WO2013037097A1

WO2013037097A1 - Method for preparing powder resin

Info

Publication number: WO2013037097A1
Application number: PCT/CN2011/002051
Authority: WO
Inventors: 饶先花; 曹民; 代惊奇; 苏成晓; 赵东辉; 曾祥斌; 刘奇祥; 蔡彤旻
Original assignee: 金发科技股份有限公司; 上海金发科技发展有限公司; 珠海万通化工有限公司
Priority date: 2011-09-14
Filing date: 2011-12-08
Publication date: 2013-03-21
Also published as: CN102352033A; CN102352033B

Abstract

A method for preparing powder resin is provided. The method comprises the following steps: (1) directly cooling a polymer precipitate obtained from a reaction system after performing polymerization reaction at a rate of 2-50℃/minute for 1-60 minutes to obtain polymer colloidal solution, wherein the solution is stirred increasingly and the stirring speed is 10-3000 rpm. (2) adding a certain amount of poor solvent to the mixture to form suspension mixture of the polymer product and the poor solvent when the temperature of the system is at 130-250℃. (3) centrifuging, filtrating or leaching the suspension polymer to remove mother liquid, and then filtrating, so as to obtain polymer crude product. (4) distilling and refining the polymer crude product in high temperature with solvent or boiling water to remove the salt and impurity in the polymer, and drying to obtain the product. The advantages of the method is obtaining size uniform polymer powder through process control, realizing rapid discharging, avoiding change of viscosity in discharging process, solving the problem of adhesion of reaction material to the wall of reaction vessel, and improving production efficiency.

Description

Method for preparing powder resin

Technical field

The present invention relates to a method of preparing a powdered resin, and more particularly to a method of preparing a high performance powdered resin.

Background technique

Many resins, such as polyaryl ether ketone resins, have the advantages of high temperature resistance, high strength, and radiation resistance, because the polymerization temperature is often

More than 300 ,, high-temperature solvents such as diphenyl sulfone are required, and other solvents cannot be adapted. Regardless of the solvent used for the synthesis, the reaction product needs to be washed and separated after the end of the polycondensation reaction, and the reaction solvent, inorganic salt, residual monomer and other compounds are removed therefrom. Among them, the most difficult to remove are alkali metal halides, alkaline earth metal halides. The presence of high levels of by-products or solvents in the polymer can cause technical defects in the final product in the formation of various extrusion molded parts, such as high levels of by-products or solvents forming streaks on the surface, causing odors, resulting in bubbles and materials. The mechanical properties are reduced. In addition, certain by-products are potentially toxic and may cause health damage. For these reasons, volatile components in the polymer are usually removed to a residual content of less than 0.1%, and in some cases, removed. To the residual content in the ppm range, post-treatment usually requires very much time and a large amount of solvent wash.

The improvement of the product post-treatment process mainly includes the following aspects: 1. The polymer can be washed by a suitable solvent, or can be washed by increasing temperature and pressure (WO 02/096974, CN 200510082627.7); 2. Separation of the inorganic salt by filtration prior to solidification of the reaction mixture (US Pat. No. 5,357,040, US Pat. No. 5,288,834, EP-A-0297,363), however, a large amount of the reaction solvent is required due to the low viscosity required thereof, and the above solvent must be removed expensively; 3. Removal of the reaction solvent by spray drying (DE-A-4301543) It is also very expensive to completely remove the solvent by evaporation; 4. The other one is degassed through the extruder, but cannot completely remove the reaction. Solvent, and at 350 ° C ~ 42 (TC's conventional processing temperature, the residence time required for degassing in the extruder is too long, causing the polymer to be thermally damaged.

Chinese Patent No. 200610005142.2 discloses a wet pulverization process in which the reaction mixture is pulverized by wet pulverization, and then the wet pulverized product is extracted and filtered by a pressure extractor. This post-treatment method still has problems such as pulverization or grinding, transfer of the material to the grinder, transfer from the grinder to the washing vessel, and further transfer to the dryer, such as high cost, product loss and contamination. Moreover, such post-processing steps in which the equipment and space are separated from each other are at risk of forming a dangerous dust-air mixture from the dry components of the reactor effluent, posing an unnecessary explosion hazard. Most of these processes are used in the production.

How to control the post-treatment process conditions, avoid the polymer pulverization process, and achieve the controllable particle size while at the same time High cooking efficiency and improved product quality have become an important research goal. The original resin post-treatment process has the disadvantages of large energy consumption and poor treatment effect. Summary of the invention

SUMMARY OF THE INVENTION An object of the present invention is to provide a post-treatment method which provides high production efficiency, energy saving, and low production cost, and obtains a resin powder of a specific particle size by controlling a post-treatment process.

The post-treatment process for preparing the resin powder of the present invention comprises the following steps: (1) firstly, the temperature is directly lowered after the end of the polymerization reaction, and the polymer is precipitated and precipitated from the reaction system to obtain a polymer colloidal liquid; the cooling rate is preferably 2 to 50. °C /min, cooling time is l~60mi. Increase the stirring speed to make the polymer colloidal liquid evenly dispersed. The stirring speed is preferably 10~3000 rev / mm; (2) When the system is cooled to 130~250 °C, Adding a certain amount of poor solvent to the mixture, so that the polymerization product system forms a suspension liquid mixture with the poor solvent; (3) separating the suspension solid-liquid to obtain the desired crude polymer product; (4) refining the crude product, dry. .

The high performance resin comprises polyaryletherketones, polyarylene ethers, polysulfones or liquid crystal polyesters; the solvent used for the polymerization is diphenyl sulfone, dimethyl sulfoxide, dimethyl sulfone, diethyl A mixture of one or more of sulfone, diethyl sulfoxide, diisopropyl sulfone, diphenyl sulfone, butyl sulfone or tetramethyl sulfone, and the solid content of the reaction system is 5% to 60% by weight.

The post-treatment process for preparing the resin powder wood adopts a cooling process, the cooling rate is 2~50 ° C / _m in , more preferably 5~30 ° C , and the temperature is lowered to 130~25 (TC, the cooling time is l~60mi n. The cooling method adopts air-cooling and water-cooling, and it is also possible to adopt the method of inputting the external cold oil cooling method in the jacketed jacket hot oil.

In the post-treatment process for preparing the resin powder, the poor solvent added to the system is water, ethanol, acetone, xylene, toluene or sulfolane, and the volume ratio of the solvent to the solvent used for the polymerization is 1:2 to 3:1. Preferably it is 1: 1 to 2: 1.

The polymerization stirring paddle is anchor type, paddle type, turbine type, push type, frame type, scraping wall type, high shear type, disc type, toothed type, ribbon type stirring slurry, planetary stirring paddle, Or multi-layered paddles, the blades of the paddle are double-leaf, multi-bladed, flat, folded, curved, or a combination of different types of mixing paddles.

The stirring speed range of the polymerization reaction before cooling is 10~1000 rev / min, and the stirring speed range during the post-treatment is 10-3000 rpm / mi. More preferably, the stirring speed is higher than the polymerization reaction speed in the post-treatment process.

The crude polymer product is removed by centrifugation, filtration or leaching, and the crude product is heated in boiling water or solvent. The salt and impurities are extracted and purified multiple times at a high temperature, and dried to obtain a product. The obtained resin powder has a uniform particle size distribution and a particle size of 50 to 500 μm.

The method for preparing a powdered resin according to the present invention has the following advantages:

1) The original pulverization process is that the polymer is precipitated by external cooling in a large amount of water, and the crude product is porous, which contains a lot of solvent, needs to be treated with a large amount of water, and the obtained product has a small bulk density; and in the process of the present invention The polymer naturally precipitates from the solution, and the product has a high bulk density. The amount of water or solvent is controllable during the discharge process. The concentration of the solvent in the mother liquor after filtration is high, which greatly reduces the waste of the solvent, saves energy, and can also greatly Improve cooking efficiency;

2) The pulverization step is reduced, thereby avoiding problems such as introduction of iron impurities in the pulverization process, generation of a large amount of smoke in the pulverization process, and generation of a large amount of noise in the pulverizer, which can greatly improve the workshop environment; all the polymers in the reaction vessel are precipitated and precipitated directly. Rinsing with water avoids the residue of the product in the reactor, and avoids a lot of cumbersome work of cleaning the reactor after multiple polymerizations;

3) The post-treatment time is short, and the viscosity of the polymer changes little during the post-treatment, which improves the uniformity of the product;

4) The solid content in the original process can not exceed 15%, otherwise the polymer can not be smoothly discharged from the reactor due to the high viscosity of the product, and the solid content of the polymer in the process of the invention is greatly improved, up to 60%, Will affect the discharge, so the amount of solvent used is small, thereby further achieving the goal of cost saving; 'Therefore, the discharging process of the invention not only greatly improves the production efficiency, improves the yield, improves the quality of the product, and saves The energy consumption, the production cost is reduced, and the workshop environment is improved, which has a multifaceted effect. DRAWINGS

1 is a microscopic enlarged picture of a product of a resin powder post-treatment process of the present invention;

2 is a microscopic enlarged picture of product particles of a resin powder post-treatment process of the prior art. detailed description

The invention is further described in the following examples, but these examples are not intended to limit the invention.

Example 1 (solid content about 15%) Aggregation process:

In a four-reactor equipped with a thermometer, a nitrogen gas tube, a condensing water separator, and an anchor stirrer, 50 Kg of purified sulfolane was added, followed by 6.67 Kg of 4,4 '-difluorobenzophenone and 3.303 Kg. Hydroquinone, when it is completely dissolved and when the temperature is raised to 80 ° C, add 3.498Kg (2% excess) of Na ₂ C0 ₃ , then add 2Kg of xylene, stir, heat, and wait for the temperature to rise to 15 (TC The system begins to azeotrope. The water separator is filled with xylene and water. The upper layer of xylene is refluxed. The lower layer of water is continuously released. When the water is recovered to the theoretical amount, the upper layer of xylene begins to clarify and transparent, and then the reflux is continued for 20 minutes. The xylene was distilled from the system, and the temperature of the system was continuously increased by heating until the temperature reached 263 265 ,. The temperature was kept constant, and the viscosity of the system increased with the polymerization reaction. After 1.5 hours, the viscosity reached a stable value and then stopped. At this time, the stirring speed was 50 rpm.

Discharge process:

Stop heating, use cooling oil to the reaction heating oil furnace to cool down, the cooling rate is 5O / min, the liquid in the reactor gradually precipitates out, slowly becomes gelatinous, increase the stirring force, the stirring speed is adjusted to 100 rpm /min, the stirring paddle produces a high shearing force, disperses the gel so as not to agglomerate, and cools to 130 ° C to add 25 L of water to the reaction vessel, and the solution gradually becomes a suspension.

The suspension was discharged and centrifuged. The discharge process is 30 minutes. The test solution had a sulfolane content of 70%. The boiled polymer was used for 5 times, each time with 300 L of deionized water, and each boiling time was 40 minutes, and the F ion content in the test solution was 0.2 mg/L, indicating that the product was refined. Dry, test product performance. The intrinsic viscosity of the sample was measured by a viscometer to be 0. 72 dl/g. The measured product fusion was 100 g/10 min. The measured particle size distribution D50 was 200 um.

Example 2 (solid content about 30%)

Aggregation process:

In a four-reactor equipped with a thermometer, a nitrogen gas tube, a condensing water separator, and a paddle stirrer, 20 kg of purified sulfolane was added, followed by 6.67 Kg of 4,4 '-difluorobenzophenone and 3.303. Kg hydroquinone (available polymer 8.64Kg, solid content is about 30%), when it is completely dissolved and when the temperature rises to 80 ° C, add 3.498g (2% excess) Na ₂ C0 ₃ , and then continue After heating, add 2Kg of xylene, stir and heat. When the temperature rises to 150 °C, the system begins to azeotrope. The water separator is filled with xylene and water. The upper layer of xylene is refluxed. The lower layer of water is continuously released. At the theoretical amount, the upper layer of xylene began to clarify and transparent, and then continued to reflux for 20 minutes, then began to distill xylene from the system, the temperature of the system was not heated. After the temperature rises to 260~262°C, the temperature is kept constant, and the viscosity of the system increases with the polymerization reaction. After 5 hours, the reaction stops after the viscosity reaches a stable value. At this time, the stirring paddle speed is 80 rpm. /min.

Discharge process:

Stop heating, add cooling oil to the reaction heating oil furnace to cool down, the cooling rate is 20 °C / min, the liquid in the reactor gradually precipitates out, slowly becomes gelatinous, increase the stirring force, the stirring paddle speed is adjusted 220 rpm, the stirring paddle produces high shear force, the gel is dispersed so as not to agglomerate, the temperature is lowered to 180 ° C, water is added to the reaction vessel (about 30 L), and the solution gradually becomes a suspension.

The suspension was discharged and centrifuged. The discharge process is 6 minutes. The test solution had a cyclobutane content of 58%. The boiled polymer was boiled 6 times, using 300 L of deionized water each time, and boiled for 40 minutes each time. The F ion content in the test solution was 0.3 mg/L, and the product was refined. Dry, test product performance. Sampling with a viscometer to test the intrinsic viscosity of 0. 85dl / g,

71g/10min„ The test particle size distribution D50 is 300um.

Example 3 (solid content about 15%)

Aggregation process:

In a four-reactor equipped with a thermometer, a nitrogen gas tube, a condensing water separator, and a propeller stirrer, 50 Kg of purified sulfolane was added, followed by 6.67 Kg of 4,4'-difluorobenzophenone and 3.303 Kg. Hydroquinone (available polymer 8.64Kg, solid content about 15 ° /.), when it is completely dissolved and when the temperature rises to 80 ° C, add 3.498Kg (2% excess) Na ₂ C0 ₃ , then Continue to heat up, add 2Kg of xylene, stir, heat, wait for the temperature to rise to 150 ° C, the system begins to azeotrope, the water separator has xylene and water condensation, the upper layer of xylene reflux, the lower layer of water is continuously released, waiting for water When the theoretical amount is recovered, the upper layer of xylene begins to clarify and transparent, and the reflux is continued for another 20 minutes. Then, xylene is distilled off from the system, and the temperature of the system is continuously increased by heating until the temperature reaches 263 ° C, and the temperature is kept constant. The polymerization was carried out to increase the viscosity and continued for 1 hour and 40 minutes, and the reaction was stopped after the viscosity reached a stable value. At this time, the stirring paddle speed was 200 rpm.

Discharge process:

Stop heating, add cooling oil to the reaction heating oil furnace to cool down, the cooling rate is 30 °C / min, the liquid in the reactor gradually precipitates out, slowly becomes gelatinous, increase the stirring force, and the stirring paddle speed is adjusted to At 500 rpm, the stirring paddle produced a high shearing force. The gel was dispersed so as not to agglomerate, and the temperature was lowered to 240 ° C. 50 L of sulfolane was added to the reaction vessel, and the solution gradually became a suspension. The suspension was discharged, centrifuged, and discharged for 4 minutes. The content of sulfolane in the mother liquor was 99%. The boiled polymer was boiled 5 times, each time with 300 L of deionized water, and each boiling time was 40 minutes, and the F ion content in the test solution was 0.35 mg/L, and the product was refined. Dry and test product performance. The intrinsic viscosity is 0.9 dl/g, and the melting index is 45 g/10 m _in . The D50 is 150.um. Example 4 (solid content about 26%)

Aggregation process:

In a four-reactor containing a thermometer, a nitrogen gas line, a condensing water separator, and a powerful combination stirrer, 25 kg of purified sulfolane was added, followed by 6.67 g of 4,4 '-difluorobenzophenone and 3.303 g. Hydroquinone (available polymer 8.64g, solid content of about 26%), when it is completely dissolved and when the temperature rises to 80 ,, 3.5Kg (2% excess) of Na ₂ C0 _{3 is added} , and then the temperature is raised again. After adding 4L of xylene, stir and heat, until the temperature rises to 150 Γ, the system begins to azeotrope, the xylene and water in the water separator are condensed, the upper layer of xylene is refluxed, and the lower layer of water is continuously released. When the water is recovered to the theoretical amount, The upper layer of xylene began to clarify and transparent, and then continued to reflux for 20 minutes, and then began to distill xylene from the system. The temperature of the system was continuously increased by heating, and after the temperature reached 265 ° C, the temperature was kept constant, and the viscosity of the system increased with the polymerization reaction. Large, after the viscosity reached a stable value after 2 hours, the reaction was stopped, and the stirring paddle speed was 95 rpm.

Discharge process:

Stop heating, add cooling oil to the reaction oil bath jacket, the cooling rate is 48 ° C / min, the liquid in the reactor gradually precipitates, slowly becomes gelatinous, increase the stirring force, the stirring paddle speed is adjusted to 100 rpm /min, the stirring paddle produces a high shearing force, disperses the gel so as not to agglomerate, lowers the temperature to 200 ° C, adds 59 L of sulfolane to the reaction vessel, and the solution gradually becomes a suspension.

The suspended matter was discharged, centrifuged, and discharged for 5 minutes, and the content of the sulfolane in the mother liquor was 100%. The boiled polymer was boiled 5 times, each time with 300 L of deionized water, each boiling time was 40 minutes, and the F ion content in the test solution was 0.35 rag/L, and the product was refined. Dry, test product performance. The viscosity of the test product was 1. 0 dl/g. The melting index is 16g/10min, and the product particle size distribution D50 is 250um.

Example 5 (solid content about 15%)

Aggregation process:

In a four-reactor equipped with a thermometer, a nitrogen gas tube, a condensing water separator, and a two-layer three-bladed propeller stirrer, 50 Kg of purified sulfolane was added, followed by 6.67 Kg of 4, 4 '-difluorodiphenyl. Ketone and 3.303Kg hydroquinone (can The polymer obtained was 8.64 Kg and the solid content was about 15%. When it was completely dissolved and the temperature was raised to 80 ° C, 3.398 Kg (2% excess) of Na ₂ C0 ₃ was added, and the temperature was further increased, and then 2 Kg of xylene was added. After stirring, heating, until the temperature rises to 150 ° C, the system begins to azeotrope, the water separator is condensed with xylene and water, the upper layer of xylene is refluxed, and the lower layer of water is continuously released. When the water is recovered to the theoretical amount, the upper layer is The toluene began to clarify and transparent, and then continued to reflux for 20 minutes, and then began to distill xylene from the system. The temperature of the system was raised from heating to a temperature of 267 to 27 (after TC, the temperature was kept constant, and the viscosity of the system increased with the polymerization reaction. Large, stop the reaction after the viscosity reaches a stable value, at which time the stirring paddle speed is 150 rpm / mir!

Discharge process:

Stop heating, use a powerful fan to cool down, the cooling rate is 4 °C / min, the liquid in the reactor gradually precipitates out, slowly becomes gelatinous, increase the stirring force, adjust the stirring paddle speed to 400 rpm, stir paddle Producing a high shearing force, the gel was dispersed so as not to agglomerate, and the temperature was lowered to 130 ° C, and 50 L of ethanol was added to the reaction vessel, and the solution gradually became a suspension.

The suspension was discharged and centrifuged. The discharge process is 55 minutes. The content of sulfolane in the mother liquor was 45%, and each time 300 L of deionized water was used, the boiling time was 40 minutes each time, and the boiling time was 5 times. The F ion content in the test solution was 0.4 mg/L, indicating that the product was refined. Drying, test product performance, test viscosity was 0.95 dl / g, melting index test, 30 g / 10 min, particle size distribution D50 was 180 um.

Example 6 (solid content about 30%)

Aggregation process:

In a four-reactor containing a thermometer, a nitrogen gas line, a condensing water separator, and a dual planetary agitator, 20 kg of purified sulfolane was added, followed by 6.67 Kg of 4,4 '-difluorobenzophenone and 3.303 Kg. Hydroquinone (available polymer 8.64Kg, solid content about 30%), when it is completely dissolved and when the temperature rises to 80Ό, add 3.498Kg (2% excess) Na ₂ C0 ₃ , and then continue to heat up, then After adding 2Kg of xylene, stir and heat, until the temperature rises to 150 °C, the system begins to azeotrope, the xylene and water in the water separator are condensed, the upper layer of xylene is refluxed, the lower layer of water is continuously released, and the water is recovered to the theoretical amount. At the same time, the upper layer of xylene began to clarify and transparent, and then continued to reflux for 20 minutes, and then began to distill out xylene from the system. The temperature of the system was continuously increased by heating until the temperature reached 267 ° C, and the temperature was kept constant. Increasingly, the reaction is stopped after the viscosity reaches a stable value, at which time the stirring paddle speed is 40 rpm / π ΰ η.

Discharge process:

Stop heating, add cooling oil to the reaction heating oil furnace to cool down, the cooling rate is 25 °C / min, the liquid in the reaction kettle Gradual precipitation, slowly become gelatinous, increase the stirring force, stir the paddle speed to 50 rev / min, the stirring paddle produces high shear force, the gel is dispersed, so that it does not become agglomerate, cooling At 130 ° C, 30 L of ethanol was added to the reaction vessel, and the solution gradually became a suspension.

The suspension was discharged, centrifuged, and discharged for 10 minutes. The mother liquor had a cyclobutane content of 46%. Each time 300L of water was used, each boiling time was 40 minutes, and the material was boiled 4 times. The F ion content in the test solution was 0.2 mg/L, and the product was refined. Dry the product and test the product properties. The logarithmic ratio viscosity was 1. 02 dl/g, the melting index was 14 g/10 min, and the particle size distribution D50 was 270 um. Example 7 (solid content about 30%)

Aggregation process:

In a four-reactor equipped with a thermometer, a nitrogen gas tube, a condensing water separator, and a four-layer paddle stirrer, 20 Kg of purified sulfolane was added, followed by 6.67 Kg of 4,4 '-difluorobenzophenone. 3.303Kg hydroquinone (available polymer 8.64Kg: solid content is about 30%), when it is completely dissolved and when the temperature rises to 80Ό, add 3.498Kg (2% excess) Na ₂ C0 ₃ and continue to heat up. After adding 2Kg of xylene, stir and heat, until the temperature rises to 150 °C, the system begins to azeotrope, the xylene and water in the water separator are condensed, the upper layer of xylene is refluxed, the lower layer of water is continuously released, and the water is recovered. In the theoretical amount, the upper layer of xylene began to clarify and transparent, and then continued to reflux for 20 minutes, and then began to distill xylene from the system. The temperature of the system was continuously increased by heating until the temperature reached 265 Torr, and the temperature was kept constant. Increasingly, the reaction is stopped after the viscosity reaches a stable value, at which time the stirring paddle speed is 95 rpm.

Discharge process:

Stop heating, add cooling oil to the reaction heating oil furnace, the cooling rate is 30 ° C / min, the liquid in the reactor gradually precipitates, slowly becomes gelatinous, increase the stirring force, the stirring speed becomes 100 rpm Anin, the stirring paddle produces a high shearing force, disperses the gel so as not to agglomerate, lowers the temperature to 180 ° C, adds 30 L of xylene to the reaction vessel, and the solution gradually becomes a suspension.

The suspension was discharged, centrifuged, and discharged for 5 minutes. The content of sulfolane in the mother liquor was 50%. Each time 300L of water, each boiling time of 40 minutes, boiled 5 times, the F ion content of the test solution was 0. 2 mg / L, the product was refined. Dry, test product performance. 2dl/克。 The measured logarithmic viscosity is 1. 2dl / g. Test melting index is 9g/10 _m in, test product particle size

D50 is 200uni o

Example 8 (solid content about 37%) Aggregation process:

In a four-reactor equipped with a thermometer, a nitrogen gas line, a condensate trap, a paddle and a turbo combination stirrer, 15 kg of purified sulfolane was added, followed by 6.67 kg of 4,4 '-difluorobenzonitrile. Ketone and 3.303Kg hydroquinone (available polymer 8.64Kg, solid content about 37%), when it is completely dissolved and when the temperature rises to 80 ° C, add 3.498Kg (2% excess) Na ₂ C0 ₃ Then continue to heat up, add 2Kg of xylene, stir, heat, wait for the temperature to rise to 150 ° C, the system begins to azeotrope, the water separator is condensed with xylene and water, the upper layer of xylene reflux, the lower layer of water is continuously released, When the water is recovered to the theoretical amount, the upper layer of xylene begins to clarify and transparent, and then the reflux is continued for 20 minutes. Then, xylene is distilled off from the system, and the temperature of the system is continuously increased by heating until the temperature reaches 267 ° C, and the temperature is kept constant. The viscosity increases with the polymerization reaction. After 1 hour, the reaction is stopped after the viscosity reaches a stable value. At this time, the stirring paddle speed is 110 rpm/mir! .

Discharge process:

Stop heating, add cooling oil to the reaction heating oil furnace to cool down, the cooling rate is 20 °C / niin, the liquid in the reactor gradually precipitates, slowly becomes gelatinous, increase the stirring force, the stirring paddle speed adjustment The high-shear force was generated for the 280 rpm stirring blade, the gel was dispersed so as not to agglomerate, the temperature was lowered to 160 ° C, and 35 L of xylene was added to the reaction vessel, and the solution gradually became a suspension.

The suspension was discharged, centrifuged, and discharged for 9 minutes. The content of sulfolane in the mother liquor was 23%. The polymer was boiled 6 times, each time with 300 L of deionized water, each time boiled for 40 minutes, the F ion content of the test solution was 0.2 mg/L, indicating that the product was refined. Dry, test product performance. The test viscosity was 0.8 dl / g. The product fusion was 85 g/10 min. The particle size distribution D50 is 350um.

Example 9 (solid content about 40%)

Aggregation process:

In a four-reactor equipped with a thermometer, a nitrogen gas tube, a condensing water separator, and a toothed impeller stirrer, 13 Kg of purified sulfolane was added, followed by 6.67 Kg of 4,4 '-difluorobenzophenone and 3.303Kg hydroquinone (available polymer 8.64Kg, solid content is about 40%), when it is completely dissolved and when the temperature rises to 80 ° C, add 3.498Kg (2% excess) Na ₂ C0 ₃ , then Continue to heat up, add 2Kg of xylene, stir, heat, wait for the temperature to rise to 150'C, the system begins to azeotrope, the water separator has xylene and water condensation, the upper layer of xylene reflux, the lower layer of water is continuously released, waiting for water When the theoretical amount is recovered, the upper layer of xylene begins to clarify and transparent, and the reflux is continued for another 20 minutes. Then, xylene is distilled off from the system, and the temperature of the system is increased. The heat is continuously rising, and after the temperature reaches 260 ,, the temperature is kept constant, and the viscosity of the system increases with the polymerization reaction. After 1 hour, the reaction is stopped after the viscosity reaches a stable value. At this point the stirrer speed is 800 rpm / _m in.

Discharge process:

Stop heating, add cooling hot oil to the heating oil furnace, the cooling rate in the kettle is about 15 °C / min, the liquid in the reactor gradually precipitates out, slowly becomes gelatinous, increase the stirring force, and the stirring paddle speed is adjusted to 2800 rpm / miri. The stirring paddle produces a high shearing force. The gel is dispersed so as not to agglomerate, the temperature is lowered to 20 CTC, and 20 L of water is added to the reaction vessel, and the solution is gradually changed into a suspension.

The 'suspension was released and centrifuged. The discharge process is 12 minutes. The content of sulfolane in the mother liquor was 45%. The polymer was boiled 4 times with 300 L, and the F ion content in the solution was detected as O mg/L, indicating that the product was purified. Dry, test product performance. The sample has an intrinsic viscosity of 0.65 dl/g. The product melt was 150 g/10 min and the test particle size distribution D50 was 50 um.

Example 10 (solid content about 30%)

Aggregation process:

In a four-port reactor equipped with a thermometer, a nitrogen gas tube, a condenser tube, and a frame stirrer, high-purity nitrogen gas was introduced, and 5 kg of purified diphenyl sulfone was added, and after heating and dissolved, 1.72 K _g 4 was sequentially added. 4 difluorobenzophenone, 726g biphenyldiol and 426g hydroquinone, of which 4,4 '-difluorobenzophenone / (hydroquinone + biphenyldiol) = 1: 1 (molar ratio ), after each addition, it needs to be dissolved before adding a substance; the pre-dried anhydrous sodium carbonate is crushed and sieved, accurately weigh 954g of powdered sodium carbonate and quickly added to the reaction system, continue at 15 (TC) After stirring for 30 minutes, the phenol in the system reacts with sodium carbonate to form a sodium salt, and then the reaction temperature is raised to 190 ° C, and the resulting sodium salt is then polymerized with 4,4'-difluorobenzophenone, reaction 30 After a minute, the temperature of the reaction system was raised to 300 ° C in 10 minutes, the reaction rate was increased, and the viscosity was increased. After the reaction for 1 hour, when the viscosity of the system did not change much, the reaction temperature was raised to 325 ° C. 10 g of hydroquinone was added to the reaction system, and the viscosity of the reaction system increased rapidly. While increasing the stirring speed, the heating was stopped after 1.5 hours. At this time the agitator speed 85 rpm / min.

Discharge process:

Stop heating, add cooling oil to the reaction heating oil furnace, and blow the reaction kettle with a powerful fan. The liquid cooling rate in the reactor is about 25 ° C / min, gradually precipitates, gradually becomes gelatinous, and the stirring is increased. Strength, the speed of the stirrer is adjusted to '95 rpm, the stirring paddle produces high shear force, the gel is dispersed, so that it does not become agglomerate, and the temperature is lowered to 13 (TC, direction 20 L of ethanol was added to the reaction vessel, and the solution gradually became a suspension.

The suspension was discharged and centrifuged. The discharge process is 12 minutes. The mother liquor contained 20% diphenyl sulfone, the polymer was boiled with 100 L of ethanol for 4 times, and the polymer was boiled with 300 L of water for 6 times. The F ion content in the solution was found to be 0 mg/L, indicating that the product was finished. Dry, test product performance. The intrinsic viscosity of the sample was 0.75 dl/g. The melting index test was 15g/min. Test particle size distribution D50 is 500

Example 11 (solid content about 5%)

Aggregation process:

In a four-port reactor equipped with a thermometer, a nitrogen gas tube, a condenser tube, and a frame stirrer, high-purity nitrogen gas was introduced, and 30 kg of purified diphenyl sulfone was added first. After heating and dissolving, 1.72 Kg 4 4 '- was sequentially added. Difluorobenzophenone, 726g of biphenyldiol and 426g of hydroquinone, of which 4,4'-difluorobenzophenone / (hydroquinone + biphenyldiol) = 1: 1 (molar ratio) After each feeding, it needs to be dissolved before adding a substance; the pre-dried anhydrous sodium carbonate is crushed and sieved, and 954 g of powdered sodium carbonate is accurately weighed and quickly added to the reaction system at 150-160 ° C. Stirring is continued for 30-50 minutes, the phenol in the system is reacted with sodium carbonate to form a sodium salt, and then the reaction temperature is raised to 190 Torr, and the resulting sodium salt is then polymerized with 4,4'-difluorobenzophenone. After the reaction for 30 minutes, the temperature of the reaction system was raised to 300 Torr in 10 minutes, the reaction rate was increased, and the viscosity was increased. After the reaction for 1 hour, when the viscosity of the system did not change much, the reaction temperature was raised to 325 Torr, and then the reaction was further carried out. 10 g of hydroquinone was added to the system again, the reaction body The viscosity increased rapidly, and the stirring speed was increased, and the heating was stopped after 1.5 hours of reaction. At this time, the stirrer speed is 12 rpm

Discharge process:

Stop heating, add cooling oil to the reaction heating oil furnace, and blow the reaction kettle with a powerful fan. The liquid cooling rate in the reactor is about 2 (TC/min, gradually precipitates, gradually becomes gelatinous, and the stirring is increased. Strength, the stirrer speed is adjusted to 40 rev / min, the stirring paddle produces high shear force, the gel is dispersed, so as not to agglomerate, the temperature is lowered to 180 ° C, and 40 ml of xylene is added to the reaction kettle. Gradually become a suspended matter.

The suspension was discharged and centrifuged. The discharge process is 10 minutes. The mother liquor contained 20% diphenyl sulfone, the polymer was boiled with 300 L of ethanol for 6 times, and the polymer was boiled for 5 times with 300 L of water. The F ion content in the solution was 0 mg/L, indicating that the product was purified. Dry, test product performance. The sample has an intrinsic viscosity of 0.776 dl/g. The fusion index is 14g/ _m in. Test particle size distribution D50 is 250um Example 12 (solid content about 30%)

Aggregation process:

In a four-reactor equipped with a thermometer, a nitrogen gas line, a condensing water separator, and a paddle stirrer, 32.5 Kg of purified sulfolane was added, followed by 8.61 Kg of 4,4 '-dichlorodiphenyl sulfone and 7.5 Kg4. , 4 '-dihydroxydiphenyl sulfone (available polymer 13.92Kg, solid content is about 30%), when it is completely dissolved and when the temperature rises to 80 ° C, add 3.498Kg (2% excess) Na ₂ C0 ₃ , continue to heat up, add 2Kg of xylene, stir, heat, until the temperature rises to 150 Ό, the system begins to azeotrope, the water separator is condensed with xylene and water, the upper layer of xylene is refluxed, the lower layer of water is continuously released, waiting When the water is recovered to the theoretical amount, the upper layer of xylene begins to clarify and transparent, and the reflux is continued for another 20 minutes. Then, xylene is distilled off from the system, and the temperature of the system is continuously increased by heating until the temperature reaches 240 ,, and the temperature is kept constant. viscosity increasing reaction, after 1 hour, until the viscosity reaches a steady value after the reaction was stopped at this time the agitator speed of 95 revolutions / _m in.

Discharge process:

Stop heating, add cooling oil to the reaction heating oil furnace, the cooling rate is 30 ° C / min, the liquid in the reaction kettle gradually precipitates out, slowly becomes gelatinous, increase the stirring force, the stirrer speed is 100 rpm /min, the stirring paddle produces a high shearing force, disperses the gel so as not to agglomerate, and adds 40 L of xylene to the reaction vessel, and the solution gradually becomes a suspension.

The amount of F ion in the test solution is 0. 2 mg / L, the amount of F ion in the test solution is 0. 2 mg / L, the amount of F ion in the test solution is 0. 2 mg / L, The product is refined. Dry, test product performance. The particle size test distribution D50 is 400TM. The sample has an intrinsic viscosity of 0.85 dl/g. The melting index test was 25g/10min.

(The melt test conditions are 370 Ό, 5Kg pressure.)

Example 13 (solid content about 60%)

Aggregation process:

In a four-reactor containing a thermometer, a nitrogen gas tube, a condensing water separator, and a paddle stirrer, 9 kg of purified sulfolane was added, followed by 8.61 kg of 4,4 dichlorodiphenyl sulfone and 7.5 kg. , 4 '-dihydroxydiphenyl sulfone (available polymer 13.92K _g , solid content of about 60%), when it is completely dissolved and when the temperature rises to 80 ° C, add 3.498g (2% excess) Na ₂ C0 ₃ , continue to heat up, add 2Kg of xylene, stir, heat, wait for the temperature to rise to 150 ° C, the system begins to azeotrope, the water separator has xylene and water condensation, the upper layer of xylene reflux, the lower layer of water Release, when the water is recovered to the theoretical amount, the upper layer of xylene begins to clarify and transparent, and then continue to reflux for 20 minutes, then start to distill xylene from the system, and the temperature of the system is increased. The heat is continuously rising until the temperature reaches 24 (TC, the temperature is kept constant, and the viscosity of the system increases with the polymerization reaction. After 1 hour, the reaction is stopped after the viscosity reaches a stable value, and the speed of the stirrer is 95 rpm.

Discharge process:

Stop heating, add cooling oil to the reaction heating oil furnace, the cooling rate is 25 °C / min, the liquid in the reaction kettle gradually precipitates out, slowly becomes gelatinous, increase the stirring force, the stirrer speed is 100 rpm /min, the stirring paddle produces a high shearing force, disperses the gel so that it does not agglomerate, cools to 130 Ό, and adds 20 L of acetone to the reaction vessel, and the solution gradually becomes a suspension.

The suspension was discharged, centrifuged, and discharged for 10 minutes. The content of sulfolane in the mother liquor was 30%. The polymer was boiled for 6 times with a water consumption of about 300 L each time, and the F ion content in the test solution was 0.2 mg/L, and the product was purified. Drying, test product performance, particle size test distribution D50 is 500um, sample intrinsic viscosity is 0. 88dl / g. The melt refers to 22g/10rain. (The test conditions for the fusion test are 370 ° C, 5 Kg pressure.)

Example 14 (solid content about 27%)

Aggregation process:

In a four-reactor equipped with a thermometer, a nitrogen gas line, a condensing water separator, and an anchor stirrer, 32.5 Kg of purified sulfolane was added, followed by 8.61 Kg of 4,4 '-dichlorodiphenyl sulfone and 5.58 Kg4. , 4 '-biphenyldiol (available polymer 12Kg, solid content of about 27%), until it is completely dissolved and when the temperature rises to 80 ° C, add 3.498Kg (2% excess) Na ₂ C0 ₃ , Continue to heat up, add 2Kg of xylene, stir, heat, wait for the temperature to rise to 150 ° C, the system begins to azeotrope, the water separator is condensed with xylene and water, the upper layer of xylene reflux, the lower layer of water is continuously released, waiting When the water is recovered to the theoretical amount, the upper layer of xylene begins to clarify and transparent, and the reflux is continued for another 20 minutes. Then, xylene is distilled off from the system, and the temperature of the system is continuously increased by heating until the temperature reaches 240 ,, and the temperature is kept constant. The viscosity of the reaction was continuously increased. After 1 hour, the reaction was stopped after the viscosity reached a stable value, and the stirring paddle rotation speed was 75 rpm.

Discharge process:

Stop heating, add cooling oil to the reaction heating oil furnace, the cooling rate is 15'C/min, the liquid in the reactor gradually precipitates out, slowly becomes gelatinous, and the stirring speed is increased. The stirring paddle speed is 85 rpm. /min, the stirring paddle produces a high shearing force, the gel is dispersed so as not to agglomerate, 30 L of xylene is added to the reaction vessel, and the solution gradually becomes a suspension. ' Release the suspension and centrifuge. The discharge process is 8 minutes. Sampling separately before and after discharge, testing the number of product viscosities According to respectively, it is 0. 80 dl/g, the content of cyclobutane in the mother liquor is 30%, and the polymer is boiled 5 times with 300 L of water. The F ion content in the detection solution is 0.3 mg/L, indicating that the product is refined. Dry the product and test the product properties. The particle size test distribution D50 is 450 _um . The intrinsic viscosity of the test sample was 0.80 dl/g, and the test melt was 36 g/min at 370 ° C and 5 Kg.

The above examples are merely illustrative of some of the reaction examples, including but not limited to.

Comparative example 1

The polymerization method was the same as in Example 1, except that the discharge was carried out in the following manner. The polymer mucilage was poured into cold water, and after sufficiently cooled, it was pulverized by a pulverizer and filtered. The discharge process is 50 minutes. The filtration mother liquor had a sulfolane content of 25%. The obtained powder was added with water, boiled for 1 hour, filtered, and repeatedly cooked 8 times until the solvent and by-product salts in the material were all removed. 5%。 The resulting powder was dried in an oven at 130 ° C for 12 hours, so that the moisture content was less than 0.5%. The intrinsic viscosity of the test sample was 0. 72 dl/g. The test index was 100 g/min at 400 ° C and 5 kg. The product particle size distribution has a D50 of 800 um.

Comparative example 2

The polymerization method was the same as in Example 10 except that the discharge was carried out in the following manner at the later stage of the polymerization. The polymer mucilage was poured into cold water, and after sufficiently cooled, it was pulverized by a pulverizer and filtered. The discharge process is 90 minutes. The obtained powder was added with ethanol, boiled 4 times, filtered, and repeatedly cooked again with deionized water for 9 times until the solvent and by-product salts in the material were all removed. 5%。 The resulting powder was dried in an oven for 130 hours, so that the moisture content was less than 0.5%. The intrinsic viscosity of the test sample was 0.75 dl/g. The test melt was 15 g/min at 400 ° C and 5 Kg. The product particle size distribution has a D50 of 1000 um.

Comparative example 3

The polymerization method was the same as in Example 13, except that the discharge was carried out in the following manner at the later stage of the polymerization. The polymer mucilage was poured into cold water, and after sufficiently cooled, it was pulverized by a pulverizer and filtered. The discharge process is 70 minutes. The obtained powder was repeatedly distilled for 8 times by adding deionized water until the solvent and by-product salts in the material were all removed. 5%。 The resulting powder was dried in an oven at 13 CTC for 12 hours, so that the moisture content was less than 0.5%. The test sample had an intrinsic viscosity of 0.98 dl/ _g . The test melt was 23 g/min at 370 ° C under 5 Kg. The product particle size distribution was D50 of 1500 um.

Comparative Example 4 The polymerization method was the same as in Example 14, except that the polymerization was carried out in the following manner at the later stage of the polymerization. The polymer mucilage was poured into cold water, and after sufficiently cooled, it was pulverized by a pulverizer and filtered. The discharge process is 120 minutes. The obtained powder was repeatedly cooked by deionized water for 9 times until the solvent and by-product salts in the material were all removed. 5%。 The moisture content is less than 0.5%. The test sample had an intrinsic viscosity of 0.97 dl/g. At 370 ° C, 5Kg The test fusion index was 40 g/min. The product particle size distribution was D50 of 1200 um. Sampling before and after discharge We compare the advantages and disadvantages of the two methods using the examples and the following data:

Table 1 Product of each example m Data comparison table

Table 2 Comparison of product data of each example

Discharge time Product melting Refer to particle size D50 Reaction system Solid content Solvent amount (L)

(min) number of washes (g/10min) (urn) Example 1 TMS 15% Water 25L 30 5 100 200 Example 2 TMS 30% Water 30L 6 6 71 300 Example 3 TMS 15% plus TMS50L 4 5 45 150 Example 4 TMS 26% plus TMS59L 5 5 16 250 Example 5 TMS 15% Ethanol 50 L 55 5 30 180 Example 6 TS 30% Ethanol 30 L 10 4 14 270 Example 7 TMS 15% Xylene 30 L 5 5 9 200 Example 8 TMS 37% xylene 35L 9 6 85 350 Example 9 TMS 40% Water 20L 12 4 150 50

Diphenyl sulfone

Example 10 30% ethanol 20L 12 6 15 500

PAEK

Example 1 1 5% xylene 40L 】 0 6 14 250 Example 12 TMS, 30% xylene 40L 3 5 25 400 PES

TMS,

Example 13 60% acetone 20L 10 6 22 500

PES

TMS,

Example 14 27% xylene 30L 8 5 36 450

PPSU

Comparative Example 1 TMS 15% Crush 50 8 100 800

Diphenyl sulfone

Comparative example 2 30% crush 90 9 15 1000

PAEK

TMS,

Comparative example 3 60% crush 70 8 23 1500

PES

TMS,

Comparative example 4 27% crush 120 9 40 1200

PPSU To further illustrate the beneficial effects of the present invention, a comparative example 4 was compared with Example 14, as shown in Table 1 Table 3 Example 14 vs. Comparative Example 4

The logarithmic reduced viscosity test method was as follows: 0.2 g of the polymer was dissolved in 98% of 20 ml of concentrated sulfuric acid, and the logarithmic viscosity was measured by an Ubbelohde viscometer at 25 Torr; the F particle content was measured by a fluoride analyzer. Fluoride ion content less than 2mg / L is qualified; bulk density test method, using lOrnl measuring cylinder to accurately measure lOml-powder sample, compaction, weighing. Calculate the bulk density p by calculating m = pV according to the formula.

Refined product (Examples 1 to 11, Comparative Examples 1 to 2) The melt index method was tested as follows: According to ASTM D 1238-04, the test conditions were at 400 ° C, 5 kg pressure, and the resin powder passed in 10 minutes. The weight value of the standard capillary is averaged in g/lOmin. (Examples 12, 13, 14, Comparative Example 3 and Comparative Example 4 were tested at 37 (TC, 5 Kg pressure) by the same method; product particle size analysis was carried out by laser particle size analyzer, and D50 is the cumulative particle size distribution percentage of the sample. The particle size corresponding to 50%.

The Tg and Tm of the polymer were tested by differential scanning calorimetry (DSC). Test conditions: Under nitrogen protection, the polymer was first raised from room temperature at a rate of 20 ° C/min to 400 °C, and then at 50 ° C. /min's cooling rate is reduced to room temperature, then The temperature increase rate of 20 ° C / _m in was raised to 400 ° C, calculated as the value of the second heating curve. The thermal decomposition temperature of the polymer was tested by thermogravimetric analysis, and the polymer was raised to 800 ° C at a rate of 5 O/min to test a thermal decomposition temperature of 5%.

Table 1 and Table 2 are comparisons of the data of the respective examples and comparative examples, and Table 3 is a comparison of Example 14 with Comparative Example 4. The obtained product is shown in Fig. 1 and Fig. 2. The magnification of Fig. 2 is the same as that of Fig. 1. As seen from the figure, under the microscope with the same magnification, the product particles obtained by the new process are relatively uniform and close to spherical. It is naturally precipitated and has a high density. The product obtained by the pulverization process is similar to a strip shape with a large number of voids and pores in the middle, so it contains a lot of solvents, which leads to a big difference between the two in the refining process. the reason.

The above examples are not intended to limit the product of the present invention, and any minor modifications, equivalent changes and modifications made to the above embodiments according to the technical spirit or composition of the composition or content of the present invention are within the scope of the technical solution of the present invention. .

Claims

Claim

A method for preparing a powdered resin, comprising the steps of: (1) firstly cooling directly after the end of the polymerization reaction, and the polymer is precipitated from the reaction system to obtain a polymer gel solution; the cooling rate is preferably 2 to 50 ° C. /min, cooling time is l~60min _; increase the stirring speed to make the polymer colloidal liquid evenly dispersed; (2) When the system is cooled to 130~250 °C, add a certain amount of poor solvent to the mixture to make the polymer The system forms a suspension liquid mixture with the poor solvent; (3) solid-liquid separation of the suspension to obtain a desired crude product of the polymer powder; (4) The crude product is refined and dried.

The method of producing a powdered resin according to claim 1, wherein the resin comprises polyaryletherketones, polyarylene ethers, and polysulfones.

3. The method for preparing a powdered resin according to claim 1, wherein the solvent used for the polymerization is diphenyl sulfone, dimethyl sulfoxide, dimethyl sulfone, diethyl sulfone, diethyl sulfoxide, A mixture of one or more of diisopropyl sulfone, diphenyl sulfone, sulfolane or tetramethyl sulfone, and the solid content of the reaction system is 5% to 60% by weight.

The method for preparing a powdered resin according to claim 1, wherein the cooling method is air-cooled, water-cooled, or a cooling method in which external cold oil is input into the jacketed jacket hot oil.

The method for preparing a powdered resin according to claim 4, characterized in that the temperature decreasing process is carried out, and the cooling rate is 5 to 30 ° C / min.

6. The method of preparing a powdered resin according to claim 1, wherein the poor solvent added to the system is water, ethanol, acetone, xylene, toluene, benzene or sulfolane, the solvent added and the volume of the solvent used for the polymerization. The ratio is 1:2~3: 1.

The method of preparing a powdered resin according to claim 6, wherein a volume ratio of the poor solvent to the solvent to be used in the polymerization is from 1:1 to 2:1.

8. The method of preparing a powdered resin according to claim 1, wherein the agitating paddle is anchor type, paddle type, turbine type, push type, frame type, scraping wall type, high shear type, disc type, tooth A blade, a ribbon agitator, a planetary paddle, or a multi-layer paddle. The paddle blade is a double-leaf, multi-blade, flat blade, hinged, curved blade or a combination of different types of paddles.

9. The method for preparing a powdered resin according to claim 1, wherein the stirring speed of the polymerization reaction is in the range of 10 to 1000 rpm, and the stirring speed in the post-treatment process is in the range of 10 to 3000 rpm, preferably after treatment. The agitation speed during the process is greater than the agitation speed during the polymerization.

10. The method for preparing a powdered resin according to claim 1, wherein the crude polymer product is subjected to centrifugation, filtration or leaching to remove the mother liquor, and the crude product is subjected to boiling water or a solvent to remove salts and impurities in the polymer at a high temperature. The extract is extracted several times and dried to obtain a product.