Process for the present end-capped preparation of benzene end-capped polyaryletherketone

Abstract

This invention discloses a method for preparing benzene-terminated polyaryletherketones (PAEs) via on-site end-capping. In the process of preparing PAEs using a first and second monomer as raw materials via aromatic nucleophilic polycondensation, a monofluorinated end-capping agent and / or a monophenolic end-capping agent are added to the polymerization system during the feeding stage. After polymerization, benzene-terminated PAEs are obtained. This invention adds the end-capping agent to the polymerization system together with the first or second monomer during feeding, avoiding the vaporization of the end-capping agent in the later stages of PAE polymerization. This allows for precise control of the end-capping process, improves the thermal stability of the polymer, and is an improvement over existing PAE preparation methods, solving the problem of poor thermal stability in current PAE products.

Description

Technical Field

[0001] This invention belongs to the field of polymer material synthesis technology and relates to a method for preparing benzene-terminated polyarylether ketones by "on-site end-capping". It is an improvement on the existing preparation methods of polyarylether ketones and improves the thermal stability of polyarylether ketones. Background Technology

[0002] Polyaryletherketone (PREE) polymers possess a range of excellent comprehensive properties, including high temperature resistance, high strength, and radiation resistance. Early PREEs were not end-capped during preparation, resulting in PREE materials containing fluorinated and hydroxyl end groups or phenolic salt end groups. This led to increased melt viscosity and poor processing stability during high-temperature processing.

[0003] Taking the nucleophilic synthesis of polyether ether ketone as an example, in order to improve the thermal stability of polyether ether ketone materials, existing technologies usually add a large amount of excess end-capping agent in the later stage of polymerization for end-capping.

[0004] The literature (Journal of Natural Science of Jilin University, (1): 116-118.) uses p-fluorobenzoylbenzene and 4,4′-difluorobenzophenone to convert polyether ketones with hydroxyl or phenolic salt end groups into fluorinated or benzene-terminated polyether ketones. p-Fluorobenzoylbenzene and 4,4′-difluorobenzophenone, as small molecule compounds, are easily volatilized at high temperatures, forming white fumes. When synthesizing polyether ketones using diphenyl sulfone as a solvent, the temperature exceeds 310℃, even reaching 320℃, which is above their boiling point. Most p-fluorobenzoylbenzene and 4,4′-difluorobenzophenone fail to achieve the desired end-capping effect, thus hindering their effectiveness. Furthermore, the vaporized p-fluorobenzoylbenzene or 4,4′-difluorobenzophenone adheres to the sidewall of the reactor top, affecting the next polymerization reaction. In addition, these end-capping agents enter the recovered reaction solvent during organic solvent purification, altering the monomer ratio for the next reaction and thus affecting the next reaction.

[0005] Monophenolic compounds can also be used as end-capping agents; adding an appropriate amount of monophenolic compound before the end of the reaction can achieve the purpose of end-capping. Patents CN103992472B and CN106750258B end-capped polyetheretherketone by adding excess phenol and 4-hydroxybiphenyl before the end of the reaction, respectively. However, in practice, this has been shown to lead to polymer chain breakage (Polymer Journal, 1992, 24, 173-186), and even breakage into small molecule compounds, resulting in a significant loss of polymer properties.

[0006] Therefore, patent CN102702459B synthesized a benzene-structured end-capping monomer and performed end-capping in the later stage of polyetheretherketone (PEEK) polymerization. Patent CN113416307A used an oligomer with the same repeating unit as polyaryletherketone (PEEK) as an end-capping agent, resulting in a slight improvement in the polymer's mechanical properties. Patent CN114437304A prepolymerized 4,4′-difluorobenzophenone and hydroquinone into a small-molecule oligomer, which was used as an end-capping agent during PEEK polymerization, thus improving the thermal stability of PEEK to some extent. However, these small-molecule oligomers or end-capping agents are difficult to obtain commercially and require additional production processes, undoubtedly increasing the production cost of PEEK. Summary of the Invention

[0007] The purpose of this invention is to address the problems existing in the prior art and provide a method for preparing benzene-terminated polyaryletherketones (PREEs) using an "on-site end-capping" method. This invention adds a small amount of benzene end-capping agent (monofluoro and / or monophenol end-capping agent) during the feeding stage. The end-capping agent participates in the reaction early in the reaction phase, becoming the end group of the PREE. This method avoids high-temperature vaporization of the end-capping agent at 310°C and above, reduces the amount of end-capping agent used, does not affect the next reaction, and avoids polymer chain breakage. Furthermore, the end-capping agents used are all commercially available, and the benzene end-group structure can reduce the generation of side reactions during polymerization.

[0008] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0009] A method for preparing benzene-terminated polyaryletherketones (POPs) using "on-site end-capping" (i.e., the end-capping agent is added to the polymerization system in the feeding stage according to the end-capping amount, and end-capping is achieved during the polymerization process) involves adding a monofluorinated end-capping agent and / or a monophenol end-capping agent to the polymerization system during the feeding stage of the process using the first and second monomers as raw materials via aromatic nucleophilic polycondensation. After polymerization, benzene-terminated POPs are obtained. At this time, the benzene-terminated POPs are crude products and require post-processing. The specific process is as follows: the product is poured into water, crushed and filtered using a pulverizer, and the solid is directly purified and filtered using organic solvents such as ethanol, acetone, or N,N-dimethylformamide. This process is repeated 5 to 6 times. Then, the product is boiled and filtered with distilled water, and this process is repeated 5 to 6 times. Finally, the product is dried in an oven.

[0010] The first polymerizing monomer is one or more of the following: difluorobenzophenone, bis(4-fluorobenzoyl)benzene, difluoroaryl ketone containing a biphenyl structure, difluoroaryl ketone containing a naphthalene structure, difluoroaryl ketone containing a bridged structure, difluoroaryl ketone containing a heterocyclic structure, difluoroaryl ketone containing heteroatoms, derivatives of difluorobenzophenone, derivatives of difluorotriphenyldione, derivatives of difluoroaryl ketone containing a biphenyl structure, derivatives of difluoroaryl ketone containing a naphthalene structure, derivatives of difluoroaryl ketone containing a bridged structure, derivatives of difluoroaryl ketone containing a heterocyclic structure, and derivatives of difluoroaryl ketone containing heteroatoms;

[0011]

[0012] The second polymerization monomer is one or more of the following: hydroquinone, biphenyl, naphthol, carbon-bridged biphenol, acetone, ether hydroquinone, diphenol sulfone, fluorene hydroquinone, heterocyclic diphenol compounds, derivatives of hydroquinone, derivatives of biphenyl, derivatives of naphthol, derivatives of carbon-bridged biphenol, derivatives of diphenol ketone, derivatives of ether hydroquinone, derivatives of diphenol sulfone, derivatives of fluorene hydroquinone, and derivatives of heterocyclic diphenol compounds.

[0013]

[0014] The monofluorinated end-capping agent is One or more of them, among which, It includes difluorobenzophenone, difluorotriphenyldione, difluoroaromatic ketone containing a biphenyl structure, difluoroaromatic ketone containing a naphthalene structure, difluoroaromatic ketone containing a bridged structure, difluoroaromatic ketone containing a heterocyclic structure, difluoroaromatic ketone containing heteroatoms, derivatives of difluorobenzophenone, derivatives of difluorotriphenyldione, derivatives of difluoroaromatic ketone containing a biphenyl structure, derivatives of difluoroaromatic ketone containing a naphthalene structure, derivatives of difluoroaromatic ketone containing a bridged structure, derivatives of difluoroaromatic ketone containing a heterocyclic structure, or derivatives of difluoroaromatic ketone containing heteroatoms. It is monophenol benzene. It is a high-boiling-point monofluorobenzene compound synthesized from any first polymerizing monomer and any monophenol benzene. A high-boiling-point monofluorobenzene compound synthesized from any difluoroaromatic compound and any monophenol benzene;

[0015] The monophenol capping agent is One or more of the following, wherein R1 is hydroxyl, alkyl, or aryl, and R2 is hydroxyl, alkyl, or aryl. This includes hydroquinone, biphenyl hydroquinone, naphthol, carbon-bridged biphenol, acetone, ether hydroquinone, diphenol sulfone, fluorene hydroquinone, heterocyclic diphenol compounds, derivatives of hydroquinone, derivatives of biphenyl hydroquinone, derivatives of naphthol, derivatives of carbon-bridged biphenol, derivatives of acetone, derivatives of ether hydroquinone, derivatives of diphenol sulfone, derivatives of fluorene hydroquinone, or derivatives of heterocyclic diphenol compounds. It is monofluorobenzene. A high-boiling-point monophenolic benzene compound synthesized from any second polymerizing monomer and any monofluorobenzene;

[0016] The total molar amount of functional groups of all the first polymer monomers added during feeding is N. b The total molar amount of functional groups of all the monofluorinated end-capping agents added during feeding is N. bThe total molar amount of functional groups of all the second polymer monomers added during feeding is N. a The total molar amount of functional groups of all the monophenol end-capping agents added during feeding is N. a ', N b +N b '>N a +N a This can reduce the occurrence of polymerization side reactions, (N) a +2N a ') / (N b +2N b ') = r, where r ranges from 0.94 to 1.00, representing the degree of polymerization of the polymer. Therefore, controlling r can yield polyarylether ketones with higher molecular weights; although the end-capping agent is added early in this invention, it will not adversely affect the polymerization reaction, and the molecular weight of the final polymer product can still reach a high value.

[0017] The polymerization reaction involved in this invention is a condensation polymerization reaction. Condensation polymerization has a stepwise characteristic. In the first step, condensation polymerization forms a dimer. The dimer reacts with the monomer to form a trimer. The dimer can also self-condense with the dimer to form a tetramer. This process continues step by step, and the molecular weight gradually increases, eventually yielding a high molecular weight polymer. Condensation polymerization does not have specific active species, and the reaction rate constants and activation energies of each step are basically equal. In the early stages of polycondensation, monomers and end-capping agents quickly participate in the reaction, transforming into oligomers such as dimers, trimers, and tetramers, resulting in a high conversion rate. Subsequently, polycondensation occurs between oligomers, causing the molecular weight to gradually increase. Therefore, before reaching the boiling point of the end-capping agent, the end-capping agent has already become one end-group structure of the polymer (the other end is the reactive site. Since the amount of end-capping agent used is relatively small, according to statistical theory, the probability of it simultaneously becoming both end-group structures of the polymer before reaching the boiling point of the end-capping agent is extremely low). As the reaction proceeds, the viscosity continuously increases, and eventually, two short polyaryletherketone chains with one end capped (one reactive site is a fluorine atom, and the other is a phenolic salt) are synthesized into a long polyaryletherketone chain with both ends capped, i.e., capped polyaryletherketone.

[0018] Existing technologies using excessive amounts of phenol and 4-hydroxybiphenyl to end-cap polyetheretherketone (PEEK) can lead to polymer chain breakage. This is because phenolic compounds such as phenol and 4-hydroxybiphenyl undergo ether exchange reactions with PEEK in the later stages of polymerization (Macromolecules, 1994, 27, 6: 1535-1547), resulting in a significant decrease in polymer viscosity, and even a shift from high viscosity to low viscosity. This invention adds a monophenol-based end-capping agent during the initial feeding phase. In the early stages of the reaction, the monophenol end-capping agent participates in the condensation reaction and becomes the end group structure of the polymer. Since the fluorine content in the polymerization system is greater than the phenol content, the ether exchange reaction is inhibited in the later stages of polymerization, thus preventing polymer chain breakage.

[0019] This invention uses commercially available common phenols or fluorides as end-capping agents, which are low in cost and easy to implement in actual production. Furthermore, common phenols or fluorides are converted into end groups of the polymer, so there is no carbonization of the end-capping agent during the thermoforming process of polyaryletherketone, which will not lead to defects in the appearance and quality of the polyaryletherketone product.

[0020] As a preferred technical solution:

[0021] The above-described method for preparing benzene-terminated polyaryletherketones by "on-site sealing" involves the aromatic nucleophilic polycondensation reaction being carried out in an organic solvent under an inert atmosphere and in the presence of a salt-forming agent.

[0022] The above-described method for preparing benzene-terminated polyaryletherketones by "on-site sealing" wherein the salting agent is sodium carbonate and / or potassium carbonate.

[0023] As described above, in a method for preparing benzene-terminated polyaryletherketones by "on-site sealing", the molar amount of the salt-forming agent is related to N. a N a The ratio of the sum of ' is 0.5 to 0.8:1.

[0024] In the above-described method for preparing benzene-terminated polyaryletherketones via on-site capping, the organic solvent is added first, and then heated to a liquid state before adding other materials. This ensures that the subsequently added materials dissolve well in the organic solvent. The melting process of the organic solvent is endothermic; once the organic solvent is completely melted, the system temperature drops to the appropriate level. At this point, the monomer and capping agent are added, effectively preventing oxidation reactions between the monomer and capping agent and air. If the organic solvent is not heated to a liquid state first, when the melting point of the organic solvent is higher than room temperature, it can cause the organic solvent and monomer to clump together. This phenomenon can lead to thermometer distortion, and in severe cases, uneven heating of the reactor, with some areas reaching high temperatures.

[0025] In the above-described method for preparing benzene-terminated polyaryletherketones by "on-site sealing", after the aromatic nucleophilic polycondensation reaction is completed, the solid content of the polymerization system (i.e., the ratio of the weight of the product to the weight of the product plus the weight of the solvent) is 25-35%.

[0026] The method for preparing benzene-terminated polyaryletherketones (PAHs) using the above-described "on-site end-capping" method, wherein the organic solvent is diphenyl sulfone; the aromatic nucleophilic polycondensation reaction is divided into four stages. In the first stage, the temperature is increased from T1 to T2 within 30 min to 1 h. This stage involves the salt-forming reaction of the second polymerizing monomer or monophenol end-capping agent with a salt-forming agent to form a phenolate, while a small amount of phenolate condenses with the first polymerizing monomer or monofluorinated end-capping agent. In the second stage, the temperature is maintained at T2 for 0.5 to 1.5 h. This stage mainly involves the condensation of the phenolate with the first polymerizing monomer or monofluorinated end-capping agent to form low molecular weight PAHs, while a small amount of the second polymerizing monomer or monophenol end-capping agent forms a phenolate. Some low molecular weight PAHs formed in this stage, such as low molecular weight... Polyether ether ketones (PEEKs) and low molecular weight PEEKs cannot dissolve well at this temperature, so a third stage is required. In the third stage, the temperature is increased from T2 to T3 within 30 min to 1 h. This stage is mainly the dissolution process of low molecular weight PEEKs to reduce the viscosity of the reaction system. Salt formation and condensation reactions also occur. In the fourth stage, the temperature is maintained at T3 for 2 to 6 h. In this stage, low molecular weight PEEKs continue to condense to form high molecular weight PEEKs. At the same time, every two PEEKs with one end group condense to form PEEKs with two end groups, thus terminating the process. T1 is 180 °C, T2 is 250–260 °C, and T3 is 310–320 °C. In the fourth stage, the viscosity of the system no longer changes within 30 min.

[0027] The method for preparing benzene-terminated polyaryletherketones by "on-site end-capping" as described above, wherein the organic solvent is sulfolane, and an azeotropic agent (p-xylene) is added to the polymerization system, the mass of which is 10% to 20% of the mass of the organic solvent; the aromatic nucleophilic polycondensation reaction is divided into four stages. In the first stage, the temperature is increased from T4 to T5 within 30 min to 1 h. In this stage, the second polymerizing monomer or monophenol end-capping agent forms a phenolate salt with the salt-forming agent, and a small amount of phenolate condenses with the first polymerizing monomer or monofluorinated end-capping agent. In the second stage, the temperature is maintained at T5 for 0.5 to 1.5 h. In this stage, the water molecules produced by the salt-forming reaction form an azeotrope with p-xylene, which is then discharged from the reaction system upon heating and condensed in a condenser. Then, the mixture is separated into layers in a separator (the upper layer is p-xylene, and the lower layer is water). When the condensed mixture enters the upper layer, the p-xylene disperses into the upper layer, while... When water enters the upper layer, it falls to the lower layer because it is immiscible with p-xylene and has a higher density. The p-xylene flows back into the reaction system to continue forming an azeotrope with water, thus achieving dehydration. At the same time, a small amount of phenol salts condense with the first polymerization monomer or monofluorinated end-capping agent. In the third stage, the temperature is increased from T5 to T6 within 30 min to 1 h. This stage is mainly the dissolution process of low molecular weight polyaryletherketones to reduce the viscosity of the reaction system. Salt formation and condensation reactions also occur. In the fourth stage, the temperature is maintained at T6 for 2 to 6 h. In this stage, low molecular weight polyaryletherketones continue to condense to form high molecular weight polyaryletherketones. At the same time, every two polyaryletherketones with one end-capped structure condense to form polyaryletherketones with two end-capped structures, thus terminating the polymerization. T4 is 80℃, T5 is 160-180℃, and T6 is 250-260℃. In the fourth stage, the viscosity of the system no longer changes within 30 min.

[0028] The method for preparing benzene-terminated polyaryletherketones by "on-site end-capping" as described above, wherein the organic solvent is N,N-dimethylformamide, N,N-dimethylacetamide, 1-methyl-2-pyrrolidone, or dimethyl sulfoxide, and an azeotropic agent (xylene) is added to the polymerization system, the mass of which is 10% to 20% of the mass of the organic solvent; the aromatic nucleophilic polycondensation reaction is divided into four stages: the first stage involves raising the temperature from T7 to T8 within 30 min to 1 h; the second stage involves holding at temperature T8 for 0.5 to 1.5 h, which is a isothermal azeotropic dehydration process; the third stage involves raising the temperature from T8 to T9 within 30 min to 1 h; and the fourth stage involves holding at temperature T9 for 2 to 6 h, which is the polymerization process; T7 is room temperature, T8 is 120 to 150 °C, and T9 is 140 to 180 °C; the fourth stage polymerization continues until the viscosity of the system no longer changes within 30 min.

[0029] This invention pertains to a reversible polycondensation reaction. If water molecules present in the raw materials or generated during the reaction are not promptly removed, a reverse reaction will occur, forming a reversible equilibrium with the forward reaction. An azeotropic agent can form an azeotrope with water molecules present in the raw materials or generated during the reaction, which are then expelled from the polymerization system under heat, allowing the forward reaction to proceed. When the organic solvent used is diphenyl sulfone (which is immiscible with water), the polymerization temperature is high, and heat alone can remove water molecules present in the raw materials or generated during the reaction. However, when the organic solvent used is sulfolane, N,N-dimethylformamide, N,N-dimethylacetamide, 1-methyl-2-pyrrolidone, or dimethyl sulfoxide, because the solvent is miscible with water in any proportion, heat alone cannot remove water molecules present in the raw materials or generated during the reaction, leading to a reverse reaction. Therefore, an azeotropic agent is required.

[0030] The above-described method for preparing benzene-terminated polyaryletherketones by "on-site sealing" results in a benzene-terminated polyaryletherketone with a melt index (the smaller the melt index, the higher the molecular weight) of 2-100 at 400℃ and 2.16 kg, and a melt index change rate (used to characterize the thermal stability of polyaryletherketones) of <2%.

[0031] Beneficial effects:

[0032] This invention uses readily available end-capping agents and adopts "on-site end-capping" process conditions, which solves the technical problem caused by the low boiling point of the end-capping agent and its volatilization during the end-capping reaction in post-end-capping. It synthesizes benzene-terminated polyaryletherketones with higher thermal stability and can meet the requirements of simple and continuous industrial production.

[0033] The end-capped polyaryletherketone of this invention does not contain end-capping agents that are poorly soluble in the purification solution, and there is no carbonization phenomenon during the thermoforming process of polyaryletherketone. The resulting polyaryletherketone product has excellent appearance and quality. Detailed Implementation

[0034] The present invention will be further described below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Furthermore, it should be understood that after reading the teachings of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the appended claims.

[0035] Unless otherwise specified, the experimental methods used in the following examples are conventional methods, performed according to the techniques or conditions described in the literature in this field or according to the product instructions. Unless otherwise specified, the materials and reagents used in the following examples are commercially available.

[0036] The sources of the relevant substances in the following embodiments are as follows:

[0037] First polymer monomer:

[0038] 4,4′-Difluorobenzophenone: Manufacturer: Jiangsu Xinhang New Material Co., Ltd.; Purity: 99.5%;

[0039] 1,3-Bis(4-fluorobenzoyl)benzene: Manufacturer: Anaiji Chemical; Purity: 98%;

[0040] [4-[4-(4-fluorobenzoyl)phenyl]phenyl]-(4-fluorophenyl)methyl ketone: Manufacturer: Chongqing Futeng Pharmaceutical Chemical Co., Ltd., CAS: 95042-13-0;

[0041] [6-(4-fluorobenzoyl)naphth-2-yl]-(4-fluorophenyl)methyl ketone: Manufacturer: Chongqing Futeng Pharmaceutical Chemical Co., Ltd., purity: 98%, CAS: 107241-17-8;

[0042] 2,2-Bis[4-(4-fluorobenzoyl)phenyl]propane: prepared according to patent US6372877 B1, with a purity of 98%, CAS: 122165-69-9;

[0043] 2,5-Thiophene dimethyl bis(4-fluorophenyl) ketone: prepared according to the literature (Tetrahedron, 2015, 71(23):4061-4069), with a purity of 98%, CAS: 136999-91-2;

[0044] 2,5-Furandimethylbis(4-fluorophenyl)methyl ketone: prepared according to patent CN108456303A, with a purity of 98%, CAS: 1145987-35-4;

[0045] Second monomer:

[0046] Hydroquinone: Manufacturer: Nanjing Xinhua Yuan Chemical Co., Ltd.; Purity: 99.5%;

[0047] 4,4'-Dihydroxybiphenyl: Manufacturer: Shanghai Bid Pharmaceutical Technology Co., Ltd.; Purity: 99%;

[0048] 4,4′-Dihydroxybenzophenone: Manufacturer: Nantong Runfeng Petrochemical Co., Ltd.; Purity: 99%;

[0049] 2,6-Dihydroxynaphthalene: Manufacturer: Anaiji Chemical; Purity: 98%;

[0050] Bisphenol AF: Manufacturer: Anaiji Chemical; Purity: 99%;

[0051] Phenolphthalein: Manufacturer: Anaiji Chemical; Purity: 99%;

[0052] 4,4'-(9-fluoreneyl)biphenol: Manufacturer: Anaiji Chemical; Purity: 98%;

[0053] 2,5-Dihydroxytoluene: Manufacturer: Anaiji Chemical; Purity: 99%;

[0054] 9,9-Bis(4-hydroxy-3-methylphenyl)fluorene: Manufacturer: Anaiji Chemical; Purity: 99%;

[0055] 4,4'-Dihydroxydiphenyl sulfone: Manufacturer: Anaiji Chemical; Purity: 99%;

[0056] End-capping agent:

[0057] 4-Fluorobenzophenone: Manufacturer: Anaiji Chemical; Purity: 98%;

[0058] 4-Fluorodiphenyl ether: Manufacturer: Aladdin Reagent (Shanghai) Co., Ltd., purity: 97%;

[0059] 4-Hydroxybenzophenone: Manufacturer: Anaiji Chemical; Purity: 98%;

[0060] 4-Phenylenol: Manufacturer: Anaiji Chemical; Purity: 98%;

[0061] Phenol: Manufacturer: Anaiji Chemical; Purity: 98%;

[0062] Prepared according to the method described in patent CN116023248A;

[0063] Prepared according to the method described in patent CN116023248A;

[0064] Prepared according to the method described in patent CN116023248A;

[0065] Prepared according to the method described in patent CN116023248A.

[0066] The methods for detecting the relevant performance in the following embodiments are as follows:

[0067] Viscosity of the fourth-stage polymerization system in aromatic nucleophilic condensation reaction: A Brookfield viscometer manufactured by Shenzhen Yongda Instrument Equipment Co., Ltd. was used for low viscosity measurement. The standard number of rotors was 4 (21#, 27#, 28#, 29#). During the test, rotor No. 0 was selected, and the lower limit of measurement was 1 mPa·s / cP.

[0068] Melt index of benzene-terminated polyaryletherketone at 400℃ and 2.16 kg: tested according to method A in standard GB / T 3682.1;

[0069] The change rate of melt index of benzene-terminated polyaryletherketone at 400℃ and 2.16 kg: according to the formula: The melt flow index was calculated using an ST-400B melt flow rate tester manufactured by Kunshan Lugong Precision Instruments Co., Ltd. The test temperature was 400℃, the pressure was 2.16kg, and the test time was 30min.

[0070] Example 1

[0071] A method for preparing benzene-terminated polyaryletherketones by "on-site sealing" includes the following specific steps:

[0072] (1) Prepare the raw materials;

[0073] Organic solvent: diphenyl sulfone;

[0074] Salt-forming agent: anhydrous sodium carbonate;

[0075] First monomer for polymerization: 4,4′-difluorobenzophenone;

[0076] Second monomer for polymerization: hydroquinone;

[0077] End-capping agent: 4-fluorobenzophenone;

[0078] (2) Preparation of polyaryletherketone;

[0079] In an inert atmosphere, the organic solvent is first heated to a liquid state, and then the first polymerizing monomer, the second polymerizing monomer, the end-capping agent, and the salt-forming agent are added to carry out an aromatic nucleophilic polycondensation reaction. The aromatic nucleophilic polycondensation reaction is divided into four stages. In the first stage, the temperature is increased from T1 to T2 within 0.5 h. In the second stage, the temperature is maintained at T2 for 1 h. In the third stage, the temperature is increased from T2 to T3 within 0.5 h. In the fourth stage, the temperature is maintained at T3 for 4 h until the viscosity of the system no longer changes within 30 min, thus obtaining benzene-terminated polyaryletherketone. Among them, T1 is 180℃, T2 is 250℃, and T3 is 310℃. The amount of organic solvent added is 350 g, the amount of the first polymerizing monomer added is 0.506 mol, the amount of the second polymerizing monomer added is 0.5 mol, the amount of the end-capping agent added is 5.766 mmol, and the amount of the salt-forming agent added is 0.567 mol.

[0080] The final benzene-terminated polyarylether ketone had a melt index of 24.7 g / 10 min at 400 °C and 2.16 kg, with a melt index change rate of 1.62%.

[0081] Comparative Example 1

[0082] A method for preparing benzene-terminated polyaryletherketone is basically the same as in Example 1, except that no capping agent is added.

[0083] The final benzene-terminated polyaryletherketone had a melt index of 19.6 g / 10 min at 400 °C and 2.16 kg, with a melt index change rate of 16.84%.

[0084] Comparing Example 1 with Comparative Example 1, it can be seen that the melt stability of benzene-terminated polyarylether ketone prepared by end-capping with 4-fluorobenzophenone is significantly improved during the polymerization process. This is because no end-capping agent was added in Comparative Example 1, resulting in a large number of phenolic and fluorine end groups in the polyarylether ketone. As it continues to polymerize in the melt state, it exhibits a high melt index change rate.

[0085] Comparative Example 2

[0086] A method for preparing benzene-terminated polyaryletherketone is basically the same as in Example 1, except that the capping agent is added at the end of the fourth stage.

[0087] The final benzene-terminated polyaryletherketone had a melt index of 18.8 g / 10 min at 400 °C and 2.16 kg, with a melt index change rate of 6.91%.

[0088] Comparing Example 1 with Comparative Example 2, it can be seen that the melt stability of the polyaryletherketone obtained by adding the end-capping agent in the later stage of polyaryletherketone polymerization is worse than that of the currently end-capped polyaryletherketone. This is because the end-capping agent was added too late in Comparative Example 2, resulting in poor end-capping effect of the end-capping agent in the high-viscosity polymerization solution, and the polyaryletherketone still has phenolic and fluorine end groups.

[0089] Example 2

[0090] A method for preparing benzene-terminated polyaryletherketones by "on-site sealing" includes the following specific steps:

[0091] (1) Prepare the raw materials;

[0092] Organic solvent: diphenyl sulfone;

[0093] Salt-forming agent: anhydrous sodium carbonate;

[0094] First monomer for polymerization: 4,4′-difluorobenzophenone;

[0095] Second monomer for polymerization: hydroquinone;

[0096] End-capping agent: 4-fluorodiphenyl ether;

[0097] (2) Preparation of polyaryletherketone;

[0098] In an inert atmosphere, the organic solvent is first heated to a liquid state, and then the first polymerizing monomer, the second polymerizing monomer, the end-capping agent, and the salt-forming agent are added to carry out an aromatic nucleophilic polycondensation reaction. The aromatic nucleophilic polycondensation reaction is divided into four stages. In the first stage, the temperature is increased from T1 to T2 within 0.5 h. In the second stage, the temperature is maintained at T2 for 1 h. In the third stage, the temperature is increased from T2 to T3 within 0.5 h. In the fourth stage, the temperature is maintained at T3 for 4 h until the viscosity of the system no longer changes within 30 min, thus obtaining benzene-terminated polyaryletherketone. Among them, T1 is 180℃, T2 is 250℃, and T3 is 310℃. The amount of organic solvent added is 350 g, the amount of the first polymerizing monomer added is 0.506 mol, the amount of the second polymerizing monomer added is 0.5 mol, the amount of the end-capping agent added is 5.766 mmol, and the amount of the salt-forming agent added is 0.567 mol.

[0099] The final benzene-terminated polyarylether ketone had a melt index of 25.8 g / 10 min at 400 °C and 2.16 kg, with a melt index change rate of 1.94%.

[0100] Example 3

[0101] A method for preparing benzene-terminated polyaryletherketones by "on-site sealing" includes the following specific steps:

[0102] (1) Prepare the raw materials;

[0103] Organic solvent: diphenyl sulfone;

[0104] Salt-forming agent: anhydrous sodium carbonate;

[0105] First monomer for polymerization: 4,4′-difluorobenzophenone;

[0106] Second monomer for polymerization: hydroquinone;

[0107] End-capping agent: 4-hydroxybenzophenone;

[0108] (2) Preparation of polyaryletherketone;

[0109] In an inert atmosphere, the organic solvent is first heated to a liquid state, and then the first polymerizing monomer, the second polymerizing monomer, the end-capping agent, and the salt-forming agent are added to carry out an aromatic nucleophilic polycondensation reaction. The aromatic nucleophilic polycondensation reaction is divided into four stages. In the first stage, the temperature is increased from T1 to T2 within 1 hour. In the second stage, the temperature is maintained at T2 for 1 hour. In the third stage, the temperature is increased from T2 to T3 within 1 hour. In the fourth stage, the temperature is maintained at T3 for 4 hours until the viscosity of the system no longer changes within 30 minutes, thus obtaining benzene-terminated polyaryletherketone. Among them, T1 is 180℃, T2 is 250℃, and T3 is 310℃. The amount of organic solvent added is 350g, the amount of the first polymerizing monomer added is 0.511mol, the amount of the second polymerizing monomer added is 0.5mol, the amount of the end-capping agent added is 5.766mmol, and the amount of the salt-forming agent added is 0.57mol.

[0110] The final benzene-terminated polyarylether ketone had a melt index of 25.8 g / 10 min at 400 °C and 2.16 kg, with a melt index change rate of 1.94%.

[0111] Example 4

[0112] A method for preparing benzene-terminated polyaryletherketones by "on-site sealing" includes the following specific steps:

[0113] (1) Prepare the raw materials;

[0114] Organic solvent: diphenyl sulfone;

[0115] Salt-forming agent: anhydrous sodium carbonate;

[0116] First monomer for polymerization: 4,4′-difluorobenzophenone;

[0117] Second monomer for polymerization: 4,4'-dihydroxybiphenyl;

[0118] End-capping agent: 4-phenylphenol;

[0119] (2) Preparation of polyaryletherketone;

[0120] In an inert atmosphere, the organic solvent is first heated to a liquid state, and then the first polymerizing monomer, the second polymerizing monomer, the end-capping agent, and the salt-forming agent are added to carry out an aromatic nucleophilic polycondensation reaction. The aromatic nucleophilic polycondensation reaction is divided into four stages. In the first stage, the temperature is increased from T1 to T2 within 1 hour. In the second stage, the temperature is maintained at T2 for 0.5 hours. In the third stage, the temperature is increased from T2 to T3 within 0.5 hours. In the fourth stage, the temperature is maintained at T3 for 2 hours until the viscosity of the system no longer changes within 30 minutes, thus obtaining benzene-terminated polyaryletherketone. Among them, T1 is 180℃, T2 is 260℃, and T3 is 320℃. The amount of organic solvent added is 350g, the amount of the first polymerizing monomer added is 0.307mol, the amount of the second polymerizing monomer added is 0.3mol, the amount of the end-capping agent added is 4.373mmol, and the amount of the salt-forming agent added is 0.343mol.

[0121] The final benzene-terminated polyarylether ketone had a melt index of 12.4 g / 10 min at 400 °C and 2.16 kg, with a melt index change rate of 1.23%.

[0122] Example 5

[0123] A method for preparing benzene-terminated polyaryletherketones by "on-site sealing" includes the following specific steps:

[0124] (1) Prepare the raw materials;

[0125] Organic solvent: diphenyl sulfone;

[0126] Salt-forming agent: anhydrous sodium carbonate;

[0127] First monomer for polymerization: 4,4′-difluorobenzophenone;

[0128] Second monomer for polymerization: 4,4′-dihydroxybenzophenone;

[0129] End-capping agent: 4-fluorobenzophenone;

[0130] (2) Preparation of polyaryletherketone;

[0131] In an inert atmosphere, the organic solvent is first heated to a liquid state, and then the first polymerizing monomer, the second polymerizing monomer, the end-capping agent, and the salt-forming agent are added to carry out an aromatic nucleophilic polycondensation reaction. The aromatic nucleophilic polycondensation reaction is divided into four stages. In the first stage, the temperature is increased from T1 to T2 within 1 hour. In the second stage, the temperature is maintained at T2 for 0.5 hours. In the third stage, the temperature is increased from T2 to T3 within 0.5 hours. In the fourth stage, the temperature is maintained at T3 for 2 hours until the viscosity of the system no longer changes within 30 minutes, thus obtaining benzene-terminated polyaryletherketone. Among them, T1 is 180℃, T2 is 260℃, and T3 is 320℃. The amount of organic solvent added is 350g, the amount of the first polymerizing monomer added is 0.303mol, the amount of the second polymerizing monomer added is 0.3mol, the amount of the end-capping agent added is 4.709mmol, and the amount of the salt-forming agent added is 0.34mol.

[0132] The final benzene-terminated polyarylether ketone had a melt index of 19.5 g / 10 min at 400 °C and 2.16 kg, with a melt index change rate of 1.54%.

[0133] Example 6

[0134] A method for preparing benzene-terminated polyaryletherketones by "on-site sealing" includes the following specific steps:

[0135] (1) Prepare the raw materials;

[0136] Organic solvent: diphenyl sulfone;

[0137] Salt-forming agent: anhydrous sodium carbonate;

[0138] First polymerization monomer: 1,3-bis(4-fluorobenzoyl)benzene;

[0139] Second monomer for polymerization: hydroquinone;

[0140] End-capping agent: 4-fluorodiphenyl ether;

[0141] (2) Preparation of polyaryletherketone;

[0142] In an inert atmosphere, the organic solvent is first heated to a liquid state, and then the first polymerizing monomer, the second polymerizing monomer, the end-capping agent, and the salt-forming agent are added to carry out an aromatic nucleophilic polycondensation reaction. The aromatic nucleophilic polycondensation reaction is divided into four stages. In the first stage, the temperature is increased from T1 to T2 within 0.5 h. In the second stage, the temperature is maintained at T2 for 0.5 h. In the third stage, the temperature is increased from T2 to T3 within 0.5 h. In the fourth stage, the temperature is maintained at T3 for 4 h until the viscosity of the system no longer changes within 30 min, thus obtaining benzene-terminated polyaryletherketone. Among them, T1 is 180℃, T2 is 260℃, and T3 is 320℃. The amount of organic solvent added is 350 g, the amount of the first polymerizing monomer added is 0.303 mol, the amount of the second polymerizing monomer added is 0.3 mol, the amount of the end-capping agent added is 4.709 mmol, and the amount of the salt-forming agent added is 0.34 mol.

[0143] The final benzene-terminated polyarylether ketone had a melt index of 7.8 g / 10 min at 400 °C and 2.16 kg, with a melt index change rate of 0.89%.

[0144] Example 7

[0145] A method for preparing benzene-terminated polyaryletherketones by "on-site sealing" includes the following specific steps:

[0146] (1) Prepare the raw materials;

[0147] Organic solvent: diphenyl sulfone;

[0148] Salt-forming agent: anhydrous sodium carbonate;

[0149] First polymerization monomer: 1,3-bis(4-fluorobenzoyl)benzene;

[0150] Second monomer for polymerization: 4,4'-dihydroxybiphenyl;

[0151] End-capping agent: 4-phenylphenol;

[0152] (2) Preparation of polyaryletherketone;

[0153] In an inert atmosphere, the organic solvent is first heated to a liquid state, and then the first polymerizing monomer, the second polymerizing monomer, the end-capping agent, and the salt-forming agent are added to carry out an aromatic nucleophilic polycondensation reaction. The aromatic nucleophilic polycondensation reaction is divided into four stages. In the first stage, the temperature is increased from T1 to T2 within 0.5 h. In the second stage, the temperature is maintained at T2 for 0.5 h. In the third stage, the temperature is increased from T2 to T3 within 0.5 h. In the fourth stage, the temperature is maintained at T3 for 2 h until the viscosity of the system no longer changes within 30 min, thus obtaining benzene-terminated polyaryletherketone. Among them, T1 is 180℃, T2 is 260℃, and T3 is 320℃. The amount of organic solvent added is 430 g, the amount of the first polymerizing monomer added is 0.308 mol, the amount of the second polymerizing monomer added is 0.3 mol, the amount of the end-capping agent added is 5.622 mmol, and the amount of the salt-forming agent added is 0.343 mol.

[0154] The final benzene-terminated polyarylether ketone had a melt index of 6.5 g / 10 min at 400 °C and 2.16 kg, with a melt index change rate of 0.91%.

[0155] Example 8

[0156] A method for preparing benzene-terminated polyaryletherketones by "on-site sealing" includes the following specific steps:

[0157] (1) Prepare the raw materials;

[0158] Organic solvent: diphenyl sulfone;

[0159] Salt-forming agent: anhydrous sodium carbonate;

[0160] First polymerization monomer: 1,3-bis(4-fluorobenzoyl)benzene;

[0161] Second monomer for polymerization: 4,4′-dihydroxybenzophenone;

[0162] End-capping agent: 4-hydroxybenzophenone;

[0163] (2) Preparation of polyaryletherketone;

[0164] In an inert atmosphere, the organic solvent is first heated to a liquid state, and then the first polymerizing monomer, the second polymerizing monomer, the end-capping agent, and the salt-forming agent are added to carry out an aromatic nucleophilic polycondensation reaction. The aromatic nucleophilic polycondensation reaction is divided into four stages. In the first stage, the temperature is increased from T1 to T2 within 1 hour. In the second stage, the temperature is maintained at T2 for 0.5 hours. In the third stage, the temperature is increased from T2 to T3 within 0.5 hours. In the fourth stage, the temperature is maintained at T3 for 2 hours until the viscosity of the system no longer changes within 30 minutes, thus obtaining benzene-terminated polyaryletherketone. Among them, T1 is 180℃, T2 is 260℃, and T3 is 320℃. The amount of organic solvent added is 450g, the amount of the first polymerizing monomer added is 0.308mol, the amount of the second polymerizing monomer added is 0.3mol, the amount of the end-capping agent added is 5.958mmol, and the amount of the salt-forming agent added is 0.344mol.

[0165] The final benzene-terminated polyaryletherketone had a melt index of 5.8 g / 10 min at 400 °C and 2.16 kg, with a melt index change rate of 1.02%.

[0166] Example 9

[0167] A method for preparing benzene-terminated polyaryletherketones by "on-site sealing" includes the following specific steps:

[0168] (1) Prepare the raw materials:

[0169] Organic solvent: sulfolane;

[0170] Azeotropic agent: p-xylene;

[0171] Salt-forming agent: a mixture of sodium carbonate and potassium carbonate in a molar ratio of 9:1;

[0172] First polymerization monomer: [4-[4-(4-fluorobenzoyl)phenyl]phenyl]-(4-fluorophenyl)methyl ketone;

[0173] Second monomer for polymerization: 4,4'-dihydroxybiphenyl;

[0174] End-capping agent: 4-phenylphenol;

[0175] (2) Preparation of polyaryletherketone:

[0176] In an inert atmosphere, the organic solvent is first heated to a liquid state, and then the first polymerizing monomer, the second polymerizing monomer, the end-capping agent, the salt-forming agent, and the azeotropic agent are added to carry out an aromatic nucleophilic polycondensation reaction. The aromatic nucleophilic polycondensation reaction is divided into four stages. In the first stage, the temperature is increased from T4 to T5 within 0.5 h. In the second stage, the temperature is maintained at T5 for 0.5 h. In the third stage, the temperature is increased from T5 to T6 within 0.5 h. In the fourth stage, the temperature is maintained at T6 for 4 h until the viscosity of the system no longer changes within 30 min, thus obtaining benzene-terminated polyaryletherketone. Among them, T4 is 80℃, T5 is 160℃, and T6 is 250℃. The amount of organic solvent added is 490 g, the amount of the first polymerizing monomer added is 0.308 mol, the amount of the second polymerizing monomer added is 0.3 mol, the amount of the end-capping agent added is 6.535 mmol, the amount of the salt-forming agent added is 0.344 mol, and the mass of the azeotropic agent is 50 g.

[0177] The final benzene-terminated polyarylether ketone had a melt index of 23.2 g / 10 min at 400 °C and 2.16 kg, with a melt index change rate of 1.72%.

[0178] Example 10

[0179] A method for preparing benzene-terminated polyaryletherketones by "on-site sealing" includes the following specific steps:

[0180] (1) Prepare the raw materials:

[0181] Organic solvent: sulfolane;

[0182] Azeotropic agent: p-xylene;

[0183] Salt-forming agent: a mixture of sodium carbonate and potassium carbonate in a molar ratio of 9:1;

[0184] First polymerization monomer: [6-(4-fluorobenzoyl)naphth-2-yl]-(4-fluorophenyl)methyl ketone;

[0185] Second polymerization monomer: 2,6-dihydroxynaphthalene;

[0186] End-capping agent: 4-hydroxybenzophenone;

[0187] (2) Preparation of polyaryletherketone:

[0188] In an inert atmosphere, the organic solvent is first heated to a liquid state, and then the first polymerizing monomer, the second polymerizing monomer, the end-capping agent, the salt-forming agent, and the azeotropic agent are added to carry out an aromatic nucleophilic polycondensation reaction. The aromatic nucleophilic polycondensation reaction is divided into four stages. In the first stage, the temperature is increased from T4 to T5 within 0.5 h. In the second stage, the temperature is maintained at T5 for 1 h. In the third stage, the temperature is increased from T5 to T6 within 1 h. In the fourth stage, the temperature is maintained at T6 for 4 h until the viscosity of the system no longer changes within 30 min, thus obtaining benzene-terminated polyaryletherketone. Among them, T4 is 80℃, T5 is 160℃, and T6 is 250℃. The amount of organic solvent added is 450 g, the amount of the first polymerizing monomer added is 0.308 mol, the amount of the second polymerizing monomer added is 0.3 mol, the amount of the end-capping agent added is 5.91 mmol, the amount of the salt-forming agent added is 0.344 mol, and the mass of the azeotropic agent is 50 g.

[0189] The final benzene-terminated polyarylether ketone had a melt index of 22.6 g / 10 min at 400 °C and 2.16 kg, with a melt index change rate of 1.13%.

[0190] Example 11

[0191] A method for preparing benzene-terminated polyaryletherketones by "on-site sealing" includes the following specific steps:

[0192] (1) Prepare the raw materials:

[0193] Organic solvent: sulfolane;

[0194] Azeotropic agent: p-xylene;

[0195] Salt-forming agent: a mixture of sodium carbonate and potassium carbonate in a molar ratio of 9:1;

[0196] First polymerization monomer: 2,2-bis[4-(4-fluorobenzoyl)phenyl]propane;

[0197] Second monomer for polymerization: Bisphenol A;

[0198] Capping agent: phenol;

[0199] (2) Preparation of polyaryletherketone:

[0200] In an inert atmosphere, the organic solvent is first heated to a liquid state, and then the first polymerizing monomer, the second polymerizing monomer, the end-capping agent, the salt-forming agent, and the azeotropic agent are added to carry out an aromatic nucleophilic polycondensation reaction. The aromatic nucleophilic polycondensation reaction is divided into four stages. In the first stage, the temperature is increased from T4 to T5 within 0.5 h. In the second stage, the temperature is maintained at T5 for 1 h. In the third stage, the temperature is increased from T5 to T6 within 1 h. In the fourth stage, the temperature is maintained at T6 for 6 h until the viscosity of the system no longer changes within 30 min, thus obtaining benzene-terminated polyaryletherketone. Among them, T4 is 80℃, T5 is 160℃, and T6 is 260℃. The amount of organic solvent added is 450 g, the amount of the first polymerizing monomer added is 0.309 mol, the amount of the second polymerizing monomer added is 0.3 mol, the amount of the end-capping agent added is 7.545 mmol, the amount of the salt-forming agent added is 0.344 mol, and the mass of the azeotropic agent is 50 g.

[0201] The final benzene-terminated polyarylether ketone had a melt index of 26.8 g / 10 min at 400 °C and 2.16 kg, with a melt index change rate of 1.32%.

[0202] Example 12

[0203] A method for preparing benzene-terminated polyaryletherketones by "on-site sealing" includes the following specific steps:

[0204] (1) Prepare the raw materials:

[0205] Organic solvent: sulfolane;

[0206] Azeotropic agent: p-xylene;

[0207] Salt-forming agent: a mixture of sodium carbonate and potassium carbonate in a molar ratio of 9:1;

[0208] First polymerization monomer: 2,5-thiophene dimethyl bis(4-fluorophenyl) methyl ketone;

[0209] Second monomer for polymerization: phenolphthalein;

[0210] End-capping agent: 4-fluorobenzophenone;

[0211] (2) Preparation of polyaryletherketone:

[0212] In an inert atmosphere, the organic solvent is first heated to a liquid state, and then the first polymerizing monomer, the second polymerizing monomer, the end-capping agent, the salt-forming agent, and the azeotropic agent are added to carry out an aromatic nucleophilic polycondensation reaction. The aromatic nucleophilic polycondensation reaction is divided into four stages. In the first stage, the temperature is increased from T4 to T5 within 1 hour. In the second stage, the temperature is maintained at T5 for 1.5 hours. In the third stage, the temperature is increased from T5 to T6 within 1 hour. In the fourth stage, the temperature is maintained at T6 for 4 hours until the viscosity of the system no longer changes within 30 minutes, thus obtaining benzene-terminated polyaryletherketone. Among them, T4 is 80℃, T5 is 180℃, and T6 is 250℃. The amount of organic solvent added is 450g, the amount of the first polymerizing monomer added is 0.301mol, the amount of the second polymerizing monomer added is 0.3mol, the amount of the end-capping agent added is 7.28mmol, the amount of the salt-forming agent added is 0.344mol, and the mass of the azeotropic agent is 50g.

[0213] The final benzene-terminated polyarylether ketone had a melt index of 27.5 g / 10 min at 400 °C and 2.16 kg, with a melt index change rate of 1.56%.

[0214] Example 13

[0215] A method for preparing benzene-terminated polyaryletherketones by "on-site sealing" includes the following specific steps:

[0216] (1) Prepare the raw materials:

[0217] Organic solvent: sulfolane;

[0218] Azeotropic agent: p-xylene;

[0219] Salt-forming agent: a mixture of sodium carbonate and potassium carbonate in a molar ratio of 9:1;

[0220] First polymerization monomer: 2,5-furandiylbis(4-fluorophenyl)methyl ketone;

[0221] Second polymerization monomer: 4,4'-(9-fluoreneyl)biphenol;

[0222] End-capping agent: 4-fluorodiphenyl ether;

[0223] (2) Preparation of polyaryletherketone:

[0224] In an inert atmosphere, the organic solvent is first heated to a liquid state, and then the first polymerizing monomer, the second polymerizing monomer, the end-capping agent, the salt-forming agent, and the azeotropic agent are added to carry out an aromatic nucleophilic polycondensation reaction. The aromatic nucleophilic polycondensation reaction is divided into four stages. In the first stage, the temperature is increased from T4 to T5 within 1 hour. In the second stage, the temperature is maintained at T5 for 1.5 hours. In the third stage, the temperature is increased from T5 to T6 within 1 hour. In the fourth stage, the temperature is maintained at T6 for 2 hours until the viscosity of the system no longer changes within 30 minutes, thus obtaining benzene-terminated polyaryletherketone. Among them, T4 is 80℃, T5 is 180℃, and T6 is 260℃. The amount of organic solvent added is 450g, the amount of the first polymerizing monomer added is 0.301mol, the amount of the second polymerizing monomer added is 0.3mol, the amount of the end-capping agent added is 7.472mmol, the amount of the salt-forming agent added is 0.344mol, and the mass of the azeotropic agent is 50g.

[0225] The final benzene-terminated polyarylether ketone had a melt index of 17.7 g / 10 min at 400 °C and 2.16 kg, with a melt index change rate of 1.02%.

[0226] Example 14

[0227] A method for preparing benzene-terminated polyaryletherketones by "on-site sealing" includes the following specific steps:

[0228] (1) Prepare the raw materials:

[0229] Organic solvent: N,N-dimethylformamide;

[0230] Azeotropic agent: p-xylene;

[0231] Salt-forming agent: potassium carbonate;

[0232] First monomer for polymerization: 4,4′-difluorobenzophenone;

[0233] Second monomer for polymerization: phenolphthalein;

[0234] End-capping agent:

[0235] (2) Preparation of polyaryletherketone:

[0236] In an inert atmosphere, the organic solvent is first heated to a liquid state, and then the first polymerizing monomer, the second polymerizing monomer, the end-capping agent, the salt-forming agent, and the azeotropic agent are added to carry out an aromatic nucleophilic polycondensation reaction. The aromatic nucleophilic polycondensation reaction is divided into four stages. In the first stage, the temperature is increased from T7 to T8 within 0.5 h. In the second stage, the temperature is held at T8 for 1 h. In the third stage, the temperature is increased from T8 to T9 within 0.5 h. In the fourth stage, the temperature is held at T9 for 3 h until the viscosity of the system no longer changes within 30 min, thus obtaining benzene-terminated polyaryletherketone. Among them, T7 is room temperature, T8 is 120℃, and T9 is 140℃. The amount of organic solvent added is 350 g, the amount of the first polymerizing monomer added is 0.302 mol, the amount of the second polymerizing monomer added is 0.3 mol, the amount of the end-capping agent added is 5.958 mmol, the amount of the salt-forming agent added is 0.344 mol, and the amount of the azeotropic agent added is 40 g.

[0237] The final benzene-terminated polyarylether ketone had a melt index of 67 g / 10 min at 400 °C and 2.16 kg, with a melt index change rate of 0.18%.

[0238] Example 15

[0239] A method for preparing benzene-terminated polyaryletherketones by "on-site sealing" includes the following specific steps:

[0240] (1) Prepare the raw materials:

[0241] Organic solvent: N,N-dimethylacetamide;

[0242] Azeotropic agent: p-xylene;

[0243] Salt-forming agent: potassium carbonate;

[0244] First monomer: furan-containing difluoroaryl ketone;

[0245] Second monomer for polymerization: 2,5-dihydroxytoluene;

[0246] End-capping agent:

[0247] (2) Preparation of polyaryletherketone:

[0248] In an inert atmosphere, the organic solvent is first heated to a liquid state, and then the first polymerizing monomer, the second polymerizing monomer, the end-capping agent, the salt-forming agent, and the azeotropic agent are added to carry out an aromatic nucleophilic polycondensation reaction. The aromatic nucleophilic polycondensation reaction is divided into four stages. In the first stage, the temperature is increased from T7 to T8 within 0.5 h. In the second stage, the temperature is held at T8 for 0.5 h. In the third stage, the temperature is increased from T8 to T9 within 0.5 h. In the fourth stage, the temperature is held at T9 for 4 h until the viscosity of the system no longer changes within 30 min, thus obtaining benzene-terminated polyaryletherketone. Among them, T7 is room temperature, T8 is 130℃, and T9 is 160℃. The amount of organic solvent added is 280 g, the amount of the first polymerizing monomer added is 0.303 mol, the amount of the second polymerizing monomer added is 0.3 mol, the amount of the end-capping agent added is 4.757 mmol, the amount of the salt-forming agent added is 0.343 mol, and the amount of the azeotropic agent added is 30 g.

[0249] The final benzene-terminated polyarylether ketone had a melt index of 48 g / 10 min at 400 °C and 2.16 kg, with a melt index change rate of 0.54%.

[0250] Example 16

[0251] A method for preparing benzene-terminated polyaryletherketones by "on-site sealing" includes the following specific steps:

[0252] (1) Prepare the raw materials:

[0253] Organic solvent: 1-methyl-2-pyrrolidone;

[0254] Azeotropic agent: p-xylene;

[0255] Salt-forming agent: potassium carbonate;

[0256] First monomer for polymerization: 4,4′-difluorobenzophenone;

[0257] Second polymerization monomer: 9,9-bis(4-hydroxy-3-methylphenyl)fluorene;

[0258] End-capping agent:

[0259] (2) Preparation of polyaryletherketone:

[0260] In an inert atmosphere, the organic solvent is first heated to a liquid state, and then the first polymerizing monomer, the second polymerizing monomer, the end-capping agent, the salt-forming agent, and the azeotropic agent are added to carry out an aromatic nucleophilic polycondensation reaction. The aromatic nucleophilic polycondensation reaction is divided into four stages. In the first stage, the temperature is increased from T7 to T8 within 1 hour. In the second stage, the temperature is maintained at T8 for 1.5 hours. In the third stage, the temperature is increased from T8 to T9 within 0.5 hours. In the fourth stage, the temperature is maintained at T9 for 4 hours until the viscosity of the system no longer changes within 30 minutes, thus obtaining benzene-terminated polyaryletherketone. Among them, T7 is room temperature, T8 is 140℃, and T9 is 180℃. The amount of organic solvent added is 400g, the amount of the first polymerizing monomer added is 0.302mol, the amount of the second polymerizing monomer added is 0.3mol, the amount of the end-capping agent added is 6.68mmol, the amount of the salt-forming agent added is 0.344mol, and the amount of the azeotropic agent added is 50g.

[0261] The final benzene-terminated polyarylether ketone had a melt index of 83 g / 10 min at 400 °C and 2.16 kg, with a melt index change rate of 0.33%.

[0262] Example 17

[0263] A method for preparing benzene-terminated polyaryletherketones by "on-site sealing" includes the following specific steps:

[0264] (1) Prepare the raw materials:

[0265] Organic solvent: dimethyl sulfoxide;

[0266] Azeotropic agent: p-xylene;

[0267] Salt-forming agent: potassium carbonate;

[0268] First monomer for polymerization: 4,4′-difluorobenzophenone;

[0269] Second polymerization monomer: 4,4'-dihydroxydiphenyl sulfone;

[0270] End-capping agent:

[0271] (2) Preparation of polyaryletherketone:

[0272] In an inert atmosphere, the organic solvent is first heated to a liquid state, and then the first polymerizing monomer, the second polymerizing monomer, the end-capping agent, the salt-forming agent, and the azeotropic agent are added to carry out an aromatic nucleophilic polycondensation reaction. The aromatic nucleophilic polycondensation reaction is divided into four stages. In the first stage, the temperature is increased from T7 to T8 within 1 hour. In the second stage, the temperature is maintained at T8 for 1.5 hours. In the third stage, the temperature is increased from T8 to T9 within 1 hour. In the fourth stage, the temperature is maintained at T9 for 6 hours until the viscosity of the system no longer changes within 30 minutes, thus obtaining benzene-terminated polyaryletherketone. Among them, T7 is room temperature, T8 is 130℃, and T9 is 150℃. The amount of organic solvent added is 290g, the amount of the first polymerizing monomer added is 0.303mol, the amount of the second polymerizing monomer added is 0.3mol, the amount of the end-capping agent added is 4.95mmol, the amount of the salt-forming agent added is 0.343mol, and the amount of the azeotropic agent added is 30g.

[0273] The final benzene-terminated polyarylether ketone had a melt index of 93 g / 10 min at 400 °C and 2.16 kg, with a melt index change rate of 0.62%.

Claims

1. A method for preparing benzene-terminated polyaryletherketones by "on-site sealing", characterized in that, In the process of preparing polyaryletherketones from first and second monomers via aromatic nucleophilic polycondensation, a monofluorinated end-capping agent and / or a monophenol end-capping agent are added to the polymerization system during the feeding stage. After polymerization, benzene-terminated polyaryletherketones are obtained. The first polymerization monomer is one or more of the following: difluorobenzophenone, bis(4-fluorobenzoyl)benzene, difluoroaryl ketone containing a biphenyl structure, difluoroaryl ketone containing a naphthalene structure, difluoroaryl ketone containing a bridging structure, difluoroaryl ketone containing a heterocyclic structure, and difluoroaryl ketone containing heteroatoms. The second polymerization monomer is one or more of the following: hydroquinone, biphenyl, naphthol, carbon-bridged biphenol, acetone, ether hydroquinone, diphenol sulfone, fluorene hydroquinone, and diphenol compounds containing heterocyclic structures; The monofluorinated end-capping agent is , , , and One or more of them, among which, It includes difluorobenzophenone, difluorotriphenyldione, difluoroaromatic ketone containing a biphenyl structure, difluoroaromatic ketone containing a naphthalene structure, difluoroaromatic ketone containing a bridging structure, difluoroaromatic ketone containing a heterocyclic structure, or difluoroaromatic ketone containing heteroatoms. It is monophenol; The monophenol capping agent is , , , and One or more of the following, wherein R1 is hydroxyl, alkyl, or aryl, and R2 is hydroxyl, alkyl, or aryl. It is hydroquinone, biphenyl hydroquinone, naphthol, carbohydrate-bridged hydroquinone, acetone, ether hydroquinone, diphenol sulfone, fluorene hydroquinone, or a diphenol compound containing a heterocyclic structure. It is monofluorobenzene; The total molar amount of functional groups of all the first polymer monomers added during feeding is N. b The total molar amount of functional groups of all the monofluorinated end-capping agents added during feeding is N. b The total molar amount of functional groups of all the second polymer monomers added during feeding is N. a The total molar amount of functional groups of all the monophenol end-capping agents added during feeding is N. a ', N b +N b '>N a +N a ', (N) a +2N a ') / (N b +2N b ')=r, where the value of r ranges from 0.94 to 1.00; The melt index of benzene-terminated polyaryletherketone at 400℃ and 2.16 kg is 2~100 g / 10 min, and the melt index change rate at 400℃ and 2.16 kg is <2%. A period of time refers to 30 minutes.

2. The method for preparing benzene-terminated polyaryletherketones according to claim 1, characterized in that, The aromatic nucleophilic condensation reaction is carried out in an organic solvent under an inert atmosphere and in the presence of a salt-forming agent.

3. The method for preparing benzene-terminated polyaryletherketones according to claim 2, characterized in that, The salt-forming agent is sodium carbonate and / or potassium carbonate.

4. The method for preparing benzene-terminated polyaryletherketones according to claim 2, characterized in that, The molar amount of the salt-forming agent and N a N a The ratio of the sum of ' is 0.5 to 0.8:

1.

5. The method for preparing benzene-terminated polyaryletherketones according to claim 2, characterized in that, When feeding materials, an organic solvent is added first, and the organic solvent is heated to a liquid state before adding other materials.

6. The method for preparing benzene-terminated polyaryletherketones according to claim 5, characterized in that, After the aromatic nucleophilic condensation reaction is completed, the solid content of the polymerization system is 25-35%.

7. The method for preparing benzene-terminated polyaryletherketones according to claim 5, characterized in that, The organic solvent is diphenyl sulfone; the aromatic nucleophilic polycondensation reaction is divided into four stages: in the first stage, the temperature is increased from T1 to T2 within 30 min to 1 h; in the second stage, the temperature is maintained at T2 for 0.5 to 1.5 h; in the third stage, the temperature is increased from T2 to T3 within 30 min to 1 h; in the fourth stage, the temperature is maintained at T3 for 2 to 6 h; T1 is 180℃, T2 is 250 to 260℃, and T3 is 310 to 320℃; in the fourth stage, the polymerization continues until the viscosity of the system no longer changes within 30 min.

8. The method for preparing benzene-terminated polyaryletherketones according to claim 5, characterized in that, The organic solvent is sulfolane, and an azeotropic agent is also added to the polymerization system. The mass of the azeotropic agent is 10% to 20% of the mass of the organic solvent. The aromatic nucleophilic polycondensation reaction is divided into four stages. In the first stage, the temperature is increased from T4 to T5 within 30 min to 1 h. In the second stage, the temperature is maintained at T5 for 0.5 to 1.5 h. In the third stage, the temperature is increased from T5 to T6 within 30 min to 1 h. In the fourth stage, the temperature is maintained at T6 for 2 to 6 h. T4 is 80°C, T5 is 160 to 180°C, and T6 is 250 to 260°C. In the fourth stage, the viscosity of the system no longer changes within 30 min.

9. A method for preparing benzene-terminated polyaryletherketones according to claim 5, characterized in that, The organic solvent is N,N-dimethylformamide, N,N-dimethylacetamide, 1-methyl-2-pyrrolidone, or dimethyl sulfoxide. An azeotropic agent is also added to the polymerization system, and the mass of the azeotropic agent is 10% to 20% of the mass of the organic solvent. The aromatic nucleophilic polycondensation reaction is divided into four stages: the first stage temperature is increased from T7 to T8 within 30 min to 1 h; the second stage temperature is maintained at T8 for 0.5 to 1.5 h; the third stage temperature is increased from T8 to T9 within 30 min to 1 h; and the fourth stage temperature is maintained at T9 for 2 to 6 h. T7 is room temperature, T8 is 120 to 150 °C, and T9 is 140 to 180 °C. In the fourth stage of polymerization, the viscosity of the system no longer changes within 30 min.

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