CN111253574B - Preparation method of polysulfone resin material with low cyclic dimer content - Google Patents
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Abstract
The invention relates to a preparation method of a polysulfone resin material with low cyclic dimer content, belonging to the technical field of polysulfone resin. The preparation method of the low-cyclic dimer content polysulfone resin material comprises the steps of taking a phenolic substance and part of 4,4 '-dichlorodiphenyl sulfone as reaction monomers, adding an aprotic exchange solvent, an acid-binding agent and a water-carrying agent, adding an end-capping agent and the other part of 4,4' -dichlorodiphenyl sulfone at a constant speed during a water-carrying reaction, evaporating the water-carrying agent for continuous polymerization, and carrying out post-treatment to obtain the low-cyclic dimer content polysulfone resin material. The target product prepared by the method has high purity and stable performance.
Description
Technical Field
The invention relates to a preparation method of a polysulfone resin material with low cyclic dimer content, belonging to the technical field of polysulfone resin.
Background
Polysulfone is a high molecular polymer, an amorphous, thermoplastic resin, characterized by: excellent mechanical property, high rigidity, wear resistance, high strength, etc. Because of its good characteristics, polysulfone has been widely used as a material in high-end fields such as medical instruments, aerospace, electronics, and the like.
At present, the most advanced production process of polysulfone high-molecular materials is a one-step polymerization method. The one-step polymerization method mainly comprises a polymerization process and a product purification process.
(1) The polymerization process comprises the following steps: the main raw materials of 4,4' -dichlorodiphenyl sulfone, bisphenol A, bisphenol S or biphenol, potassium carbonate or potassium bicarbonate, sodium carbonate and the like are polymerized in a solvent, and the common solvent comprises dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and the like. Because dimethyl sulfoxide contains sulfone groups, the solvent has excellent thermal stability and is more suitable for synthesizing sulfone materials. The process can select toluene, xylene and the like as dehydrating agents.
(2) The purification process of the polymer comprises the following steps: and slowly pouring the polymerized liquid after the polymerization into water or alcohol for precipitation so as to separate the polysulfone from the polymer solution. The separated polysulfone is boiled in high-temperature water to remove salt, and then the polysulfone is dried, granulated and the like.
In the polysulfone material synthesized by the traditional polymerization process, the content of the cyclic dimer is 1.7-2.5 wt%. The cyclic dimer is slowly crystallized and separated out when the sulfone polymer is dissolved in the aprotic exchange solvent, and is also crystallized and separated out in the high-temperature melting and processing process of the sulfone polymer. The presence of large amounts of cyclic dimers can cause serious problems for polysulfone spinning applications. For example, the cyclic dimer can be slowly crystallized in the polysulfone membrane casting solution, and the crystal can block a filter head of spinning equipment, so that the membrane forming processing performance of the polysulfone material is seriously influenced, and the phenomena of membrane filaments becoming brittle, easy to break, lacking in elasticity and the like are further caused. The molecular structure of the cyclic dimer is as follows:
therefore, a new synthesis process needs to be developed to reduce the content of cyclic dimer in polysulfone resin material.
Disclosure of Invention
The invention aims to provide a preparation method of a polysulfone resin material with low cyclic dimer content, which has the advantages of low production cost, energy saving, environmental protection, high purity of prepared target products and stable performance.
The preparation method of the low-cyclic dimer content polysulfone resin material comprises the steps of taking a phenolic substance and part of 4,4 '-dichlorodiphenyl sulfone as reaction monomers, adding an aprotic exchange solvent, an acid-binding agent and a water-carrying agent, adding an end-capping agent and the other part of 4,4' -dichlorodiphenyl sulfone at a constant speed during a water-carrying reaction, evaporating the water-carrying agent for continuous polymerization, and carrying out post-treatment to obtain the low-cyclic dimer content polysulfone resin material.
The polysulfone resin material can be Polysulfone (PSU), Polyethersulfone (PES), polyphenylsulfone (PPSU), polyarylethersulfone, polyarylsulfone and other high polymer materials.
The phenolic substance is one or more of bisphenol A, bisphenol S or 4,4' -dihydroxybiphenyl.
The aprotic exchange solvent is one or more of dimethyl sulfoxide, sulfolane, N-dimethylformamide, N-dimethylacetamide or N-methylpyrrolidone.
The acid-binding agent is one or more of potassium bicarbonate, sodium bicarbonate, cesium carbonate, sodium hydroxide, potassium carbonate or sodium carbonate.
The water-carrying agent is toluene, xylene or chlorobenzene.
The end capping agent is a phenolic monomer. The phenolic monomer is one or more of bisphenol S, phenol, p-cresol, p-ethylphenol, p-methoxyphenol, p-tert-butylphenol or 2-isopropylphenol.
The preparation method of the polysulfone resin material with low cyclic dimer content specifically comprises the following steps:
(1) putting all phenolic reaction monomers, an acid binding agent, 10-95% of 4,4 '-dichlorodiphenyl sulfone, 50-90% of a solvent and all water-carrying agents into a reaction kettle according to a reaction proportion, vacuumizing and purging the reaction kettle with nitrogen, wherein the nitrogen standard is high-purity nitrogen, adding the water-carrying agents at the temperature of 110 ℃ and 150 ℃ for carrying out water-carrying reaction for 2-8h, dissolving an end-capping agent and 5-90% of 4,4' -dichlorodiphenyl sulfone in the remaining 10-50% of the solvent during the water-carrying period, and replenishing into the reaction kettle at a constant speed for 0-6 h, preferably 1-4 h;
(2) after the water is carried out, evaporating all water-carrying agents, heating to 160-205 ℃, continuing to polymerize for 4-10h, wherein the solid content is 22-42%, and finishing the reaction when the viscosity in the kettle reaches 4000-;
(3) after the reaction is finished, opening a bottom valve at the bottom of the kettle, slowly transferring the polymerization solution into water to completely separate out the polysulfone material, mechanically crushing the polymerization solution into powder, boiling the powder in water at high temperature for multiple times, and drying the powder for 8 to 16 hours in vacuum to remove water and solvent steam to finally obtain a powdery target product.
The end-capping agent is charged in a molar ratio of 0.1 to 10%, preferably 0.5 to 8%, based on the mass of phenolic monomer.
The molar ratio of the phenol monomer to the dichlorodiphenyl sulfone to the acid-binding agent to the end-capping agent is 0.85-1: 1: 1.05-3: 0.005-0.15.
The total mass of the aprotic exchange solvent is 2.5-5 times of the total mass of the phenolic reaction monomer and the dichlorodiphenyl sulfone.
The dosage of the water-carrying agent is 10-50% of the mass of the aprotic exchange solvent.
In order to reduce the generation of cyclic dimer in the polymerization process of polysulfone resin materials, the invention provides a blocking technology in the polymerization process of polysulfone materials, which greatly reduces the self-cyclization probability of dimer and successfully reduces the cyclic dimer content in products such as polysulfone, polyethersulfone, polyphenylsulfone and the like through the blocking and end group structure design and the optimization of a supplement process. The molecular structure of the polysulfone resin material synthesized by using the end-capping technology is as follows:
in the polysulfone material synthesized by the traditional polymerization process, the content of the cyclic dimer is 1.7-1.9 wt%, the content of the cyclic dimer is only 1.1-1.2 wt% after the novel end capping technology is utilized for optimization, and the integral content reduction rate is 35.29-36.84%. During the reaction with water, part of 4,4' -dichlorodiphenyl sulfone and an end-capping agent are added at a constant speed, and the content of cyclic dimer generated by polymerization is reduced through the synergistic effect of two modes of molecular structure design and end group blocking; and then evaporating the water-carrying agent for continuous polymerization, and performing post-treatment to obtain the polysulfone resin material with the low cyclic dimer content. The generation of the cyclic dimer is mainly because a large amount of ABAB type dimer oligomers are easily formed in the early polymerization stage, and the dimer has the tendency of connection and self-cyclization in a terminating reaction, so that the monomer amount in the early polymerization reaction is insufficient by batch input of 4,4' -dichlorodiphenyl sulfone, only an ABA type structure can be formed, and the content of the cyclic dimer is successfully reduced; and subsequently, adding 4,4' -dichlorodiphenyl sulfone and an end-capping reagent into the reaction kettle at a constant speed, keeping the balance of the molar ratio of the materials in the reaction, and finally obtaining the sulfone polymer with the molecular weight of Mw =40000 and 100000, thereby completely meeting the daily use and processing requirements of customers.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention has low production cost, energy saving and environmental protection;
(2) the target product prepared by the method has high purity and stable performance, the integral content reduction rate of the cyclic dimer is 35.29-36.84%, and the cyclic dimer can be applied to high-end fields such as hollow fiber membranes, medical instruments, aerospace, electronics and the like;
(3) the invention efficiently solves the fatal defect of the sulfone products, reaches the level of the same level as the foreign imported products, and has certain guiding significance for the industrial production of sulfone series products.
Drawings
FIG. 1 is a process flow diagram according to the present invention.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the practice of the invention.
Example 1
4.3kg of 4,4' -dichlorodiphenyl sulfone, 6.6kg of bisphenol A, 5.2kg of potassium carbonate, 35kg of solvent N, N-Dimethylacetamide (DMAC) and 15kg of xylene were charged in a 100L polymerization reactor. 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, introducing the nitrogen to the normal pressure for reaction, carrying out nitrogen protection in the whole polymerization reaction, carrying out water at 150 ℃ for 2 hours, dissolving an end capping agent bisphenol S and p-cresol into 35kg of N, N-dimethylacetamide at a constant speed, and adding the mixture into the reaction kettle, wherein the total mass of the end capping agent bisphenol S and the p-cresol is 42g (the mass ratio of the two is 1: 1) and 4.6kg of 4,4' -dichlorodiphenylsulfone.
All dimethylbenzene is evaporated, the temperature is raised to 162 ℃, and polymerization is continued for 10 h. The solid content is maintained at 22-30%, and the reaction is finished when the viscosity in the kettle reaches 6000 centipoises.
After the reaction is finished, opening a bottom valve at the bottom of the kettle, slowly pouring the polymerization solution into water to completely separate out the polysulfone material, mechanically crushing the polymerization solution into powder, boiling the powder in water at high temperature for multiple times, and drying the purified polysulfone material to obtain a powdery product.
The relevant data were obtained by Gel Permeation Chromatography (GPC) analysis:
polysulfone cyclic dimer content 1.15%, Mw =68520, Mn =42216, MWD = 1.62.
Example 2
Into a 100L polymerization reactor were charged 35kg of sulfolane, 7.2kg of bisphenol S, 6kg of potassium hydrogencarbonate, 4.1kg of 4,4' -dichlorodiphenyl sulfone, and 20kg of xylene. 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, introducing the nitrogen to the normal pressure for reaction, carrying out nitrogen protection in the whole polymerization reaction, carrying out water at 155 ℃ for 6 hours, and compounding end capping agents of p-ethylphenol and p-cresol into 37g (the mass ratio of the p-ethylphenol to the p-cresol is 2: 3) and 4.8kg of 4,4' -dichlorodiphenyl sulfone in 25kg of sulfolane and adding the mixture into the reaction kettle at a constant speed.
After the water is brought up, all the dimethylbenzene is evaporated out, the temperature is raised to 200 ℃, the polymerization is continued for 4 hours, and the reaction is ended when the viscosity is 8000 centipoises.
And when the polyether sulfone polymerization solution reaches the target molecular weight, opening a bottom valve at the bottom of the kettle, slowly pouring the polymerization solution into water to completely separate out the polysulfone material, mechanically crushing the polymerization solution into powder, boiling the powder in water at high temperature for multiple times, and drying the purified polysulfone material to obtain a powdery product.
The relevant data were obtained by Gel Permeation Chromatography (GPC) analysis:
polyether sulfone cyclic dimer content 1.21%, Mw =143420, Mn =83871, MWD = 1.71.
Example 3
30kg of dimethyl sulfoxide (DMSO), 5.3kg of biphenol, 5.8kg of potassium carbonate, 4.5kg of 4,4' -dichlorodiphenyl sulfone and 20kg of xylene are added into a 100L polymerization reaction kettle. 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, introducing the nitrogen to the normal pressure for reaction, carrying out nitrogen protection in the whole polymerization reaction, carrying out water at 155 ℃ for 5 hours, and dissolving 36g (the mass ratio of the two is 3: 7) of end capping agent bisphenol Z and phenol and 4.4kg of 4,4' -dichlorodiphenyl sulfone in 30kg of dimethyl sulfoxide and supplementing the mixture into the reaction kettle at a constant speed.
After the water is carried out, all dimethylbenzene is evaporated out, the temperature is raised to 180 ℃, the polymerization is continued for 8 hours, and the polymerization reaction is finished when the viscosity is 11000 centipoises.
And when the polyphenylsulfone polymerization solution reaches the target molecular weight, opening a bottom valve at the bottom of the kettle, slowly pouring the polymerization solution into water to completely separate out the polysulfones, mechanically crushing the polysulfones into powder, boiling the powder in water at high temperature for multiple times, and drying the purified polyphenylsulfone material to obtain a powdery product.
The relevant data were obtained by Gel Permeation Chromatography (GPC) analysis:
polyphenylsulfone ring dimer content 1.11%, Mw =33080, Mn =19232, MWD = 1.72.
Example 4
4.9kg of 4,4' -dichlorodiphenyl sulfone, 6.4kg of bisphenol A, 5kg of potassium carbonate, 40kg of solvent N, N-Dimethylacetamide (DMAC) and 18kg of xylene were charged in a 100L polymerization reactor. 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, introducing the nitrogen to the normal pressure for reaction, carrying out nitrogen protection in the whole polymerization reaction, carrying out water at 150 ℃ for 8 hours, compounding 40g (the mass ratio of the bisphenol S and the p-methoxyphenol is 1: 1) of end capping agent and 4kg of 4,4' -dichlorodiphenyl sulfone in 20kg of N, N-dimethylacetamide, and adding the mixture into the reaction kettle at a constant speed.
All dimethylbenzene was distilled off, and the temperature was raised to 164 ℃ to continue the polymerization for 5 hours. The reaction was terminated when the viscosity in the kettle reached 15000 cps.
After the reaction is finished, opening a bottom valve at the bottom of the kettle, slowly pouring the polymerization solution into water to completely separate out the polysulfone material, mechanically crushing the polymerization solution into powder, boiling the powder in water at high temperature for multiple times, and drying the purified polysulfone material to obtain a powdery product.
The relevant data were obtained by Gel Permeation Chromatography (GPC) analysis:
polysulfone cyclic dimer content 1.13%, Mw =52493, Mn =31622, MWD = 1.66.
The following conclusions can be drawn from the data of the above examples: by using the end-capping reagent and optimizing the supplementing process, the content of cyclic dimer in the sulfone material is obviously reduced, the product quality is greatly improved, and the same level of foreign imported products is achieved.
Comparative example 1
8.9kg of 4,4' -dichlorodiphenyl sulfone, 6.6kg of bisphenol A, 5.2kg of potassium carbonate, 42g of the total compound mass of end capping agents bisphenol S and p-cresol (the mass ratio of the two is 1: 1), 70kg of solvent N, N-Dimethylacetamide (DMAC) and 15kg of xylene are added into a 100L polymerization reaction kettle. 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, introducing nitrogen to the normal pressure for reaction, carrying out nitrogen protection in the whole polymerization reaction, carrying out water at 150 ℃ for 2 hours, steaming out all dimethylbenzene, heating to 162 ℃, and continuing to polymerize for 10 hours. The solid content is maintained at 22-30%, and the reaction is finished when the viscosity in the kettle reaches 6000 centipoises.
After the reaction is finished, opening a bottom valve at the bottom of the kettle, slowly pouring the polymerization solution into water to completely separate out the polysulfone material, mechanically crushing the polymerization solution into powder, boiling the powder in water at high temperature for multiple times, and drying the purified polysulfone material to obtain a powdery product.
The relevant data were obtained by Gel Permeation Chromatography (GPC) analysis:
polysulfone ring dimer content 1.95%, Mw =68031, Mn =41586, MWD =1.62, cyclic dimer =1.95 wt%.
Compared with the same experimental conditions, the additional operation is not carried out, and the content of the polysulfone cyclic dimer is increased by 0.8 percent.
Comparative example 2
Into a 100L polymerization reactor were charged 35kg of sulfolane, 7.2kg of bisphenol S, 6kg of potassium hydrogencarbonate, 4.1kg of 4,4' -dichlorodiphenyl sulfone, and 20kg of xylene. Vacuumizing the kettle to be less than or equal to-0.08 MPa, introducing nitrogen to enable the pressure in the kettle to be more than or equal to 0.00MPa, replacing the nitrogen for three times, introducing the nitrogen to the normal pressure for reaction, carrying out nitrogen protection in the whole polymerization reaction, carrying out water at 155 ℃ for 6 hours, compounding end capping agents of p-ethylphenol and p-cresol into 37g (the mass ratio of the p-ethylphenol to the p-cresol is 2: 3) and 4.8kg of 4,4' -dichlorodiphenyl sulfone during the water carrying period, and dissolving the end capping agents of p-ethylphenol and p-cresol into 25kg of sulfolane by supplementing 20% of mass in the first 2 hours, 50% in the middle 2 hours, 30% in the later 2 hours and slowly.
After the water is brought up, all the dimethylbenzene is evaporated out, the temperature is raised to 200 ℃, the polymerization is continued for 4 hours, and the reaction is ended when the viscosity is 8000 centipoises.
And when the polyether sulfone polymerization solution reaches the target molecular weight, opening a bottom valve at the bottom of the kettle, slowly pouring the polymerization solution into water to completely separate out the polysulfone material, mechanically crushing the polymerization solution into powder, boiling the powder in water at high temperature for multiple times, and drying the purified polysulfone material to obtain a powdery product.
The relevant data were obtained by Gel Permeation Chromatography (GPC) analysis:
polyether sulfone cyclic dimer content 1.64%, Mw =143420, Mn =83871, MWD = 1.71.
Compared with the same experimental conditions, the content of the polyether sulfone cyclic dimer is increased by 0.43 percent by supplementing the non-uniform speed operation.
Comparative example 3
4.3kg of 4,4' -dichlorodiphenyl sulfone, 6.6kg of bisphenol A, 5.2kg of potassium carbonate, 42g of the total mass of a mixture of end capping agents bisphenol S and p-cresol (the mass ratio of the two is 1: 1), 35kg of solvent N, N-Dimethylacetamide (DMAC) and 15kg of xylene are added into a 100L polymerization reaction kettle. 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, introducing the nitrogen to the normal pressure for reaction, carrying out nitrogen protection in the whole polymerization reaction, carrying out water at 150 ℃ for 2 hours, dissolving 4.6kg of 4,4' -dichlorodiphenyl sulfone in 35kg of N, N-dimethylacetamide, and adding the solution into the reaction kettle at a constant speed.
All dimethylbenzene is evaporated, the temperature is raised to 162 ℃, and polymerization is continued for 10 h. The solid content is maintained at 22-30%, and the reaction is finished when the viscosity in the kettle reaches 6000 centipoises.
After the reaction is finished, opening a bottom valve at the bottom of the kettle, slowly pouring the polymerization solution into water to completely separate out the polysulfone material, mechanically crushing the polymerization solution into powder, boiling the powder in water at high temperature for multiple times, and drying the purified polysulfone material to obtain a powdery product.
The relevant data were obtained by Gel Permeation Chromatography (GPC) analysis:
polysulfone cyclic dimer content 1.45%, Mw =67316, Mn =41754, MWD = 1.61.
Compared with the same experimental conditions, the end-capping reagent is not supplemented, and the content of the polysulfone cyclic dimer is increased by 0.3 percentage point.
Claims (5)
1. A preparation method of a polysulfone resin material with low cyclic dimer content is characterized by comprising the following steps: adding a solvent, an acid-binding agent and a water-carrying agent into a phenolic substance and part of 4,4 '-dichlorodiphenyl sulfone serving as reaction monomers, adding an end-capping agent and the other part of 4,4' -dichlorodiphenyl sulfone at a constant speed during a water-carrying reaction, evaporating the water-carrying agent to continue polymerization, and performing post-treatment to obtain the polysulfone resin material with the low cyclic dimer content;
the end capping agent is a phenol monomer; the phenolic monomer is one or more of bisphenol S, phenol, p-cresol, p-ethylphenol, p-methoxyphenol, p-tert-butylphenol or 2-isopropylphenol;
the method comprises the following steps:
(1) putting all phenolic reaction monomers, an acid binding agent, 10-95% of 4,4' -dichlorodiphenyl sulfone, 50-90% of a solvent and all water carrying agents into a reaction kettle according to a reaction proportion, vacuumizing and purging the reaction kettle with nitrogen, carrying out water carrying for 2-8 hours at the temperature of 110-;
(2) after the water is carried out, evaporating all water-carrying agents, heating to 160-205 ℃, continuing to polymerize for 4-10h, wherein the solid content is 22-42%, and finishing the reaction when the viscosity in the kettle reaches 4000-;
(3) after the reaction is finished, transferring the polymerization solution into water to separate out polysulfone materials, crushing the polymerization solution into powder, boiling the powder in water at high temperature for multiple times, and drying the powder for 8 to 16 hours in vacuum to finally obtain a powdery target product;
the phenolic substance is one or more of bisphenol A, bisphenol S or 4,4' -dihydroxybiphenyl.
2. The method for preparing the polysulfone resin material with low cyclic dimer content according to claim 1, wherein: the solvent is one or more of dimethyl sulfoxide, sulfolane, N-dimethylformamide, N-dimethylacetamide or N-methylpyrrolidone.
3. The method for preparing the polysulfone resin material with low cyclic dimer content according to claim 1, wherein: the acid-binding agent is one or more of potassium bicarbonate, sodium bicarbonate, cesium carbonate, sodium hydroxide, potassium carbonate or sodium carbonate.
4. The method for preparing the polysulfone resin material with low cyclic dimer content according to claim 1, wherein: the water-carrying agent is toluene, xylene or chlorobenzene.
5. The method for preparing the polysulfone resin material with low cyclic dimer content according to claim 1, wherein: when the reaction is carried out with water, the temperature is 110-150 ℃, the reaction lasts for 2-8h, and the time for adding the end-capping reagent at constant speed is 1-4 h.
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| CN114058015A (en) * | 2021-12-23 | 2022-02-18 | 广东优巨先进新材料股份有限公司 | Preparation method of polyarylethersulfone |
| CN114891219A (en) * | 2022-03-28 | 2022-08-12 | 桂林理工大学 | High-performance multi-element polysulfone resin and preparation method and application thereof |
| CN114561013B (en) * | 2022-04-28 | 2022-07-19 | 富海(东营)新材料科技有限公司 | Process for purifying polysulfone resin material by critical phase-change extraction method |
| CN115058009B (en) * | 2022-05-17 | 2023-10-20 | 万华化学集团股份有限公司 | Preparation method of sulfone polymer with low cyclic polymer content |
| CN116515114A (en) * | 2023-04-28 | 2023-08-01 | 珠海万通特种工程塑料有限公司 | Polymerization method of aromatic sulfone polymer |
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