阅读说明：本技术 一种聚芳香醚的制备方法 (Preparation method of polyaromatic ether ) 是由 张中标 穆琰琰 郭潇帆 刘洋 刘钰玮 赵满 王羽巍 宋爱茹 于 2021-07-02 设计创作，主要内容包括：本发明涉及一种聚芳香醚的制备方法,其包括以下步骤：(1)将二卤单体、双酚单体、磷酸钠和溶剂进行混合,形成反应体系；(2)使反应体系在惰性气氛下进行聚合反应,所述反应过程中无水生成。本发明的方法能够在较高温度下无水产生聚合制备聚芳醚酮、聚芳醚腈以及聚醚酰亚胺等聚芳香醚,剔除了分水剂的使用以及简化了溶剂回收工艺。(The invention relates to a preparation method of polyaromatic ether, which comprises the following steps: (1) mixing a dihalogen monomer, a bisphenol monomer, sodium phosphate and a solvent to form a reaction system; (2) and (3) carrying out polymerization reaction on the reaction system under an inert atmosphere, wherein no water is generated in the reaction process. The method can be used for preparing polyaromatic ethers such as polyaryletherketone, polyarylethernitrile, polyetherimide and the like by anhydrous polymerization at higher temperature, eliminates the use of a water separating agent and simplifies a solvent recovery process.)

1. A method for preparing a polyaromatic ether, comprising the steps of:

(1) mixing a dihalogen monomer, a bisphenol monomer, sodium phosphate and a solvent to form a reaction system;

(2) and (3) carrying out polymerization reaction on the reaction system under an inert atmosphere, wherein no water is generated in the reaction process.

2. The process according to claim 1, wherein the polymerization temperature is above 200 ℃.

3. The process according to claim 1 or 2, characterized in that the temperature of the polymerization reaction is 210 ℃ to 300 ℃, preferably 230 ℃ to 270 ℃.

4. The process according to any one of claims 1 to 3, characterized in that the mass ratio of the sodium phosphate to the dihalogen monomer is from 1.0 to 3.0:1, preferably from 1.5 to 2.5: 1.

5. The method according to any one of claims 1 to 4, wherein the mass ratio of the sodium phosphate to the bisphenol monomer is 0.5 to 4.0:1, preferably 1.0 to 3.5: 1.

6. The method of any one of claims 1-5, wherein the polyaromatic ether comprises one or more of a polyaryl ether ketone, a polyaryl ether nitrile, and a polyetherimide.

7. The process according to any one of claims 1 to 6, characterized in that said dihalogen monomer is selected from one or more of the following:

wherein, X is halogen or hydroxyl, preferably fluorine, chlorine or bromine.

8. The process according to any one of claims 1 to 7, characterized in that said dihalogen monomer is selected from one or more of the following:

9. the method of any one of claims 1-8, wherein the bisphenol monomer is selected from one or more of the following:

10. the method of any one of claims 1-9, wherein the solvent comprises one or more of N, N-dimethylformamide, N' -dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, N-butylpyrrolidone, 1, 3-dimethyl-2-imidazolidinone, sulfolane, diphenylsulfone, or dimethylsulfoxide.

Technical Field

The invention relates to the field of polyaromatic ether synthesis, in particular to a preparation method of polyaromatic ether.

Technical Field

The polyaromatic ether is an important high-performance polymer material, has high thermal stability, chemical stability and mechanical strength, has various structures and wide sources, and plays an irreplaceable role in the fields of national defense and military industry, aerospace, high-end manufacturing and the like. The preparation of these polymeric materials is achieved primarily by aromatic nucleophilic displacement polycondensation of activated dihalides with bisphenols. One process requires the addition of a water-splitting agent, removal of water produced during the reaction, and then heating for polymerization. Most of the water-separating agents are inflammable and explosive aromatic compounds, and the use of the water-separating agents not only can bring cost increase on environmental protection and safety, but also can complicate a solvent recovery process in a post-treatment process, and finally leads to increase of production cost. In another process, the generated water can be directly distilled out without adding a water separating agent, and then the temperature is raised for polymerization. Although the process eliminates the water dividing link of the water dividing agent, if the water dividing is not thorough or the water dividing time is too long, the molecular weight is not high or the product has darker color.

Disclosure of Invention

Aiming at the problems of the prior art, the invention provides a preparation method of polyaromatic ether. The method adopts sodium phosphate as alkali, disodium hydrogen phosphate is generated after polymerization, no water is generated, water diversion is not needed, and the disodium hydrogen phosphate is not easy to decompose at high temperature, so that anhydrous generation and synthesis of the polyaromatic ether polymer which can be prepared only by polymerization at higher temperature are realized. In addition, the method also shortens the production period and simplifies the solvent recovery.

The preparation method of the polyaromatic ether provided by the invention comprises the following steps:

(1) mixing a dihalogen monomer, a bisphenol monomer, sodium phosphate and a solvent to form a reaction system;

(2) and (3) carrying out polymerization reaction on the reaction system under an inert atmosphere, wherein no water is generated in the reaction process.

According to some embodiments of the present invention, the method further comprises the step of (3) washing and drying the product of the polymerization reaction in the step (2) to obtain the polyaromatic ether.

In the prior art, potassium phosphate is used as a base, water is not generated, and water is not required to be separated, but the potassium phosphate has a large molecular weight (the molecular weight is 212.27, and the molecular weight of potassium carbonate is 138.21), and only one molecule of hydrogen halide can be theoretically accepted by one molecule of hydrogen halide (the potassium carbonate can accept two molecules of hydrogen halide theoretically), so the dosage is large, and the price is high. Meanwhile, dipotassium hydrogen phosphate is condensed at about 200 ℃ to generate potassium pyrophosphate and water, and the water can destroy polymers or block polymerization, so that the dipotassium hydrogen phosphate cannot be used in the preparation of polyaromatic ether requiring higher reaction temperature. The sodium phosphate adopted in the invention has the alkalinity similar to that of potassium phosphate, the disodium hydrogen phosphate can generate dehydration reaction at about 250 ℃, and the sodium phosphate has smaller molecular weight (molecular weight of 163.94), and has small dosage and lower price under the same condition. The invention adopts sodium phosphate as alkali, and realizes the preparation of the polyaromatic ether at lower cost at higher temperature.

According to some embodiments of the invention, the temperature of the polymerization reaction is above 200 ℃. In some embodiments, the temperature of the polymerization reaction is 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃, or any value in between. In some embodiments, the temperature of the polymerization reaction is from 210 ℃ to 300 ℃. In some embodiments, the temperature of the polymerization reaction is 230 ℃ to 270 ℃.

According to some embodiments of the invention, the mass ratio of the sodium phosphate to the dihalogen monomer is 1.0 to 3.0:1, such as 1.2:1, 1.4:1, 1.6:1, 1.8:1, 2.0:1, 2.1:1, 2.3:1, 2.6:1, 2.8:1, or any value therebetween. In some embodiments of the invention, the mass ratio of the sodium phosphate to the dihalogen monomer is from 1.5 to 2.5: 1.

According to some embodiments of the invention, the mass ratio of the sodium phosphate to the bisphenol monomer is 0.5-4.0:1, such as 0.6:1, 0.7:1, 0.9:1, 1.2:1, 1.4:1, 1.5:1, 1.7:1, 2.0:1, 2.1:1, 2.3:1, 2.5:1, 2.7:1, 2.9:1, 3.3:1, 3.6:1, 3.8:1 or any value therebetween. In some embodiments of the invention, the mass ratio of the sodium phosphate to the bisphenol monomer is 1.0-3.5: 1.

According to some embodiments of the invention, the reaction time of the polymerization reaction is from 1h to 10 h.

According to some embodiments of the invention, the polyaromatic ether comprises one or more of a polyaryl ether ketone, a polyaryl ether nitrile, and a polyetherimide.

According to some embodiments of the invention, the dihalogen monomer is selected from one or more of the following:

wherein, X is halogen or hydroxyl, preferably fluorine, chlorine or bromine. According to some embodiments of the invention, the dihalogen monomer is selected from one or more of the following:

according to some embodiments of the invention, the bisphenol monomer is selected from one or more of the following:

according to some embodiments of the invention, the solvent comprises one or more of N, N-dimethylformamide, N' -dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, N-butylpyrrolidone, 1, 3-dimethyl-2-imidazolidinone, sulfolane, diphenylsulfone, or dimethylsulfoxide.

Compared with the prior art, the invention has the following beneficial effects:

1. the preparation of polymers such as polyaryletherketone, polyarylethernitrile, polyetherimide and the like by anhydrous polymerization is realized, the use of a water separating agent is eliminated, and the solvent recovery process is simplified;

2. compared with potassium phosphate, sodium phosphate has less consumption and low cost.

Detailed Description

The present invention will be further illustrated by the following specific examples, but the scope of the present invention is not limited thereto.

The viscosity measurement method comprises the following steps:

1. 0.2g of the polymer was taken, 20ml of NMP (or 98% or 95% concentrated sulfuric acid) was added to the flask, stirred at room temperature, and the solubility was observed, and after complete dissolution, a filtration test was performed.

2. The clean and dry viscometer is placed vertically in a constant temperature water tank so that the pellet is completely immersed on the water surface. Pipette 10ml of the filtered solution (concentration c)₁). The B ball was injected from the tube 2, and the temperature was maintained in a thermostatic bath at 25 ℃ for 3 minutes, followed by measurement. A rubber tube is sleeved on the tube 1 and clamped by a clamp to prevent air from being ventilated. The solution is sucked from ball B into ball C through capillary and ball A by sucking ball in tube 3, then the sucking ball and rubber tube in tube 1 are released simultaneously, and tube 1 is vented to atmosphere. At which time liquid begins to flow back to ball B. The eye is used to watch the descending liquid level, and the time required for the liquid level to flow between the scale 1 and the scale 2 is accurately measured by a stopwatch and recorded. The above procedure was repeated twice, with each measurement differing by no more than 0.1 second. Taking the average value of two times as t₁I.e. the time of the solution flow.

3. The solution was diluted with 5ml of NMP (or 98% or 95% concentrated sulfuric acid) by pipette to obtain a diluted solution having a concentration c₂Is the initial concentration c₁2/3 according to the above procedure, the solution (concentration c)₂) Has an outflow time of t₂. Similarly, 5ml and 10ml of NMP (or 98% or 95% concentrated sulfuric acid) were added in this order to adjust the solution concentration to 1/2 and 1/3 (note that each time the pure solvent was added, the mixture was mixed uniformly and the temperature was kept constant, and then the flow time was measured and recorded.

4. Pouring the solution in the viscometer into a recovery bottle, washing and drying, sucking 10ml of pure NMP (or 98% or 95% concentrated sulfuric acid) solution by using a clean pipette, transferring the solution into the viscometer (paying attention to the fact that the solution is not attached to the wall of the tube as much as possible), keeping the temperature for 2 minutes, and measuring the outflow time t of the solution according to the steps₀。

5. The viscosity is calculated from the measured times.

Examples of the dihalogen monomer, the bisphenol monomer, the base and the solvent which are suitable for the production process of the present invention are shown in tables 1 to 4, respectively.

TABLE 1

TABLE 2

TABLE 3

(Code)	Structure of the product
		NaP	Na3PO4

TABLE 4

Example 1

Under nitrogen, HQ22.022g (200mmol), DFDPK43.640g (200mmol), NaP75.426g (460mmol) and SFL358g were charged into a 500mL four-port reaction flask. Heating to 270 ℃ under electric stirring, keeping for 1h5min, cooling, pouring into deionized water, and washing with deionized water under electromagnetic stirring at room temperature for 4 times. Then the mixture is put into a normal pressure oven to be dried for 4h at 120 ℃ and a vacuum oven to be dried overnight at 120 ℃ under the vacuum degree (less than-0.01 mPa), and finally the offwhite powder polymer is obtained, the yield is 96.0 percent, and the viscosity is 0.49dL/g (98 percent sulfuric acid).

Example 2

Under nitrogen protection, a 500mL four-neck reaction flask was charged with HQ11.011g (100mmol), DCBN17.201g (100mmol), NaP37.706g (230mmol), and SFL118 g. Heating to 250 ℃ under electric stirring, keeping for 4h, cooling, pouring into deionized water, and electromagnetically stirring and washing for 4 times at room temperature by using the deionized water. Then the mixture is put into a normal pressure oven to be dried for 4h at the temperature of 120 ℃ and dried overnight in a vacuum oven at the temperature of 120 ℃ under the vacuum degree (less than-0.01 mPa), and finally the offwhite powder polymer is obtained, the yield is 93.6 percent, and the viscosity is 0.06dL/g (98 percent sulfuric acid).

Example 3

Under nitrogen protection, a 500mL four-necked reaction flask was charged with BP14.897g (80mmol), DCBN13.761g (80mmol), NaP30.164g (184mmol) and SFL118 g. Heating to 250 ℃ under electric stirring, keeping for 4h, cooling, pouring into deionized water, and electromagnetically stirring and washing for 4 times at room temperature by using the deionized water. Then drying in a normal pressure oven at 120 ℃ for 4h and a vacuum oven at 120 ℃ overnight under a vacuum degree (less than-0.01 mPa) to obtain pink powder polymer with the yield of 97.8 percent and the viscosity of 0.19dL/g (NMP).

Example 4

Under nitrogen, a 500mL four-necked reaction flask was charged with DODPK17.138g (80mmol), DCBN13.761g (80mmol), NaP30.164g (184mmol), and SFL128 g. Heating to 250 ℃ under electric stirring, keeping for 4h, cooling, pouring into deionized water, and electromagnetically stirring and washing for 4 times at room temperature by using the deionized water. Then drying in a normal pressure oven at 120 ℃ for 4h and a vacuum oven at 120 ℃ overnight under a vacuum degree (less than-0.01 mPa) to obtain a brown powder polymer with a yield of 99.9% and a viscosity of 0.16dL/g (NMP).

Example 5

26DON16.017g (100mmol), DCBN17.201g (100mmol), NaP37.706g (230mmol) and SFL140g were added to a 500mL four-necked reaction flask under nitrogen protection. Heating to 250 ℃ under electric stirring, keeping for 4h, cooling, pouring into deionized water, and electromagnetically stirring and washing for 4 times at room temperature by using the deionized water. Then drying in a normal pressure oven at 120 ℃ for 4h and a vacuum oven at 120 ℃ overnight under a vacuum degree (less than-0.01 mPa) to obtain a brown powder polymer with a yield of 98.3 percent and insolubility in an organic solvent.

Example 6

Under nitrogen protection, a 500mL four-necked reaction flask was charged with BPA13.697g (60mmol), DCBN10.321g (60mmol), NaP22.624g (138mmol), and SFL101 g. Heating to 240 ℃ under electric stirring, keeping the temperature for 3h, cooling, pouring the mixture into deionized water, and electromagnetically stirring and washing the deionized water at room temperature for 4 times. Then the mixture is put into a normal pressure oven to be dried for 4h at the temperature of 120 ℃ and dried overnight in a vacuum oven at the temperature of 120 ℃ under the vacuum degree (less than-0.01 mPa), finally brown powder polymer is obtained, the yield is 96.0 percent, and the viscosity is 0.09dL/g (98 percent sulfuric acid).

Example 7

Under nitrogen protection, a 500mL four-necked reaction flask was charged with 26.202g (50mmol) of IM4 monomer, BPA11.300g (50mmol), NaP18.665g (114mmol), and SFL157 g. Heating to 230 ℃ under electric stirring, keeping for 6h, cooling, pouring into deionized water, and electromagnetically stirring and washing for 4 times at room temperature by using the deionized water. Then the mixture is put into a normal pressure oven to be dried for 4h at 120 ℃ and a vacuum oven to be dried overnight at 120 ℃ under the vacuum degree (less than-0.01 mPa), and finally the light yellow powder polymer is obtained, the yield is 91.9 percent, and the viscosity is 0.20dL/g (NMP).