A side group halogen-containing bisphenol compound, a preparation method and application thereof
A high-purity halogenated 2-aryl-3,3-bis(hydroxyaryl)benzopyrrolidone derivative was prepared by ammonolysis of phenolphthalein and aromatic primary amine derivative hydrochloride and purification steps. This solved the problem of the difficulty in preparing high-purity halogenated phenolphthalein derivatives, achieved high-yield and high-purity products, and improved the performance of polymers.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- DALIAN INSTITUTE OF CHEMICAL PHYSICS CHINESE ACADEMY OF SCIENCES
- Filing Date
- 2023-04-07
- Publication Date
- 2026-05-01
AI Technical Summary
Existing technologies are difficult to efficiently prepare and separate high-purity halogenated phenolphthalein derivatives, which limits their application in polymer synthesis, and existing methods also consume a lot of resources.
Halogen-containing 2-aryl-3,3-bis(hydroxyaryl)benzopyrrolidone derivatives were prepared by ammonolysis of phenolphthalein and aromatic primary amine derivative hydrochloride, followed by quenching, separation, and purification steps. The product was purified using sodium hydroxide solution and activated carbon, and then recrystallized to obtain a high-purity product.
The overall yield of halogen-containing 2-aryl-3,3-bis(hydroxyaryl)benzopyrrolidone derivatives was higher than 60%, and the purity was higher than 98%, making them suitable for industrial production. The heat resistance of the polymer was improved and the dielectric constant was reduced.
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Figure CN118772041B_ABST
Abstract
Description
A halogenated bisphenol compound with a side group, its preparation method and application Technical Field
[0001] This application relates to a halogenated bisphenol compound with a side group, its preparation method, and its application, belonging to the field of polymer materials. Background Technology
[0002] Phenolphthalein derivatives have been used as monomers of aromatic dihydroxy compounds to prepare polyaryl ether resins. However, the preparation and separation of high-purity halogenated phenolphthalein derivatives are currently difficult, failing to meet the requirements for use in polymer synthesis. Furthermore, existing methods for preparing and separating halogenated phenolphthalein derivatives are resource-intensive. Therefore, methods for preparing and separating halogenated phenolphthalein derivatives suitable for polymer synthesis still need improvement. Summary of the Invention
[0003] According to one aspect of this application, a method for preparing a halogenated bisphenol compound with a side group is provided, comprising the following steps:
[0004] Step 1: Dissolve phenolphthalein and the hydrochloride salt of the aromatic primary amine derivative in the aromatic primary amine derivative, perform ammonolysis reaction, quench and separate to obtain crude halogen-containing 2-aryl-3,3-bis(hydroxyaryl)benzopyrrolidone derivative.
[0005] Step 2: The crude halogen-containing 2-aryl-3,3-bis(hydroxyaryl)benzopyrrolidone derivative is purified to obtain the halogen-containing 2-aryl-3,3-bis(hydroxyaryl)benzopyrrolidone derivative.
[0006] The hydrochloride salt of the aromatic primary amine derivative has the structure shown in Formula I:
[0007]
[0008] Formula I, where R1 is -F, -CF3, or -OCF3.
[0009] The synthesis route is as follows:
[0010]
[0011] Where R1 is -F, -CF3, or -OCF3.
[0012] Optionally, the hydrochloride salt of the aromatic primary amine derivative is selected from at least one of 4-(trifluoromethoxy)aniline hydrochloride, 4-(trifluoromethyl)aniline hydrochloride, 3-(trifluoromethoxy)aniline hydrochloride, 3-(trifluoromethyl)aniline hydrochloride, 2-(trifluoromethoxy)aniline hydrochloride, 2-(trifluoromethyl)aniline hydrochloride, 4-fluoroaniline hydrochloride, 3-fluoroaniline hydrochloride, and 2-fluoroaniline hydrochloride;
[0013] The aromatic primary amine derivative is selected from at least one of 4-(trifluoromethoxy)aniline, 3-(trifluoromethoxy)aniline, 2-(trifluoromethoxy)aniline, 4-(trifluoromethyl)aniline, 3-(trifluoromethyl)aniline, 2-(trifluoromethyl)aniline, 4-fluoroaniline, 3-fluoroaniline, and 2-fluoroaniline.
[0014] It should be noted that the aromatic primary amine derivatives in the above preparation method correspond to the aromatic primary amine derivatives in the hydrochloride salt of the aromatic primary amine derivatives.
[0015] Optionally, the molar ratio of phenolphthalein, the hydrochloride of the aromatic primary amine derivative, and the aromatic primary amine derivative is 1:0.8 to 1.1:2 to 8.
[0016] Optionally, the molar ratio of the phenolphthalein, the hydrochloride of the aromatic primary amine derivative, and the aromatic primary amine derivative is selected from any value among 1:0.8:2, 1:0.9:0.3, 1:1:4, 1:1.05:4.5, 1:1.1:5, and 1:1.1:8, or a range between any two ratios.
[0017] Optionally, the ammonolysis reaction is specifically carried out by: purging with nitrogen and stirring, at a temperature of 160–200°C, for a time of 4–24 hours.
[0018] Optionally, the specific operation of the quenching separation is as follows: after the phenolphthalein fluorescence spot disappears as detected by TLC, the reaction is stopped, the reaction solution is poured into deionized water in an ice-water bath, stirred and allowed to settle, and then filtered. The filter cake is washed with deionized water until neutral, and dried to obtain a crude product of halogen-containing 2-aryl-3,3-bis(hydroxyaryl)benzopyrrolidone derivative, wherein the drying temperature is 120-150℃.
[0019] Optionally, the purification includes the following steps:
[0020] a. Add sodium hydroxide solution and activated carbon to the crude halogen-containing 2-aryl-3,3-bis(hydroxyaryl)benzopyrrolidone derivative, filter I, and obtain the filtrate;
[0021] b. Add hydrochloric acid to the filtrate obtained in step a, stir to precipitate, filter II, and obtain filter cake;
[0022] c. Dry the filter cake obtained in step b, recrystallize it, and obtain the halogen-containing 2-aryl-3,3-bis(hydroxyaryl)benzopyrrolidone derivative;
[0023] In step c, the solvent for recrystallization is an alcohol solution, and the alcohol in the alcohol solution includes methanol and ethanol.
[0024] Optionally, the volume ratio of alcohol to water in the methanol solution is 1 to 8:1.
[0025] Optionally, the mass ratio of the filter cake to the methanol solution is 14.5 to 16.
[0026] Optionally, in step c, the drying temperature is 120–150°C.
[0027] Optionally, in step b, the volume ratio of the filtrate to the hydrochloric acid is 1:0.125 to 0.2;
[0028] The concentration of the hydrochloric acid is 6–10 mol / L.
[0029] Optionally, in step a, the mass ratio of the crude halogen-containing 2-aryl-3,3-bis(hydroxyaryl)benzopyrrolidone derivative to the sodium hydroxide solution is 1g:3-12g.
[0030] Optionally, the mass ratio of the crude halogen-containing 2-aryl-3,3-bis(hydroxyaryl)benzopyrrolidone derivative to activated carbon is 1g:0.05-0.12g.
[0031] The preparation method of a specific halogenated bisphenol compound with a side group is as follows:
[0032] A method for synthesizing a halogen-containing 2-aryl-3,3-bis(hydroxyaryl)benzopyrrolidone derivative, the method comprising the following steps:
[0033] (1) Using phenolphthalein and the hydrochloride salt of aromatic primary amine derivatives as raw materials and the corresponding aromatic primary amine derivatives as solvents, crude halogenated 2-aryl-3,3-bis(hydroxyaryl)benzopyrrolidone derivatives were prepared.
[0034] (2) The crude halogenated 2-aryl-3,3-bis(hydroxyaryl)benzopyrrolidone derivative obtained in step (1) is purified to obtain the pure halogenated 2-aryl-3,3-bis(hydroxyaryl)benzopyrrolidone derivative.
[0035] Phenolphthalein and aromatic primary amine derivatives are readily available and simple raw materials. However, the aromatic primary amine derivatives need to be prepared beforehand as their hydrochloride salts. The remaining raw materials require no pretreatment.
[0036] In step (1), the molar ratio of phenolphthalein, the hydrochloride salt of the aromatic primary amine derivative, and the aromatic primary amine derivative is 1:0.8:2 to 1:1.1:8. Preferably, it is 1:1:4.
[0037] The chemical reaction equation for the synthesis method of the halogen-containing 2-aryl-3,3-bis(hydroxyaryl)benzopyrrolidone derivative described in this invention is as follows:
[0038]
[0039] Preferably, the specific operation in step (1) is as follows: 1 part phenolphthalein, 1-1.1 parts hydrochloride of the aromatic primary amine derivative, and 4-5 parts of the aromatic primary amine derivative are added to a reaction vessel by molar amount. Nitrogen gas is turned on for purging, and the mixture is stirred. The temperature is raised to 200°C and maintained for 22-24 hours, with continuous stirring during the heat treatment. Then, the mixture is quenched and separated to obtain the crude product of halogen-containing 2-aryl-3,3-bis(hydroxyaryl)benzopyrrolidone derivative.
[0040] The specific operation of quenching separation in step (1) is as follows: After the phenolphthalein fluorescence spot disappears as detected by TLC, the reaction is stopped, the reaction solution is poured into deionized water in an ice-water bath, stirred and allowed to settle, and then filtered. The filter cake is washed with deionized water until neutral, and dried to obtain crude halogen-containing 2-aryl-3,3-bis(hydroxyaryl)benzopyrrolidone derivative (Ⅰ). The drying temperature is 120-150℃.
[0041] The specific operation of step (2) is as follows: Add sodium hydroxide solution and activated carbon powder to the crude halogen-containing 2-aryl-3,3-bis(hydroxyaryl)benzopyrrolidone derivative obtained in step (1), filter, add hydrochloric acid to the filtrate, and stir until no more white solid precipitates, filter, and dry the filter cake. Recrystallize the filter cake using a mixed solvent of methanol and water to obtain the pure halogen-containing 2-aryl-3,3-bis(hydroxyaryl)benzopyrrolidone derivative; wherein, the drying temperature is 120-150℃, and the ratio of the recrystallization mixed solvent is methanol:water (v:v) = 5:1.
[0042] According to another aspect of this application, a bisphenol compound with a halogenated side group is provided, wherein the side group of the bisphenol compound contains both an imide and a halogen.
[0043] The halogenated bisphenol compound with the side group is a halogenated 2-aryl-3,3-bis(hydroxyaryl)benzopyrrolidone derivative.
[0044] It has the structure shown in Formula II:
[0045]
[0046] In Equation II, R1 is -F, -CF3, or -OCF3.
[0047] According to another aspect of this application, the use of a side-group halogenated bisphenol compound or a side-group halogenated bisphenol compound obtained according to the above preparation method in the preparation of Cardo-type halogenated polyetherketone polymers is provided.
[0048] The Cardo-type halogenated polyetherketone polymer has the structure shown in Formula III;
[0049]
[0050] R is C6~C 18 Halogenated aromatic groups;
[0051] The value of n ranges from 5 to 200.
[0052] The beneficial effects that this application can produce include:
[0053] 1) The preparation method provided in this application can achieve a comprehensive yield of halogen-containing 2-aryl-3,3-bis(hydroxyaryl)benzopyrrolidone derivatives of more than 60%, and the purity of the purified halogen-containing 2-aryl-3,3-bis(hydroxyaryl)benzopyrrolidone derivatives of more than 98%.
[0054] 2) The preparation method provided in this application has the characteristics of readily available raw materials and easy purification, and is suitable for industrial production.
[0055] 3) The halogen-containing 2-aryl-3,3-bis(hydroxyaryl)benzopyrrolidone derivatives provided in this application have high purity and can be used in the synthesis of polyaryl ether compounds, which can improve the heat resistance of polymers and reduce the dielectric constant. Attached Figure Description
[0056] Figure 1 shows the NMR spectra of the products prepared in Examples 1 to 3 of this application. Detailed Implementation
[0057] The present application is described in detail below with reference to the embodiments, but the present application is not limited to these embodiments.
[0058] Unless otherwise specified, the raw materials and catalysts used in the embodiments of this application were all purchased commercially.
[0059] The analysis method in the embodiments of this application is as follows:
[0060] Purity analysis of halogen-containing derivatives of 2-aryl-3,3-bis(hydroxyaryl)benzopyrrolidone was performed using high performance liquid chromatography.
[0061] In the embodiments of this application, the conversion rate and selectivity are calculated as follows:
[0062] In the embodiments of this application, the carbon molar number of the conversion rate of halogen-containing derivatives of 2-aryl-3,3-bis(hydroxyaryl)benzopyrrolidone was calculated:
[0063] Using phenolphthalein as a 1 molar equivalent, the conversion rate of the halogenated derivative of 2-halogenated aryl-3,3-bis(hydroxyaryl)benzopyrrolidone was calculated by comparing the molar amount of the purified halogenated derivative with the molar amount of PHT.
[0064] The references used in this application are explained here:
[0065] The code for the bisphenol monomer (Ia) is PPPBP-X;
[0066] The code for difluorobenzophenone (Ib) is DFK;
[0067] The code for Cardo-type halogenated polyetherketone polymer (II) is PEK-X.
[0068] Example 1
[0069] 4-(trifluoromethoxy)aniline hydrochloride was prepared by mixing a solution of 1,4-dioxane with hydrogen chloride and 4-(trifluoromethoxy)aniline, and the chemical reaction equation is as follows:
[0070]
[0071] Weigh 2.79 g of 4-(trifluoromethoxy)aniline and add it to 16 mL of 4 M dioxane hydrochloride solution. Stir at room temperature for 1.5 h. Then evaporate the solution to dryness by vacuum distillation to obtain 3.36 g of 4-(trifluoromethoxy)aniline hydrochloride.
[0072] 2-(4-trifluoromethoxy)aryl-3,3-bis(hydroxyaryl)benzopyrrolidone was prepared from phenolphthalein and 4-(trifluoromethoxy)aniline hydrochloride in a system using 4-(trifluoromethoxy)aniline as solvent. The chemical reaction equation is as follows:
[0073]
[0074] Weigh 5g of phenolphthalein, 3.36g of 4-(trifluoromethoxy)aniline hydrochloride, and 11.14g of 4-(trifluoromethoxy)aniline into a reaction vessel. Purge with nitrogen, start stirring, heat to 180℃, and maintain this temperature with stirring for 24h. The reaction mixture gradually turns blue. Monitor the reaction using TLC until the phenolphthalein fluorescence disappears. Slowly pour the reaction mixture into 13mL of 6mol / L hydrochloric acid in an ice-water bath, and dilute with water to 50mL. A large amount of blue solid appears. Stir for 2h, filter, and wash the filter cake with water until neutral.
[0075] The filter cake was dissolved in 35 mL of 1 mol / L NaOH solution, and 0.6 g of activated carbon was added. The mixture was stirred for 2 h. The activated carbon was filtered to obtain a red filtrate. 6.5 mL of 6 mol / L hydrochloric acid was slowly added dropwise while stirring the filtrate, resulting in a white solid. This was filtered, and the filter cake was washed until neutral. It was then dried at 150 °C for 6 h, and its purity was determined to be 97.8% by liquid chromatography. Recrystallization was performed using methanol:water (V:V) = 5:1. The crystals were filtered, washed, and dried at 150 °C for 12 h to obtain 5.80 g of colorless to white crystals, with a yield of 77%. The purity was determined to be 98.7% by liquid chromatography.
[0076] Example 2
[0077] 3-(trifluoromethoxy)aniline hydrochloride was prepared by mixing a solution of 1,4-dioxane with hydrogen chloride and 3-(trifluoromethoxy)aniline, and the chemical reaction equation is as follows:
[0078]
[0079] Weigh 5.54 g of 3-(trifluoromethoxy)aniline and add it to 20 mL of 4 M dioxane hydrochloride solution. Stir at room temperature for 1.5 h. Then evaporate the solution to dryness by vacuum distillation to obtain 6.68 g of 3-(trifluoromethoxy)aniline hydrochloride.
[0080] 2-(3-trifluoromethoxy)aryl-3,3-bis(hydroxyaryl)benzopyrrolidone was prepared from phenolphthalein and 3-(trifluoromethoxy)aniline hydrochloride in a system using 3-(trifluoromethoxy)aniline as solvent. The chemical reaction equation is as follows:
[0081]
[0082] 10 g of phenolphthalein, 6.68 g of 3-(trifluoromethoxy)aniline hydrochloride, and 22.28 g of 3-(trifluoromethoxy)aniline were weighed and added to a reaction vessel. Nitrogen purging was initiated, and stirring was started. The temperature was raised to 180 °C and maintained at this temperature with stirring for 22 h. The reaction mixture gradually turned red. The reaction was monitored by TLC until the phenolphthalein fluorescence disappeared. The reaction mixture was slowly poured into 25 mL of 6 mol / L hydrochloric acid in an ice-water bath, and diluted with water to 100 mL, resulting in a large amount of red solid. The mixture was stirred for 2 h, filtered, and the filter cake was washed with water until neutral.
[0083] The filter cake was dissolved in 70 mL of 1 mol / L NaOH solution, and 1 g of activated carbon was added. The mixture was stirred for 2 h. The activated carbon was filtered to obtain a red filtrate. 12 mL of 6 mol / L hydrochloric acid was slowly added dropwise while stirring the filtrate, resulting in a white solid. This was filtered, and the filter cake was washed until neutral. It was then dried at 150 °C for 6 h, and its purity was determined to be 97.1% by liquid chromatography. Recrystallization was performed using methanol:water (V:V) = 5:1. The crystals were filtered, washed, and dried at 150 °C for 12 h to obtain 7.05 g of colorless to white crystals, with a yield of 47%. The purity was determined to be 98.0% by liquid chromatography.
[0084] Example 3
[0085] 3-(trifluoromethyl)aniline hydrochloride was prepared by mixing a solution of 1,4-dioxane with hydrogen chloride and 3-(trifluoromethyl)aniline, and the chemical reaction equation is as follows:
[0086]
[0087] Weigh 5.06 g of 3-(trifluoromethyl)aniline and add it to 20 mL of 4 M dioxane hydrochloride solution. Stir at room temperature for 2 h. Then evaporate the solution to dryness by vacuum distillation to obtain 6.22 g of 3-(trifluoromethyl)aniline hydrochloride.
[0088] 2-(3-trifluoromethyl)aryl-3,3-bis(hydroxyaryl)benzopyrrolidone was prepared from phenolphthalein and 3-(trifluoromethyl)aniline hydrochloride in a system using 3-(trifluoromethyl)aniline as solvent. The chemical reaction equation is as follows:
[0089]
[0090] 10 g of phenolphthalein, 6.22 g of 3-(trifluoromethyl)aniline hydrochloride, and 20.02 g of 3-(trifluoromethyl)aniline were weighed and added to a reaction vessel. Nitrogen purging was initiated, and stirring was started. The temperature was raised to 180 °C and maintained at this temperature with stirring for 24 h. The reaction mixture gradually turned reddish-brown. The reaction was monitored by TLC until the phenolphthalein fluorescence disappeared. The reaction mixture was slowly poured into 25 mL of 6 mol / L hydrochloric acid in an ice-water bath, and diluted with water to 100 mL, resulting in a large amount of reddish-brown solid. The mixture was stirred for 2 h, filtered, and the filter cake was washed with water until neutral.
[0091] The filter cake was dissolved in 70 mL of 1 mol / L NaOH solution, and 1.1 g of activated carbon was added. The mixture was stirred for 2 h. The activated carbon was filtered to obtain a red filtrate. 12 mL of 6 mol / L hydrochloric acid was slowly added dropwise while stirring the filtrate, resulting in a white solid. This was filtered, and the filter cake was washed until neutral. It was then dried at 150 °C for 6 h, and the purity was determined to be 97.0% by liquid chromatography. Recrystallization was performed using methanol:water (V:V) = 5:1. The crystals were filtered, washed, and dried at 150 °C for 12 h to obtain 8.87 g of colorless to white crystals, with a yield of 61%. The purity was determined to be 98.0% by liquid chromatography.
[0092] Example 4
[0093] 4-(trifluoromethoxy)aniline hydrochloride was prepared by mixing a solution of 1,4-dioxane with hydrogen chloride and 4-(trifluoromethoxy)aniline, and the chemical reaction equation is as follows:
[0094]
[0095] Weigh 2.79 g of 4-(trifluoromethoxy)aniline and add it to 10 mL of 4 M dioxane hydrochloride solution. Stir at room temperature for 2 h. Then evaporate the solution to dryness by vacuum distillation to obtain 3.34 g of 4-(trifluoromethoxy)aniline hydrochloride.
[0096] 2-(4-trifluoromethoxy)aryl-3,3-bis(hydroxyaryl)benzopyrrolidone was prepared from phenolphthalein and 4-(trifluoromethoxy)aniline hydrochloride in a system using 4-(trifluoromethoxy)aniline as solvent. The chemical reaction equation is as follows:
[0097]
[0098] Weigh 5g of phenolphthalein, 3.34g of 4-(trifluoromethoxy)aniline hydrochloride, and 8.36g of 4-(trifluoromethoxy)aniline into a reaction vessel. Purge with nitrogen, start stirring, heat to 160℃, and maintain this temperature with stirring for 36h. The reaction mixture gradually turns blue. Monitor the reaction using TLC until the phenolphthalein fluorescence disappears. Slowly pour the reaction mixture into 10mL of 6mol / L hydrochloric acid in an ice-water bath, and dilute with water to 50mL. A large amount of blue solid appears. Stir for 2h, filter, and wash the filter cake with water until neutral.
[0099] The filter cake was dissolved in 35 mL of 1 mol / L NaOH solution, and 0.6 g of activated carbon was added. The mixture was stirred for 2 h. The activated carbon was filtered to obtain a red filtrate. 6.5 mL of 6 mol / L hydrochloric acid was slowly added dropwise while stirring the filtrate, resulting in a white solid. This was filtered, and the filter cake was washed until neutral. It was then dried at 150 °C for 6 h, and its purity was determined to be 97.3% by liquid chromatography. Recrystallization was performed using methanol:water (V:V) = 5:1. The crystals were filtered, washed, and dried at 150 °C for 12 h to obtain 4.29 g of colorless to white crystals, with a yield of 57%. The purity was determined to be 98.5% by liquid chromatography.
[0100] Example 5
[0101] 3-(trifluoromethyl)aniline hydrochloride was prepared by mixing a solution of 1,4-dioxane with hydrogen chloride and 3-(trifluoromethyl)aniline, and the chemical reaction equation is as follows:
[0102]
[0103] Weigh 1.52 g of 3-(trifluoromethyl)aniline and add 6 mL of 4 M dioxane hydrochloride solution. Stir at room temperature for 2 h. Then evaporate to dryness by vacuum distillation to obtain 1.86 g of 3-(trifluoromethyl)aniline hydrochloride.
[0104] 2-(3-trifluoromethyl)aryl-3,3-bis(hydroxyaryl)benzopyrrolidone was prepared from phenolphthalein and 3-(trifluoromethyl)aniline hydrochloride in a system using 3-(trifluoromethyl)aniline as solvent. The chemical reaction equation is as follows:
[0105]
[0106] Weigh 5g of phenolphthalein, 1.86g of 3-(trifluoromethyl)aniline hydrochloride, and 7.60g of 3-(trifluoromethyl)aniline into a reaction vessel. Purge with nitrogen, start stirring, heat to 160℃, and maintain this temperature with stirring for 36h. The reaction mixture gradually turns reddish-brown. Monitor the reaction using TLC until the phenolphthalein fluorescence disappears. Slowly pour the reaction mixture into 10mL of 6mol / L hydrochloric acid in an ice-water bath, and dilute with water to 100mL. A large amount of reddish-brown solid appears. Stir for 2h, filter, and wash the filter cake with water until neutral.
[0107] The filter cake was dissolved in 35 mL of 1 mol / L NaOH solution, and 1.1 g of activated carbon was added. The mixture was stirred for 2 h. The activated carbon was filtered to obtain a red filtrate. 6 mL of 6 mol / L hydrochloric acid was slowly added dropwise while stirring the filtrate, resulting in a white solid. This was filtered, and the filter cake was washed until neutral. It was then dried at 150 °C for 6 h, and the purity was determined to be 97.2% by liquid chromatography. Recrystallization was performed using methanol:water (V:V) = 5:1. The crystals were filtered, washed, and dried at 150 °C for 12 h to obtain 4.05 g of colorless to white crystals, with a yield of 56% and a purity of 98.6% by liquid chromatography.
[0108] As shown in Figure 1, the 1H NMR spectra of Examples 1-3 are of high purity, with no impurity peaks, and the assignment and splitting of each hydrogen atom are consistent with the structure of the compound shown.
[0109] Application Example 1
[0110] Using PPPBP-mCF and DFK as raw materials, m-trifluoromethylphenyl modified PEK-InmCF was prepared in a system with TMS as solvent, potassium carbonate as catalyst, and toluene as dehydrating agent. The chemical reaction equation is as follows:
[0111]
[0112] In a dry 100 mL round-bottom three-necked flask equipped with a mechanical stirrer, water separator, condenser, and nitrogen inlet / outlet pipes, 4.614 g (0.01 mol) of PPPBP-mCF, 2.182 g (0.01 mol) of 4,4-difluorobenzophenone, 1.587 g (0.0115 mol) of anhydrous potassium carbonate, 25 mL of toluene, and 16 mL of sulfolane (TMS) were added sequentially. The mixture was stirred and heated to 140 °C. After the toluene was dehydrated for 2 hours, the temperature was slowly increased to 150 °C and maintained for 0.5 hours. The temperature was then increased to 200 °C and the reaction continued for 3 hours. The system became a white, transparent, viscous liquid. After cooling to room temperature and diluting with an appropriate amount of DMAc, the liquid was slowly poured into an aqueous ethanol solution to obtain a filamentous white polymer. The polymer was filtered, washed 6-8 times with water, and dried under vacuum at 150 °C for 12 hours, where n was 208.
[0113] Application Example 2
[0114] Using PPPBP-mOCF and DFK as raw materials, m-trifluoromethoxyphenyl-modified PEK-InmOCF was prepared in a system with TMS as solvent, potassium carbonate as catalyst, and toluene as dehydrating agent. The chemical reaction equation is as follows:
[0115]
[0116] In a dry 100 mL round-bottom three-necked flask equipped with a mechanical stirrer, water separator, condenser, and nitrogen inlet / outlet pipes, 4.774 g (0.01 mol) of PPPBP-mOCF, 2.182 g (0.01 mol) of difluorobenzophenone, 1.587 g (0.0115 mol) of anhydrous potassium carbonate, 25 mL of toluene, and 16 mL of sulfolane (TMS) were added sequentially. The mixture was stirred and heated to 140 °C. After the toluene was dehydrated for 2 hours, the temperature was slowly increased to 150 °C and maintained for 0.5 hours. The temperature was then increased to 200 °C and the reaction continued for 3 hours. The system became a white, transparent, viscous liquid. After cooling to room temperature and diluting with an appropriate amount of DMAc, the liquid was slowly poured into an aqueous ethanol solution to obtain a filamentous white polymer. The polymer was filtered, washed 6-8 times with water, and dried under vacuum at 150 °C for 12 hours, where n was 165.
[0117] Application Example 3
[0118] Using PPPBP-pOCF and DFK as raw materials, PEK-InpOCF modified with trifluoromethoxyphenyl was prepared in a system with TMS as solvent, potassium carbonate as catalyst, and toluene as dehydrating agent. The chemical reaction equation is as follows:
[0119]
[0120] In a dry 100 mL round-bottom three-necked flask equipped with a mechanical stirrer, water separator, condenser, and nitrogen inlet / outlet pipes, 4.774 g (0.01 mol) of PPPBP-pOCF, 2.182 g (0.01 mol) of difluorobenzophenone, 1.587 g (0.0115 mol) of anhydrous potassium carbonate, 25 mL of toluene, and 16 mL of sulfolane (TMS) were added sequentially. The mixture was stirred and heated to 140 °C. After the toluene removed water for 2 hours, the temperature was slowly increased to 150 °C and maintained for 0.5 hours. The temperature was then increased to 200 °C and the reaction continued for 3 hours. The system became a white, transparent, viscous liquid. After cooling to room temperature and diluting with an appropriate amount of DMAc, the liquid was slowly poured into an aqueous ethanol solution to obtain a filamentous white polymer. The polymer was filtered, washed 6-8 times with water, and dried under vacuum at 150 °C for 12 hours, where n was 145.
[0121] Application Comparative Example 1
[0122] PEK-In was prepared using PPPBP and DFK as raw materials in a system with TMS as solvent, potassium carbonate as catalyst, and toluene as dehydrating agent. The chemical reaction equation is as follows:
[0123]
[0124] In a dry 100 mL round-bottom three-necked flask equipped with a mechanical stirrer, water separator, condenser, and nitrogen inlet / outlet pipes, 3.934 g (0.01 mol) of PPPBP, 2.182 g (0.01 mol) of difluorobenzophenone, 1.587 g (0.0115 mol) of anhydrous potassium carbonate, 25 mL of toluene, and 16 mL of sulfolane (TMS) were added sequentially. The mixture was stirred and heated to 140 °C. After the toluene was dehydrated for 2 hours, the temperature was slowly increased to 150 °C and maintained for 0.5 hours. The temperature was then increased to 200 °C and the reaction continued for 3 hours. The system became a white, transparent, viscous liquid. After cooling to room temperature and diluting with an appropriate amount of DMAc, the liquid was slowly poured into an aqueous ethanol solution to obtain a filamentous white polymer. The polymer was filtered, washed 6-8 times with water, and dried under vacuum at 150 °C for 12 hours. The value of n was 53.
[0125] Test Example 1
[0126] The polyaryletherketone films prepared in Examples 1-3 were subjected to thermal stability tests at 50–800 °C and 10 °C / min, and their water absorption rates were tested after immersion in deionized water at 23 °C for 24 h. The specific test data are shown in Table 1.
[0127] Table 1: Test data on thermal stability and water absorption of low dielectric polyaryletherketone films obtained in the examples
[0128] Polymer Td 5％ (°C)T g (°C) Water Absorption Rate (%) Comparison Application Example 1: 545 241 1.09 Application Example 1: 521 213 0.51 Application Example 2: 538 197 0.51 Application Example 3: 527 228 0.85 surface
[0129] Test Example 2
[0130] The polyaryletherketone films prepared in Examples 1-3 were subjected to dielectric property tests and free volume tests at 10 GHz. The specific test data are shown in Table 2.
[0131] Table 2: Dielectric properties and free volume of polymers
[0132]
[0133] As can be seen from Tables 1 and 2, the introduction of halogen-containing side groups reduces the water absorption rate of the material. Furthermore, with a larger free volume fraction and a comparable dielectric constant, the dielectric loss is lower.
[0134] The above description is merely a few embodiments of this application and is not intended to limit this application in any way. Although this application discloses preferred embodiments as described above, it is not intended to limit this application. Any changes or modifications made by those skilled in the art without departing from the scope of the technical solution of this application using the disclosed technical content are equivalent to equivalent implementation cases and fall within the scope of the technical solution.
Claims
1. A bisphenol compound with a halogenated side group, characterized in that, The halogenated bisphenol compound with side groups has the structure shown in Formula II: Equation II; in Equation II, R1 is -F, -CF3 or -OCF3.
2. A method for preparing the halogenated bisphenol compound with a side group as described in claim 1, characterized in that, Includes the following steps: Step 1: Dissolve phenolphthalein and the hydrochloride salt of an aromatic primary amine derivative in the corresponding aromatic primary amine derivative, perform ammonolysis, quench and separate to obtain a crude bisphenol compound containing halogenated side groups; Step 2: Purify the crude bisphenol compound containing halogenated side groups to obtain the bisphenol compound containing halogenated side groups; wherein, the hydrochloride salt of the aromatic primary amine derivative has the structure shown in Formula I: Formula I, where R1 is -F, -CF3, or -OCF3; the purification includes the following steps: a. adding sodium hydroxide solution and activated carbon to the crude bisphenol compound with halogenated side groups, filtering to obtain a filtrate; b. adding hydrochloric acid to the filtrate obtained in step a, stirring to precipitate, filtering to obtain a filter cake; c. drying the filter cake obtained in step b, recrystallizing to obtain the bisphenol compound with halogenated side groups; wherein, in step c, the solvent for recrystallization is an alcohol solution, and the alcohol in the alcohol solution is one or both of methanol and ethanol.
3. The preparation method according to claim 2, characterized in that, The hydrochloride salt of the aromatic primary amine derivative is selected from at least one of 4-(trifluoromethoxy)aniline hydrochloride, 4-(trifluoromethyl)aniline hydrochloride, 3-(trifluoromethoxy)aniline hydrochloride, 3-(trifluoromethyl)aniline hydrochloride, 2-(trifluoromethoxy)aniline hydrochloride, 2-(trifluoromethyl)aniline hydrochloride, 4-fluoroaniline hydrochloride, 3-fluoroaniline hydrochloride, and 2-fluoroaniline hydrochloride; the aromatic primary amine derivative is selected from at least one of 4-(trifluoromethoxy)aniline, 3-(trifluoromethoxy)aniline, 2-(trifluoromethoxy)aniline, 4-(trifluoromethyl)aniline, 3-(trifluoromethyl)aniline, 2-(trifluoromethyl)aniline, 4-fluoroaniline, 3-fluoroaniline, and 2-fluoroaniline; the aromatic primary amine derivative corresponds to the hydrochloride salt of the aromatic primary amine derivative.
4. The preparation method according to claim 2, characterized in that, The molar ratio of phenolphthalein, the hydrochloride of the aromatic primary amine derivative, and the aromatic primary amine derivative is 1:0.8~1.1:2~8.
5. The preparation method according to claim 2, characterized in that, The ammonolysis reaction is specifically carried out by: purging with nitrogen and stirring, at a temperature of 160~200℃, for a time of 4~24h.
6. The preparation method according to claim 2, characterized in that, In step c, the volume ratio of alcohol to water in the alcohol solution is 1~8:1; the mass ratio of the filter cake to the alcohol solution is 1:4.5~16; and the drying temperature is 120~150℃.
7. The preparation method according to claim 2, characterized in that, In step b, the volume ratio of the filtrate to the hydrochloric acid is 1:0.125~0.2; the concentration of the hydrochloric acid is 6~10 mol / L.
8. The preparation method according to claim 2, characterized in that, In step a, the mass ratio of the crude halogenated bisphenol compound with side groups to sodium hydroxide solution is 1g:3~12g; the mass ratio of the crude halogenated bisphenol compound with side groups to activated carbon is 1g:0.05~0.12g.
9. The use of the halogenated bisphenol compound of claim 1 in the preparation of Cardo-type halogenated polyetherketone polymers; said Cardo-type halogenated polyetherketone polymer having the structure shown in Formula III; Formula III; R is a phenyl group attached to R1 as described in claim 1; n ranges from 5 to 200.