CN111621013A - Preparation method of polyether sulfone resin - Google Patents
Preparation method of polyether sulfone resin Download PDFInfo
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- CN111621013A CN111621013A CN202010405412.9A CN202010405412A CN111621013A CN 111621013 A CN111621013 A CN 111621013A CN 202010405412 A CN202010405412 A CN 202010405412A CN 111621013 A CN111621013 A CN 111621013A
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- 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 relates to a preparation method of polyether sulfone resin. The method comprises the following steps: mixing bisphenol S, a dichloro monomer, an acid-binding agent, a water-carrying agent and a solvent, heating to form salt under the protection of nitrogen, and refluxing to separate water; evaporating to remove the water-carrying agent and simultaneously carrying out prepolymerization reaction; adding a chain extender and a catalyst for continuous reaction; and precipitating the polymer solution to obtain the polyether sulfone resin. The invention adopts the self-made dimercapto chain extender containing the carbamate group, can efficiently and rapidly complete the chain extension reaction, and obtains the polyether sulfone resin with high molecular weight by polymerization in a short time. Due to the improvement of the chain extension efficiency, the high-boiling-point polar solvent adopted by the conventional preparation method is avoided, and the medium-high-boiling-point polar solvent is used, so that the reaction time and the reaction temperature are reduced, and the economic efficiency is remarkably improved. In addition, due to the introduction of the urethane group, the melt index of the obtained polyether sulfone resin is remarkably reduced, and the polyether sulfone resin is beneficial to processing and molding, but the use strength of the resin is not influenced.
Description
Technical Field
The invention belongs to the field of high molecular polymer synthesis, and particularly relates to a method for low-temperature polymerization of polyether sulfone resin.
Technical Field
The polyether sulfone is a high-temperature special engineering plastic with a main chain containing aromatic ether bonds and sulfone groups, has the glass transition temperature of over 220 ℃, has various excellent performances of corrosion resistance, high temperature resistance, creep resistance, impact resistance, flame retardance and the like, and is widely applied to various fields of electronics, medical treatment, machinery, automobiles and the like.
However, polyethersulfones have traditionally been prepared by slow polymerization at high temperatures for long periods of time using high boiling, highly polar solvents such as diphenyl sulfone, sulfolane (EP2225328a1, US20100310804a1, CN 85105138A). The method has various defects when being applied to actual chemical production, such as difficult recovery and treatment of waste solvent, high production energy consumption, low reaction efficiency, more side reactions under high temperature and the like.
In order to overcome the defects, the patent CN105482118A adopts a difluoride monomer to replace a dichlorine monomer, and utilizes the characteristic of stronger fluorine atoms to improve the nucleophilic reaction activity. The method can adopt solvents with lower boiling points such as DMF, DMAc and the like to complete polymerization at lower temperature, but on one hand, the acquisition cost of the difluoro monomer is higher, and on the other hand, the reaction time of the method is very long (more than 15h), so the method has great use limitation.
Patent CN1268526A provides a method for preparing polyethersulfone by improving solid content of reactants. The method solves the problem of overhigh reaction viscosity caused by solid content improvement by adopting the organic silicon diluent, and shortens the reaction time. However, the residue of the silicone diluent in the resin in this process is a difficult problem to solve, and the reaction temperature is still high (220 ℃).
Patent CN103642030A provides another method for increasing reaction solid content and accelerating polymerization, namely increasing the salt forming temperature (above 200 ℃), completing salt forming prepolymerization at higher temperature in one step, and increasing the reaction solid content to 35% -45% in the polymerization stage, so as to accelerate the polymerization reaction and shorten the reaction time. In the method, salt formation at high temperature easily causes instability of bisphenol salt, so that the color of a final product is darkened, and in addition, higher cost is required for purification and recovery of the adopted high-temperature water separating agent.
Patent CN110272546A discloses a preparation method of polyethersulfone, which uses dimethyl sulfone as a reaction solvent and a mixed salt of potassium carbonate and barium carbonate with a weight ratio of 6:1 as an acid-binding agent, thereby effectively shortening the reaction time and improving the reaction yield. However, this process requires the consumption of a large amount of mixed carbonate (1.45 to 1.95 times the weight of bisphenol S), making the desalting of the crude product difficult and economically inefficient.
Besides the restriction of reaction conditions, the traditional polyethersulfone material has the problems of high melt index, difficult molding and processing, and particularly high difficulty in melt extrusion, and the use of the material is severely limited. For this reason, it is a common practice to introduce a ketone group into the main chain by copolymerization to improve the regularity of the molecular chain, thereby improving resin flowability. For example, US20100310804a1 reports a method for preparing polyethersulfone ketone, which uses sodium carbonate and potassium carbonate as salt forming agents to polymerize in diphenylsulfone at 275 ℃ to obtain resin with better fluidity. Patent CN103626991A discloses a polyether sulfone ketone resin which is prepared by taking dihalo benzophenone as a ketone-containing monomer and controlling the molar ratio of sulfone to ketone to 5-9: 1, wherein the processing temperature is not higher than 350 ℃ and the melt index is 10-30 g/10 min. However, the common disadvantages of the above methods are: the polymerization reaction is difficult, the polymerization period is long, and the color of the product is dark.
Therefore, there is a need in the art to develop a new polyethersulfone synthesis process, which reduces the reaction temperature and shortens the reaction time while ensuring the qualified performance of the resin, and the reaction solvent preferably avoids the use of a high-boiling-point solvent which is difficult to recover, and adopts a common solvent which is cheap and easy to obtain. Meanwhile, the prepared resin has good processing fluidity and excellent service performance, and the application field of the polyether sulfone resin is expanded.
Disclosure of Invention
The invention provides a preparation method of polyether sulfone resin. According to the method, the dimercapto chain extender is adopted, so that the polymerization speed in the middle and later stages of the polymerization reaction is increased, and finally the preparation of the polyether sulfone with high molecular weight is realized. Because the nucleophilic activity of the dimercapto in a catalytic environment is stronger, the rapid chain growth can be realized at a lower temperature, so that the whole polymerization process can avoid using high-boiling solvents such as sulfolane and the like, and instead, the high-boiling solvents such as DMF, DMAc and the like are used. In addition, urethane groups are introduced into the chain extender molecules, so that the high-temperature fluidity of the polymer is improved, and the processing performance of the polyether sulfone resin is obviously improved.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a preparation method of polyether sulfone resin comprises the following steps:
(1) mixing bisphenol S, a dichloro monomer, an acid-binding agent, a water-carrying agent and a solvent, heating to form salt under the protection of nitrogen, and refluxing to separate water;
(2) evaporating to remove the water-carrying agent and simultaneously carrying out prepolymerization reaction;
(3) adding a chain extender and a catalyst for continuous reaction;
(4) and precipitating the polymer solution to obtain the polyether sulfone resin.
In the present invention, the molar ratio of the dichloromonomer to the bisphenol S in the step (1) is (1.01 to 1.2):1, preferably (1.05 to 1.1): 1. The amount of the dichloromonomers is suitably large, so that the terminal group of the prepolymer after the preliminary prepolymerization reaction is mainly an aromatic chlorine group, and the prepolymer is conveniently polymerized with dimercapto in the chain extension stage. Here, the excess of the dichloromonomer has a significant advantage that the bisphenol S salt formed in the salt formation stage can be completely converted into the phenoloxy ether bond as soon as possible, thereby preventing the deterioration of the bisphenol S salt due to long-term exposure and the resultant deactivation of the terminal groups.
The dichloro monomer is selected from one or more of dichlorodiphenyl sulfone, dichlorodiphenyl ether, dichlorobenzophenone and dichlorobiphenyl.
In the present invention, the molar ratio of the metal atom to the bisphenol S in the acid-binding agent is (2-3): 1, preferably (2.2-2.5): 1. The reason why a significant excess of acid scavenger is required is: on one hand, the acid-binding agent needs to participate in the salifying reaction of phenolic hydroxyl, and on the other hand, the acid-binding agent is used for maintaining enough alkali environment of the whole reaction system so as to be beneficial to the promotion of nucleophilic reaction. However, a large excess of acid-binding agent induces side reactions and stresses the latter in salt removal.
The acid-binding agent is selected from one or more of sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium ethoxide, potassium ethoxide and sodium hydride, and preferably potassium carbonate.
In the invention, the water-carrying agent in the step (1) is one or more of toluene, xylene, ethylbenzene, trimethylbenzene, durene and dimethylcyclohexane, and xylene is preferred. No matter what water-carrying agent is adopted, enough hydrophobicity is ensured, and the azeotropic point of the water-carrying agent and the reaction solvent is more than 100 ℃, so that the produced water can be conveniently discharged. The dosage of the water-carrying agent is 25-50 wt% of the solvent.
The solvent is selected from one or more of dimethylformamide, dimethylacetamide, pyridine, N-methylpyrrolidone, N-ethylpyrrolidone and dimethyl sulfoxide, and is preferably dimethylacetamide.
Preferably, the dosage of the solvent is 1.8-3 times of the theoretical mass of the polyether sulfone resin product. The theoretical mass of the polyether sulfone resin product is the mass of the sum of the mass of the fed monomers with the byproduct salt subtracted.
In the present invention, the removal of the water-carrying agent by evaporation and the prepolymerization reaction may be carried out simultaneously. When the water diversion is finished, the monomer concentration is higher, the formed bisphenol S salt can quickly generate a micromolecule prepolymer with a dichloro monomer, the monomer concentration is reduced along with the advance of the prepolymerization, and the prepolymerization speed is gradually slowed down. In practical operation, the time taken for distilling off the water-carrying agent is about less than or equal to the time taken for the prepolymerization, and when the water-carrying agent is distilled off, the prepolymerization reaction is carried out for a while.
In order to obtain a better prepolymerization effect, the reaction can be continued for a period of time after the water-carrying agent is distilled off, but it needs to be noted that the addition of the subsequent chain extender does not need to wait for the prepolymerization reaction to be completely finished, and the prepolymerization speed is only reduced to a certain degree. The method has the advantages of greatly saving the whole reaction time and improving the production efficiency. The change of the prepolymerization speed can be characterized by measuring the reaction heat release, the viscosity change of the system and the like. Generally, the whole prepolymerization lasts for about 1-2 hours, and then the chain extender can be added for the next chain extension reaction.
The salt-forming prepolymerization reaction equation is exemplified as follows:
In the invention, the chain extender adopted in the step (3) has the following structural formula:
wherein R is an organic group with 1-20 carbon atoms and is the residue of dithiol, and the dithiol comprises one or more of ethanedithiol, propanedithiol, butanedithiol, pentanethiol, hexanedithiol, ethylene glycol dimercaptoacetate and butanediol dimercaptoacetate; r' is an organic group with 1-20 carbon atoms and is the residue of diisocyanate, and the diisocyanate comprises one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, m-xylylene diisocyanate and tetramethyl-m-xylylene diisocyanate; m is an integer of 1 to 10.
The preparation method of the chain extender comprises the following steps: diisocyanates are prepared with dithiols in the presence of solvents. The diisocyanate includes, but is not limited to, diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), isophorone diisocyanate (IPDI), Toluene Diisocyanate (TDI), Hexamethylene Diisocyanate (HDI), m-Xylylene Diisocyanate (XDI), and the like. The dithiols include, but are not limited to, ethanedithiol, propanedithiol, butanedithiol, pentanethiol, hexanedithiol, ethylene glycol dimercaptoacetate, butylene glycol dimercaptoacetate, and the like.
Chain extenders of different m values can be prepared by controlling the molar ratio of the reaction of the dithiol and the diisocyanate. When the m values are different, the influence of the chain extender on the polyether sulfone is correspondingly different, for example, when m is 1-2, the obtained polyether sulfone resin has a high melt index and high mechanical strength and hydrolysis resistance; when m is 4-8, the melt index of the polyether sulfone resin is lower, the flowability is better, and the mechanical strength and the hydrolysis resistance are slightly reduced. Experiments show that even when m is 1, the chain extender can obviously improve the melt index of the polyether sulfone and improve the flowability. Preferably, when the molar ratio of the diisocyanate to the dithiol is controlled to be 1/2-3/4, that is, when m is 1-3, the overall performance of the final resin is better. In addition, it is not preferable to set the value of m to be too large, because when the value of m is larger than 10, the resulting dithiol compound tends to have a complicated branched structure and a large amount of by-products.
The dosage of the chain extender is 1-10%, preferably 5-8% of the molar weight of the dichloro monomer.
In the step (3), the catalyst is one or more of Pd/C, Pd/alumina, Pd/silica, cuprous acetate, cuprous chloride, copper bromides, cuprous iodide, cuprous sulfide, copper acetylacetonate and Schiff base Cu. The low-temperature rapid reaction of the step (3) can be realized.
In the step (3) of the present invention, the amount of the catalyst is 0.1 to 0.5 wt% based on the weight of the dichloromonomer.
The sulfydryl of the dimercapto compound has higher nucleophilic reaction activity, the reaction of the mercaptan and the aromatic halide is realized by directly substituting halogen atoms of the aromatic halide by mercaptan anions, and the reaction can also rapidly occur at normal temperature under the catalytic environment of Pd and Cu.
It is emphasized that the dimercapto compound can only react at normal or low temperature under the action of the Pd and/or Cu catalyst, since the terminal chlorine needs to be activated in a catalytic environment to achieve a rapid reaction with the mercapto anion. If the catalyst is not present, the whole reaction time is prolonged, and the reaction temperature is correspondingly increased.
Normally, the conventional polymerization process (preparation of polyether sulfone resin from prepolymer) requires reaction at a high temperature of more than 200 ℃ with sulfolane as a solvent to achieve a relatively ideal reaction rate. In the step (3) of the present invention, the reaction can be carried out even if the reaction temperature is lowered to 100 ℃ or lower. Certainly, in practical application, the chain extension reaction can be directly carried out by using the reaction waste heat (empirically, the reaction waste heat is about 110-130 ℃) in the step (2), so that the cooling time is saved, and the production efficiency is improved. However, the reaction using the residual heat is only an optional but not essential condition, that is, the chain extension reaction of step (3) can be well performed even if the residual heat is not used, but the reaction solution obtained by the prepolymerization reaction is waited to be cooled to room temperature of 25 ℃. Compared with the traditional process, the invention has the advantage of greatly reducing the energy consumption due to the obvious reduction of the reaction temperature.
The reaction temperature of the step (3) is 0-140 ℃, and preferably 80-130 ℃; the reaction time is 0.5-2 h.
In particular practice, the process of the invention can complete the entire polymerization step in no more than 5 hours compared to the overall reaction time of more than 10 hours for conventional polymerization processes. In terms of reaction temperature, the chain extension reaction of the dimercapto and the chlorine-terminated prepolymer under the catalytic environment in the step (3) can occur at normal temperature, but considering that a small part of bisphenol S salt in a reaction system continues to react with the chlorine-terminated prepolymer, the reaction temperature can be actually increased properly, and tests show that the chain extension reaction can prepare qualified polyether sulfone resin at the temperature of below 140 ℃. On the other hand, because the distillation of the hydrocarbon water-carrying agent is obviously required to be realized above the boiling point (the invention does not suggest the distillation of the water-carrying agent by adopting a reduced pressure distillation method because the requirement on the air tightness of the device is too high), the residual heat of the distilled water-carrying agent can be completely utilized to directly supply the chain extension reaction without additionally heating or removing heat for the reaction system. For example, o-xylene is used as a water-carrying agent, after the o-xylene is distilled off at 145 ℃, heating is stopped, a chain extender and a catalyst are directly added, the chain extension reaction is carried out by utilizing the residual temperature, and the polymerization reaction is basically finished when the temperature is gradually and naturally reduced to 100-110 ℃, so that a high-viscosity resin solution is obtained.
As the temperature required by the chain extension reaction is not high, the conditions are loose, the whole preparation process does not need to adopt high-boiling-point solvents such as diphenyl sulfone and sulfolane, and can adopt medium-boiling-point and high-boiling-point polar solvents such as DMF (dimethyl formamide), DMAc (dimethyl formamide) and the like, and the advantages of low cost, convenient recovery, simple process and higher economic and environmental benefits are achieved.
The chain extension reaction equation is as follows:
in the formula (I), the compound is shown in the specification,
represents the chain extender of the present invention.
Preferably, the step (4) of the present invention comprises the following specific steps: and (4) pouring the reactant obtained in the step (3) into a precipitating agent under the condition of high-strength stirring to form flocculent solid suspension, and then filtering to obtain a polyether sulfone resin finished product. And (3) the volume amount of the precipitating agent is 2-3 times of the volume of the reactant obtained in the step (3).
The precipitating agent is one or more of water, methanol and ethanol, and preferably water.
Preferably, after step (4) of the present invention is completed, a person skilled in the art may perform a re-purification operation on the obtained polyethersulfone resin by using a conventional post-treatment method, such as water washing, alcohol washing, drying, and the like, to further improve the quality of the resin. The present invention is not particularly limited to post-treatment means, but it is emphasized that any post-treatment process is optional and not essential.
The invention has the positive effects that: the method has the advantages that the bis-mercapto chain extender in a catalytic environment is adopted to prepare the polyether sulfone, so that the time and temperature of polymerization reaction are obviously reduced, the production efficiency is greatly improved, and the overall energy consumption is reduced; the polar solvent with medium and high boiling points is adopted to replace sulfolane and diphenyl sulfone, so that the solvent cost is reduced, the recovery rate of the solvent is improved, and great environmental and economic benefits are brought; in addition, due to the introduction of the carbamate group in the chain extender, the melt index of the obtained polyether sulfone resin is remarkably reduced, the processing and molding are facilitated, and the use strength of the resin is not influenced.
The polyether sulfone resin is suitable for the fields of various electronic and electric components, printed copper-clad plates, water treatment valves, pipe fittings, medical instruments and the like.
Detailed Description
(1) The molecular weight and distribution test method comprises the following steps:
a detection instrument: shimadzu LC-20A liquid chromatograph
Light source: SPD-20A D2 lamp
Wavelength range: SPD-20A 190nm-700nm
Flow rate setting range: 0.001mL/min-10.000mL/min
The infusion mode is as follows: tandem double plunger
The sample preparation method comprises the following steps: 1% THF solution
(2) Melt index test method:
testing an instrument: vitaceae MEITUP MKT-400
The test method comprises the following steps: 343 ℃, 2.16kg and 10min
(3) Mercapto equivalent test method:
referring to national standards: GB/T1792-2015.
In the specific embodiment of the present invention, the main raw material sources are as follows:
table 1 main raw materials
| Chemical reagent | Specification of | Origin of origin |
| Bisphenol S | AR | Aladdin reagent |
| 4, 4' -dichlorodiphenyl sulfone | AR | Dormitory cloud peak |
| 4, 4' -dichlorodiphenyl ether | AR | Wuhan Fude chemical industry |
| 4, 4' -dichlorobenzophenone | AR | Biochemistry of Mecline |
| Dicyclohexylmethane diisocyanate | AR | Wanhua chemistry |
| Hexamethylene diisocyanate | AR | Wanhua chemistry |
| Diphenylmethane diisocyanate | AR | Wanhua chemistry |
| Isophorone diisocyanate | AR | Wanhua chemistry |
| Ethanedithiol | AR | Shanghai nation chemical industry |
| 1, 3-propanedithiol | AR | Shanghai nation chemical industry |
| 1, 6-hexanedithiol | AR | Shanghai nation chemical industry |
| 1, 4-butanedithiol | AR | Shanghai nation chemical industry |
| Pd/C catalyst | CP | Shaanxi Rui material |
| Pd/copper oxide catalyst | CP | Shaanxi Rui material |
| Bis (mercaptoacetic acid) ethylene glycol ester | AR | Jinjinle chemical |
| Brominating imino ketone | AR | Aladdin reagent |
| Copper acetylacetonate | AR | Aladdin reagent |
Preparation of chain extender
Dissolving 18.9g of ethanedithiol in 200ml of butanone distilled to remove water in a four-neck flask filled with nitrogen and a reflux water separator, heating to 65 ℃ after fully dissolving, slowly dropwise adding 26.2g of dicyclohexylmethane diisocyanate, controlling the temperature to gradually heat to reflux, reacting for 2 hours, separating out a product after cooling, washing for 2 times by using acetone after filtering, and drying in vacuum to obtain a target dimercapto compound (a chain extender X)1)37.5g, yield 83.2%. The compound was tested to have a thiol equivalent of 220 and the number of repeating units was found to be about 1, i.e., m is 1.
Chain extenders with different structures and different mercapto equivalent weights can be prepared by selecting different types of dithiols and diisocyanates or adjusting the reaction molar ratio of the dithiols and the diisocyanates (see the preparation of the chain extender in Table 2 for details), and the rest conditions are the same as the above.
Table 2 preparation of chain extenders
Example 1
93g of N, N-dimethylacetamide (containing water by molecular sieve) dehydrated by molecular sieve was poured into a four-necked flask connected with a condenser, a water separator, a mechanical stirrer and a thermometer<500ppm) and 23g o-xylene, set at 400 RPM. Bisphenol S23.84g, dichlorodiphenyl sulfone 28.72g and sodium hydroxide 8.38g are put into a flask at one time, and nitrogen is introduced for protection. Gradually heating to 150 ℃ to ensure that the system is azeotropic, and taking out the water system by the o-xylene until no water carrying phenomenon is observed, wherein the whole process lasts for about 1.5 h. Then, o-xylene was distilled off, and the reaction was continued at reflux temperature for 20 min. Subsequently, the heating was stopped and 1.783g of chain extender X was added to the flask10.029g of Pd/C catalyst, at room temperature (about 135 ℃ C.) for 2 hours to obtain a polymer solution. And pouring the polymer solution into 250ml of water under the condition of high-strength stirring for precipitation, filtering, boiling for 3-4 times, and drying for 6 hours at 180 ℃ in a vacuum oven to obtain 45.2g of a polyether sulfone resin finished product.
Example 2
Adding 1195.5g of dichlorodiphenyl ether, 855.26g of potassium carbonate, 1238.96g of bisphenol S, 3749g of N, N-dimethylformamide and 1874g of toluene into a reaction kettle connected with a reflux condensing device, pumping air in the kettle to negative pressure, and introducing nitrogen to completely replace the air in the kettle; heating to ensure that the temperature in the kettle is 110-112 ℃, reacting for 1 hour at constant temperature, and maintaining the toluene to flow back until all the generated water is taken out. The toluene was then evaporated off, heating was stopped, and the reaction was cooled to room temperature (25 ℃). 198.3g of chain extender X is continuously added into the reaction kettle2And 3.587g of copper acetylacetonate, and stirred to react for 1 hour to obtain a polymer solution. Under high-intensity stirring, 9000g of methanol is used to precipitate the polymer solution, which is then repeatedly washed 3 times with water and dried for 4 hours in a forced air drying oven at 150 ℃ to obtain 2036g of finished polyether sulfone powder.
Example 3
1394g of dimethyl sulfoxide (water content) with water removed by redistilling is added into a glass-lined kettle connected with a water separator and a reflux condenser pipe<300ppm), accurately weighing 227.52g of bisphenol S and 287.16g of dichlorodiphenyl sulfone, stirring at normal temperature to dissolve, adding 188.47g of potassium carbonate, roughly dispersing, adding 418g of ethyl benzene, heating under the protection of nitrogen, stirring until the temperature reaches 180 ℃, starting the system to flow back, collecting water brought out by the water carrying agent, and stopping water diversion. Evaporating ethylbenzene, cooling to 120 deg.C, maintaining, and addingChain extender X353.7g and 1.44g of cuprous bromide, the reaction was carried out for 30min, and the reaction was stopped when no further increase in the viscosity of the system was observed. And under the condition of high-strength stirring, putting the obtained polymer solution into 2L of industrial ethanol, precipitating and crushing, repeatedly carrying out alcohol boiling for 2 times and water boiling for 1 time by using the industrial ethanol, and drying for 5 hours at 160 ℃ in an air-blast drying oven to obtain 450g of polyether sulfone resin.
Example 4
581g of dimethylacetamide and 232g of toluene are poured into a four-neck flask connected with a spherical condenser pipe, a mechanical stirrer and a thermometer, exactly 104.28g of bisphenol S, 143.58g of dichlorodiphenyl sulfone and 44.16g of sodium carbonate are weighed, the materials are put into a reaction bottle at one time, air in the bottle is repeatedly replaced by nitrogen, stirring is started, the temperature is gradually increased to 110-112 ℃ and maintained, the toluene is boiled and condensed, reflows and is separated by water, the temperature is continuously increased after the separation of water is finished, and the toluene is continuously evaporated. When the toluene is completely evaporated, 44g of chain extender X is added4And 0.287g of Pd/alumina catalyst at 80 ℃ for 2 h. And pouring the polymer solution into 1.5L of hot water for precipitation under the condition of high-strength stirring, repeatedly washing the precipitate for 5 times, and drying the precipitate for 4 hours in a vacuum oven at 160 ℃ to obtain 230g of finished polyether sulfone.
Example 5
1697g of N-methylpyrrolidone is put into an oil bath kettle equipped with a reflux device in advance, accurately weighing the bisphenol S417.12g and the dichlorobenzophenone 452g, stirring the materials in batches and slowly adding the materials into the oil bath kettle, and after the two monomers are completely dissolved, adding 224.4g of potassium hydroxide and 594g of o-xylene. Boiling and refluxing o-xylene in the system at 155 ℃ under the protection of nitrogen in the whole process, gradually taking out water, raising the temperature to 165 ℃ after water separation is finished, and continuously distilling off the o-xylene until the reflux is finished. Stopping heating, reducing the temperature in the kettle to about 130 ℃, and immediately adding the chain extender X575.31g of Pd/C catalyst (0.452 g) was reacted in a still at room temperature (about 127 ℃ C.) for 1.5 hours. After the reaction is finished, the solution is properly cooled, under the condition of high-strength stirring, the polymer solution is precipitated and crushed by 5000g of water, boiled for 4 times by water, and fully dried in a vacuum oven at 140 ℃ for 4 hours to obtain 756g of polyether sulfone resin.
Comparative example 1:
pouring 133g of melted sulfolane and 44g of o-xylene into a four-neck flask connected with a water separator, a condensation pipe and an aeration conduit, accurately weighing 50g of bisphenol S, 57.43g of dichlorodiphenyl sulfone and 34.55g of potassium carbonate, putting into a reaction bottle at one time, gradually heating to 144 ℃ under the protection of nitrogen to boil the system, condensing, refluxing and separating water, continuously heating after the water separation is finished, and continuously evaporating to remove the o-xylene. The temperature is continuously increased to 220 ℃, the reaction is maintained for 18 hours at the temperature, and the stirring speed is gradually increased along with the increase of the viscosity of the system. After the polymerization reaction, under the condition of high-intensity stirring, the polymer solution is precipitated and smashed by using 1.2L of ethanol, boiled for 4 times and fully dried by an air drying oven to obtain 82g of powdery polyether sulfone resin.
Comparative example 2:
pouring 360g of melted sulfolane and 72g of o-xylene into a four-neck flask connected with a water separator, a condenser pipe and a ventilation conduit, accurately weighing S119.18g of bisphenol, 143.58g of dichlorodiphenyl sulfone and 82.27g of potassium carbonate, putting into a reaction bottle at one time, gradually heating to 144 ℃ under the protection of nitrogen to boil the system, condensing, refluxing and separating water, continuously heating after the water separation is finished, and continuously evaporating to remove the o-xylene. The heating was stopped, and 5.412g of 1, 3-propanedithiol and 0.144g of Pd/C catalyst were immediately charged and reacted at 100 ℃ for 1 hour. After the reaction is finished, the solution is properly cooled, under the condition of high-strength stirring, the polymer solution is precipitated and crushed by 700g of water, boiled for 4 times by water, and fully dried in a vacuum oven at 140 ℃ for 4 hours to obtain 220g of polyether sulfone resin.
Comparative example 3:
720g of melted sulfolane and 180g of o-xylene are poured into an oil bath kettle connected with a water separator, a condensation pipe and a ventilation guide pipe, 238.35g of bisphenol S, 287.16g of dichlorodiphenyl sulfone and 164.54g of potassium carbonate are accurately weighed, the temperature is gradually increased under the protection of nitrogen until the system is boiled, return water is condensed and collected in the water separator, and the o-xylene is evaporated after the water separation reaches a theoretical value. Stopping heating, and immediately adding the self-made bis-mercapto chain extender X117.83g, and a slow increase in the viscosity of the system was observed after 8 hours of reaction at 150 ℃. After the reaction is finished, the solution is properly cooled, the polymer solution is precipitated by 1500g of water under the condition of high-intensity stirring, and then boiled for 3 times by water,after the obtained product was sufficiently dried in a vacuum oven at 130 ℃ for 3 hours, 445g of a polyether sulfone resin was obtained.
The example and comparative product parameters are shown in Table 3:
TABLE 3 example and comparative product parameters
As is apparent from Table 3, the molecular weight of the polyethersulfone resin obtained in examples 1-5 is significantly improved compared with that of the polyethersulfone resin obtained in the conventional polymerization process (comparative example 1), and the molecular weight distribution is narrower, which indicates that the polyethersulfone resin prepared by the method of the present invention has a good molecular weight control level. Considering that examples 1 to 5 were carried out at a lower reaction temperature and in a shorter reaction time than the comparative examples, it is further demonstrated that the process of the present invention has significant advantages over the conventional process. Meanwhile, as can be seen from the melt index, the melt index of the polyether sulfone resin obtained in the embodiment is higher, which indicates that the processing fluidity is better, and the flexibility of the chain extender is also embodied in a molecular chain.
In addition, example 2 has a higher melt index than comparative example 2 (simple aliphatic dithiol chain extension), indicating better melt flow, indicating that the urethane-incorporated propanedithiol/HDI chain extender improves the resin process flow properties better than the simple propanedithiol chain extender. In contrast, comparative example 3 shows that the molecular weight of the polyethersulfone resin obtained through a long-term high-temperature reaction is inferior to that of example 1 without adding a chain extension reaction catalyst, and the molecular weight distribution is broader, indicating the necessity of adding a chain extension reaction catalyst.
Finally, it should be noted that the above-mentioned embodiments only illustrate the preferred embodiments of the present invention, and do not limit the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that various changes and modifications can be made by modifying the technical solution of the present invention or equivalent substitutions within the scope of the present invention defined by the claims.
Claims (10)
1. A preparation method of polyether sulfone resin comprises the following steps:
(1) mixing bisphenol S, a dichloro monomer, an acid-binding agent, a water-carrying agent and a solvent, heating to form salt under the protection of nitrogen, and refluxing to separate water;
(2) evaporating to remove the water-carrying agent and simultaneously carrying out prepolymerization reaction;
(3) adding a chain extender and a catalyst for continuous reaction;
(4) and precipitating the polymer solution to obtain the polyether sulfone resin.
2. The method according to claim 1, wherein the molar ratio of the dichloro monomer to the bisphenol S in the step (1) is (1.01-1.2): 1, preferably (1.05-1.1): 1.
3. The method of claim 1 or 2, wherein the dichloromonomer is selected from one or more of dichlorodiphenyl sulfone, dichlorodiphenyl ether, dichlorobenzophenone, and dichlorobiphenyl.
4. The method according to any one of claims 1 to 3, wherein the molar ratio of metal atoms to bisphenol S in the acid scavenger is (2-3): 1, preferably (2.2-2.5): 1.
5. The method according to any one of claims 1 to 4, wherein the acid scavenger is selected from one or more of sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium ethoxide, potassium ethoxide, sodium hydride, preferably potassium carbonate.
6. A process according to any one of claims 1 to 5, characterised in that the chain extender has the formula
Wherein R is the residue of dithiol with 1-20 carbon atoms, and the dithiol is selected from ethanedithiol, propanedithiol, butanedithiol, pentanethiol, hexanedithiol, glycol dimercaptoacetate and dimercaptoacetic acidOne or more of butanediol esters; r' is the residue of diisocyanate with 1-20 carbon atoms, and the diisocyanate is selected from one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, m-xylylene diisocyanate and tetramethyl-m-xylylene diisocyanate; m is an integer of 1 to 10.
7. A process according to any one of claims 1 to 6, characterised in that the preparation of the chain extender comprises the steps of: the diisocyanate and the dithiol are prepared in the presence of a solvent, wherein the diisocyanate is selected from one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, m-xylylene diisocyanate and tetramethyl m-xylylene diisocyanate, and the dithiol is selected from one or more of ethylene glycol thiol, propylene glycol thiol, butylene glycol dithiol, glutaric alcohol, hexanedithiol, ethylene glycol dimercaptoacetate and butylene glycol dimercaptoacetate.
8. A process according to any one of claims 1 to 7, characterised in that the chain extender is used in a quantity of 1 to 10%, preferably 5 to 8%, of the molar quantity of the dichloromonomers.
9. The process of any one of claims 1 to 8, wherein the catalyst is one or more of Pd/C, Pd/alumina, Pd/silica, cuprous acetate, cuprous chloride, cuprous bromide, cuprous iodide, cuprous sulfide, copper acetylacetonate, schiff base Cu; and/or the catalyst is used in an amount of 0.1 to 0.5 wt% based on the weight of the dichloromonomer.
10. The process according to any one of claims 1 to 9, wherein the reaction temperature in step (3) is 0 to 140 ℃, preferably 80 to 130 ℃; the reaction time is 0.5-2 h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113444239A (en) * | 2021-06-11 | 2021-09-28 | 天津师范大学 | High-efficiency preparation method of polyaromatic ether |
| CN115058009A (en) * | 2022-05-17 | 2022-09-16 | 万华化学集团股份有限公司 | Preparation method of sulfone polymer with low cyclic polymer content |
| CN115724770A (en) * | 2021-08-30 | 2023-03-03 | 万华化学（宁波）有限公司 | Isocyanate composition with stable activity and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1185029A (en) * | 1966-10-15 | 1970-03-18 | Dunlop Co Ltd | Improvements in and relating to Polysulphones having Terminal Functional Groups |
| US5342905A (en) * | 1993-01-29 | 1994-08-30 | Miles Inc. | Process for making an ester containing polyether sulfone |
| CN105330863A (en) * | 2015-11-30 | 2016-02-17 | 广东优巨先进材料研究有限公司 | Method for adding chain extender to middle piece to synthesize high-strength polyether sulphone resin |
| CN105348532A (en) * | 2015-11-30 | 2016-02-24 | 江门市优巨新材料有限公司 | Industrial synthesis method for high-thermal-stability end capping tree-shaped polyether sulphone resin |
-
2020
- 2020-05-14 CN CN202010405412.9A patent/CN111621013B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1185029A (en) * | 1966-10-15 | 1970-03-18 | Dunlop Co Ltd | Improvements in and relating to Polysulphones having Terminal Functional Groups |
| US5342905A (en) * | 1993-01-29 | 1994-08-30 | Miles Inc. | Process for making an ester containing polyether sulfone |
| CN105330863A (en) * | 2015-11-30 | 2016-02-17 | 广东优巨先进材料研究有限公司 | Method for adding chain extender to middle piece to synthesize high-strength polyether sulphone resin |
| CN105348532A (en) * | 2015-11-30 | 2016-02-24 | 江门市优巨新材料有限公司 | Industrial synthesis method for high-thermal-stability end capping tree-shaped polyether sulphone resin |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113444239A (en) * | 2021-06-11 | 2021-09-28 | 天津师范大学 | High-efficiency preparation method of polyaromatic ether |
| CN113444239B (en) * | 2021-06-11 | 2022-11-04 | 天津师范大学 | High-efficiency preparation method of polyaromatic ether |
| CN115724770A (en) * | 2021-08-30 | 2023-03-03 | 万华化学（宁波）有限公司 | Isocyanate composition with stable activity and preparation method and application thereof |
| CN115724770B (en) * | 2021-08-30 | 2024-04-09 | 万华化学（宁波）有限公司 | Isocyanate composition with stable activity and preparation method and application thereof |
| CN115058009A (en) * | 2022-05-17 | 2022-09-16 | 万华化学集团股份有限公司 | Preparation method of sulfone polymer with low cyclic polymer content |
| 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 |
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