CN109354686B - Preparation method of polysulfone resin - Google Patents
Preparation method of polysulfone resin Download PDFInfo
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- CN109354686B CN109354686B CN201811398231.7A CN201811398231A CN109354686B CN 109354686 B CN109354686 B CN 109354686B CN 201811398231 A CN201811398231 A CN 201811398231A CN 109354686 B CN109354686 B CN 109354686B
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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 provides a preparation method of polysulfone resin, and relates to the field of high polymer materials. The invention firstly forms salt and then polymerizes, ensures that the reaction monomers have polymerization reaction under the condition that the molar ratio is 1:1, greatly improves the speed of the polymerization reaction and shortens the reaction time. Meanwhile, after the polymerization reaction is carried out for a certain time, an end-capping agent is added to ensure that the reaction monomers have a certain depolymerization effect while the polymerization reaction is carried out, so that the progress of the polymerization reaction is controlled, and the purpose of terminating the reaction is achieved. According to the description of the embodiment, the weight average molecular weight of the polysulfone resin prepared by the preparation method is 7-10 ten thousand, the melt index is 10-30 g/10min (365 ℃,5kg), and the molecular weight distribution Mn/Mw is 1.4-1.5.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a preparation method of polysulfone resin.
Background
The polysulfone resin is a high-performance engineering plastic, and has the properties of heat resistance, hot water resistance, creep resistance, dimensional stability, impact resistance, chemical resistance, non-toxicity, flame retardance and the like, so that the polysulfone resin is widely applied to the fields of electronics, electric appliances, machinery, automobiles, medical appliances, food processing, non-sticking coatings and the like.
At present, in the process of preparing the polysulfone resin, the reaction rate of the reaction monomer is high under the condition that the molar ratio is 1:1, and a target product with certain molecular weight and thermal processing performance cannot be accurately obtained. Therefore, the reaction is carried out under the condition that the reaction monomer is more than 1:1 or less than 1:1 in the prior art so as to better control the reaction.
Disclosure of Invention
The invention aims to provide a polysulfone resin with certain molecular weight and thermal processing performance, which can be accurately obtained by reacting monomers at a molar ratio of 1: 1.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of polysulfone resin, which comprises the following steps:
mixing a reaction monomer, a salt forming agent, a water diversion agent and sulfolane, and carrying out a salt forming reaction to obtain a salt forming system;
heating the salt forming system, carrying out polymerization reaction, mixing the obtained polymer system with an end capping agent after 2-4 hours, and carrying out end capping to obtain polysulfone resin;
wherein the reaction monomer is 4,4' -dichlorodiphenyl sulfone and bisphenol derivative monomer;
the bisphenol derivative monomer is 4,4 '-biphenol, 4' -dihydroxydiphenylsulfone or 2, 2-bis (4-hydroxyphenyl) propane;
the molar ratio of the 4,4' -dichlorodiphenyl sulfone to the bisphenol derivative monomer is 1: 1.
preferably, the salt forming agent is one or more of sodium carbonate, potassium carbonate and sodium hydroxide.
Preferably, the molar ratio of the salt forming agent to the reaction monomer is (0.5-0.6): 1.
preferably, the water separating agent is one or more of toluene, xylene, ethylbenzene and diethylbenzene.
Preferably, the solid content of the reaction monomer in the system obtained by mixing the reaction monomer, the salt forming agent, the water diversion agent and the sulfolane is 20-40%.
Preferably, the temperature of the salt forming reaction is 200-210 ℃, and the time of the salt forming reaction is 1-2 hours.
Preferably, the temperature of the polymerization reaction is 220-230 ℃.
Preferably, the end-capping agent is one or more of 4-chlorobenzenesulfone, p-methylbenzoyl chloride, benzoyl chloride and 4-fluorobenzophenone end-capping agent.
Preferably, the molar ratio of the end-capping agent to the reactive monomer is (0.5-3): 100.
preferably, the end-capping temperature is 220-230 ℃.
The invention provides a preparation method of polysulfone resin, which comprises the following steps: mixing a reaction monomer, a salt forming agent, a water diversion agent and sulfolane, and carrying out a salt forming reaction to obtain a salt forming system; heating the salt forming system, carrying out polymerization reaction, mixing the obtained polymer system with an end capping agent after 2-4 hours, and carrying out end capping to obtain polysulfone resin; wherein the reaction monomer is 4,4' -dichlorodiphenyl sulfone and bisphenol derivative monomer; the bisphenol derivative monomer is 4,4 '-biphenol, 4' -dihydroxydiphenylsulfone or 2, 2-bis (4-hydroxyphenyl) propane; the molar ratio of the 4,4' -dichlorodiphenyl sulfone to the bisphenol derivative monomer is 1: 1. the invention firstly forms salt and then polymerizes, ensures that the reaction monomers have polymerization reaction under the condition that the molar ratio is 1:1, greatly improves the speed of the polymerization reaction and shortens the reaction time. Meanwhile, after the polymerization reaction is carried out for a certain time, an end-capping agent is added to ensure that the reaction monomers have a certain depolymerization effect while the polymerization reaction is carried out, so that the progress of the polymerization reaction is controlled, and the purpose of terminating the reaction is achieved. According to the description of the embodiment, the weight average molecular weight of the polysulfone resin prepared by the preparation method is 7-10 ten thousand, the melt index is 10-30 g/10min (365 ℃,5kg), and the molecular weight distribution Mn/Mw is 1.4-1.5.
Detailed Description
The invention provides a preparation method of polysulfone resin, which comprises the following steps:
mixing a reaction monomer, a salt forming agent, a water diversion agent and sulfolane, and carrying out a salt forming reaction to obtain a salt forming system;
heating the salt forming system, carrying out polymerization reaction, mixing the obtained polymer system with an end capping agent after 2-4 hours, and carrying out end capping to obtain polysulfone resin;
wherein the reaction monomer is 4,4' -dichlorodiphenyl sulfone and bisphenol derivative monomer;
the bisphenol derivative monomer is 4,4 '-biphenol, 4' -dihydroxydiphenylsulfone or 2, 2-bis (4-hydroxyphenyl) propane;
the molar ratio of the 4,4' -dichlorodiphenyl sulfone to the bisphenol derivative monomer is 1: 1.
in the invention, the reaction process for preparing the polysulfone resin is as follows:
in the present invention, all the raw materials are commercially available products well known to those skilled in the art unless otherwise specified.
According to the invention, a reaction monomer, a salt forming agent, a water diversion agent and sulfolane are mixed to carry out a salt forming reaction, so as to obtain a salt forming system. In the invention, the reaction monomer is 4,4' -dichlorodiphenyl sulfone and bisphenol derivative monomer; the molar ratio of the 4,4' -dichlorodiphenyl sulfone to the bisphenol derivative monomer is 1: 1; the bisphenol derivative monomer is 4,4 '-biphenol, 4' -dihydroxydiphenylsulfone or 2, 2-bis (4-hydroxyphenyl) propane.
In the invention, the salt forming agent is preferably one or more of sodium carbonate, potassium carbonate and sodium hydroxide; when the salt forming agent is more than two of the specific substances, the proportion of the specific substances is not limited in any way, and the specific substances can be mixed according to any proportion. In the invention, the molar ratio of the salt forming agent to the reaction monomer is preferably (0.5-0.6): 1, more preferably (0.52 to 0.58): 1, most preferably (0.54-0.56): 1.
in the invention, the water-dividing agent is preferably one or more of toluene, xylene, ethylbenzene and diethylbenzene; when the water separating agent is more than two of the specific substances, the proportion of the specific substances is not limited in any way, and the specific substances can be mixed according to any proportion. In the invention, the mass ratio of the water diversion agent to the sulfolane is preferably (10-25): 100, more preferably (15 to 20): 100.
in the invention, the water-separating agent is favorable for completely separating water in a salt-forming reaction stage, is favorable for reaction, simultaneously reduces energy consumption, avoids the oxidation influence of overhigh temperature in the salt-forming stage on a monomer, and further obtains the polysulfone resin with better performance.
In the invention, the solid content of the system obtained by mixing the reaction monomer, the salt forming agent, the water diversion agent and the sulfolane is preferably 20-40%, more preferably 25-35%, and most preferably 28-32%.
In the present invention, the reaction monomer, the salt forming agent, the water separating agent and the sulfolane are preferably mixed in sequence with the reaction monomer, the salt forming agent and the water separating agent. In the present invention, the sulfolane is preferably liquid sulfolane.
In the invention, the mixing temperature is preferably 70-90 ℃, more preferably 75-85 ℃, and most preferably 78-82 ℃. In the present invention, the mixing is preferably performed under stirring conditions, and the stirring is not particularly limited in the present invention, and may be performed by a stirring process known to those skilled in the art.
In the invention, the temperature of the salt forming reaction is preferably 200-210 ℃, more preferably 202-208 ℃, and most preferably 204-206 ℃; in the invention, the time of the salt forming reaction is preferably 1 to 2 hours, more preferably 1.2 to 1.8 hours, and most preferably 1.4 to 1.6 hours. In the present invention, the salt-forming reaction is preferably carried out under stirring, and the stirring is not particularly limited in the present invention, and may be carried out by a stirring process well known to those skilled in the art.
In the invention, the salifying reaction device is preferably a stainless steel reaction kettle provided with a nitrogen pipe, a water separator with a condensation pipe, a high-efficiency stirrer and an in-kettle polymerization viscosity monitoring viscometer. In the invention, after the salt-forming reaction is started, water in the system and a water diversion agent are subjected to azeotropic distillation, cooling water begins to drip in a condensation pipe, the water is layered in a water knockout drum, the azeotropic system is continuously subjected to water reduction along with the reaction, and the salt-forming reaction is completed after water is not obviously discharged from the condensation pipe.
After a salt forming system is obtained, the salt forming system is heated and then subjected to polymerization reaction, and the obtained polymerization system is mixed with an end capping agent for capping after 2-4 hours, so that the polysulfone resin is obtained.
In the invention, the polymerization reaction temperature is preferably 220-230 ℃, more preferably 222-228 ℃, and most preferably 224-226 ℃. In the present invention, the polymerization system obtained by the polymerization reaction and the end-capping agent are mixed at the time of polymerization reaction for 2 to 4 hours, more preferably 2.5 to 3.5 hours, and most preferably 2.8 to 3.2 hours.
In the present invention, the polymerization apparatus is preferably a stainless steel reaction vessel equipped with a nitrogen gas-passing pipe, a water separator with a condenser, a high-efficiency stirrer, and an in-vessel polymerization viscosity-monitoring viscometer. In the invention, after the polymerization reaction is carried out for 2-4 hours, the viscosity of the polymerization mucus in the reaction kettle, which is displayed in the viscometer, reaches 6500-7500 Pa.s, and then the polymerization mucus can be mixed with the end capping agent.
In the invention, the end-capping agent is preferably one or more of 4-chlorobenzenesulfone, p-methylbenzoyl chloride, benzoyl chloride and 4-fluorobenzophenone end-capping agent; when the end-capping agent is two or more of the above specific substances, the specific substances are not particularly limited in proportion, and may be mixed in any proportion.
In the invention, the molar ratio of the end-capping agent to the reactive monomer is preferably (0.5-3): 100, more preferably (0.8 to 2.5): 100, most preferably (1.5-2): 100.
in the invention, the temperature of the end capping is preferably 220-230 ℃, more preferably 222-228 ℃, and most preferably 224-226 ℃; in the present invention, the temperature of the end-capping is preferably the same as the temperature of the polymerization reaction. The end-capping time is not limited at all, and the viscosity of the polymerization viscous liquid displayed in the polymerization viscous liquid monitoring viscometer in the reaction kettle can reach 4500-6000 Pa.s.
In the invention, after the end capping is completed, the method also preferably comprises the steps of cooling, washing, filtering and drying the obtained end-capped product system to obtain the polysulfone resin.
The cooling is not particularly limited in the present invention, and the cooling may be performed by a cooling process known to those skilled in the art.
In the present invention, the washing is preferably boiling washing with deionized water, and in the present invention, the number of washing is preferably 1 to 10, more preferably 6 to 8. In the invention, the purpose of the washing is to ensure that the conductivity of the obtained polysulfone resin in water is less than 5 us/cm.
The filtration is not particularly limited in the present invention, and may be performed by a filtration process known to those skilled in the art.
In the present invention, the drying is preferably vacuum drying, and the vacuum drying is not particularly limited in the present invention, and may be vacuum drying known to those skilled in the art.
In order to further illustrate the present invention, the following examples are provided to describe the preparation method of polysulfone resin in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
100.00kg of sulfolane is added into a 200L stainless steel reaction kettle which is provided with a nitrogen pipe, a condensation water separator, a high-efficiency stirrer and a kettle polymerization viscous liquid monitoring viscometer, the stirring temperature is raised to 80 ℃, 20.26kg of 4,4 '-dichlorodiphenyl sulfone and 13.14kg of 4,4' -biphenyl diphenol are sequentially added in sequence, after the 4,4 '-dichlorodiphenyl sulfone and the 4,4' -biphenyl diphenol are completely dissolved, 10.0kg of sodium carbonate and 15.0L of dimethylbenzene are sequentially added into the system, the stirring is continued, the temperature is raised to 210 ℃, a salt forming reaction is carried out, water in the system and a water separating agent are subjected to azeotropic distillation, cooling water starts to be in a condensation pipe, the water is separated in the water separator, the water amount in the azeotropic system is less and less along with the reaction, and the water outlet in a condenser is completed after the time is not obviously elapsed, and the salt forming stage is completed for 1.5. After the salifying reaction is finished, heating to 230 ℃, keeping the temperature for 2 hours, adding 4-chloro-diphenyl sulfone when the viscosity displayed by the polymerization viscosity monitoring viscometer in the kettle reaches 7000 Pa.s, wherein the mole number of the 4-chloro-diphenyl sulfone is 2% of that of a reaction monomer, and after 30 minutes, finishing end capping when the viscosity displayed by the polymerization viscosity monitoring viscometer is 4500 Pa.s; and cooling the end-capped product system, boiling and washing for 10 times until the conductivity of water is below 5us/cm, filtering, and drying in vacuum until the moisture weight content is lower than 0.5% to obtain the polyphenylsulfone resin (PPSU).
The PPSU resin has MI of 25.5g/10min (365 ℃,5kg), weight average molecular weight Mw of 7.8 ten thousand, and molecular weight distribution Mn/Mw of 1.5.
Example 2
The preparation process is the same as that of example 1, except that 4-chloro-diphenyl sulfone is added in an amount of 1% by mole based on the reaction monomers; the end capping was completed when the viscosity indicated by the polymeric viscosity monitoring viscometer was 4500Pa · s.
The PPSU resin has MI of 12.5g/10min (365 ℃,5kg), weight average molecular weight Mw of 10 ten thousand, and molecular weight distribution Mn/Mw of 1.4.
Example 3
100.00kg of sulfolane is added into a 200L stainless steel reaction kettle which is provided with a nitrogen pipe, a condensation water separator, a high-efficiency stirrer and a kettle polymerization viscous liquid monitoring viscometer, the temperature is raised to 80 ℃ by stirring, 17.85kg of 4,4 '-dichlorodiphenyl sulfone and 15.55kg of 4,4' -dihydroxydiphenyl sulfone are sequentially added in sequence, after the 4,4 '-dichlorodiphenyl sulfone and the 4,4' -dihydroxydiphenyl sulfone are completely dissolved, 10.0kg of sodium carbonate and 15.0L of dimethylbenzene are sequentially added into the system by stirring, the temperature is raised to 210 ℃ by stirring continuously, a salt forming reaction is carried out, water in the system and a water separating agent are subjected to azeotropic distillation, cooling water is dripped into a condensation pipe, the water is layered in the water separator, the azeotropic amount of water in the system is less and less along with the reaction, and the salt forming stage is completed after the water outlet in a condenser is not obvious for 1.5 hours. After the salifying reaction is finished, heating to 230 ℃, keeping the temperature for 2 hours, adding 4-chloro-diphenyl sulfone when the viscosity displayed by the polymerization viscosity monitoring viscometer in the kettle reaches 7000 Pa.s, wherein the mole number of the 4-chloro-diphenyl sulfone is 2% of that of a reaction monomer, and after 30 minutes, finishing end capping when the viscosity displayed by the polymerization viscosity monitoring viscometer is 4500 Pa.s; and cooling the end-capped product system, boiling and washing for 10 times until the conductivity of water is below 5us/cm, filtering, and drying in vacuum until the moisture weight content is lower than 0.5% to obtain the polyether sulfone resin (PES).
The PES resin melt means that MI is 24g/10min (365 ℃,5kg), the weight average molecular weight Mw is 8.8 ten thousand, and the molecular weight distribution Mn/Mw is 1.4.
Example 4
Adding 100kg of sulfolane into a 200L stainless steel reaction kettle provided with a nitrogen pipe, a condensation water separator, a high-efficiency stirrer and a kettle polymerization viscous liquid monitoring viscometer, stirring and heating to 80 ℃, sequentially adding 18.57kg of 4,4 '-dichlorodiphenyl sulfone and 14.76kg of 2, 2-bis (4-hydroxyphenyl) propane, adding 10kg of potassium carbonate and 15L of toluene into the system after the 4,4' -dichlorodiphenyl sulfone and the 2, 2-bis (4-hydroxyphenyl) propane are completely dissolved, continuously stirring, heating to 180 ℃, carrying out a salt forming reaction, carrying out azeotropic distillation on water and a water separating agent in the system, starting to drip cooling water in a condensation pipe, layering in a water separator, and continuously carrying out reaction, wherein the water amount in an azeotropic system is less and less, and the salt formation stage is completed after the water outlet in a condenser is not obvious, and the time lasts for 1.5 hours. After the salt forming reaction is finished, heating to 200 ℃, keeping the temperature for 2 hours, adding 4-chloro-diphenyl sulfone when the viscosity displayed by the polymerization viscosity monitoring viscometer in the kettle reaches 7500 Pa.s, wherein the mole number of the 4-chloro-diphenyl sulfone is 1 percent of that of a reaction monomer, and after 30 minutes, finishing end capping when the viscosity displayed by the polymerization viscosity monitoring viscometer is 4500 Pa.s; and cooling the end-capped product system, boiling and washing for 10 times until the conductivity of water is below 5us/cm, filtering, and drying in vacuum until the water content is lower than 0.5% by weight to obtain the polysulfone resin (PSU).
The PSU resin mentioned above means MI of 20g/10min (343 ℃,5kg), weight average molecular weight Mw of 8 ten thousand, and molecular weight distribution Mn/Mw of 1.5.
From the above examples, the weight average molecular weight of the polysulfone resin prepared by the preparation method provided by the invention is 7-10 ten thousand, the melt index is 10-30 g/10min (365 ℃,5kg), and the molecular weight distribution Mn/Mw is 1.4-1.5. Namely, the preparation method can well control the molecular weight of the product and improve the hot processing performance of the product.
In view of the foregoing description of the preferred embodiment of the present invention, it should be noted that various modifications and adaptations of the invention may occur to those skilled in the art without departing from the spirit of the invention and should be considered within the scope of the invention.
Claims (6)
1. A preparation method of polysulfone resin comprises the following steps:
mixing a reaction monomer, a salt forming agent, a water diversion agent and sulfolane, and carrying out a salt forming reaction to obtain a salt forming system;
heating the salifying system, carrying out polymerization reaction, mixing the obtained polymerization system with an end capping agent after 2-4 hours, and carrying out end capping to obtain polysulfone resin;
wherein the reaction monomer is 4,4' -dichlorodiphenyl sulfone and bisphenol derivative monomer;
the bisphenol derivative monomer is 4,4 '-biphenol, 4' -dihydroxydiphenylsulfone or 2, 2-bis (4-hydroxyphenyl) propane;
the molar ratio of the 4,4' -dichlorodiphenyl sulfone to the bisphenol derivative monomer is 1: 1;
the solid content of the reaction monomer in the system obtained by mixing the reaction monomer, the salt forming agent, the water separating agent and the sulfolane is 20-40%;
the end-capping agent is one or more of 4-chlorobenzenesulfone, p-methylbenzoyl chloride, benzoyl chloride and 4-fluorobenzophenone end-capping agent;
the molar ratio of the end capping agent to the reaction monomer is (0.5-3): 100, respectively;
the temperature of the end sealing is 220-230 ℃.
2. The method of claim 1, wherein the salt forming agent is one or more of sodium carbonate, potassium carbonate and sodium hydroxide.
3. The method of claim 1, wherein the molar ratio of the salt forming agent to the reactive monomer is (0.5 to 0.6): 1.
4. the preparation method according to claim 1, wherein the water separating agent is one or more of toluene, xylene, ethylbenzene and diethylbenzene.
5. The preparation method of claim 1, wherein the temperature of the salt forming reaction is 200-210 ℃, and the time of the salt forming reaction is 1-2 hours.
6. The method of claim 1, wherein the polymerization temperature is 220 to 230 ℃.
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