Polyphenyl sulfone resin and preparation method thereof

Abstract

The invention discloses a polyphenyl sulfone resin and a preparation method thereof, and relates to the field of high-temperature-resistant high polymer materials. According to the method, a feeding mode of firstly adding a solvent and then adding a monomer is adopted, meanwhile, an external circulation pipeline is additionally arranged on equipment, so that secondary decomposition of the monomer is reduced, mixing of raw materials and intermediate products in the reaction process is further increased, the reaction rate is increased, and in a GPC chromatographic curve obtained through gel permeation chromatography testing, the synthesized polyphenyl sulfone is lg (Mw1) gt; 5.3 and 1g (Mw2) 1t; the sum of the percentages of 3.6 and 3.6 accounts for less than 1.2% of the total percentage, and the obtained polyphenyl sulfone has excellent dimensional stability.

Description

Technical Field

[0001] The invention relates to the field of high-performance polymer material synthesis, in particular to a polyphenylsulfone resin and a preparation method thereof. Background Art

[0002] Sulfone polymer is an amorphous non-crystalline polymer. The main types of sulfone polymers on the market are polysulfone, polyphenylsulfone, and polyethersulfone. Among the three sulfone polymers, polyphenylsulfone has better thermal stability, mechanical properties, corrosion resistance, non-biological toxicity, and good flame retardant properties. Therefore, it is widely used in aerospace, mechanical electronics, food and medicine and other fields.

[0003] Due to the application of polyphenylsulfone in plumbing pipes, electronic parts and other fields, higher requirements are placed on its dimensional stability. Summary of the invention

[0004] In order to meet the requirements for excellent dimensional stability of polyphenylsulfone in the fields of electronic appliances, plumbing pipes and fittings, the present invention provides a high-quality polyphenylsulfone.

[0005] The technical solution adopted by the present invention is as follows:

[0006] First, the present invention provides a polyphenylene sulfone resin having the following characteristics:

[0007] In the GPC chromatogram curve obtained from the gel permeation chromatography test, P[lg(Mw1)]+P[lg(Mw2)]<1.2%, wherein lg(Mw1)>5.3, lg(Mw2)<3.6;

[0008] In the above formula, P is a percentage, Mw1 and Mw2 are mass average molecular weights. That is, P[lg(Mw1)]+P[lg(Mw2)] means that in the GPC chromatogram, the mass average molecular weight is greater than 10 5.3 and less than 10 3.6 The percentage of polymer molecular chains in the entire polymer molecular chains.

[0009] In addition, the present invention provides a method for preparing the above polyphenylene sulfone, the steps are as follows:

[0010] 1) Start stirring of two reaction kettles at room temperature, add 50-70% of the reaction solvent into the main reaction kettle, add 30-50% of the reaction solvent and a mixture (bisphenol, dichlorodiphenyl sulfone and alkaline catalyst) prepared in a certain proportion into the upper kettle to obtain a suspension, close the kettle covers of the two reaction kettles, perform nitrogen vacuum replacement for multiple times, and ensure that the reaction process is in a nitrogen atmosphere after replacement;

[0011] 2) The oil temperature of the main reactor is set to 180-250°C, and the temperature is started to rise. After the temperature inside the main reactor rises to 140-180°C, the stirring speed of the high-level reactor is increased to 300-500rpm, the bottom valve of the high-level reactor is opened, and the suspension is added to the main reactor. At this time, the internal temperature of the main reactor is 120-160°C. As the internal temperature gradually rises, the reaction solvent begins to be brought out;

[0012] 3) As the reaction solvent is continuously taken out, water is also continuously taken out. When the water carrying rate reaches more than 80%, the external circulation of the main reactor is started, and the reaction liquid reaches the top of the reactor from the bottom of the reactor through the external circulation pipeline. The circulation time is 0.5 to 4 hours. At this time, the water carrying rate reaches more than 95%, and the external circulation of the main reactor is stopped, and the reaction is continued for 1 to 3 hours;

[0013] 4) Adding a solvent to the high-temperature reaction liquid during polymerization to cool and dilute it, thereby stopping the polymerization and obtaining a polymer solution.

[0014] In the present invention, in a preferred embodiment, the bisphenol in step 1) is 4,4'-biphenol;

[0015] The dichlorodiphenyl sulfone is 4,4'-dichlorodiphenyl sulfone;

[0016] The alkaline catalyst is one or more of sodium hydroxide, potassium hydroxide, cesium hydroxide, sodium carbonate, sodium bicarbonate, cesium carbonate, potassium bicarbonate, and potassium carbonate;

[0017] The molar ratio of bisphenol, dichlorodiphenyl sulfone and alkaline catalyst is 1: (0.97-1.03): (1.05-2.6);

[0018] The reaction solvent is one or more of sulfolane, diphenyl sulfone, N-methylpyrrolidone, N-ethylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone. The amount of the solvent is 60-80 wt% of the total amount of the reaction solution (reaction solvent + mixture), preferably 65%-70%;

[0019] In the present invention, in a preferred embodiment, the suspension is added when the internal temperature in step 2) is in the range of 140 to 180°C, preferably 150 to 170°C;

[0020] In the present invention, in a preferred embodiment, in step 3), the external circulation is started, and the circulation time is 0.5 to 4 hours, preferably 1 to 3 hours; after the external circulation is stopped, the reaction time is continued for 1 to 3 hours, preferably 2 to 3 hours.

[0021] In the present invention, the polymer solution of step 4) is crushed, washed and dried to obtain the high-quality polyphenylsulfone of the present invention, wherein the solvent used is selected from one or more of cyclopentane, diphenyl sulfone, N-methylpyrrolidone, N-ethylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone, the temperature of the solvent is 20-40°C, preferably 25-30°C, and the amount used is 10-40wt% of the solvent used in the reaction, preferably 30-40wt%.

[0022] Compared with the prior art, the present invention has the following advantages:

[0023] 1. The present invention adopts a feeding method of adding solvent first and then monomer, which reduces the side reaction of monomer during the front-end heating process, reduces monomer loss, and improves product quality;

[0024] 2. The present invention adopts a mixing method of adding an external circulation pipeline outside the reactor to improve the mixing effect between monomers, increase the mass transfer and heat transfer efficiency, and thus reduce the content of low polymers;

[0025] 3. The polyphenylene sulfone obtained by the present invention has a lower polydispersity coefficient d, and the sum of the percentages of lg(Mw1)>5.3 and lg(Mw2)<3.6 is less than 1.2%, which is beneficial to reducing the water absorption rate and swelling rate of the polymer, thereby obtaining polyphenylene sulfone with high dimensional stability. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 It is a reaction schematic diagram of the present invention. The dilution tank in the figure is a high-position kettle. DETAILED DESCRIPTION

[0027] In order to better understand the technical solution of the present invention, the following examples will further illustrate the method provided by the present invention, but the present invention is not limited to the listed examples, and should also include any other known changes within the scope of the claims of the present invention.

[0028] Example 1

[0029] 1) Start stirring of the two reaction kettles, add 15Kg of N-methylpyrrolidone to the main reaction kettle at room temperature; add a mixture of 15Kg of N-methylpyrrolidone and 4.66Kg of 4,4'-biphenol, 7.25Kg of 4,4-dichlorodiphenyl sulfone, and 4.15Kg of potassium carbonate to the upper kettle to obtain a suspension. Close the kettle cover and replace with nitrogen three times. After replacement, ensure that the reaction process is in a nitrogen atmosphere;

[0030] 2) The oil temperature of the main reactor is set to 200°C and the temperature is started to rise. When the temperature inside the main reactor rises to 140°C, the speed of the high-position reactor is set to 500rpm, the high-position reactor bottom valve is opened, and the suspension is placed in the main reactor. The internal temperature drops to about 120°C, and then the temperature gradually rises, and the reaction solvent begins to be taken out;

[0031] 3) As the reaction solvent is continuously taken out, water is also taken out. When the water carrying rate reaches 80%, the external circulation of the main reactor is started, and the reaction liquid reaches the top of the reactor from the bottom of the reactor through the external circulation pipeline. The circulation time is 1 hour. At this time, the water carrying rate reaches more than 95%, and the external circulation of the main reactor is stopped, and the reaction is continued for 2 hours;

[0032] 4) 10 kg of N-methylpyrrolidone was added to the high-temperature reaction liquid during polymerization to cool and dilute it, so as to stop the polymerization and obtain a polymer solution.

[0033] Example 2

[0034] 1) Start stirring of the two reactors, add 15Kg of N,N-dimethylacetamide to the main reactor at room temperature, add a mixture of 15Kg of N,N-dimethylacetamide and 4.66Kg of 4,4'-biphenol, 7.25Kg of 4,4'-dichlorodiphenyl sulfone, and 4.15Kg of potassium carbonate to the high-position reactor to obtain a suspension. Close the lid of the reactor and replace with nitrogen three times. After replacement, ensure that the reaction process is in a nitrogen atmosphere;

[0035] 2) The oil temperature of the main reactor was set to 180°C and the temperature was started to rise. When the temperature inside the main reactor rose to 160°C, the rotation speed of the high-position reactor was set to 500 rpm, the high-position reactor bottom valve was opened, and the suspension was placed in the main reactor. The internal temperature dropped to about 140°C, and then the temperature gradually increased, and the reaction solvent began to be taken out;

[0036] 3) As the reaction solvent is continuously taken out, water is also taken out. When the water carrying rate reaches 80%, the external circulation of the main reactor is started, and the reaction liquid reaches the top of the reactor from the bottom of the reactor through the external circulation pipeline. The circulation time is 3 hours. At this time, the water carrying rate reaches more than 95%, and the external circulation of the main reactor is stopped, and the reaction is continued for 3 hours;

[0037] 4) 10 kg of N,N-dimethylacetamide was added to the high-temperature reaction liquid during polymerization to cool and dilute it, so as to stop the polymerization and obtain a polymer solution.

[0038] Example 3

[0039] 1) Start the main reaction kettle and stir. At room temperature, add 15 kg of N-methylpyrrolidone to the main reaction kettle, add the remaining 15 kg of N-methylpyrrolidone and a mixture of 4.75 kg of 4,4'-biphenol, 7.18 kg of 4,4'-dichlorodiphenyl sulfone, and 3.18 kg of sodium carbonate, add to the high-position kettle to obtain a suspension, close the kettle cover, and perform nitrogen replacement 3 times. After replacement, ensure that the reaction process is in a nitrogen atmosphere;

[0040] 2) The oil temperature of the main reactor was set to 220°C and the temperature began to rise. When the temperature inside the main reactor rose to 170°C, the speed of the high-position reactor was set to 500 rpm, the high-position reactor bottom valve was opened, and the suspension was placed in the main reactor. The internal temperature dropped to about 150°C, and then the temperature gradually increased, and the reaction solvent began to be taken out;

[0041] 3) As the reaction solvent is continuously taken out, water is also taken out. When the water carrying rate reaches 80%, the external circulation is started, and the reaction liquid reaches the top of the reactor from the bottom of the reactor through the external circulation pipeline. The circulation time is 3 hours. At this time, the water carrying rate reaches more than 95%, the external circulation is stopped, and the reaction is continued for 2 hours;

[0042] 4) 10 kg of N-methylpyrrolidone was added to the high-temperature reaction liquid during polymerization to cool and dilute it, so as to stop the polymerization and obtain a polymer solution.

[0043] Comparative Example 1

[0044] The difference from Example 1 is that: in a one-pot method, all the N-methylpyrrolidone, 4,4'-biphenol, 4,4'-dichlorodiphenyl sulfone and potassium carbonate required for the reaction are added into the reaction kettle without adding an external circulation pipeline.

[0045] 1) At room temperature, 4.66 kg of 4,4'-biphenol, 7.25 kg of 4,4'-dichlorodiphenyl sulfone, 4.15 kg of potassium carbonate, and 30 kg of N-methylpyrrolidone were added to a reactor, and after uniform stirring, the temperature of the reactor was set to 200°C;

[0046] 2) As the temperature rises, the reaction solvent begins to be taken out, and water is also taken out. When the water carrying rate reaches more than 95%, the water carrying time is about 4 hours. After the water carrying is completed, the reaction is continued for 3 hours;

[0047] 3) 10 kg of N-methylpyrrolidone was added to the high temperature reaction solution to cool and dilute it. The polymerization was completed to obtain the final reaction solution.

[0048] Comparative Example 2

[0049] The difference from Example 1 is that: in a one-pot method, all the mass of N-methylpyrrolidone, 4,4'-biphenol, 4,4'-dichlorodiphenyl sulfone and potassium carbonate required for this reaction are added into the reaction kettle, and an external circulation pipeline is added.

[0050] 1) At room temperature, 4.66 kg of 4,4'-biphenylene glycol, 7.25 kg of 4,4'-dichlorodiphenyl sulfone, 4.15 kg of potassium carbonate, and 30 kg of N-methylpyrrolidone were added to a reactor, and after uniform stirring, the temperature of the reactor was set to 200°C;

[0051] 2) When the water rate reaches 80%, the external circulation of the reactor is started, and the reaction liquid reaches the top of the reactor from the bottom of the reactor through the external circulation pipeline. The circulation time is 2 hours. At this time, the water rate reaches more than 95%, the external circulation is stopped, and the reaction is continued for 3 hours;

[0052] 3) 10 kg of N-methylpyrrolidone was added to the high temperature reaction solution to cool and dilute it. The polymerization was completed to obtain the final reaction solution.

[0053] Comparative Example 3

[0054] The difference from Example 1 is that the solvent is added first and then the monomer, and no external circulation pipeline is added.

[0055] 1) Start stirring, add 15 kg of N-methylpyrrolidone to the main reaction kettle at room temperature; add a mixture of 15 kg of N-methylpyrrolidone and 4.66 kg of 4,4'-biphenol, 7.25 kg of 4,4'-dichlorodiphenyl sulfone, and 4.15 kg of potassium carbonate to the high-position kettle to obtain a suspension, close the kettle cover, and perform nitrogen replacement 3 times. After replacement, ensure that the reaction process is in a nitrogen atmosphere;

[0056] 2) The oil temperature of the main reactor was set to 200°C and the temperature was started to rise. When the temperature inside the main reactor rose to 140°C, the speed of the high-position reactor was set to 500 rpm, the high-position reactor bottom valve was opened, and the suspension was placed in the main reactor. The internal temperature dropped to about 120°C, and then the temperature gradually increased, and the reaction solvent began to be taken out;

[0057] 3) As the reaction solvent is taken out, water is also taken out. When the water carrying rate reaches more than 95%, the water carrying time is about 4 hours. After the water carrying is completed, the reaction is continued for 3 hours;

[0058] 4) 10 kg of N-methylpyrrolidone was added to the high temperature reaction solution to cool and dilute it. The polymerization was completed to obtain the final reaction solution.

[0059] Test method:

[0060] Moisture test: Use Karl Fischer titrator; take fractions less than 0.01g, add them to the titrator, test the moisture content, and calculate the moisture content in each fraction using the formula: moisture content = total fraction amount * moisture content. The total moisture content is the sum of the moisture content measured each time.

[0061] GPC test: The instrument used is LC-20AD XR; the mobile phase is DMF containing 20mmol / L lithium bromide. The powder to be tested is prepared into a 0.1wt% DMF solution, 0.5-1mL of the test solution is taken, and a clear solution is obtained after filtration. The solution is added to the test sample tray for testing, and the obtained GPC curve is integrated, and the specific lg (Mw) value is taken to calculate the percentage.

[0062] Water absorption test: Dissolve polyphenylsulfone powder in NMP at a certain concentration to prepare a casting solution, spread the casting solution on a glass plate into a smooth film, dry, demould and dry again to obtain a homogeneous film; cut the film into 20*30mm block films, weigh them after drying, record them as W0; soak the film at 80℃ for 24h, take it out, wipe off the surface moisture and weigh it, which is W1, and calculate the water absorption:

[0063] Water absorption rate = (W 1 -W 0 ) / W0*100

[0064] Swelling rate test: Cut the film into 20*30mm block films, and record the length and width of the test film after drying as L0; soak the film at 80℃ for 24h, take it out and wipe off the surface moisture, and record the length and width of the test film as L1. The swelling rate is obtained by calculation:

[0065] Swelling ratio = (L 1 -L 0 ) / L0*100

[0066] Related performance test results

[0067] The performance test data of Examples 1-3 and Comparative Examples 1-3 are shown in Table 1.

[0068] Table 1 Performance test data

[0069]

[0070] Through the performance test results of the embodiments and comparative examples, we can conclude that:

[0071] In Examples 1 to 3, a feeding method of adding the solvent first and then the monomer is adopted, and an external circulation mixing method is adopted at the same time, so as to reduce the side decomposition of the monomer, enhance the mixing efficiency between the monomers, increase the reaction rate, reduce the content of ultra-high molecular weight polyphenylsulfone and oligomers, thereby improving the length uniformity of the polymer molecular chain, thereby controlling the content of diphenyl in the molecular chain, reducing the absorption rate and swelling rate of the polyphenylsulfone membrane, and showing excellent dimensional stability.

[0072] In Comparative Example 1, the feeding method of adding the solvent first and then the monomer is not adopted, and no external circulation pipeline is added to circulate the reaction liquid; this results in a high content of heat-sensitive components such as high oligomers and the like, and uneven molecular chain lengths, and a significant increase in water absorption and swelling at a high temperature of 80°C, resulting in reduced dimensional stability.

[0073] In comparative example 2, the feeding method of adding the solvent first and then the monomer is not adopted, but an external circulation pipeline is added to circulate the reaction liquid; the molecular weight of polyphenylsulfone is unstable, and the increase of the high oligomer content will also cause the absorption rate and swelling rate to increase, and the dimensional stability to decrease.

[0074] In comparative example 3, the feeding method of adding the solvent first and then the monomer is adopted, but no external circulation pipeline is added to circulate the reaction liquid; during the polymerization process, the mixing effect of the raw materials and intermediates becomes worse, the polymer molecular chain is short, the uniformity is reduced, the absorption rate and swelling rate are reduced, and the dimensional stability is reduced.

[0075] To summarize the above analysis results, the combination of the feeding method of adding the solvent first and then the monomer and the mixing method of adding an external circulation pipeline can effectively improve the reaction efficiency, improve the mixing between the raw materials and the intermediates, and improve the length uniformity of the polymer molecular chain, so as to obtain a polyphenylene sulfone resin with excellent dimensional stability, so as to be better used in the field of dimensional stability in plumbing pipes and electronic appliances.

[0076] Although the content of the present invention has been described in detail through the above preferred embodiments, it should be appreciated that the above description should not be considered as limiting the present invention. Those skilled in the art will appreciate that, under the guidance of this specification, some modifications or adjustments may be made to the present invention. These modifications or adjustments should also be within the scope defined by the claims of the present invention.

Claims

1. A polyphenylsulfone, characterized in that It has the following characteristics: In the GPC chromatogram curve obtained from the gel permeation chromatography test, P[lg(Mw1)]+P[lg(Mw2)]<1.2%, wherein lg(Mw1)>5.3, lg(Mw2)<3.6; In the above formula, P is a percentage, and Mw1 and Mw2 are mass average molecular weights.

2. A method for preparing the polyphenylsulfone according to claim 1, comprising: 1) starting stirring of two reaction kettles at room temperature, adding 50-70% of the reaction solvent into the main reaction kettle, adding 30-50% of the reaction solvent and the prepared mixture of bisphenol, dichlorodiphenyl sulfone and alkaline catalyst into the upper kettle to obtain a suspension, closing the kettle covers of the two reaction kettles, performing nitrogen vacuum replacement for multiple times, and ensuring that the reaction process is in a nitrogen atmosphere after replacement; 2) Set the oil temperature of the main reactor to 180-250°C and start heating. After the temperature inside the main reactor rises to 140-180°C, turn on the stirring of the high-position reactor and add the suspension into the main reactor. As the temperature inside the reactor gradually rises, the reaction solvent begins to be taken out; 3) As the reaction solvent is continuously taken out, water is also continuously taken out. When the water carrying rate reaches more than 80%, the external circulation of the main reactor is started, and the reaction liquid reaches the top of the reactor from the bottom of the reactor through the external circulation pipeline. When the water carrying rate reaches more than 95%, the external circulation of the main reactor is stopped and the reaction is continued; 4) Adding a solvent to the high-temperature reaction liquid during polymerization to cool and dilute it, thereby stopping the polymerization and obtaining a polymer solution.

3. The method according to claim 2, wherein: The bisphenol in step 1) is 4,4'-biphenol; and / or The dichlorodiphenyl sulfone is 4,4'-dichlorodiphenyl sulfone; and / or The alkaline catalyst is one or more of sodium hydroxide, potassium hydroxide, cesium hydroxide, sodium carbonate, sodium bicarbonate, cesium carbonate, potassium bicarbonate, and potassium carbonate.

4. The method according to claim 2 or 3, wherein: In step 1), the molar ratio of bisphenol, dichlorodiphenyl sulfone and alkaline catalyst is 1: (0.97-1.03): (1.05-2.6).

5. The method according to claim 2, wherein: In step 1), the reaction solvent is one or more of sulfolane, diphenyl sulfone, N-methylpyrrolidone, N-ethylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and 1,3-dimethyl-2-imidazolidinone.

6. The method according to any one of claims 2 to 5, wherein: The amount of the solvent used in step 1) is 60-80 wt % of the total amount of the reaction solution.

7. The method according to claim 2, wherein: When the internal temperature in step 2) is 150-170°C, the suspension is added.

8. The method according to claim 2, wherein: In step 3), the external circulation is started, and the circulation time is 0.5 to 4 hours, preferably 1 to 3 hours; after the external circulation is stopped, the reaction time is continued for 1 to 3 hours, preferably 2 to 3 hours.

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