CN112409596B - Polysulfone and preparation method thereof - Google Patents
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
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Abstract
The invention discloses polysulfone and a preparation method thereof, wherein the method comprises the following steps: 1) adding an organic bisphenol compound, 4' -dichlorodiphenyl sulfone, a salt forming agent, a catalyst and an aprotic polar solvent into a reaction vessel, heating to the boiling point of the aprotic polar solvent, and evaporating part of the solvent; 2) keeping the temperature, and reacting for a certain time to obtain a viscous polysulfone solution; 3) introducing a blocking agent into a system for blocking; 4) and (4) separating out the product in a precipitating agent, and performing post-treatment to obtain polysulfone powder. The invention adopts a one-step method to prepare polysulfone, does not need a non-water-soluble hydrocarbon solvent, has simple operation, reduces the post-treatment difficulty and the production cost, simultaneously adopts calixarene crown ether as a catalyst, increases the reaction activity, shortens the reaction time, and obtains a product with high molecular weight and narrow molecular weight distribution.
Description
Technical Field
The invention relates to polysulfone and a preparation method thereof, in particular to a method for preparing polysulfone by high-efficiency catalysis and the polysulfone obtained by the method, belonging to the field of high polymer materials.
Background
Polysulfone is an important thermoplastic special engineering plastic, mainly Polyethersulfone (PES), bisphenol a Polysulfone (PSU), polyphenylene sulfone (PPSU), etc. Polysulfone resins have excellent properties, such as excellent mechanical properties, high temperature resistance, chemical resistance, aging resistance, etc. The characteristics enable the material to be widely applied to various fields such as aerospace, national defense, electronics and electrical, medical treatment, nuclear power, oil wells, ships, magnetic wires, military industry, automobile manufacturing industry, food processing and the like.
The preparation method of the polysulfone mainly comprises a one-step method and a two-step method, wherein the two-step method comprises the steps of carrying out reflux water carrying on a water-insoluble hydrocarbon solvent to promote bisphenol to react with strong base to generate bisphenol salt, evaporating the water-insoluble hydrocarbon solvent to dryness, and then polymerizing the bisphenol salt with 4,4' -dichlorodiphenyl sulfone in an aprotic polar solvent to obtain the polysulfone. The method has the advantages of complicated steps, complex process, long reaction time, high energy consumption, wide molecular weight distribution of the obtained product and deep color. The polysulfone is prepared by adopting a one-step method, only one solvent is needed in the whole process, and the materials are fed once, so that the phenomena that oxidation is caused by air entering a kettle during the reaction process and organic steam overflows to cause harm to human bodies and the environment are avoided. However, the one-step method usually adopts potassium carbonate or sodium carbonate as a salt forming agent, which has low reactivity with bisphenol, and the solubility of the generated bisphenol salt in an aprotic polar solvent is low, which belongs to a heterogeneous reaction, so that the reaction activity can be improved and the reaction time can be reduced by adding a phase transfer catalyst.
The phase transfer catalyst mainly comprises onium salts, polyethers and calixarenes. The onium salt catalyst has low catalytic efficiency, can achieve catalytic effect only by adding a large amount of catalyst in a system, and is easy to decompose under high temperature and alkaline conditions to generate various side reactions. Although a certain effect is achieved by adopting crown ether catalysts to prepare polysulfone in the United states patent US5235019, the reaction time is long, the catalytic efficiency is not high, and the catalysts are expensive and have high toxicity, so that the catalysts are obviously not suitable for the environmental protection requirements of the modern society on materials. The calixarene catalyst serving as a third-generation supermolecule host behind crown ether and cyclodextrin can complex an ionic guest, has high catalytic activity, is unstable in conformation and is easy to reverse, and the catalytic action is influenced to a certain extent. In order to fix the conformation of the calixarene and improve the complexing stability of the calixarene and alkali metal ions, a polyethylene glycol chain can be introduced into the lower edge of the calixarene to form a basket-type calixarene crown ether structure. The stable conformation and the introduction of additional cavities greatly improve the catalytic efficiency of the catalyst.
Disclosure of Invention
The invention provides a preparation method of polysulfone, which does not need a non-water-soluble hydrocarbon solvent, has simple operation and reduces the post-treatment difficulty and the production cost, and simultaneously adopts calixarene crown ether as a catalyst, thereby increasing the reaction activity, shortening the reaction time, and obtaining the product with high molecular weight and narrow molecular weight distribution.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows, and the method specifically comprises the following steps:
1) adding an organic bisphenol compound, 4' -dichlorodiphenyl sulfone, a salt forming agent, a catalyst and an aprotic polar solvent into a reaction vessel, heating to the boiling point of the aprotic polar solvent, and evaporating part of the solvent;
2) keeping the temperature of the system obtained in the step 1) at the boiling point of the aprotic polar solvent, and stirring for reacting for a certain time (for example, 3-10 hours) to obtain a viscous polysulfone solution;
3) and (3) introducing an end-capping agent (methane chloride and/or methane chloride) into the polysulfone solution obtained in the step 2) for end-capping.
The method of the present invention may further comprise:
4) and (3) separating out the product in a precipitating agent, and carrying out post-treatment to obtain polysulfone powder.
Further, the organic bisphenol compound adopted in the step 1) is one or more of bisphenol A, bisphenol S, bisphenol F, hydroquinone, resorcinol, dihydroxy benzophenone, dihydroxy diphenyl ether, 4' -biphenol, hexafluorobisphenol A, tetrabromobisphenol A and dihydroxy naphthalene; the salt forming agent is potassium carbonate and/or sodium carbonate.
Further, the molar ratio of the organic bisphenol compound to the salt forming agent in the step 1) is 1: 1-1: 2, preferably 1: 1.3-1: 1.7.
preferably, the catalyst in step 1) is an organic matter satisfying the following structure:
further, the aprotic polar solvent in step 1) is one or more of N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and sulfolane.
Preferably, in step 1), the aprotic polar solvent is used in an amount such that the system has a solid content of 10% to 30%, preferably 15% to 25%.
Preferably, in the step 1), the molar ratio of the bisphenol salt (generated by the organic bisphenol compound and the salt forming agent) to the 4,4' -dichlorodiphenyl sulfone is 1: 0.995-1: 0.95, preferably 1: 0.99-1: 0.97.
preferably, in step 1), the amount of polycondensation catalyst used is 1 to 10 wt.%, preferably 3 to 6 wt.%, based on the total mass of theoretical product (one hundred percent of monomer conversion).
The reaction of step 1) preferably comprises: adding an organic bisphenol compound, 4' -dichlorodiphenyl sulfone, a salt forming agent, a catalyst and an aprotic polar solvent into a reaction vessel, heating to 150-290 ℃, and distilling off part of the solvent (the amount of the solvent depends on the reaction scale, and the amount of the solvent is distilled off, wherein 480-520 g of the solvent needs to be distilled off when 1mol of bisphenol salt is generated);
preferably, the step 2) reaction comprises: keeping the temperature of the system obtained in the step 1) at 150-290 ℃, and stirring for reaction for 3-10 h to obtain a viscous polysulfone solution.
Further, the reaction of step 3) preferably comprises: introducing chloromethane and/or monochloroethane gas (95-105L, for example about 100L of end-capping gas is needed for each mol of product) into the polysulfone system obtained in the step 2), and simultaneously cooling the system to 150 +/-5 ℃ for reaction for 0.5 +/-0.2 h to obtain the end-capped polysulfone.
In the reaction, a part of solvent is evaporated to take away the byproduct water generated in the reaction to obtain the high polymer, and the amount of the evaporated solvent is generally as follows: 480 to 520g of the solvent was distilled off for every 1mol of bisphenol salt formed.
In the present invention, the mixture of polysulfones can be isolated and purified according to post-treatment procedures well known to those skilled in the art.
Specifically, the polysulfone-containing solution should be filtered to remove the by-product NaCl/KCl and excess salt-forming agent. Precipitating polymer solid in a proper precipitating agent, repeatedly boiling and washing for many times, and drying to obtain pure polysulfone powder.
The present invention further relates to a capped polysulfone obtainable by the above preparation process.
The weight average molecular weight of the end-capped polysulfone as determined by gel permeation chromatography is in the range of 3.0-10.0X 104Preferably 3.5 to 9.0X 104The molecular weight distribution index PDI is 3.5-4.8, preferably 3.65-4.7.
In addition, the present invention also relates to the above catalyst for preparing polysulfone:
the invention further relates to a preparation method of the catalyst, which comprises the following steps:
A) preparation of tetraethyleneglycol di-p-toluenesulfonate: dripping polyethylene glycol-4 and 4-methylbenzenesulfonyl chloride (the molar ratio can be 1: 1.5-2.5, such as 1:1.85) into a reaction vessel, reacting in an organic solvent under an alkaline condition, pouring the reaction liquid into ice water, dripping acid for neutralization, extracting, washing with water, drying, filtering, and removing the organic solvent to obtain tetraethyleneglycol di-p-toluenesulfonate;
B) preparation of p-tert-butylcalix [4] -1, 3-crown-5: adding solvent, p-tert-butylcalix [4] arene, tetraethyleneglycol di-p-toluenesulfonate and potassium carbonate (the molar ratio of the p-tert-butylcalix [4] arene, the tetraethyleneglycol di-p-toluenesulfonate and the potassium carbonate can be 1:1.05-1.5:1.05-1.5, such as 1:1.13:1.13) into a reaction vessel under the protection of nitrogen, stirring, refluxing, filtering, evaporating the filtrate under reduced pressure to remove the solvent, dissolving the residue, separating liquid after acidification, washing an organic layer, drying, evaporating under reduced pressure to remove the solvent, and separating by silica gel column chromatography to obtain white solid p-tert-butylcalix [4] -1, 3-crown-5.
The invention has the positive effects that:
(1) compared with the traditional two-step method, the one-step method adopted by the invention does not use a non-water-soluble hydrocarbon solvent, the aprotic polar solvent can be used as a water-carrying agent and a reaction solvent, the materials are fed once, and the kettle is not required to be opened for feeding in the whole reaction process, so that the process flow and the post-treatment difficulty are greatly simplified, and the production cost is reduced. The bisphenol salt has high reaction activity, is very easy to oxidize at high temperature, is carried out in a nitrogen atmosphere by a one-step method, and completely isolates air, so that the side oxidation reaction and the harm to human bodies and environment caused by organic steam overflow due to kettle opening and feeding at high temperature are avoided, the molecular weight of the product is easy to control, and the appearance is excellent.
(2) In a solid-liquid reaction system, the catalytic efficiency of the macrocyclic catalyst is higher than that of the onium salt, and the macrocyclic catalyst has better heat resistance and is suitable for high-temperature reaction. The calixarene catalyst is used as a third-generation supermolecule host after crown ether and cyclodextrin, has a size-adjustable hydrophobic cavity, can be matched with and identify an ionic object, and has good thermal stability, chemical stability and high catalytic activity. The calixarene reacts with cheap and easily available polyethylene glycol, and crown ether rings can be introduced into molecules to obtain a brand new catalyst, namely the calixarene crown ether. The property of the catalyst is not only simple addition of calixarene and crown ether, but also a synergistic effect, greatly enhances the complexing ability with guest ions, and greatly improves the catalytic efficiency.
Detailed Description
The following examples are given according to the above polysulfone preparation process and are not intended to limit the scope of the present invention.
Example 1:
57mmol of sodium hydroxide/12 mL of water and 20mmol of polyethylene glycol-4/20 mL of tetrahydrofuran are sequentially added into a 100mL four-mouth bottle with a ice salt bath, stirred for 1.5h, and 37mmol of 4-methylbenzenesulfonyl chloride/20 mL of tetrahydrofuran is slowly dropped into the system (about 2h) to react for 2.5h below 5 ℃. Pouring the reaction solution into ice water, dropping a plurality of drops of 1M dilute hydrochloric acid, extracting with dichloromethane, sequentially washing an organic phase with water, washing with saturated salt water, and drying with anhydrous magnesium sulfate. Filtering and removing the organic solvent to obtain the tetraethyleneglycol di-p-toluenesulfonate.
Under the protection of nitrogen, acetonitrile 300mL and 6.75mmol of p-tert-butyl cup [4] are added into a three-neck flask in sequence]Aromatic hydrocarbon, 7.64mmol of tetraethyleneglycol di-p-toluenesulfonate and 7.64mmol of potassium carbonate are stirred and refluxed for reaction for 24 hours at the temperature of 80 ℃. Filtering, evaporating the filtrate under reduced pressure to remove solvent, dissolving the residue with dichloromethane, acidifying with dilute hydrochloric acid, separating, washing the organic layer with saturated sodium bicarbonate solution and distilled water, drying with anhydrous sodium sulfate, evaporating under reduced pressure to remove solvent, and separating by silica gel column chromatography to obtain white solid p-tert-butyl cup [4]]-1, 3-crown-5.1H NMRδ:7.19(s,2H,OH)，7.07(s，4H，ArH)，6.75(s,4H,ArH)，4.37(d,J＝13.1Hz，4H，ArCH2)，4.07(s，8H，OCH2)，3.97(t,J＝5.5Hz,4H,OCH2)，3.84(t,J＝5.5Hz,4H,OCH2)，3.29(d,J＝13.1Hz,4H,ArCH2)，1.31(s,18H,CH3 in tBu)，0.91(s，18H，CH3 in tBu)；EI(+)-MS m/z:825{[M+H2O+H]+})。
Placing a four-mouth flask with a water separator, a condenser and a mechanical stirrer into an oil bath reactor, and sequentially placing the flask in the oil bath reactor0.25mol of bisphenol A, 0.375mol of potassium carbonate, 0.24875mol of 4,4' -dichlorodiphenylsulfone, and 5.48g of p-tert-butylcalix [4]]And (3) starting to stir and purge the 1, 3-crown-5, 500g N, N-dimethylacetamide with nitrogen for 0.5h, raising the temperature of the oil bath to 185 ℃ (the system temperature is 166 ℃), evaporating 130g of N, N-dimethylacetamide, and continuing to react for 5h to obtain a yellow viscous polysulfone solution. Introducing monochloroethane gas (gas flow rate is 1L/min) into the system for end capping, simultaneously reducing the oil bath temperature to 150 ℃, and stirring for reaction for 0.5 h. Diluting the reaction solution to 10% of solid content, filtering to remove salt, separating out in water to obtain white flocculent solid, boiling in water for multiple times, filtering, and drying to obtain pure polysulfone product. Molecular weight M by Gel Permeation Chromatography (GPC)W＝5.5×104Molecular weight distribution index PDI of 3.78; measured by Differential Scanning Calorimetry (DSC), the glass transition temperature Tg＝187℃。
Example 2:
catalyst preparation of t-butylcalix [4] -1, 3-crown-5 reference was made to example 1.
In a four-necked flask equipped with an oil bath heater, a stirrer, a water separator and a condenser, 0.1mol of bisphenol S, 0.1mol of sodium carbonate, 0.098mol of 4,4' -dichlorodiphenylsulfone and 0.455g of p-tert-butyl cup [4] were placed in the flask in this order]And (3) starting to stir and purge nitrogen for 0.5h by using-1, 3-crown-5 and 409.68g of N, N-dimethylformamide, raising the temperature of the oil bath to 170 ℃ (the system temperature is 153 ℃), evaporating to remove 125g of N, N-dimethylformamide, and continuing to react for 3h to obtain a yellow viscous polysulfone solution. And introducing methane chloride gas (gas flow rate is 1L/min) into the system for end capping, simultaneously reducing the oil bath temperature to 150 ℃, and stirring for reaction for 10 min. Diluting the reaction solution to 10% of solid content, filtering to remove salt, separating out in methanol to obtain white flocculent solid, boiling with water for many times, filtering, and drying to obtain pure polysulfone product. Molecular weight M by Gel Permeation Chromatography (GPC)W＝3.9×104Molecular weight distribution index PDI of 3.66; measured by Differential Scanning Calorimetry (DSC), glass transition temperature Tg＝185℃。
Example 3:
catalyst preparation of t-butylcalix [4] -1, 3-crown-5 reference was made to example 1.
1mol of bisphenol A, 2mol of potassium carbonate, 0.95mol of 4,4' -dichlorodiphenyl sulfone and 42.04g of p-tert-butyl cup [4]]Putting 1, 3-crown-5 and 0.98kg of sulfolane into a reaction kettle with a temperature control, stirring and reflux water diversion device at one time, purging with nitrogen for 0.5h, raising the temperature of the reaction kettle to 300 ℃ (the system temperature is 285 ℃), evaporating to remove 120g of sulfolane, and continuing to react for 10h to obtain a yellow viscous polysulfone solution. And introducing methane chloride gas (gas flow rate is 1L/min) into the system for end capping, simultaneously reducing the oil bath temperature to 150 ℃, and stirring for reaction for 100 min. Diluting the reaction solution to 10% of solid content, filtering to remove salt, precipitating in ethanol to obtain white flocculent solid, boiling in water for multiple times, filtering, and drying to obtain pure polysulfone product. Molecular weight M by Gel Permeation Chromatography (GPC)W＝6.9×104Molecular weight distribution index PDI 4.57; measured by Differential Scanning Calorimetry (DSC), glass transition temperature Tg＝192℃。
Example 4:
catalyst preparation of t-butylcalix [4] -1, 3-crown-5 reference was made to example 1.
4mol of bisphenol A, 6mol of potassium carbonate, 3.96mol of 4,4' -dichlorodiphenyl sulfone and 88.5g of p-tert-butylcalix [4]]-1, 3-crown-5, 7.08 kgN-methyl pyrrolidone, putting into a reaction kettle with a temperature control, stirring and reflux water diversion device at one time, purging with nitrogen for 0.5h, raising the temperature of an oil bath to 225 ℃ (system temperature 203 ℃), evaporating to remove 2.08 gN-methyl pyrrolidone, and continuing to react for 10h to obtain a yellow viscous polysulfone solution. Introducing monochloroethane gas (gas flow rate is 10L/min) into the system for end capping, simultaneously reducing the oil bath temperature to 150 ℃, and stirring for reaction for 40 min. Diluting the reaction solution to 10% of solid content, filtering to remove salt, separating out in ethanol to obtain white flocculent solid, boiling with water for multiple times, filtering, and drying to obtain pure polysulfone product. Molecular weight M by Gel Permeation Chromatography (GPC)W＝7.5×104Molecular weight distribution index PDI 3.95; measured by Differential Scanning Calorimetry (DSC), the glass transition temperature Tg＝194℃。
Comparative example 1:
in the area ofPlacing a water heater, a condenser pipe and a mechanically-stirred four-neck flask into an oil bath reactor, sequentially adding 0.25mol of bisphenol A, 0.375mol of potassium carbonate, 0.24875mol of 4,4' -dichlorodiphenyl sulfone and 500g of N, N-dimethylacetamide into the flask, starting stirring and purging with nitrogen for 0.5h, raising the temperature of the oil bath to 185 ℃ (the system temperature is 166 ℃), evaporating to remove 130g of N, N-dimethylacetamide, and continuing to react for 5h to obtain a yellow viscous polysulfone solution. Introducing monochloroethane gas (gas flow rate is 1L/min) into the system for end capping, simultaneously reducing the oil bath temperature to 150 ℃, and stirring for reaction for 0.5 h. Diluting the reaction solution to 10% of solid content, filtering to remove salt, separating out in water to obtain white flocculent solid, boiling in water for multiple times, filtering, and drying to obtain pure polysulfone product. Molecular weight M by Gel Permeation Chromatography (GPC)W＝3.6×104Molecular weight distribution index PDI 5.66; measured by Differential Scanning Calorimetry (DSC), the glass transition temperature Tg＝183℃。
Comparative example 2:
a four-neck flask with a water separator, a condenser and a mechanical stirrer was placed in an oil bath reactor, and 0.25mol of bisphenol A, 0.375mol of potassium carbonate, 0.24875mol of 4,4' -dichlorodiphenylsulfone and 5.48g of p-tert-butyl cup [4] were sequentially added to the flask]Aromatic hydrocarbon and 500g N, N-dimethylacetamide are stirred and purged with nitrogen for 0.5h, the oil bath temperature is increased to 185 ℃ (the system temperature is 166 ℃), 130g of N, N-dimethylacetamide is distilled off, and the reaction is continued for 5h to obtain yellow viscous polysulfone solution. Introducing monochloroethane gas (gas flow rate is 1L/min) into the system for end capping, simultaneously reducing the oil bath temperature to 150 ℃, and stirring for reaction for 0.5 h. Diluting the reaction solution to 10% of solid content, filtering to remove salt, separating out in water to obtain white flocculent solid, boiling in water for multiple times, filtering, and drying to obtain pure polysulfone product. Molecular weight M by Gel Permeation Chromatography (GPC)W＝4.37×104Molecular weight distribution index PDI 4.51; measured by Differential Scanning Calorimetry (DSC), the glass transition temperature Tg＝186℃。
The implementation of the comparative example shows that the reaction time can be effectively shortened and the monomer conversion rate can be improved by adopting the calixarene crown ether catalytic reaction, and the obtained polysulfone resin has narrow molecular weight distribution and excellent performance.
Claims (7)
1. A preparation method of polysulfone comprises the following steps:
1) adding an organic bisphenol compound, 4' -dichlorodiphenyl sulfone, a salt forming agent, a catalyst and an aprotic polar solvent into a reaction vessel, heating to the boiling point of the aprotic polar solvent, and evaporating part of the solvent;
2) keeping the temperature of the system obtained in the step 1) at the boiling point of the aprotic polar solvent, and stirring for reacting for a certain time to obtain a viscous polysulfone solution;
3) introducing an end-capping reagent into the polysulfone solution obtained in the step 2) to cap,
wherein, the catalyst in the step 1) is an organic matter which satisfies the following structure:
2. the method of making according to claim 1, further comprising:
4) and (3) precipitating the product obtained in the step 3) in a precipitating agent, and carrying out post-treatment to obtain polysulfone powder.
3. The method of claim 1, wherein the organic bisphenol compound used in step 1) is one or more of bisphenol a, bisphenol S, bisphenol F, hydroquinone, resorcinol, dihydroxybenzophenone, dihydroxydiphenyl ether, 4' -biphenol, hexafluorobisphenol a, tetrabromobisphenol a, dihydroxynaphthalene; the salt forming agent is potassium carbonate and/or sodium carbonate;
the mol ratio of the organic bisphenol compound to the salt forming agent in the step 1) is 1: 1-1: 2.
4. the method according to claim 1,
the mol ratio of the organic bisphenol compound to the salt forming agent in the step 1) is 1: 1.3-1: 1.7.
5. the production method according to claim 1,
the aprotic polar solvent in the step 1) is one or more of N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and sulfolane; and/or
In the step 1), the solid content of the system is 10-30 percent; and/or
In the step 1), the molar ratio of the bisphenol salt to the 4,4' -dichlorodiphenyl sulfone is 1: 0.995-1: 0.95; and/or
In the step 1), the amount of the polycondensation catalyst is 1-10 wt% of the total mass of the theoretical product.
6. The method of claim 5, wherein:
in the step 1), the solid content of the system is 15-25%; and/or
In step 1), the molar ratio of bisphenolate to 4,4' -dichlorodiphenyl sulfone is 1: 0.99-1: 0.97; and/or
In the step 1), the amount of the polycondensation catalyst is 3-6 wt% of the total mass of the theoretical product.
7. The preparation method according to claim 1, wherein the reaction temperature in step 1) is 150 to 290 ℃, and the mass of the evaporated solvent is 120 to 130 g; and/or
Step 2), the reaction temperature is 150-290 ℃, and the reaction time is 3-10 h; and/or
The end-capping agent in the step 3) is methane chloride and/or methane chloride; and/or
Step 3) the reaction comprises: introducing methane chloride and/or chloroethane gas into the polysulfone system obtained in the step 2), and simultaneously cooling the system to 150 +/-5 ℃ for reaction for 0.5 +/-0.2 h to obtain the end-capped polysulfone; and/or
In the step 4), the precipitating agent is selected from one or more of methanol, ethanol and water.
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| CN112409596A (en) | 2021-02-26 |
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