CN112239540B - Industrial purification process and purification device for polysulfone resin material - Google Patents
Industrial purification process and purification device for polysulfone resin material Download PDFInfo
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Abstract
The invention discloses an industrial purification process of polysulfone resin materials, which comprises the following steps: and continuously conveying the polysulfone resin solution obtained by the polymerization reaction to an opening die with an opening immersed in the precipitation liquid, so that the polysulfone resin solution is slowly extruded and precipitated at the opening, and the precipitated polysulfone resin is a strip with uniform thickness. The strip-shaped objects are pulled into a film by a conveying device at a constant speed, then the film is fed to a press roll, and then the multi-stage press roll with gradually decreasing gaps is used for cold pressing in sequence, so that the thickness of the film is gradually reduced, and the film is immersed in the precipitation liquid when the film pulling and cold pressing processes are carried out. The process method has the advantages of scientific and reasonable design, simplicity, practicability, low production cost, energy conservation, environmental protection and high production efficiency. The prepared target product has high purity, low ash content and stable performance, and can be applied to various high-end fields.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to an industrial purification process and purification device for polysulfone resin materials.
Background
Polysulfone is a slightly amber amorphous transparent or translucent high molecular polymer, is an amorphous thermoplastic resin, and has the following characteristics: excellent mechanical property, high rigidity, wear resistance, high strength, high heat stability and excellent mechanical property even at high temperature. The long-term use temperature is 160 ℃, the short-term use temperature is 190 ℃, the hydrolysis resistance is realized, the dimensional stability is good, the molding shrinkage rate is small, and the flame retardant is non-toxic, radiation resistant, flame retardant and self-extinguishing. Polysulfones have excellent electrical properties over a wide range of temperatures and frequencies.
The most advanced production process of the polysulfone resin at present mainly comprises a one-step polymerization method and a corresponding post-treatment purification process.
(1) The polymerization process comprises the following steps: the main raw materials of 4,4 '-dichlorodiphenyl sulfone, bisphenol A, bisphenol S, 4' -dihydroxybiphenyl, potassium carbonate or bicarbonate, sodium carbonate and the like are polymerized in a solvent. And after the polymerization liquid reaches the target viscosity, post-treatment and purification are carried out on the polysulfone material.
(2) Post-treatment purification process of polymer: the purification process of the polysulfone material is particularly important because the process affects various performance indexes such as light transmittance, haze and yellowness of the polysulfone material such as Polysulfone (PSU), Polyethersulfone (PESU) and polyphenylsulfone (PPSU). The polymer solution after the completion of the polymerization contains unreacted inorganic salts such as potassium carbonate or potassium hydrogencarbonate, and potassium chloride and unreacted phenolate which are by-products of the reaction. Such salts are very easily wrapped in the product and therefore cannot be thoroughly cleaned, the purification technology is difficult and the production cost is high. Only by overcoming the technical problem, the polysulfone product with high purity, high light transmittance and no impurities can be obtained.
The most common purification process is the water boiling method. After the polymerization reaction is finished, slowly transferring the polymerization liquid into water, so that the polymerization liquid is subjected to phase separation, and the polysulfone material is slowly separated out to form a solid. The core technology is mainly that a high-speed cutter is used for crushing polysulfone into superfine powder, and deionized water with the temperature of about 90 ℃ is used for soaking and washing for multiple times so as to realize product purification. The disadvantages of the process are obvious: 1. the soaking time is longer, the production period is prolonged, and the cost is increased. 2. The produced waste water is more, the recycling treatment difficulty is large, and the cost is high. 3. Because the polysulfone material belongs to a non-hydrophilic material, the surface tension of water is large, the surface layer of the polysulfone material can only be cleaned by a water boiling method, but not in a full-soaking state, and polysulfone particles with large particle size and inorganic salt wrapped in the polysulfone particles cannot be effectively removed, so that the problems of high ash content, low purity and reduced product performance of the product are inevitably caused. The complaints of the customers are many in the using process, and the customer requirements cannot be met.
Therefore, it is urgently needed to develop a brand-new, efficient and stable purification process, and to abandon a traditional process which is tedious, long in time consumption, high in energy consumption and poor in effect.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide an industrial purification process of polysulfone resin materials and a purification device thereof, so as to solve at least one of the technical problems.
The invention is realized by the following steps:
in a first aspect, an embodiment of the present invention provides an industrial purification process of a polysulfone resin material, including the following steps:
and continuously conveying the polysulfone resin solution obtained by the polymerization reaction to an opening die with an opening immersed in the precipitation liquid, so that the polysulfone resin solution is slowly extruded and precipitated at the opening, and the precipitated polysulfone resin is a strip with uniform thickness.
And (3) drawing the strip-shaped object into a film by a uniform-speed conveying device, feeding the film to a press roll, and sequentially cold-pressing the film by a multi-stage press roll with gradually decreasing gaps, so that the thickness of the film is gradually reduced, and the film is immersed in the precipitation liquid when the film drawing and cold-pressing processes are carried out.
In a second aspect, an embodiment of the invention provides a purification device for polysulfone resin materials, which comprises an opening die, a settling liquid tank, a conveying device and a multistage cold pressing roller cold pressing device, wherein the opening die is provided with an inlet end for polysulfone resin solution, an opening of the opening die corresponds to an input end of the conveying device, the multistage cold pressing roller cold pressing device is arranged above the conveying device, the opening die, the conveying device and the multistage cold pressing roller cold pressing device are all arranged in the settling liquid tank, and when the purification device is in a working state, the opening die, the conveying device and the multistage cold pressing roller cold pressing device are immersed in settling liquid in the settling liquid tank.
The technical scheme of the invention has the following beneficial effects: the polysulfone resin solution obtained by polymerization reaction is made into a strip with a certain thickness through a die, and then cold pressing is carried out on the strip by a multi-stage press roller, so that the solvent, inorganic salt and byproducts wrapped in the strip can overflow to the surface of the membrane along with the rupture of the membrane, and the surface of the membrane can be immersed in a precipitation liquid, so that the overflowing impurities can be cleaned in real time. The method is repeated, so that the polysulfone resin material achieves the effect of full replacement with the precipitation liquid, the washing effect is further enhanced, the production period is greatly shortened, the ash content and impurities of the product are reduced, and the quality of the polysulfone resin material is improved. Moreover, the method is simple and easy to implement, low in production cost, energy-saving, environment-friendly and high in production efficiency.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a schematic process flow diagram of an embodiment of the present invention.
Icon: 110-a reaction kettle; 101-a stirring device; 102-gear pump; 120-open mold; 121-opening; 130-a precipitation liquid tank; 131-a precipitation solution; 140-a transfer device; 150-multistage cold-pressing roller cold-pressing device; 160-polysulfone-based thin films; 170-deionized water tank; 180-deionized water.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The industrial purification process of polysulfone resin material and the purification device thereof provided by the present invention are specifically described below.
In a first aspect, some embodiments of the present invention provide an industrial purification process of a polysulfone-based resin material, which includes the following steps: continuously conveying the polysulfone resin solution obtained through the polymerization reaction to the opening 121 and immersing the opening 121 in the opening mold 120 in the precipitation liquid 131, so that the polysulfone resin solution is slowly extruded and precipitated at the opening 121, and the precipitated polysulfone resin is a strip with uniform thickness; the strip-shaped objects are pulled into a film by a conveying device 140 with uniform speed, then the film is fed to a press roll, and then the film is sequentially cold-pressed by a plurality of stages of press rolls with gradually decreasing gaps, so that the thickness of the film is gradually reduced, and the film is immersed in the precipitation liquid 131 when the film pulling and cold pressing processes are carried out.
In the technical scheme, the polysulfone resin solution obtained by the polymerization reaction is conveyed to the open die 120, the die opening 121 is immersed in the precipitation liquid 131, the polysulfone resin solution is slowly precipitated at the die opening, the polysulfone resin material is drawn into a film through the conveying device 140, and the film is cold-pressed by the multi-stage pressing rollers in the precipitation liquid 131, so that the thickness of the polymer film is gradually reduced. Each cold press will result in a thinner and thinner film with partial edge cracking and solvent entrapped inside to spill inorganic salts and byproducts to the film surface. Meanwhile, in the cold pressing process, byproducts and inorganic salts wrapped by water, alcohols and polysulfone materials are subjected to displacement washing once. The technical innovation point of the process is that the precipitation characteristic of the polysulfone resin material is utilized, so that the precipitation process of the film of the polysulfone resin material from soft to hard exists in the precipitation liquid 131, and inorganic salt and byproducts are continuously precipitated in the process of cold pressing for multiple times, so as to achieve the purpose of purification.
The duration of the process of hardening the film of the polysulfone resin material from soft in the precipitation liquid 131 is about 3-5 minutes, after 3 minutes, the film becomes hard, the purification effect becomes poor, and after 5 minutes, the film precipitation process is finished and becomes a hard film. At this time, the compression roller can not extrude the impurities wrapped in the film, the purification effect is greatly reduced, and the process is disabled. Therefore, in some embodiments, the sequential cold pressing process through the multi-stage pressing rolls is controlled within 5min when the polysulfone resin solution is extruded out of the opening 121 (i.e., die feeding). Further preferably, the time for feeding the polysulfone resin solution from a die head of the die is timed, and the time for replacement and purification through a compression roller is 1-3 min.
Further, in order to achieve a better purification effect of cold pressing, the thickness variation of cold pressing affects the purification effect to a certain extent, therefore, in some embodiments, the multi-stage compression rollers sequentially cold press the film from 2.0-5.0mm to 0.01-2 mm. For example, the film is gradually pressed from 5mm to 0.1 mm. The more cold pressing times, the larger the thickness difference of cold pressing, and the better the purification effect.
Specifically, in some embodiments, the number of the multi-stage compression rollers is 2-20, the range of the cold pressing gap of the compression roller for extruding the material is 0.01-5.00mm, the cold pressing gap is gradually decreased, the diameter range of the compression roller is 0.05-1.00m, the length of the compression roller is 0.1-3.0m, and the rotating linear speed is 0.1-5.0 m/min.
In order to further optimize the effect of cold pressing purification, in some embodiments, the number of the multi-stage compression rollers is preferably 8-15, the range of the cold pressing gap of the compression roller extrusion material is 0.01-0.05mm, the range of the diameter of the compression roller is 0.1-1.00m, the length of the compression roller is 0.5-2.5m, and the rotating linear speed is 0.1-3.0 m/min.
Further, in some embodiments, the precipitation solution 131 comprises N, N-dimethylacetamide and water, and the mass ratio of N, N-dimethylacetamide to water is 10-20: 80-90 ℃, and the using temperature of the precipitation liquid 131 is 30-60 ℃. The composition, proportion and use temperature of the precipitation liquid 131 can enable the precipitation liquid 131 and the polysulfone resin to have a better precipitation washing effect, and further improve the product purity. Wherein, the weight application range of the precipitation liquid 131 and the polysulfone resin is as follows: when the weight of the resin is 20-100kg, the dosage of the precipitation solution 131 is about 300-400 kg.
Further, in some embodiments, the polysulfone resin solution in the above technical scheme is obtained by adding a solvent, an acid-binding agent and a water-carrying agent into a mixture of a phenolic substance and a sulfone substance as a reaction monomer to perform a polymerization reaction.
Wherein the sulfone is 4,4 '-dichlorodiphenyl sulfone, and the phenolic substance comprises one or more of bisphenol A, bisphenol S and 4, 4' -dihydroxybiphenyl. According to the difference of sulfones, the corresponding polysulfone resin material can be Polysulfone (PSU), Polyethersulfone (PES), polyphenylsulfone (PPSU), polyarylethersulfone, polyarylsulfone and other high polymer materials.
In some embodiments, the solvent comprises one or more of dimethyl sulfoxide, sulfolane, N-dimethylformamide, N-dimethylacetamide, and N-methylpyrrolidone.
In some embodiments, the acid scavenger comprises one or more of potassium bicarbonate, sodium bicarbonate, cesium carbonate, sodium hydroxide, potassium carbonate, and sodium carbonate.
In some embodiments, the water-carrying agent comprises one or more of toluene, xylene, and chlorobenzene.
Further, in order to further remove some impurities remaining on the polysulfone surface after cold pressing, in some embodiments, the film obtained after cold pressing sequentially by a plurality of pressing rollers is washed by deionized water 180. When the weight of the resin is 100kg-500kg, the deionized water 180 used for purification is about 1 ton-2 tons. When the weight of the resin is more than 500kg, the deionized water 180 used for purification is about 5 to 6 times of the resin. Further, after washing, the polysulfone thin-film 160 may be pulverized into powder and dried, thereby obtaining a high-purity, high-transmittance, impurity-free polysulfone resin.
Some embodiments of the present invention further provide an industrial purification process of a polysulfone resin material, which specifically includes:
(1) the raw materials, the acid-binding agent, the solvent and the water-carrying agent are all put into the reaction kettle 110 according to the proportion, the reaction kettle 110 is vacuumized and purged by nitrogen, the standard of the nitrogen is high-purity nitrogen, the total time of the water-carrying agent with water and the polymerization reaction at the temperature of more than 150 ℃ is 12-20 hours, the temperature in the kettle reaches 150-. The total time for purifying the polymerization liquid in the reaction kettle 110 is about 0.1-5 hours.
(2) After the reaction is finished, the bottom valve at the bottom of the kettle is opened, the polymerization solution is conveyed to the opening mold 120 through the gear pump 102 at a constant speed, meanwhile, the mold is wholly immersed in the precipitation solution 131, and the polysulfone material is pulled into a film through the conveying device 140 along with the gradual precipitation of the polysulfone resin solution at the mold opening. The polysulfone resin solution is extruded into strips with uniform thickness through an opening 121 of the die, the strips are drawn into a film through a conveyor belt at a uniform speed, the film is automatically fed to a press roll under the environment of a precipitation liquid 131, and the film is pressed to 0.01-2mm from 2.0-5.0mm through multi-stage press rolls with gradually decreasing gaps. And (3) feeding the film purified by the multi-stage compression roller process into a new deionized water tank 170, and washing the trace impurities on the surface again. And finally, crushing the polysulfone film 160 into powder, drying, and obtaining the polysulfone resin with high purity, high light transmittance and no impurities through a brand new process route.
Further, some embodiments of the present invention also provide a purification apparatus for polysulfone resin material, referring to fig. 1, which includes a reaction kettle 110, an open mold 120, a settling tank 130, a conveying apparatus 140, and a multi-stage cold-roll cold-pressing apparatus 150.
The reaction kettle 110 is a conventional sealed reaction vessel, and a stirring device 101 is arranged in the reaction kettle; the bottom end of the reaction kettle 110 is communicated with the open mold 120 through the gear pump 102, the open mold 120 has an inlet end for introducing the polysulfone resin solution, the opening 121 of the open mold 120 corresponds to the inlet end of the conveyer 140, that is, the polysulfone resin solution is slowly extruded from the opening 121 of the open mold 120 and is pulled into the polysulfone film 160 by the conveyer 140. The multistage cold pressing roller cold pressing device 150 is arranged above the conveying device 140, and a cold pressing gap is formed between the multistage cold pressing roller cold pressing device 150 and the conveying device 140, so that the polysulfone film 160 is cold pressed step by step through the multistage cold pressing rollers. And the die head, the conveying device 140 and the multistage cold roll cold pressing device 150 of the open die 120 are all arranged in the precipitation liquid tank 130, and when the purifying device is in a working state, the die head, the conveying device 140 and the multistage cold roll cold pressing device 150 of the open die 120 are immersed in the precipitation liquid 131 in the precipitation liquid tank 130. Therefore, in the step-by-step cold pressing process, the polysulfone thin film 160 becomes thinner continuously, and in the thinning process, the polysulfone thin film 160 can sufficiently act on the precipitation liquid 131 to wash away impurities such as inorganic salts precipitated on the surface, and the purity of the polysulfone thin film 160 is improved continuously.
Specifically, the open die 120 has an inverted trapezoidal structure, the opening 121 is located below, the length of the opening 121 is 0.1-2.0m, the thickness of the opening 121 is 2.0-5.0mm, and the feeding speed of the opening 121 to the conveyor 140 is 0.1-5.0 m/min.
Wherein, the conveying device 140 is a conveying belt, the mirror surface polishing degree of the conveying belt and the surface of the compression roller is less than 0.4um, the film drawing speed of the conveying belt is 0.1-5.0m/min, which is slightly faster than or consistent with the feeding speed of the die head, preferably slightly faster. The conveyor belt is a stainless steel conveyor belt, and the material of the press roller and the conveyor belt is SUS316L or dual-phase steel 2205.
Further, referring again to fig. 1, the purification apparatus further comprises a deionized water tank 170, and the output port of the multi-stage cold roll cold press apparatus 150 is correspondingly connected to the deionized water tank 170. The deionized water tank 170 contains deionized water 180 which allows for further washing of the cold pressed washed film.
Wherein the length range of the precipitation liquid tank 130 is 0.5-20.0 m, the width range is 0.5-5.0 m, and the height range is 0.5-5.0 m. The deionized water tank 170 has a length ranging from 0.5 to 20.0 meters, a width ranging from 0.5 to 5.0 meters, and a height ranging from 0.5 to 5.0 meters.
The features and properties of the present invention are described in further detail below with reference to examples, which, however, do not limit the practice of the invention.
The precipitation liquid tanks used in the following examples are all 1 meter long, 0.5 meter wide and 0.5 meter high. The deionized water tank 170 has a length of 1m, a width of 0.5m and a height of 0.5 m. The volume occupied by the removal equipment was about 300kg total deionized water 180. The number of rollers may be adjusted in different embodiments, and the rollers are uniformly arranged in the precipitation bath 130, and will not be described in more detail here. The thickness and width of the polysulfone-based film 160 are determined according to the mold size of the corresponding embodiment.
Example 1
The industrial purification process of the polysulfone resin material provided by the embodiment specifically includes:
8.81kg of 4, 4-dichlorodiphenyl sulfone, 7.32kg of bisphenol S, 5.45kg of potassium carbonate, 60kg of sulfolane serving as a solvent and 15kg of dimethylbenzene serving as a water-carrying agent are added into a 100L polymerization reaction kettle. All the raw materials are put into a reaction kettle 110, the kettle is vacuumized to be less than or equal to-0.08 MPa, nitrogen is introduced to ensure that the pressure in the kettle is more than or equal to 0.00MPa, the reaction is carried out under normal pressure in the kettle after the nitrogen is replaced for three times, the polymerization temperature is 200 ℃, and the polymerization time is 14 hours. The reaction was complete when the polyethersulfone resin solution reached a target viscosity of 8000 mpa.s.
After the reaction is finished, a bottom valve at the bottom of the kettle is opened, the polyethersulfone resin solution is conveyed into an open die 120 through a gear pump 102, the open die 120 is immersed into a precipitation liquid 131, the polyethersulfone resin solution is fed and precipitated at the speed of 0.35m/min, and the polyethersulfone resin solution is extruded into a uniform strip with the width of 0.35m and the thickness of 2mm through an opening 121 (namely a gap) of the die. The conveyor belt pulls the noodles into a film at a speed of 0.38m/min and feeds them to the press rolls in the environment of the precipitation liquor 131. The weight ratio of the components of the precipitation liquid 131 is N, N-dimethylacetamide: water = 15%: 85 percent of the polymer film is pressed from 2mm to 0.05mm through a cold pressing process of adjusting the press roll gap of 8 levels to 2.0mm, 1.0mm, 0.5mm, 0.4mm, 0.3mm, 0.2mm, 0.1mm and 0.05mm in a gradually decreasing manner. The film purified by the multi-stage compression roller process enters a new deionized water tank 170, and the trace impurities on the surface are washed again. From the beginning of the feed to the end, the purification process takes about 54 minutes for the entire time in the precipitation tank 130, 60 minutes for the entire time in the new deionized water tank 170, and 114 minutes for the entire time. And finally, crushing the polyether sulfone film into powder, and drying by using drying equipment to obtain the high-purity impurity-free polyether sulfone resin.
The detected ash value of the polyether sulfone is 0.006%, compared with the ash value of 0.4% in the traditional process, the product purity is improved by 98.5%; the purity of the product is 99.994%.
Example 2
The industrial purification process of the polysulfone resin material provided by the embodiment specifically includes:
9.1kg of 4, 4-dichlorodiphenyl sulfone, 6.35kg of bisphenol A, 5.3kg of potassium carbonate, 65kg of solvent dimethyl sulfoxide and 15kg of water-carrying agent xylene are added into a 100L polymerization reaction kettle. After all the raw materials are put into a reaction kettle 110, vacuumizing the kettle to be less than or equal to-0.08 MPa, introducing nitrogen to ensure that the pressure in the kettle is more than or equal to 0.00MPa, replacing the nitrogen for three times, and then keeping the reaction in the kettle at normal pressure, wherein the polymerization temperature is 160 ℃, and the polymerization time is 12 hours. The reaction was complete when the polysulfone polymerization solution reached a target viscosity of 8000 mpa.s.
After the reaction, the bottom valve of the reactor was opened, the polysulfone polymeric solution was transferred into the open die 120 by the gear pump 102, and the open die 120 was immersed in the precipitation liquid 131, the polysulfone polymeric solution was precipitated at a rate of 0.35m/min, and the polysulfone polymeric solution was extruded through the opening 121 (i.e., the gap) of the open die 120 into a uniform bar having a width of 0.3m and a thickness of 2 mm. The conveyor belt pulls the noodles into a film at a speed of 0.36m/min and feeds them to the press rolls in the environment of the precipitation liquor 131. The weight ratio of the components of the precipitation liquid 131 is N, N-dimethylacetamide: water = 12%: 88 percent, and the thickness of the polymer film is pressed from 2.0mm to 0.01mm through a cold pressing process of adjusting the press roll gap of 10 stages to be 2.0mm, 1.5mm, 1.0mm, 0.8mm, 0.5mm, 0.2mm, 0.1mm, 0.05mm, 0.03mm and 0.01mm in a gradual reduction manner. The film purified by the multi-stage compression roller process enters a new deionized water tank 170, and the trace impurities on the surface are washed again. From the beginning of the feed to the end, the purification process takes about 59 minutes for the entire time in the precipitation tank 130, 65 minutes for the entire time in the new deionized water tank 170, and 124 minutes for the entire time. And finally, crushing the polysulfone film into powder, and drying by using drying equipment to obtain the high-purity impurity-free polysulfone resin.
The detected ash value of the polysulfone is 0.001%, and compared with the ash value of 0.4% in the traditional process, the product purity is improved by 99.75%; the purity of the product is 99.999%.
Example 3
The industrial purification process of the polysulfone resin material provided by the embodiment specifically includes:
8.81kg of 4, 4-dichlorodiphenyl sulfone, 7.32kg of bisphenol S, 5.45kg of potassium carbonate, 60kg of sulfolane serving as a solvent and 15kg of dimethylbenzene serving as a water-carrying agent are added into a 100L polymerization reaction kettle. After all the raw materials are put into a reaction kettle 110, vacuumizing the kettle to be less than or equal to-0.08 MPa, introducing nitrogen to ensure that the pressure in the kettle is more than or equal to 0.00MPa, replacing the kettle with nitrogen for three times, keeping the reaction in the kettle at normal pressure, wherein the polymerization temperature is 200 ℃, and the polymerization time is 14 hours. The reaction was complete when the polyethersulfone polymerization solution reached a target viscosity of 8000 mpa.s.
After the reaction is finished, opening a bottom valve at the bottom of the kettle, conveying the polyether sulfone polymerization solution to an open die 120 through a gear pump 102, immersing the open die 120 into the precipitation solution 131, feeding and precipitating the polyether sulfone polymerization solution at the speed of 0.35m/min, and extruding the polyether sulfone polymerization solution into a uniform strip with the width of 0.35m and the thickness of 2mm through an opening 121 (namely a gap) of the open die 120. The conveyor belt pulls the noodles into a film at a speed of 0.38m/min and feeds them to the press rolls in the environment of the precipitation liquor 131. The weight composition proportion of the components of the precipitation liquid 131 is N, N-dimethylacetamide: water = 15%: 85 percent, and the thickness of the polymer film is pressed from 2.0mm to 0.1mm through a cold pressing process of adjusting the press roll gap of 8 levels to 2.0mm, 1.5mm, 1.0mm, 0.5mm, 0.4mm, 0.3mm, 0.2mm and 0.1mm in a gradual reduction manner. From the beginning of the feed to the end, the entire purification process takes about 54 minutes in the precipitation tank 130, 60 minutes in the new deionized water tank 170, and 114 minutes in total. And finally, crushing the polyether sulfone film into powder, and drying by using drying equipment to obtain the high-purity impurity-free polyether sulfone resin.
The detected ash value of the polyether sulfone is 0.089%, compared with the ash value of 0.4% in the traditional process, the product purity is improved by 77.75%; the purity of the product was 99.911%.
Example 4
The industrial purification process of the polysulfone resin material provided by the embodiment specifically includes:
9.1kg of 4, 4-dichlorodiphenyl sulfone, 6.35kg of bisphenol A, 5.3kg of potassium carbonate, 65kg of solvent dimethyl sulfoxide and 15kg of water-carrying agent xylene are added into a 100L polymerization reaction kettle. After all the raw materials are put into a reaction kettle 110, vacuumizing the kettle to be less than or equal to-0.08 MPa, introducing nitrogen to ensure that the pressure in the kettle is more than or equal to 0.00MPa, replacing the nitrogen for three times, and then keeping the reaction in the kettle at normal pressure, wherein the polymerization temperature is 160 ℃, and the polymerization time is 12 hours. The reaction was complete when the polysulfone polymerization solution reached a target viscosity of 8000 mpa.s.
After the reaction is finished, the bottom valve of the kettle is opened, the polysulfone polymeric solution is conveyed into the open die 120 through the gear pump 102, the open die 120 is immersed into the precipitation liquid 131, the polysulfone polymeric solution is precipitated at the speed of 0.35m/min, and the polysulfone polymeric solution is extruded into a uniform strip with the width of 0.3m and the thickness of 2mm through the gap of the open die 120. The conveyor belt pulls the noodles into a film at a speed of 0.36m/min and feeds them to the press rolls in the environment of the precipitation liquor 131. The weight composition proportion of the components of the precipitation liquid 131 is N, N-dimethylacetamide: water = 12%: 88 percent, and the thickness of the polymer film is pressed from 2.0mm to 0.03mm through a cold pressing process of adjusting the press gap of 6 stages to 2.0mm, 1.0mm, 0.8mm, 0.4mm, 0.1mm and 0.03mm in a gradually decreasing manner. From the beginning of the feed to the end, the purification process takes about 59 minutes for the entire time in the precipitation tank 130, 65 minutes for the entire time in the new deionized water tank 170, and 124 minutes for the entire time. And finally, crushing the polysulfone film into powder, and drying by using drying equipment to obtain the high-purity impurity-free polysulfone resin.
The detected ash value of the polysulfone is 0.14%, and compared with the ash value of 0.4% in the traditional process, the product purity is improved by 65%; the purity of the product is 99.86%.
Example 5
The industrial purification process of the polysulfone resin material provided by the embodiment specifically includes:
9.1kg of 4, 4-dichlorodiphenyl sulfone, 6.35kg of bisphenol A, 5.3kg of potassium carbonate, 65kg of solvent dimethyl sulfoxide and 15kg of water-carrying agent xylene are added into a 100L polymerization reaction kettle. After all the raw materials are put into a reaction kettle 110, vacuumizing the kettle to be less than or equal to-0.08 MPa, introducing nitrogen to ensure that the pressure in the kettle is more than or equal to 0.00MPa, replacing the nitrogen for three times, and then keeping the reaction in the kettle at normal pressure, wherein the polymerization temperature is 160 ℃, and the polymerization time is 12 hours. The reaction was complete when the polysulfone polymerization solution reached a target viscosity of 8000 mpa.s.
After the reaction, the bottom valve of the reactor was opened, the polysulfone polymeric solution was transferred into the open die 120 by the gear pump 102, and the open die 120 was immersed in the precipitation liquid 131, the polysulfone polymeric solution was precipitated at a rate of 0.35m/min, and the polysulfone polymeric solution was extruded through the opening 121 (i.e., slit) of the open die 120 into a uniform bar having a width of 0.3m and a thickness of 2 mm. The conveyor belt pulls the noodles into a film at a speed of 0.36m/min and feeds them to the press rolls in the environment of the precipitation liquor 131. The weight composition proportion of the components of the precipitation liquid 131 is N, N-dimethylacetamide: water = 5%: 95 percent, and the thickness of the polymer film is pressed from 2.0mm to 0.05mm through a cold pressing process of adjusting the 10-stage press roll gap to be 2.0mm, 1.0mm, 0.5mm, 0.4mm, 0.3mm, 0.2mm, 0.1mm and 0.05mm in a gradual reduction manner. The film purified by the multi-stage compression roller process enters a new deionized water tank 170, and the trace impurities on the surface are washed again. From the beginning of the feed to the end, the purification process takes about 59 minutes for the entire time in the precipitation tank 130, 65 minutes for the entire time in the new deionized water tank 170, and 124 minutes for the entire time. And finally, crushing the polysulfone film into powder, and drying by using drying equipment to obtain the high-purity impurity-free polysulfone resin.
The detected ash value of the polysulfone is 0.169%, and compared with the ash value of 0.4% in the traditional process, the product purity is improved by 57.75%; the purity of the product was 99.831%.
Comparative example 1
The industrial purification process of the polysulfone resin material provided by the comparative example specifically comprises the following steps:
9.1kg of 4, 4-dichlorodiphenyl sulfone, 6.35kg of bisphenol A, 5.3kg of potassium carbonate, 65kg of solvent dimethyl sulfoxide and 15kg of water-carrying agent xylene are added into a 100L polymerization reaction kettle. After all the raw materials are put into a reaction kettle 110, vacuumizing the kettle to be less than or equal to-0.08 MPa, introducing nitrogen to ensure that the pressure in the kettle is more than or equal to 0.00MPa, replacing the nitrogen for three times, and then keeping the reaction in the kettle at normal pressure, wherein the polymerization temperature is 160 ℃, and the polymerization time is 12 hours. The reaction was complete when the polysulfone polymerization solution reached a target viscosity of 8000 mpa.s.
After the reaction, the bottom valve of the reactor was opened, the polysulfone polymeric solution was transferred into the open die 120 by the gear pump 102, and the open die 120 was immersed in the precipitation liquid 131, the polysulfone polymeric solution was precipitated at a rate of 0.24m/min, and the polysulfone polymeric solution was extruded through the opening 121 (i.e., slit) of the open die 120 into a uniform bar having a width of 0.3m and a thickness of 2 mm. The strip was drawn into a film by a conveyor belt at a speed of 0.25m/min and fed to a press roll in the environment of the precipitation liquid 131. The weight composition proportion of the components of the precipitation liquid 131 is N, N-dimethylacetamide: water = 12%: 88 percent, and the thickness of the polymer film is pressed from 2.0mm to 0.05mm through a cold pressing process of adjusting the 10-stage press roll gap to be 2.0mm, 1.0mm, 0.5mm, 0.4mm, 0.3mm, 0.2mm, 0.1mm and 0.05mm in a gradual reduction manner. The film purified by the multi-stage compression roller process enters a new deionized water tank 170, and the trace impurities on the surface are washed again. From the beginning of the feed to the end, the entire purification process takes about 85 minutes in the precipitation tank 130, 90 minutes in the new deionized water tank 170, and 175 minutes in the entire process. And finally, crushing the polysulfone film into powder, and drying by using drying equipment to obtain the high-purity impurity-free polysulfone resin.
The polysulfone is solidified after being completely purified in the precipitation liquid 131 after the polysulfone is precipitated from the beginning to the end of the cold pressing process and stays in the precipitation liquid 131 for more than 3 minutes. The detected ash value of the polysulfone is 0.21%, and compared with the ash value of 0.4% in the traditional process, the product purity is improved by 47.5%; the purity of the product is 99.79%.
Comparative example 2
The industrial purification process of the polysulfone resin material provided by the comparative example specifically comprises the following steps:
9.1kg of 4, 4-dichlorodiphenyl sulfone, 6.35kg of bisphenol A, 5.3kg of potassium carbonate, 65kg of solvent dimethyl sulfoxide and 15kg of water-carrying agent xylene are added into a 100L polymerization reaction kettle. All the raw materials are put into a reaction kettle 110, the kettle is vacuumized to be less than or equal to-0.08 MPa, nitrogen is introduced to ensure that the pressure in the kettle is more than or equal to 0.00MPa, the reaction is carried out under normal pressure in the kettle after the nitrogen is replaced for three times, the polymerization temperature is 160 ℃, and the polymerization time is 12 hours. The reaction was complete when the polysulfone polymerization solution reached a target viscosity of 8000 mpa.s.
After the reaction is finished, opening a bottom valve at the bottom of the kettle, transferring the polysulfone polymeric solution into deionized water 180 for resin precipitation, crushing the resin into ultrafine powder, transferring the ultrafine powder into a washing kettle, and soaking and washing the product by using 180 kg of deionized water, wherein the soaking temperature is 85 ℃, and the soaking time is 2 hours. And (4) removing corresponding water from the soaked and washed polysulfone through a centrifugal machine, and transferring the polysulfone into a washing kettle again for soaking and washing. After repeating the above steps for 6 times, the total time of the soaking purification process is about 12 hours, and the total dosage of the deionized water 180 is about 1.8 tons. After soaking and washing are finished, the polysulfone product is centrifuged to obtain wrapped liquid, and then the wrapped liquid is dried to obtain the final polysulfone product.
The detected polysulfone ash value is 0.42%, and the product purity is 99.58%.
In the above examples and comparative examples, the general procedure for determining ash content in various plastics (resins and compounds) and suitable experimental conditions were defined with reference to GB/T9345.
In summary, compared with the prior art, the embodiment of the invention has the following beneficial effects:
(1) according to the embodiment of the invention, through brand-new principle exploration and process development, the optimal process conditions are invented, the efficiency is high, the stability is high, the ash content is reduced to 0.01-0.02%, the electric energy consumption (about 40-55%) and the natural gas energy consumption (about 20-25%) in the rectification desalting stage are greatly reduced, and the comprehensive production cost is reduced by 30%.
(2) The method can reduce the polymer ash content to 0.01-0.02% after 1 purification. In the traditional process, soaking and purification are repeated for at least 6 times according to the same water ratio, and the amount of generated waste water is 6 times of that of the waste water, so that the waste water amount is huge.
(3) The purification process provided by the embodiment of the invention can reduce the wastewater treatment capacity by 60-80%, and the purification saves the usage of deionized water by about more than 10 tons based on 1 ton of polysulfone resin production, and simultaneously saves high energy consumption caused by recycling a large amount of wastewater, and saves the cycle of a single purification process by more than 5 hours.
(4) The purification process provided by the embodiment of the invention has the advantages of high automation degree, safety, environmental protection, labor cost saving, no need of manual intervention, stable quality of products in different batches, high product purity, low ash content and impurity content and stable performance, and can be applied to high-end fields of medical instruments, aerospace, electronics and the like.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. An industrial purification process of polysulfone resin material is characterized in that: the industrial purification process comprises the following steps:
continuously conveying the polysulfone resin solution obtained by the polymerization reaction to an opening die with an opening immersed in the precipitation liquid, so that the polysulfone resin solution is slowly extruded and precipitated at the opening, and the precipitated polysulfone resin is a strip-shaped object with uniform thickness;
drawing the strip-shaped objects into a film by a uniform-speed conveying device, feeding the film to a press roll, and sequentially cold-pressing the film by a plurality of stages of press rolls with gradually decreasing gaps, so that the thickness of the film is gradually reduced, and the film is immersed in a precipitation liquid when the film drawing and cold-pressing processes are carried out;
beginning timing by extruding and separating out the polysulfone resin solution at the opening, and controlling the process of sequentially cold pressing by a multi-stage press roller within 5 min;
the precipitation liquid comprises N, N-dimethylacetamide and water, wherein the mass ratio of the N, N-dimethylacetamide to the water is 10-20: 80-90 ℃, wherein the using temperature of the precipitation liquid is 30-60 ℃; the number of the multi-stage compression rollers is 2-20, the range of the cold pressing clearance of materials extruded by the compression rollers is 0.01-5.00mm, the cold pressing clearance is gradually reduced step by step, the diameter range of the compression rollers is 0.05-1.00m, the length of the compression rollers is 0.1-3.0m, and the linear speed of rotation is 0.1-5.0m/min, and the multi-stage compression rollers are sequentially cold pressed to gradually press the film from 2.0-5.0mm to 0.01-2 mm.
2. The industrial purification process according to claim 1, wherein: the open die is of an inverted trapezoidal structure, the length of an opening is 0.1-2.0m, the thickness of the opening is 2.0-5.0mm, and the feeding speed of the opening is 0.1-5.0 m/min.
3. The industrial purification process according to any one of claims 1 to 2, wherein: and washing the film obtained by sequentially cold pressing the film by a plurality of stages of compression rollers by deionized water.
4. The industrial purification process according to any one of claims 1 to 2, wherein: the conveying device is a conveying belt, the mirror surface polishing degree of the surfaces of the conveying belt and the pressing roller is less than 0.4um, and the film drawing speed of the conveying belt is 0.1-5.0 m/min.
5. A purification apparatus for polysulfone-based resin material, which is used for implementing the industrial purification process for polysulfone-based resin material as claimed in claim 1, characterized in that: it includes opening mould, settling liquid groove, conveyer and multistage cold pressing roller cold pressing device, the opening mould has polysulfone resin solution and leads to the end, the opening of opening mould corresponds conveyer's input, multistage cold pressing roller cold pressing device set up in conveyer's top, just the opening mould conveyer with multistage cold pressing roller cold pressing device all set up in the settling liquid groove, when the purification device is in operating condition, the opening mould conveyer with multistage cold pressing roller cold pressing device immerse in the settling liquid groove.
6. The purification device of polysulfone resin material according to claim 5, wherein: the device further comprises a deionized water tank, and an output port of the multi-stage cold pressing roller cold pressing device is connected to the deionized water tank.
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| PCT/CN2021/137191 WO2022135184A1 (en) | 2020-12-21 | 2021-12-10 | Industrial purification process and device for polysulfone resin material |
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| CN113103647A (en) * | 2021-04-12 | 2021-07-13 | 王健 | Production and processing method of elastomer modified asphalt waterproof coiled material |
| CN113980288B (en) * | 2021-12-23 | 2022-05-13 | 山东海科创新研究院有限公司 | Purification process and purification system for polymer |
| CN116178720A (en) * | 2022-11-30 | 2023-05-30 | 山东海科创新研究院有限公司 | Purification method of casting film grade polyethersulfone resin and obtained product |
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| GB1431030A (en) * | 1974-04-17 | 1976-04-07 | Trw Inc | Method of removing an undesired component from a polysulphone resin |
| JP3640701B2 (en) * | 1995-05-19 | 2005-04-20 | 旭化成ケミカルズ株式会社 | Purified polysulfone resin and polysulfone resin purification method |
| EP1774610A2 (en) * | 2004-05-22 | 2007-04-18 | Foster-Miller, Inc. | Solid polymer electrolyte membranes |
| JP4848629B2 (en) * | 2004-10-12 | 2011-12-28 | 東洋紡績株式会社 | Method for producing polyarylene polymer |
| JP2012178418A (en) * | 2011-02-25 | 2012-09-13 | Nomura Micro Sci Co Ltd | Method and apparatus for collecting polishing agent |
| CN102888003B (en) * | 2012-10-10 | 2014-03-05 | 四川飞亚新材料有限公司 | High polymer material precipitation method and industrial production method of polysulfone resin |
| US9908974B2 (en) * | 2014-04-30 | 2018-03-06 | Kureha Corporation | Polyarylene sulfide production method and polyarylene sulfide production apparatus |
| CN105601926B (en) * | 2015-06-08 | 2018-10-12 | 四川理工学院 | The preparation method of polyphenylene sulfone resins |
| CN105254890A (en) * | 2015-09-23 | 2016-01-20 | 中橡集团炭黑工业研究设计院 | Preparation method of polyethersulfone resin |
| KR101815933B1 (en) * | 2015-12-01 | 2018-01-09 | 주식회사 삼양사 | Preparation and purification of polysulfone polymer |
| CN106220853B (en) * | 2016-09-12 | 2018-09-28 | 李涛 | A kind of polysulfone resin industrialized producing technology |
| CN106861447B (en) * | 2017-03-02 | 2019-07-16 | 北京航空航天大学 | A kind of preparation method of polysulfone fibre film |
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| CN108329472A (en) * | 2018-01-25 | 2018-07-27 | 威海帕斯砜新材料有限公司 | A kind of synthetic method of polysulfones series plastics |
| CN111303427B (en) * | 2020-05-14 | 2020-09-04 | 富海(东营)新材料科技有限公司 | Industrial purification process of high-purity low-ash polysulfone resin |
| CN112008952A (en) * | 2020-09-18 | 2020-12-01 | 浙江道明光电科技有限公司 | Polyimide precipitation method |
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