CN113278150B - Polyether sulfone and preparation method thereof - Google Patents
Polyether sulfone and preparation method thereof Download PDFInfo
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Abstract
The invention discloses polyether sulfone and a preparation method thereof. The methodBisphenol is used as a unique monomer, polyphosphoric acid with a high boiling point is used as a dispersant dehydrating agent, a dehydration reaction is carried out by heating and raising the temperature, the reaction is maintained at a higher temperature, bisphenol is dehydrated and polymerized simultaneously, polyether sulfone or polyether sulfone solution is formed after polymerization, stirring and standing are stopped after a specified molecular weight is reached, and layering is carried out, wherein the upper layer contains polyether sulfone or polyether sulfone solution, and the lower layer contains polyphosphoric acid. The upper layer is treated to obtain the product polyether sulfone powder with the bulk density of 380-450kg/m3The powder color reaches RAL0009000, the molecular weight distribution Mw/Mn is less than or equal to 2, the content of ultrahigh molecular weight impurities is less than or equal to 0.2 percent, and the content of cyclic polymer impurities is less than or equal to 1.8 percent. The lower layer can be regenerated into high-purity polyphosphoric acid and phosphorus pentoxide for recycling. The method has simple feeding, basically does not generate waste gas and solid waste, and has simpler post-treatment method compared with the traditional method.
Description
Technical Field
The invention relates to a preparation process of a polymer, in particular to a polyether sulfone synthesis process.
Background
The polyether sulfone is a heat-resistant high polymer material, is widely applied to the aspects of electronic-grade thin films, water permeable films, blood permeable films, special environment materials and the like, and has wide application fields.
The traditional synthesis method of polyether sulfone is that dichlorodiphenyl sulfone and bisphenol S are used as monomers, a certain amount of acid-binding agent (such as sodium hydroxide) is added, and in an aprotic polar solvent (such as DMF) system, the materials are heated to form salt, and the generated water is separated out, and then the materials are polymerized to form polyether sulfone reaction liquid. The reaction solution after polymerization contains a large amount of inorganic salt, polyether sulfone, monomer by-products, solvent and products after solvent decomposition. And then filtering the reaction solution to remove salt, separating the materials, crushing the materials into powder, washing the powder for a plurality of times and drying the powder to form the polyether sulfone powder.
In this production process, the following drawbacks exist:
(1) two monomer feeds are required. The purity and content of the two monomers are somewhat fluctuating, which results in the actual molar ratio of the two monomer feeds in a fixed weight ratio often differing during the actual feed. In addition, the monomer dichlorodiphenyl sulfone is unstable in the presence of an acid-binding agent and water, and can be consumed by a plurality of side reactions, and the molar ratio of the monomer materials can be changed in the reaction process. The polymerization reaction is very sensitive to the material proportion, small molar ratio change can cause the smooth polymerization, the total result is that the molecular weight of the finished product of the polyether sulfone is unstable, and the product percent of pass is not high;
(2) during polymerization and post-treatment, a large amount of aqueous solvent, separated liquid and filtered salt cake are generated, and the components of the solid and the solution are complex, so that the recovery treatment is very difficult, labor and time are wasted, and the recovery rate is low;
(3) the acid-binding agent can react with bisphenol s, is a disposable consumable product and cannot be recycled and reused after use. The acid binding agent is an alkaline substance, and can also generate side reaction with the solvent at high temperature, so that the solvent is decomposed, and the recovery rate of the solvent is reduced;
(4) the activation energy of polyether sulfone polymerization is high, and the polymerization time of the process is long;
(5) the product after solvolysis can react with polyether sulfone to cause color blacking, so that the appearance of the product is poor;
(6) the end group of the produced polyether sulfone contains chlorine element, has high physiological toxicity and is not beneficial to popularization in the environment contacting with blood.
(7) The existing technology mostly adopts a gas end-capping agent, which causes great pollution and is difficult to recover.
Therefore, a simple and green polyether sulfone synthesis process is needed.
Disclosure of Invention
The invention provides polyether sulfone and a preparation method thereof. Greatly simplifies the polyether sulfone synthesis process, greatly reduces the exhaust emission, simplifies the post-treatment process and saves the material consumption. The method is completely superior to the prior art in the aspects of energy consumption, environmental protection, flow and product quality.
The specific principle is that bisphenol is used as a unique monomer, polyphosphoric acid with a high boiling point is used as a dispersant dehydrating agent, phosphorus pentoxide is selectively added as an auxiliary dehydrating agent, and a solvent is selectively added or not added. Upon heating, the bisphenol and the molten polyphosphoric acid are mixed into a slurry. And then carrying out dehydration reaction, maintaining the reaction at a higher temperature, carrying out polymerization while dehydrating the bisphenol, forming polyether sulfone or polyether sulfone solution after polymerization, stopping stirring and standing for layering after the specified molecular weight is reached, distributing the polyether sulfone or polyether sulfone solution with lower density on the upper layer, discharging polyphosphoric acid on the bottom layer, and putting the polyphosphoric acid and the phosphorus pentoxide into recovery equipment to continuously generate polyphosphoric acid and phosphorus pentoxide for next use. The remaining polyethersulfone layer was discharged directly, solidified and chopped to form a substantially uniform powder, which was washed to remove a small amount of polyphosphoric acid.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a method of preparing a polyethersulfone comprising the steps of: bisphenol and polyphosphoric acid are subjected to dehydration reaction. As a preferable scheme, the simple and convenient green polyether sulfone synthesis process comprises the following steps:
1) putting bisphenol and polyphosphoric acid into a reaction kettle, optionally adding phosphorus pentoxide, and optionally adding a solvent;
2) nitrogen replacement in a reaction kettle, heating to 60-100 ℃, preferably 70-90 ℃ to liquefy polyphosphoric acid, and then nitrogen replacement; air is wrapped in polyphosphoric acid before liquefaction, and the air is further removed by nitrogen gas exchange after liquefaction, so that the low air content in the reaction kettle is ensured, wherein the oxygen partial pressure is less than or equal to 50ppm, preferably less than or equal to 30 ppm;
3) then reacting at 160 ℃ and preferably at 160 ℃ and 140 ℃, and when the reaction is stopped by self heat release, heating to 350 ℃ and continuing the reaction to reach the target molecular weight, and adding an end-capping reagent to terminate the reaction;
4) stopping stirring, and demixing the reaction solution, wherein the upper layer contains polyether sulfone and the lower layer contains polyphosphoric acid.
In a preferable embodiment, in step 4), the polyphosphoric acid is recovered and regenerated, the polyethersulfone layer is separated into a separation liquid (the separation liquid is a poor solvent for polyethersulfone, and can be water, alcohol, ketone or a mixture thereof), the polyphosphoric acid and pyrophosphoric acid attached to the surface of the separation liquid are quickly dissolved and washed away, and the obtained polyethersulfone solid particles are crushed into blocks and subjected to post-treatment such as washing.
The bisphenol is a sulfuryl-containing bisphenol and is selected from the following structures:
the molar ratio of polyphosphoric acid to bisphenol is 3-8: 1.
in step 1), the molar ratio of the phosphorus pentoxide to the bisphenol is 0-6: 1, preferably 0.1 to 6: 1.
in step 1) of the present invention, phosphorus pentoxide acts as a dehydrating agent, and compared with polyphosphoric acid, the amount of phosphorus pentoxide dehydrated per unit weight is larger, that is, the same amount of water is removed, and the dosage of phosphorus pentoxide is smaller. The reaction effect is basically equal to that of polyphosphoric acid, but phosphorus pentoxide has high melting point and is difficult to liquefy, and the phosphorus pentoxide can be contacted with bisphenol powder, so that the phosphorus pentoxide is difficult to initiate polymerization, and is not suitable for being used independently. The polyphosphoric acid, although slightly lower in dehydration amount, is easily liquefied and can be rapidly mixed with bisphenol to initiate the reaction.
In the step 1), the dosage of the solvent is 0-5 times of the mass of the polyether sulfone.
The polyether sulfone and the solvent form a solution, and if the solution is too thin, the concentration of the base end of the molecule is too low along with the increase of the polymerization degree, so that the polymerization efficiency is influenced; too much solvent occupies a large amount of reaction kettle space, and the yield of one-time polymerization is low; too much solvent can cause the post-treatment to be complicated, and the advantage of simple post-treatment can be avoided; a small amount of solvent participates in the polymerization, so that the polyether sulfone formed by polymerization can be dissolved, and the polyether sulfone is better contacted with a dehydrating agent (polyphosphoric acid or phosphorus pentoxide), the polymerization process is accelerated, and the reaction temperature is reduced.
In step 1) of the present invention, the solvent is preferably selected from polar aprotic solvents, such as dimethylformamide, dimethylacetamide, methylpyrrolidone, and sulfolane. Halogenated hydrocarbons such as chloroform, tetrachloroethane are also preferred.
As a preferable scheme, in the step 3) of the present invention, if no solvent is used, after the reaction is stopped from the heat release, the temperature is raised to 160-350 ℃ to continue the reaction; when the solvent is used, the temperature is raised to 140-170 ℃ to continue the reaction after the reaction is stopped by self-heat release.
If no solvent is used in the step (3), the glass transition temperature of the polyether sulfone is always increased along with the increase of the molecular weight in the polymerization process. At this time, if the polyether sulfone is not heated at a high temperature, the curing reaction of the polyether sulfone gradually slows down, and after the heating, the polyether sulfone is melted and the dehydrating agent fully reacts, so that the reaction is continuously carried out. The glass transition temperature of the polyether sulfone is 160-225 ℃, and a small amount of decomposition is carried out at the temperature of more than 360 ℃. Therefore, the reaction temperature was set to 160-350 ℃ and at this temperature, the dehydrating agent was stably present.
If the solvent exists in the step (3), the produced polyether sulfone can be partially or completely dissolved in the solvent, molecules can move freely, and the polyether sulfone can be fully contacted with the dehydrating agent for smooth polymerization, so that higher temperature is not required. The boiling point of the solvent is generally below 210 ℃, and too high a boiling point easily causes pressure build-up in the kettle or solvent decomposition.
In step 3) of the present invention, the end-capping reagent is typically a small molecular weight (less than 500) organic molecule containing 1 or several reactive hydroxyl groups, suitable examples include, but are not limited to, alcohols, phenols or carboxylic acids. But are not limited to phenol, methanol, acetic acid, 4-hydroxydiphenyl sulfone.
In the step 4), the temperature during liquid separation may be 130-; if a solvent is included, 100-150 ℃ is preferred.
The bulk density of the polyether sulfone powder prepared by the method is higher than that of the polyether sulfone powder prepared by the traditional method, and reaches 380-450kg/m3The method is favorable for drying, storage and transportation, has better powder color, reaches RAL0009000, has better molecular weight distribution (Mw/Mn is less than or equal to 2), and has low proportion of ultrahigh molecular weight impurities (less than or equal to 0.2 percent) and low proportion of cyclopolymer impurities (less than or equal to 1.8 percent) shown by GPC analysis, thereby being favorable for application of downstream products.
In addition, the beneficial effects of the invention also include:
(1) the type of the polymerized monomer is reduced to one, the problem of monomer proportioning is not involved, and the product quality and batch stability are not easily influenced by the fluctuation of feeding proportion; almost no waste gas is discharged in the reaction process;
(2) an acidic system is used for replacing an alkaline system, so that the problems of pollution, product discoloration, low solvent recovery rate and the like caused by the decomposition of an alkaline system solvent are well controlled, and the dehydrating agent polyphosphoric acid can be recovered and regenerated;
(3) the post-treatment is extremely simple, the product polyether sulfone is collected by adopting a layered liquid separation mode, the water consumption for washing is greatly reduced compared with the water consumption for separating materials in the prior art, the crushed powder material in the process has higher bulk density, the space of post-treatment equipment is saved, the defect of flying dust can not occur during drying, and the resource is saved;
(4) energy is saved, and the reaction time is shortened;
(5) the end capping agent has various choices, can be added quantitatively, and is beneficial to environmental protection.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following examples.
GPC conditions:
equipment: shimadzu LC20A mobile phase DMF run-in: 100 microliter
Flow rate of mobile phase: 1 ml/min column temperature: 50 deg.C
A detector: and RI.
Example 1
Feeding stage
75kg (300mol) of bisphenol S was placed in a 1000L reactor, 304kg (900mol) of polyphosphoric acid preheated and melted at 60 ℃ was added, and a vacuum tube and a nitrogen tube were connected.
And (3) performing vacuum nitrogen replacement for three times, heating to 60 ℃, melting polyphosphoric acid to be liquid, starting a stirrer in the reaction kettle, stirring the materials into thin paste, performing vacuum nitrogen replacement for three times again, and ensuring that the oxygen partial pressure in the kettle is less than 50 ppm.
Polymerisation stage
Slowly heating until the temperature in the reaction kettle reaches 130 ℃, starting the dehydration reaction, and controlling the temperature in the system at 130-160 ℃ after the system starts to release heat. After the system exotherm becomes slow, the system is continuously heated and maintained at 260-280 ℃ for reaction.
End capping stage
On-line monitoring to reach 5000 centipoises, adding 460g of end-capping reagent 4-hydroxydiphenyl sulfone, and stirring and reacting for 30min at the temperature of 260 ℃ and 280 ℃.
Post-treatment stage
The stirring is stopped and the layers are separated by keeping at 260 ℃ and 280 ℃, wherein the polyether sulfone layer floats on the upper layer. The system temperature is controlled at 260 ℃ and 280 ℃, the lower layer polyphosphoric acid is separated out, and the polyphosphoric acid layer is heated to regenerate phosphorus pentoxide or high-purity polyphosphoric acid.
And then separately separating a polyether sulfone powder layer, washing the separated polyether sulfone layer with three batches of pure water of 300kg respectively, crushing and drying to obtain white powder with the size of about 1mm x 1mm, wherein the color RAL0009000 is obtained, and the bulk density of the dried white powder is about 400kg/m3。
Example 2
Feeding stage
241.5kg (600mol) of bisphenol (bisphenol is bis (4-hydroxybiphenyl) sulfone) was charged into a 4000L reactor, 1622kg (4800mol) of polyphosphoric acid preheated and melted at 80 ℃ and 511kg (3600mol) of phosphorus pentoxide were added, and a vacuum tube and a nitrogen tube were connected.
And (3) performing vacuum nitrogen replacement for three times, heating to 100 ℃, melting polyphosphoric acid to be liquid, starting a stirrer in the reaction kettle, stirring the materials into thin paste, performing vacuum nitrogen replacement for three times again, and ensuring that the oxygen partial pressure in the kettle is less than 50 ppm.
Polymerisation stage
Slowly heating until the temperature in the reaction kettle reaches 140 ℃, starting the dehydration reaction, and controlling the temperature in the system at 140-160 ℃ after the system starts to release heat. After the system exotherm becomes slow, the system is continuously heated and maintained at 300-320 ℃ for reaction.
End capping stage
On-line monitoring to reach 4500 centipoises, 340g of end-capping agent diphenol is added, and the reaction is stirred for 40min at the temperature of 300 ℃ and 320 ℃.
Post-treatment stage
The temperature is maintained at 300-320 ℃, the stirring is stopped, and the layers are separated, wherein the polyether sulfone floats on the upper layer. The temperature of the system is controlled to be 300-320 ℃, the lower layer polyphosphoric acid is separated out, and the polyphosphoric acid layer is heated to regenerate phosphorus pentoxide or high-purity polyphosphoric acid.
And then separately separating out a polyether sulfone layer, washing the separated polyether sulfone powder with three batches of pure water of 700kg respectively, crushing and drying. A white powder of about 1.5mm by 1.5mm size was obtained, colour RAL 0009000. After drying, the bulk density is about 420kg/m3。
Example 3
150kg of bisphenol S (600mol) was placed in a 2000L reactor, 1000kg of polyphosphoric acid (2959mol) preheated to melt at 80 ℃ and 300kg of sulfolane were added, and a vacuum tube and a nitrogen tube were connected.
And (3) performing vacuum nitrogen replacement for three times, heating to 80 ℃, melting polyphosphoric acid to be liquid, starting a stirrer in the reaction kettle, stirring the materials into emulsion, and performing vacuum nitrogen replacement for three times again, wherein the partial pressure of oxygen in the kettle is less than 40 ppm.
Polymerisation stage
Slowly heating until the temperature in the reaction kettle reaches 120 ℃, starting the dehydration reaction, and controlling the temperature in the system at 120-140 ℃. After the system exotherm becomes slow, the system is continuously heated and maintained at 150-170 ℃ for reaction.
End capping stage
On-line monitoring to 450 centipoises, 488g of n-amyl alcohol as an end-capping agent is added, and the reaction is stirred for 50min at the temperature of 120 ℃ and 130 ℃.
Post-treatment stage
The temperature is maintained at 120 ℃ and 130 ℃, the stirring is stopped, and the layers are separated, wherein the polyether sulfone solution floats on the upper layer. Controlling the system temperature at 120-.
And then separating out a polyether sulfone solution layer, separating out polyether sulfone solution by using 800kg of ethanol, crushing, washing by using three batches of pure water with 700kg of pure water, drying, and performing next post-treatment link to obtain white powder with the size of about 1mm by 1mm and the color RAL 0009000. After drying, the bulk density is about 450kg/m3。
Example 4
250kg (1000mol) of bisphenol S was placed in a 2000L reactor, 1352kg (4000mol) of polyphosphoric acid preheated and melted at 80 ℃ and 568kg (4000mol) of phosphorus pentoxide and 400kg of dimethyl sulfone were added, and a vacuum tube and a nitrogen tube were connected.
And (3) heating to 80 ℃ after three times of vacuum nitrogen replacement, melting polyphosphoric acid to be liquid, starting a stirrer in the reaction kettle, stirring the materials into suspension liquid, and performing vacuum nitrogen replacement again for three times, wherein the oxygen partial pressure in the kettle is less than 50 ppm.
Polymerisation stage
Slowly heating until the temperature in the reaction kettle reaches 130 ℃, starting the dehydration reaction, and controlling the temperature in the system at 130-140 ℃. After the system exotherm becomes slow, the heating is continued to maintain the reaction at 145-165 ℃.
End capping stage
On-line monitoring to reach 900 centipoises, adding 900g of end-capping reagent phenol, and stirring and reacting for 45min at the temperature of 145-.
Post-treatment stage
The stirring was stopped and the layers were separated by maintaining the temperature at 145-155 deg.C, wherein the polyethersulfone solution floated on the top layer. Controlling the system temperature at 145-155 ℃, separating out the lower layer polyphosphoric acid, and heating the polyphosphoric acid layer to regenerate phosphorus pentoxide or high-purity polyphosphoric acid.
And then separating out a polyether sulfone solution layer, separating out the polyether sulfone solution by using 1200kg of pure water, crushing, washing by using three batches of 1000kg of pure water respectively, and drying to obtain white powder with the size of about 2mm x 2mm, wherein the color is RAL 0009000. After drying, the bulk density is about 380kg/m3。
Example 5
300kg (1200mol) of bisphenol S was charged into a 2000L reactor, 1825kg (5400mol) of polyphosphoric acid preheated and melted at 80 ℃ and 767kg (5400mol) of phosphorus pentoxide and 500kg of dimethylacetamide were added, and a vacuum tube and a nitrogen tube were connected.
And (3) performing vacuum nitrogen replacement for three times, heating to 80 ℃, melting polyphosphoric acid to be liquid, starting a stirrer in the reaction kettle, stirring the materials into emulsion, and performing vacuum nitrogen replacement for three times again, wherein the partial pressure of oxygen in the kettle is less than 30 ppm.
Polymerisation stage
Slowly heating until the temperature in the reaction kettle reaches 130 ℃, starting the dehydration reaction, and controlling the temperature in the system at 130-140 ℃. After the system exotherm becomes slow, the system is continuously heated and maintained at 150-170 ℃ for reaction.
End capping stage
On-line monitoring to 550 centipoises, adding 1000g of benzoic acid as an end-capping agent, and stirring and reacting for 45min at the temperature of 150 ℃ and 170 ℃.
Post-treatment stage
The temperature is maintained at 140 ℃ and 130 ℃, the stirring is stopped, and the layers are separated, wherein the polyether sulfone solution floats on the upper layer. The system temperature is controlled to be 130-140 ℃, and the lower layer polyphosphoric acid is separated out to be recovered and heated to regenerate the phosphorus pentoxide.
And then separately separating out a polyether sulfone solution layer, separating out the polyether sulfone solution by using 1500kg of pure water, crushing, and washing by using three batches of 1200kg of pure water, wherein the total consumption of water is 3600 kg.
About 0.5mm x 0.5mm size white powder 276kg, color RAL0009000, was obtained. After drying, the bulk density is about 440kg/m3. 451kg of dimethylacetamide was recovered from the solvent, and the recovery rate was 90%.
The GPC data are shown in Table 1 below.
TABLE 1 polyethersulfone GPC data
Comparative example 1
This comparative example compares with example 5, using a prior art method for synthesizing polyethersulfone:
150kg of bisphenol S (600mol), 172.1kg (600mol) of dichlorodiphenyl sulfone and 125kg (901mol) of potassium carbonate were charged into a 2000L reactor, 1000kg of dimethylacetamide was added, and a vacuum tube and a nitrogen tube were connected.
The vacuum nitrogen is replaced for three times, and the oxygen partial pressure in the kettle is less than 30 ppm.
Polymerisation stage
Stirring was started and heating was carried out to 166 ℃ and the water formed was separated off. 600kg of aqueous solvent were separated off. The polymerization was continued at a controlled system internal temperature of 166-170 ℃ while a large amount of carbon dioxide and dimethylamine decomposed from the solvent were evolved, amounting to about 26.4 kg.
End capping stage
On-line monitoring to 350 centipoises, introducing 1000L of chloroethane, and stirring and reacting for 45min at the temperature of 150 ℃ and 170 ℃.
Post-treatment stage
The reaction solution was maintained at 130 ℃ and 140 ℃ to remove about 300kg of the solvent-containing salt by pressure filtration, filtrate 1 was collected, the salt was washed with 300kg of fresh dimethylacetamide and filtered, filtrate 2 was collected, and filtrates 1 and 2 were combined. The filtrate was poured into a tank and precipitated with 1500kg of pure water, and crushed into powder by a high-speed crusher. Filtering, and recycling the solvent from the filtrate in a recycling system, wherein the recycling rate of the solvent is about 70 percent.
The filter cake was a powder, washed with five batches of 1200kg each of pure water, consuming 6000kg of water, filtered and dried to give 275kg of powder of about 0.5mm by 0.5mm size, with color RAL 0959020. The powder is in the form of porous sponge under enlarged observation, and has a bulk density of about 180kg/m after drying3。
The GPC data are shown in Table 2 below.
TABLE 2 GPC data for comparative example 1 product
Compared with the comparative example 1, the monomer is reduced in the example 5, so the requirement on the feeding proportion of monomer polymerization is greatly reduced, the washing times and the water consumption are greatly reduced, the end capping agent is added according to the requirement by adopting non-toxic solid benzoic acid, and almost no residue is left after the reaction. Comparative example 1 employs gaseous ethyl chloride, which is highly dangerous to store, large in use amount and necessitates the use of a complicated tail gas recovery apparatus.
The acid-binding agent potassium carbonate of the comparative example 1 has almost no way of recycling, and can be discarded only when solid wastes are used, while the embodiment adopts the dehydration principle, dehydrating agents (polyphosphoric acid and phosphorus pentoxide) and easy recycling.
The proportion of the ultra-high molecular weight (0.1396% peak 1) to the low molecular weight (1.5846% peak 3) of the product in example 5 is low, and the proportion of the main peak is 98.2757%. Mw/Mn is 1.95, and the molecular weight distribution is good.
The proportion of the ultra-high molecular weight (peak 1.6736% 1) and low molecular weight (peak 2.0156% 3) of the product of comparative example 1 was high, and the proportion of the main peak 96.3108% was low. Mw/Mn was 2.02, and the molecular weight distribution was not good.
From the above examples and comparative examples, the process of the present invention greatly simplifies the polyethersulfone synthesis process, reduces waste gas emissions, simplifies the post-treatment process and saves material usage. The method is completely superior to the prior art in the aspects of energy consumption, environmental protection, flow and product quality.
It will be appreciated by those skilled in the art that modifications or adaptations to the invention may be made in light of the teachings of the present specification. Such modifications or adaptations are intended to be within the scope of the present invention as defined in the claims.
Claims (10)
1. A method of preparing a polyethersulfone comprising the steps of: carrying out dehydration reaction on bisphenol and polyphosphoric acid;
the bisphenol is selected from the following structural formulas
the temperature of the reaction is 120-160 ℃, the temperature is raised to 350 ℃ to continue the reaction when the self-heat release of the reaction is stopped, and the end-capping reagent is added to terminate the reaction when the target molecular weight is reached.
2. The method of claim 1, comprising the steps of: 1) putting bisphenol and polyphosphoric acid into a reaction kettle, optionally adding phosphorus pentoxide, and optionally adding a solvent;
2) nitrogen replacement is carried out on the reaction kettle, the polyphosphoric acid is liquefied by heating to 60-100 ℃, and then nitrogen replacement is carried out for 1-3 times;
3) then reacting at the temperature of 120-160 ℃, heating to the temperature of 140-350 ℃ to continue the reaction after the reaction self-heat release is stopped, and adding an end-capping reagent to terminate the reaction when the target molecular weight is reached.
3. The method of claim 1, comprising the steps of: 1) putting bisphenol and polyphosphoric acid into a reaction kettle, optionally adding phosphorus pentoxide, and optionally adding a solvent;
2) nitrogen replacement is carried out on the reaction kettle, the polyphosphoric acid is liquefied by heating to 70-90 ℃, and then nitrogen replacement is carried out for 1-3 times;
3) then reacting at the temperature of 140 ℃ and 160 ℃, heating to the temperature of 140 ℃ and 350 ℃ to continue the reaction after the reaction is stopped from heat release so as to reach the target molecular weight, and adding an end-capping reagent to terminate the reaction.
4. The method according to claim 2 or 3, wherein the method further comprises the steps of 4) layering the reaction solution, wherein the upper layer contains polyether sulfone, and the lower layer contains polyphosphoric acid; and treating the upper layer with a separating liquid, and crushing and washing the obtained polyether sulfone solid.
5. The method according to claim 2 or 3, wherein the molar ratio of phosphorus pentoxide to bisphenol is from 0 to 6: 1.
6. the method according to claim 2 or 3, wherein the molar ratio of phosphorus pentoxide to bisphenol is from 0.1 to 6: 1.
7. the method as claimed in claim 2 or 3, wherein in step 3), no solvent is used, and the reaction is continued by raising the temperature to 160-350 ℃ after the reaction self-exotherms are stopped; or, using a solvent, and raising the temperature to 140-170 ℃ to continue the reaction after the reaction is stopped from heat release.
8. A method according to any of claims 1 to 3, wherein the capping agent is selected from one or more of alcohols, phenols, carboxylic acids.
9. A method according to any one of claims 1 to 3, wherein the end-capping agent is selected from one or more of phenol, methanol, acetic acid, 4-hydroxydiphenylsulfone.
10. A polyethersulfone prepared according to any of claims 1-9, characterized in that the polyethersulfone powder has a bulk density of 380-450kg/m3The powder color reaches RAL0009000, the molecular weight distribution Mw/Mn is less than or equal to 2, the content of ultrahigh molecular weight impurities is less than or equal to 0.2 percent, and the content of cyclic polymer impurities is less than or equal to 1.8 percent.
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| US4415720A (en) * | 1980-10-01 | 1983-11-15 | Imperial Chemical Industries Plc | Production of aromatic polysulphones |
| CN105732984A (en) * | 2015-09-29 | 2016-07-06 | 江西师范大学 | Preparation method of polypyrrolone/sulfonated polyether sulfone proton exchange membrane |
| CN110229335A (en) * | 2019-06-26 | 2019-09-13 | 中国科学院长春应用化学研究所 | A kind of fluorine-containing polysulfones and preparation method thereof |
-
2021
- 2021-04-26 CN CN202110450808.XA patent/CN113278150B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4415720A (en) * | 1980-10-01 | 1983-11-15 | Imperial Chemical Industries Plc | Production of aromatic polysulphones |
| CN105732984A (en) * | 2015-09-29 | 2016-07-06 | 江西师范大学 | Preparation method of polypyrrolone/sulfonated polyether sulfone proton exchange membrane |
| CN110229335A (en) * | 2019-06-26 | 2019-09-13 | 中国科学院长春应用化学研究所 | A kind of fluorine-containing polysulfones and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 九·一二聚砜(聚苯砜醚)的合成;武汉大学高分子化学教研室等;《武汉大学学报(理学版)》;19731231(第02期);第45-58页 * |
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