them prone to breakage. Therefore, it is expected that among all polyaryl ketones, those without ether bonds, such as polyphenylene ketone (PPK) and polyphenylene ketone ketone (PPKK), will have the best mechanical and heat resistance properties. However, to date, research reports on ether-free polyaryl ketones such as PPK and PPKK are relatively rare, and no mature products have yet been launched. In 1983, Teikoku Chemical reported a synthesis method using aromatic acyl chlorides as acylating agents and trifluoromethanesulfonic acid as a catalyst and solvent in patent US4398020. This reaction not only requires a large amount of catalyst but also makes it difficult to obtain high molecular weight products. In 2019, Hitachi Chemical reported a synthesis method using aromatic carboxylic acids as acylating agents and phosphorus pentoxide / methanesulfonic acid as a catalyst and solvent in patent US10351670B2, but the synthesized polymer side chains contain ether bonds, resulting in less than ideal high-temperature resistance. Summary of the Invention
[0006] To address the shortcomings of existing technologies, the present invention aims to provide a method for synthesizing polyaromatic ketone compounds.
[0007] To achieve this objective, the present invention adopts the following technical solution: On one hand, the present invention provides a method for synthesizing polyaromatic ketone compounds, the method comprising the following steps: The polyaryl ketone compound is obtained by Friedel-Crafts acylation of monomers at reaction temperatures of 100-350°C (e.g., 100°C, 150°C, 200°C, 250°C, 300°C, or 350°C) using a high-boiling-point organic Lewis base as a solvent and a Lewis acid as a catalyst. The monomers are: a) aromatic diacyl halide compounds and aromatic compounds containing two active hydrogen atoms; and / or, b) aromatic compounds with an acyl halide at one end and an active hydrogen atom at the other end.
[0008] In this invention, a high-boiling-point organic Lewis base is used as a solvent, and an aromatic acyl halide compound and an aromatic compound containing active hydrogen are subjected to a Friedel-Crafts acylation reaction at high temperature to prepare a polyarylene compound, thereby obtaining a high molecular weight polyarylene compound.
[0009] Preferably, the high-boiling-point organic Lewis base is any one or a combination of at least two of diphenyl sulfone, toluene sulfone, diphenyl sulfoxide, nitrobenzene, benzonitrile, benzophenone, acetophenone, phenylacetone, and diacetylbenzene, with diphenyl sulfone being the most preferred.
[0010] Generally, Friedel-Crafts acylation reactions require Lewis acid catalysts with an equivalence greater than the total equivalence of ether bonds and acyl chlorides in the reaction mixture. When a Lewis base is added, an equivalent amount of catalyst is also required. However, in this invention, only a catalytic amount of catalyst needs to be added.
[0011] Preferably, the Lewis acid includes, but is not limited to, one or a combination of at least two of aluminum chloride, aluminum bromide, zinc chloride, zinc bromide, ferric chloride, ferrous chloride, cuprous chloride, magnesium chloride, calcium chloride, or antimony chloride, with aluminum chloride or zinc chloride being the most preferred.
[0012] Preferably, the amount of Lewis acid is 0.01%-100% of the molar number of acyl halide units in the reactants (e.g., 0.01%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, or 100%, etc.), more preferably 0.1%-50%, and more preferably 1%-25%.
[0013] In general, Friedel-Crafts acylation reactions require the addition of an equivalent amount of Lewis acid catalyst if a Lewis base is added. However, in this invention, not only is the organic Lewis base used directly as a solvent, but no additional Lewis acid catalyst is needed.
[0014] Preferably, the Friedel-Crafts acylation reaction is first carried out at 100-150°C (e.g., 100°C, 105°C, 110°C, 115°C, 120°C, 125°C, 130°C, 135°C, 140°C, 145°C, or 150°C, etc.) for 30-60 minutes (e.g., 30 minutes, 35 minutes, 40 minutes, 45 minutes, 50 minutes, 55 minutes, or 60 minutes, etc.), and then, depending on whether the reaction is to synthesize polyarylether ketones or fully aromatic polyketones, whether magnesium chloride or calcium chloride is added, and the solvent selected for the reaction system, the reaction is carried out for 0-3 hours (e.g., 1 hour, 2 hours, or 3 hours). Within a certain time frame, adjust the reaction temperature to a range of 150-350℃ (e.g., 150℃, 160℃, 170℃, 180℃, 190℃, 200℃, 210℃, 220℃, 230℃, 240℃, 250℃, 260℃, 270℃, 280℃, 290℃, 300℃, 310℃, or 350℃, etc.) and react at this temperature for 1-48 hours (e.g., 1 hour, 6 hours, 11 hours, 16 hours, 21 hours, 26 hours, 31 hours, 36 hours, 41 hours, or 48 hours, etc.) until no hydrogen chloride gas is produced. When the reaction solvent is a low-boiling-point solvent such as benzophenone, the maximum reaction temperature is preferably between 150-250℃ (e.g., 150℃, 160℃, 170℃, 180℃, 185℃, 190℃, 195℃, 200℃, 205℃, 210℃, 215℃, 220℃, 225℃, 230℃, 235℃, 240℃, 245℃, or 250℃, etc.). When the reaction solvent is a sulfone solvent with a higher boiling point such as diphenyl sulfone, the maximum reaction temperature is preferably between 150-350℃ (e.g., 150℃, 160℃, 170℃, 180℃, 190℃, 200℃, 215℃, 230℃, 245℃, 260℃, 275℃, 290℃, 305℃, 320℃, 335℃, or 350℃, etc.).
[0015] Preferably, the Friedel-Crafts acylation reaction may require the addition of a weak Lewis acid, such as magnesium chloride or calcium chloride, to further obtain polyarylene compounds with higher molecular weights.
[0016] Preferably, the amount of the weak Lewis acid is 1%-100% of the molar number of acyl halide units in the reactants (e.g., 1%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 100%), more preferably 10%-50%, and even more preferably 10%-25%.
[0017] The reaction of this invention is carried out at high temperatures, with the temperature control range between 100-350°C (e.g., 100°C, 150°C, 200°C, 250°C, 300°C, or 350°C). Due to the use of only a catalytic amount of Lewis acid catalyst, coupled with the moderating effect of the organic Lewis base, the catalytic activity and reaction rate are relatively mild. In Friedel-Crafts acylation reactions catalyzed by Lewis acids, low-temperature environments are commonly used. However, at low temperatures, catalysts such as aluminum chloride can complex with ether bonds or carbonyl groups, and the complexed catalyst loses its activity. To ensure the reaction proceeds completely, it is generally required to add a catalyst in amounts greater than the total equivalent of ether bonds, acyl chlorides, and Lewis bases in the reaction mixture. In this invention, the reaction begins at a lower temperature, such as 100-150°C (e.g., 100°C, 105°C, 110°C, 115°C, 120°C, 125°C, 130°C, 135°C, 140°C, 145°C, or 150°C, etc.). After a period of time, the reaction rate decreases, at which point the temperature is gradually increased to adjust the reaction rate. At relatively high temperatures, the complexation strength between the catalyst and the ether bond or carbonyl group weakens; the gradual increase in temperature allows the catalyst to continue catalyzing the reaction until it is complete. In this stage, where aluminum chloride or zinc chloride is mainly used as a catalyst without the addition of magnesium chloride or calcium chloride, the final and highest reaction temperature is set between 150-300℃ (e.g., 150℃, 160℃, 170℃, 180℃, 190℃, 200℃, 210℃, 220℃, 230℃, 240℃, 250℃, 260℃, 270℃, 280℃, 290℃, or 300℃, etc.) depending on the polyaromatic ketone to be synthesized. When synthesizing polyaromatic ether ketones containing ether bonds, excessively high temperatures may cause some ether bonds to break. Therefore, the maximum reaction temperature should preferably not exceed 250℃ and can be set between 150-250℃ (e.g., 150℃, 160℃, 170℃, 180℃, 185℃, 190℃, 195℃, 200℃, 205℃, 210℃, 215℃, 220℃, 225℃, 230℃, 235℃, 240℃, 245℃, or 250℃, etc.). When synthesizing fully aromatic polyketones without ether bonds, the reaction system is relatively stable. Therefore, the final reaction temperature can be set higher to obtain the highest possible molecular weight. Thus, the final reaction temperature can be set between 150-300℃ (e.g., 150℃, 160℃, 170℃, 180℃, 190℃, 200℃, 210℃, 220℃, 230℃, 240℃, 250℃, 260℃, 270℃, 280℃, 290℃, or 300℃, etc.), preferably between 250-300℃.
[0018] In this invention, without the addition of a weak Lewis acid such as magnesium chloride or calcium chloride, the reaction temperature is between 100-300℃ (e.g., 100℃, 120℃, 140℃, 160℃, 180℃, 200℃, 220℃, 240℃, 260℃, 280℃, or 300℃, etc.). The highest reaction temperature is set between 150-300℃ (e.g., 150℃, 160℃, 170℃, 180℃, 195℃, 210℃, 225℃, 240℃, 255℃, 270℃, 285℃, or 300℃, etc.) depending on the polyaromatic ketone to be synthesized. When synthesizing polyaromatic ether ketones containing ether bonds, the highest reaction temperature is set between 150-250℃ (e.g., 150℃, ...). The maximum reaction temperature is set between 160℃, 170℃, 180℃, 185℃, 190℃, 195℃, 200℃, 205℃, 210℃, 215℃, 220℃, 225℃, 230℃, 235℃, 240℃, 245℃, or 250℃, etc., preferably between 200-220℃; when synthesizing fully aromatic polyketides without ether bonds, the maximum reaction temperature is set between 150-300℃ (e.g., 150℃, 160℃, 170℃, 180℃, 190℃, 200℃, 210℃, 220℃, 230℃, 240℃, 250℃, 260℃, 270℃, 280℃, 290℃, or 300℃, etc.), preferably between 250-300℃.
[0019] When a weak Lewis acid such as magnesium chloride or calcium chloride is added, the maximum reaction temperature is set between 150-350℃ (e.g., 150℃, 160℃, 170℃, 180℃, 190℃, 200℃, 210℃, 220℃, 230℃, 240℃, 250℃, 260℃, 270℃, 280℃, 290℃, 300℃, 310℃, or 350℃, etc.) depending on the polyaromatic ketone to be synthesized. In the synthesis of polyaromatic ether ketones containing ether bonds, the maximum reaction temperature is set between 150-250℃ (e.g., 150℃, 160℃, 170℃, 180℃, 185℃, 190℃, 195℃, 200℃, 205℃, 210℃, 215℃, 220℃, 225℃, 230℃, 235℃, 240℃, 245℃, or 250℃, etc.), preferably between 200-220℃. Between 0°C; when synthesizing fully aromatic polyketides without ether bonds, the maximum reaction temperature is set between 150-350°C (e.g., 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, 215°C, 230°C, 245°C, 260°C, 275°C, 290°C, 305°C, 320°C, 335°C, or 350°C, etc.), preferably between 300-320°C.
[0020] In this invention, inorganic Lewis bases can be selectively added as needed to adjust the reaction. The inorganic Lewis bases include, but are not limited to, one or a combination of at least two of lithium chloride, sodium chloride, sodium bromide or potassium chloride.
[0021] Preferably, the amount of the inorganic Lewis base is 1%-100% of the molar number of acyl halide units in the reactants (e.g., 1%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 100%, etc.).
[0022] Because the catalyst complexes with ether bonds or carbonyl groups, the reaction system typically becomes very viscous in the later stages of the reaction, significantly limiting the increase in molecular weight. However, in the system of this invention, only a catalytic amount of catalyst greatly reduces the amount of complex, while the high temperature increases the solubility of the polymer in the reaction system, making it easier to obtain high molecular weight products. Furthermore, the catalytic reaction rate can be further adjusted and potential side reactions suppressed by adding appropriate amounts of inorganic Lewis bases such as lithium chloride, sodium chloride, and potassium chloride, and the viscosity of the reaction system in the later stages can be further reduced, thereby increasing the molecular weight.
[0023] Even without the influence of complexes, at certain molecular weights, some polyaromatic ketones (especially polyphenylene ketone (PPK) and polyphenylene ketone ketone (PPKK)) will precipitate from the reaction system due to intermolecular interactions. Adding weak Lewis acids such as magnesium chloride or calcium chloride can reduce these intermolecular interactions because they may form weak, dynamic complexes with ether bonds or carbonyl groups, thereby increasing the polymer's solubility. Simultaneously, magnesium chloride and calcium chloride, as Lewis acids, can also catalyze acylation reactions, making the reaction more complete.
[0024] Magnesium chloride or calcium chloride are very weak Lewis acids and are generally considered unsuitable as catalysts for Friedel-Crafts acylation reactions. This is correct, as magnesium chloride or calcium chloride exhibits almost no catalytic activity at normal temperatures. However, in this invention, a high-temperature environment of around 200°C can trigger their catalytic activity, thereby enabling the polymer to dissolve effectively in the reaction system while magnesium chloride or calcium chloride also acts as a co-catalyst.
[0025] Preferably, the aromatic diacyl halide compound has the structural formula X-CO-Ar-CO-X, where X is a halogen (e.g., F, Cl, Br, etc.) and Ar represents an aromatic group.
[0026] Preferably, the aromatic diacyl halide compound is any one or a combination of at least two of the following compounds: ; Where X is a chlorine or bromine atom, and Y represents a single bond or -O-, -S-, -CO-, -SO2-, -CH2-, -C(CH3)2-, -C(CF3)2-, -Ph- (phenylene), -O-Ph-, -O-Ph-O-, etc.
[0027] More preferably, the representative aromatic diacyl halide compound is terephthaloyl chloride, isophthaloyl chloride, 2,6-naphthalenedilicate chloride, 4,4'-biphenyldicarboxylate chloride, and 4,4'-dicarboxylate diphenyl ether, etc., with the following structural formula: .
[0028] Preferably, the aromatic compound containing two active hydrogen atoms has the structural formula H-Ar-H, where Ar represents an aromatic group.
[0029] Preferably, the aromatic compound containing two active hydrogen atoms is any one or a combination of at least two of the following compounds: ; Where Y represents a single bond, -O-, -S-, -CH2-, -C(CH3)2-, -Ph- (phenylene), -O-Ph-, -O-Ph-O-, -O-Ph-CO-Ph-O-, and R can be -H, -CH3, -C2H5, -OCH3, -OC2H5, etc.
[0030] More preferably, the aromatic compound containing two active hydrogen atoms, naphthalene, biphenyl, 2,2'-dimethoxybiphenyl, diphenyl ether, and 4,4'-diphenoxybenzophenone, or a combination of at least two of these, has the following structure: .
[0031] Preferably, the aromatic compound with one end being an acyl halide and the other end being an active hydrogen has the structural formula X-CO-Ar-H, where X is a halogen and Ar represents an aromatic group.
[0032] Preferably, the aromatic compound with one end being an acyl halide and the other end being an active hydrogen is any one or a combination of at least two of the following compounds: ; Where X is a chlorine or bromine atom, Y represents a single bond, -O-, -S-, -CH2-, -C(CH3)2-, -Ph- (phenylene), -O-Ph-, -O-Ph-O-, and R can be -H, -CH3, -C2H5, -OCH3, -OC2H5, etc.
[0033] More preferably, the representative aromatic compounds with one end being an acyl halide and the other end being active hydrogen are any one or a combination of at least two of 2-naphthoyl chloride, 4-phenylbenzoyl chloride, 4-phenoxybenzoyl chloride, 4-phenoxyphenoxy-benzoyl chloride, and 4'-phenoxy-4-bibenzoyl chloride, with the following structural formula: .
[0034] In addition, diphenyl ether, biphenyl, benzoyl chloride, 4-phenylbenzoyl chloride and 2-naphthoyl chloride can also be added as capping agents to the corresponding reactions.
[0035] In this invention, the method for synthesizing polyaromatic ketone compounds specifically includes the following steps: A high-boiling-point organic Lewis base solvent, polymerization monomer, and Lewis acid catalyst are added to the reaction apparatus. Nitrogen gas is purged to replace the air in the apparatus. The mixture is then heated to 100-150°C (e.g., 100°C, 105°C, 110°C, 115°C, 120°C, 125°C, 130°C, 135°C, 140°C, 145°C, or 150°C) and maintained for 30-60 minutes (e.g., 30 minutes, 35 minutes, 40 minutes, 45 minutes, 50 minutes, 55 minutes, or 60 minutes). The reaction temperature is then adjusted to 150-300°C (e.g., 150°C, 160°C, 170°C, 180°C, 195°C, 210°C, 225°C, 240°C, 255°C, 270°C, 285°C, or 300°C) within 0-3 hours (e.g., 0 hours, 0.5 hours, 1 hour, 2 hours, or 3 hours). React at 50-300℃ (e.g., 150℃, 160℃, 170℃, 180℃, 195℃, 210℃, 225℃, 240℃, 255℃, 270℃, 285℃, or 300℃, etc.) for 1-48 hours (e.g., 1 hour, 6 hours, 11 hours, 16 hours, 21 hours, 26 hours, 31 hours, 36 hours, or 48 hours, etc.) until no hydrogen chloride gas is produced. If you choose to add... Magnesium chloride or calcium chloride is added, and the mixture is reacted at 150-350℃ (e.g., 150℃, 160℃, 170℃, 180℃, 190℃, 200℃, 210℃, 220℃, 230℃, 240℃, 250℃, 260℃, 270℃, 280℃, 290℃, 300℃, 310℃ or 350℃, etc.) for 1-48 hours until no hydrogen chloride gas is produced, to obtain the polyaryl ketone compound.
[0036] It should be noted that the Friedel-Crafts acylation reaction is first carried out at 100-150℃ for 30-60 minutes, and then the reaction temperature is adjusted to a certain temperature between 150-350℃ within 0-3 hours. Here, 0 hours means that if the previous reaction was carried out at 150℃, the subsequent reaction is also carried out at 150℃, and there is no need to further adjust the temperature. Instead, the reaction can be carried out at 150℃.
[0037] After the above reaction is completed, the reaction mixture temperature can be lowered to around 200°C, or the reaction mixture can be transferred directly to a stainless steel beaker while still hot. After cooling to room temperature, the reaction mixture is crushed, washed with a mixture of dichloromethane and methanol to remove the solvent, and the filtered solid is washed first with 5% hydrochloric acid solution, then with deionized water, and finally dried in a vacuum oven at 150°C to obtain the target polymer. For reactions using solvents with lower melting points, such as benzophenone, the reaction mixture can also be left in a three-necked round-bottom flask and cooled to room temperature. Then, a mixture of methanol and dichloromethane is added for soaking and stirring, followed by filtration, washing, and drying. In addition to dichloromethane and methanol, the organic solvents used for post-treatment can also be one or more of the following: dichloroethane, chloroform, ethanol, acetone, N,N-dimethylformamide, N-methylpyrrolidone, etc.
[0038] Compared with the prior art, the present invention has the following beneficial effects: This invention uses a high-boiling-point organic Lewis base as a solvent and a Lewis acid as a catalyst to carry out a Friedel-Crafts acylation reaction of an aromatic acyl halide compound and an aromatic compound containing active hydrogen at high temperature to prepare polyaromatic ketone compounds, which can obtain polyaromatic ketone compounds with higher molecular weight. Detailed Implementation
[0039] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.
[0040] The intrinsic viscosity (IV) of the polymer prepared in the following example was determined as follows: 0.10 g of polymer was dissolved in 100 mL of concentrated sulfuric acid. The resulting solution was diluted at 25 ± 0.1 °C and the viscosity at 4 points was measured by Ubbelohde viscometer. The intrinsic viscosity was then derived.
[0041] Comparative Example 1, Polyetherketoneketone (PEKK) (terephthaloyl chloride / isophthaloyl chloride ratio of 4:1) Under nitrogen protection, 32.48 g of terephthaloyl chloride (160 mmol), 34.10 g of diphenyl ether (200.3 mmol), 20.0 g of N,N-dimethylformamide (DMF, 274 mmol), and 300 mL of dichloromethane were added to a 2000 mL three-necked round-bottom flask equipped with a mechanical stirrer, nitrogen inlet, and exhaust gas treatment device. The flask and reaction solution were then cooled in an ice-cold ethanol bath with stirring. At -35 °C, 120.0 g of anhydrous aluminum chloride (900 mmol) was slowly added while maintaining the reaction temperature below -15 °C. The temperature was then raised to 10 °C and reacted for 15 minutes, followed by cooling to -35 °C. 8.12 g of isophthaloyl chloride (40 mmol) and 13.3 g of anhydrous aluminum chloride (100 mmol) were added sequentially, and the temperature was then slowly raised to 20 °C and reacted overnight. The three-necked round-bottom flask and reactants were then cooled to -40°C in an ice-cold ethanol bath. 150 mL of methanol was slowly added while maintaining the temperature inside the flask below -10°C. Next, a 5% hydrochloric acid solution was added at room temperature, followed by filtration. The resulting solid was washed first with a 5% hydrochloric acid solution, then with deionized water. Finally, it was dried in a vacuum oven at 150°C to obtain the target polymer. The intrinsic viscosity (IV) was 0.48 dL / g.
[0042] Comparative Example 2, Polyphenylene ketone (PPKK) (terephthaloyl chloride / isophthaloyl chloride ratio of 3:1) Under nitrogen protection, 30.45 g of terephthaloyl chloride (150 mmol), 30.90 g of biphenyl (200.4 mmol), and 200 mL of o-dichlorobenzene were added to a 2000 mL three-necked round-bottom flask equipped with a mechanical stirrer, nitrogen inlet, and exhaust gas treatment device. The flask and reaction mixture were then cooled in an ice-cold ethanol bath with stirring. At -15 °C, 40.0 g of anhydrous aluminum chloride (300 mmol) was slowly added while maintaining the reaction temperature below -5 °C. The temperature was then raised to 10 °C and reacted for 15 minutes, followed by cooling to -15 °C. Then, 10.15 g of isophthaloyl chloride (50 mmol) and 20.0 g of anhydrous aluminum chloride (150 mmol) were added sequentially, followed by a slow heating to 100 °C and a reaction for 60 minutes. The flask and reaction mixture were then cooled to -40 °C in an ice-cold ethanol bath, and 1000 mL of methanol was slowly added while maintaining the internal temperature below 0 °C. After stirring at room temperature for one hour, the mixture was filtered. The resulting solid was washed successively with methanol, 5% hydrochloric acid solution, deionized water, and formic acid. Finally, it was dried in a vacuum oven at 150°C to obtain the target polymer. The intrinsic viscosity (IV) was 0.57 dL / g.
[0043] Example 1, Preparation of polyetherketone (PEK) In a 2000 mL three-necked round-bottom flask equipped with a mechanical stirrer, nitrogen inlet, oil-water separator, and exhaust gas treatment device, 200 g of benzophenone, 53.00 g of 4-phenoxybenzoyl chloride (233 mmol), 4.00 g of aluminum chloride (30 mmol), and 80 mg of biphenyl (0.52 mmol) were added, followed by purging with nitrogen for 5 minutes. The reaction system was then heated to 150 °C under nitrogen protection using a heating mantle and held for 30 minutes. The temperature was then increased to 180 °C and held for 30 minutes, followed by a further increase to 200 °C and reacted for 24 hours. After the reactants cooled to room temperature, 100 mL of methanol and 500 mL of dichloromethane were added, and the mixture was stirred overnight at room temperature. The mixture was then filtered. The resulting solid was washed first with dichloromethane and methanol, then with 5% hydrochloric acid solution, and finally with deionized water. The final product was dried in a vacuum oven at 150 °C to obtain the target polymer. The intrinsic viscosity (IV) is 0.65 dL / g.
[0044] Example 2, Preparation of polyetherketone (PEK) In a 2000 mL three-necked round-bottom flask equipped with a mechanical stirrer, nitrogen inlet, oil-water separator, and exhaust gas treatment device, add 200 g of diphenyl sulfone, 54.20 g of 4-phenoxybenzoyl chloride (233 mmol), 4.10 g of zinc chloride (30 mmol), and 100 mg of diphenyl ether (0.59 mmol), and then purge with nitrogen for 5 minutes. Next, under nitrogen protection, slowly heat the reaction system to 150 °C using a heating mantle and maintain for 60 minutes. Then, increase the reaction temperature to 200 °C and maintain for 2 hours until almost no hydrogen chloride gas is produced. Add 15.0 g of magnesium chloride (158 mmol) and continue the reaction overnight at 220 °C. Afterward, stop heating and transfer the reaction mixture to a stainless steel beaker while still hot. After cooling to room temperature, crush the reaction mixture, wash away the solvent with a mixture of dichloromethane and methanol, and wash the filtered solid first with 5% hydrochloric acid solution, then with deionized water. Finally, the target polymer was obtained by drying in a vacuum oven at 150°C. The intrinsic viscosity (IV) was 0.73 dL / g.
[0045] Example 3, Preparation of polyetherketoneketone (PEKK) (terephthaloyl chloride / isophthaloyl chloride ratio of 4:1) In a 2000 mL three-necked round-bottom flask equipped with a mechanical stirrer, nitrogen inlet, and exhaust gas treatment device, add 200 g of diphenyl sulfone, 32.48 g of terephthaloyl chloride (160 mmol), 8.12 g of isophthaloyl chloride (40 mmol), 34.10 g of diphenyl ether (200.3 mmol), and 2.73 g of zinc chloride (20 mmol), then purge with nitrogen for 5 minutes. Next, under nitrogen protection, heat the reaction system to 150 °C using a heating mantle and maintain for 30 minutes. Then, slowly increase the reaction temperature to 200 °C in stages over 2 hours and maintain for 2 hours until almost no hydrogen chloride gas is produced. Add 10.0 g of magnesium chloride (105 mmol) and continue the reaction at 210 °C for 5 hours. Then stop heating and transfer the reaction mixture to a stainless steel beaker while still hot. After cooling to room temperature, crush the reaction mixture, wash away the solvent with a mixture of dichloromethane and methanol, and wash the filtered solid first with 5% hydrochloric acid solution, then with deionized water. Finally, the target polymer was obtained by drying in a vacuum oven at 150°C. The intrinsic viscosity (IV) was 0.87 dL / g.
[0046] Example 4, Preparation of polyetherketoneketone (PEKK) (terephthaloyl chloride / isophthaloyl chloride ratio of 3:1) In a 2000 mL three-necked round-bottom flask equipped with a mechanical stirrer, nitrogen inlet, and exhaust gas treatment device, add 200 g benzophenone, 30.45 g terephthaloyl chloride (150 mmol), 34.10 g diphenyl ether (200.3 mmol), 2.05 g zinc chloride (15 mmol), and 2.00 g aluminum chloride (15 mmol), then purge with nitrogen for 5 minutes. Next, under nitrogen protection, heat the reaction system to 150 °C using a heating mantle and maintain for 30 minutes. Then, slowly raise the temperature to 180 °C and maintain for 60 minutes, followed by the addition of 10.15 g isophthaloyl chloride (50 mmol) and maintaining for 30 minutes. The temperature is then raised to 200 °C and maintained for 2 hours, followed by the addition of 15.0 g magnesium chloride (158 mmol) and the reaction continues at 200 °C for 24 hours. After the reactants have cooled to room temperature, add 100 mL methanol and 500 mL dichloromethane, and continue stirring overnight at room temperature. The mixture was then filtered. The resulting solid was washed first with dichloromethane and methanol, then with 5% hydrochloric acid solution, and finally with deionized water. The final product was dried in a vacuum oven at 150°C to obtain the target polymer. The intrinsic viscosity (IV) was 0.82 dL / g.
[0047] Example 5, Preparation of polyetherketoneketone (PEKEKK) In a 2000 mL three-necked round-bottom flask equipped with a mechanical stirrer, nitrogen inlet, and exhaust gas treatment device, 200 g of diphenyl sulfone, 30.45 g of terephthaloyl chloride (150 mmol), 55.00 g of 4,4'-diphenoxybenzophenone (150 mmol), and 2.73 g of zinc chloride (20 mmol) were added, followed by purging with nitrogen for 5 minutes. The reaction mixture was then heated to 150 °C under nitrogen protection using a heating mantle and maintained for 30 minutes. The temperature was then gradually increased to 200 °C in stages over 2 hours and maintained for 2 hours until almost no hydrogen chloride gas was produced. 15.0 g of magnesium chloride (158 mmol) was added, and the reaction was continued at 200 °C for 5 hours. Heating was then stopped, and the reaction mixture was transferred to a stainless steel beaker while still hot. After cooling to room temperature, the reaction mixture was crushed, washed with a mixture of dichloromethane and methanol to remove the solvent, and the filtered solid was washed first with 5% hydrochloric acid solution and then with deionized water. Finally, the target polymer was obtained by drying in a vacuum oven at 150°C. The intrinsic viscosity (IV) was 0.81 dL / g.
[0048] Example 6, Preparation of polyphenylene ketone (PPK) In a 2000 mL three-necked round-bottom flask equipped with a mechanical stirrer, nitrogen inlet, and exhaust gas treatment device, add 200 g of diphenyl sulfone, 65.00 g of 4-phenylbenzoyl chloride (300 mmol), 100 mg of biphenyl (0.65 mmol), and 4.00 g of aluminum chloride (30 mmol), and then purge with nitrogen for 5 minutes. Next, under nitrogen protection, heat the reaction system to 150 °C using a heating mantle and maintain for 30 minutes. Then, slowly increase the reaction temperature to 250 °C in stages over 1.5 hours, adding 15.0 g of magnesium chloride (158 mmol) and maintaining for 30 minutes each time. Afterward, slowly heat to 330 °C and maintain for 1 hour until no hydrogen chloride gas is produced. Then, lower the reaction temperature to approximately 200 °C and transfer the reaction mixture to a stainless steel beaker while still hot. After cooling to room temperature, crush the reaction mixture, wash away the solvent with a mixture of dichloromethane and methanol, and wash the filtered solid first with 5% hydrochloric acid solution, then with deionized water. Finally, the target polymer was obtained by drying in a vacuum oven at 150°C. The intrinsic viscosity (IV) was 1.21 dL / g.
[0049] Example 7, Preparation of polyphenylene ketone (PPKK) (terephthaloyl chloride / isophthaloyl chloride ratio of 4:1) In a 2000 mL three-necked round-bottom flask equipped with a mechanical stirrer, nitrogen inlet, and exhaust gas treatment device, add 300 g of diphenyl sulfone, 32.48 g of terephthaloyl chloride (160 mmol), 30.90 g of biphenyl (200.4 mmol), and 3.00 g of aluminum chloride (22.5 mmol), then purge with nitrogen for 5 minutes. Next, under nitrogen protection, heat the reaction system to 150 °C using a heating mantle and maintain for 30 minutes. Then, slowly raise the temperature to 250 °C and maintain for 1 hour. Next, add 8.12 g of isophthaloyl chloride (40 mmol) and maintain for 30 minutes. Add 15.0 g of sodium chloride (257 mmol), and then slowly increase the reaction temperature to 300 °C in stages over 1.5 hours, maintaining this temperature for another 1.5 hours until no hydrogen chloride gas is produced. Finally, lower the reaction temperature to approximately 200 °C and transfer the reaction mixture to a stainless steel beaker while still hot. After cooling to room temperature, the reaction mixture was pulverized, and the solvent was washed away with a mixture of dichloromethane and methanol. The filtered solid was first washed with 5% hydrochloric acid solution, and then with deionized water. Finally, it was dried in a vacuum oven at 150°C to obtain the target polymer. The intrinsic viscosity (IV) was 0.97 dL / g.
[0050] Example 8, Preparation of polyphenylene ketone (PPKK) (terephthaloyl chloride / isophthaloyl chloride ratio of 4:1) In a 2000 mL three-necked round-bottom flask equipped with a mechanical stirrer, nitrogen inlet, and exhaust gas treatment device, add 300 g of diphenyl sulfone, 32.48 g of terephthaloyl chloride (160 mmol), 30.90 g of biphenyl (200.4 mmol), and 2.73 g of zinc chloride (20 mmol), then purge with nitrogen for 5 minutes. Next, under nitrogen protection, heat the reaction system to 150 °C using a heating mantle and maintain for 30 minutes. Then slowly raise the temperature to 250 °C and maintain for 1 hour, followed by the addition of 8.12 g of isophthaloyl chloride (40 mmol) and maintaining for 30 minutes. Add 20.0 g of magnesium chloride (210 mmol) and maintain for 30 minutes. Then slowly heat to 330 °C and react overnight until no hydrogen chloride gas is produced. Then lower the reaction temperature to approximately 200 °C and transfer the reaction mixture to a stainless steel beaker while still hot. After cooling to room temperature, the reaction mixture was pulverized, and the solvent was washed away with a mixture of dichloromethane and methanol. The filtered solid was first washed with 5% hydrochloric acid solution, and then with deionized water. Finally, it was dried in a vacuum oven at 150°C to obtain the target polymer. The intrinsic viscosity (IV) was 1.23 dL / g.
[0051] Example 9, Polyphenylene ketone (PPKK) (terephthaloyl chloride / isophthaloyl chloride ratio of 3:1) In a 2000 mL three-necked round-bottom flask equipped with a mechanical stirrer, nitrogen inlet, and exhaust gas treatment system, add 200 g of diphenyl sulfone, 30.45 g of terephthaloyl chloride (150 mmol), 30.90 g of biphenyl (200.4 mmol), and 545 mg of zinc chloride (4.0 mmol), then purge with nitrogen for 5 minutes. Next, under nitrogen protection, heat the reaction system to 150 °C using a heating mantle and maintain for 30 minutes. Then, raise the temperature to 250 °C and maintain for 1 hour, followed by the addition of 10.15 g of isophthaloyl chloride (50 mmol) and maintaining for 30 minutes. Then, slowly increase the reaction temperature to 300 °C in stages over 1 hour, adding 15.0 g of magnesium chloride (158 mmol) and maintaining for 30 minutes each time. Afterward, heat to 320 °C and react overnight until no hydrogen chloride gas is produced. Then, lower the reaction temperature to approximately 200 °C and transfer the reaction mixture to a stainless steel beaker while still hot. After cooling to room temperature, the reaction mixture was pulverized, and the solvent was washed away with a mixture of dichloromethane and methanol. The filtered solid was first washed with 5% hydrochloric acid solution, and then with deionized water. Finally, it was dried in a vacuum oven at 150°C to obtain the target polymer. The intrinsic viscosity (IV) was 1.15 dL / g.
[0052] The applicant declares that the above embodiments illustrate the synthesis method of the present invention, but the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must rely on the above embodiments to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.
Claims
1. A method for synthesizing polyaromatic ketone compounds, characterized in that, The method includes the following steps: Using a high-boiling-point organic Lewis base as a solvent and a Lewis acid as a catalyst, the polymer monomers are subjected to a Friedel-Crafts acylation reaction at a reaction temperature of 100-350°C to obtain the polyaromatic ketone compound. The polymer monomers are: a) aromatic diacyl halide compounds and aromatic compounds containing two active hydrogen atoms; and / or, b) aromatic compounds with an acyl halide at one end and an active hydrogen at the other end. The high-boiling-point organic Lewis base includes any one or a combination of at least two of diphenyl sulfone, toluene sulfone, diphenyl sulfoxide, benzonitrile, benzophenone, acetophenone, phenylacetone, or diacetylbenzene.
2. The method according to claim 1, characterized in that, The high-boiling-point organic Lewis base further includes nitrobenzene, which is used as a single solvent or as a mixed solvent with the high-boiling-point organic Lewis base of claim 1; when nitrobenzene is used as a single solvent, the amount of Lewis acid catalyst is 0.01-100% of the molar number of acyl halide units in the reactants.
3. The method according to claim 1, characterized in that, The Lewis acid includes one or a combination of at least two of the following: aluminum chloride, aluminum bromide, zinc chloride, zinc bromide, ferric chloride, ferrous chloride, cuprous chloride, magnesium chloride, calcium chloride, or antimony chloride. The amount of Lewis acid used is 0.01%-100% of the molar number of acyl halide units in the reactants.
4. The method according to claim 1, characterized in that, The Friedel-Crafts acylation reaction further includes the addition of a weak Lewis acid; the weak Lewis acid includes magnesium chloride or calcium chloride. The amount of the weak Lewis acid is 1%-100% of the molar number of acyl halide units in the reactants; Without the addition of a weak Lewis acid, the reaction temperature is between 100-300℃. The maximum reaction temperature is set according to the different polyaromatic ketones to be synthesized. When synthesizing polyaromatic ether ketones containing ether bonds, the maximum reaction temperature is set between 150-250℃. When synthesizing fully aromatic polyketones without ether bonds, the maximum reaction temperature is set between 150-300℃. After adding a weak Lewis acid, the maximum reaction temperature is set according to the type of polyaromatic ketone to be synthesized. When synthesizing polyaromatic ether ketones containing ether bonds, the maximum reaction temperature is set between 150-250℃. When synthesizing fully aromatic polyketones without ether bonds, the maximum reaction temperature is set between 150-350℃.
5. The method according to claim 1, characterized in that, The reaction also includes the addition of an inorganic Lewis base for adjustment; The inorganic Lewis base includes one or a combination of at least two of lithium chloride, sodium chloride, sodium bromide or potassium chloride; The amount of the inorganic Lewis base is 1%-100% of the molar number of acyl halide units in the reactants.
6. The method according to claim 1, characterized in that, The aromatic diacyl halide compound has the structural formula X-CO-Ar-CO-X, where X is a halogen atom and Ar represents an aromatic group; The aromatic compound containing two active hydrogen atoms has the structural formula H-Ar-H, where Ar represents an aromatic group; The aromatic compound with an acyl halide at one end and an active hydrogen at the other end has the structural formula X-CO-Ar-H, where X is a halogen and Ar represents an aromatic group.
7. The method according to claim 1, characterized in that, The aromatic diacyl halide includes any one or a combination of at least two of the following compounds: ； Where X is a chlorine or bromine atom, and Y represents a single bond or -O-, -S-, -CO-, -SO2-, -CH2-, -C(CH3)2-, -C(CF3)2-, -Ph-, -O-Ph-, -O-Ph-O-; The aromatic compound containing two active hydrogen atoms is any one or a combination of at least two of the following compounds: ； Where Y represents a single bond, -O-, -S-, -CH2-, -C(CH3)2-, -Ph-, -O-Ph-, -O-Ph-O-, -O-Ph-CO-Ph-O-, and R represents -H, -CH3, -C2H5, -OCH3, -OC2H5; The aromatic compound having an acyl halide at one end and an active hydrogen at the other end is any one or a combination of at least two of the following compounds: ； Where X is a chlorine or bromine atom, Y represents a single bond, -O-, -S-, -CH2-, -C(CH3)2-, -Ph-, -O-Ph-, -O-Ph-O-, and R is -H, -CH3, -C2H5, -OCH3, -OC2H5.
8. The method according to claim 1, characterized in that, The aromatic diacyl halide includes any one or a combination of at least two of terephthaloyl chloride, isophthaloyl chloride, 2,6-naphthalenedicarboxyl chloride, 4,4'-biphenyldicarboxyl chloride and 4,4'-dicarboxyl chloride diphenyl ether; The aromatic compound containing two active hydrogen atoms is any one or a combination of at least two of naphthalene, biphenyl, 2,2'-dimethoxybiphenyl, diphenyl ether and 4,4'-diphenoxybenzophenone. The aromatic compound having an acyl halide at one end and an active hydrogen at the other end is any one or a combination of at least two of 2-naphthoyl chloride, 4-phenylbenzoyl chloride, 4-phenoxybenzoyl chloride, 4-phenoxyphenoxy-benzoyl chloride or 4'-phenoxy-4-bibenzoyl chloride.