A polyphenylsulfone resin and a method for its preparation

Abstract

This invention discloses a polyphenylene sulfone resin and its preparation method, relating to the field of high-temperature resistant polymer materials. The invention employs a method of adding solvent first and then monomer, while simultaneously adding an external circulation pipeline to the equipment to reduce monomer by-decomposition, further increasing the mixing of raw materials and intermediate products during the reaction process, and improving the reaction rate. In the GPC chromatogram obtained by gel permeation chromatography, the sum of the percentages of lg(Mw1)>5.3 and lg(Mw2)<3.6 is less than 1.2% of the total, indicating that the obtained polyphenylene sulfone exhibits excellent dimensional stability.

Description

Technical Field

[0001] This invention relates to the field of high-performance polymer material synthesis, specifically a polyphenylsulfone resin and its preparation method. Background Technology

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

[0003] Due to the application of polyphenylsulfone in plumbing fittings, electronic components and other fields, there are higher requirements for its dimensional stability. Summary of the Invention

[0004] In order to meet the requirements of excellent dimensional stability of polyphenylsulfone in fields such as electronics, electrical appliances, and plumbing fittings, this invention provides a high-quality polyphenylsulfone.

[0005] The technical solution adopted in this invention is as follows:

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

[0007] In the GPC chromatographic curve obtained by gel permeation chromatography, P[lg(Mw1)]+P[lg(Mw2)]<1.2%, where lg(Mw1)>5.3 and lg(Mw2)<3.6;

[0008] In the above formula, P represents a percentage, and Mw1 and Mw2 represent the mass-average molecular weights. That is, P[lg(Mw1)] + P[lg(Mw2)] indicates that in the GPC chromatographic curve, the mass-average molecular weight is greater than 10. 5.3 With less than 10 3.6 The percentage of polymer molecular chains that make up the entire polymer molecular chain.

[0009] In addition, the present invention provides a method for preparing the above-mentioned polyphenylsulfone, the steps of which are as follows:

[0010] 1) Turn on the stirring of the two reaction vessels at room temperature, add 50-70% of the reaction solvent to the main reaction vessel, and add 30-50% of the reaction solvent and the mixture prepared in a certain proportion (bisphenol, dichlorodiphenyl sulfone and alkaline catalyst) to the high-level vessel to obtain a suspension. Close the lids of the two reaction vessels and perform nitrogen vacuum replacement multiple times. After replacement, ensure that the reaction process is in a nitrogen atmosphere.

[0011] 2) Set the oil temperature of the main reactor to 180-250℃ and start heating. After the temperature inside the main reactor rises to 140-180℃, turn the stirring speed of the high-level vessel to 300-500 rpm, open the bottom valve of the high-level vessel, and add the suspension into the main reactor. At this time, the internal temperature of the main reactor is 120-160℃. As the internal temperature gradually rises, the reaction solvent begins to be carried out.

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

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

[0014] In this invention, in a preferred embodiment, the bisphenol mentioned in step 1) is 4,4'-biphenyl.

[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, and 1,3-dimethyl-2-imidazolinone. The amount of solvent used is 60-80 wt% of the total reaction solution (reaction solvent + mixture), preferably 65%-70%.

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

[0020] In the preferred embodiment of the present invention, 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 continues for 1 to 3 hours, preferably 2 to 3 hours.

[0021] In this invention, the polymer solution obtained in step 4) is pulverized, washed, and dried to obtain the high-quality polyphenylsulfone described in this invention. The solvent used is selected from one or more of sulfolane, diphenylsulfone, N-methylpyrrolidone, N-ethylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and 1,3-dimethyl-2-imidazolinone. The temperature of the solvent is 20-40°C, preferably 25-30°C, and the amount used is 10-40 wt% of the solvent used in the reaction, preferably 30-40 wt%.

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

[0023] 1. This invention adopts a feeding method of adding solvent first and then monomer, which reduces the side reactions generated by monomer during the initial heating process, reduces monomer loss, and improves product quality;

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

[0025] 3. The polyphenylene sulfone obtained by this 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 and swelling rate of the polymer, thereby obtaining polyphenylene sulfone with high dimensional stability. Attached Figure Description

[0026] Figure 1 This is a schematic diagram of a reaction according to the present invention. The dilution tank in the diagram is the high-level vessel. Detailed Implementation

[0027] To better understand the technical solution of the present invention, the following embodiments will further illustrate the method provided by the present invention. However, the present invention is not limited to the listed embodiments, but should also include any other well-known modifications within the scope of the claims of the present invention.

[0028] Example 1

[0029] 1) Start stirring in both reactors. At room temperature, add 15 kg of N-methylpyrrolidone to the main reactor. Add a mixture of 15 kg of N-methylpyrrolidone, 4.66 kg of 4,4'-biphenylhydrazine, 7.25 kg of 4,4-dichlorodiphenyl sulfone, and 4.15 kg of potassium carbonate to the high-level reactor to obtain a suspension. Close the reactor lid and purge with nitrogen three times, ensuring a nitrogen atmosphere during the reaction process after each purging.

[0030] 2) Set the oil temperature of the main reactor to 200℃ and start heating. When the temperature inside the main reactor reaches 140℃, set the speed of the high-level reactor to 500rpm, open the bottom valve of the high-level reactor, and put the suspension into the main reactor. The internal temperature drops to about 120℃, and then the temperature gradually rises, and the reaction solvent begins to be carried out.

[0031] 3) As the reaction solvent is continuously carried out, water is also carried out. When the water removal rate reaches 80%, the external circulation of the main reactor is turned on. The reaction liquid travels from the bottom of the reactor to the top of the reactor through the external circulation pipeline. The circulation time is 1 hour. At this time, the water removal rate reaches more than 95%. The external circulation of the main reactor is stopped, and the reaction continues for 2 hours.

[0032] 4) Add 10 kg of N-methylpyrrolidone to the high-temperature reaction solution in the polymerization process to cool and dilute it, thereby stopping the polymerization and obtaining a polymer solution.

[0033] Example 2

[0034] 1) Start stirring in both reactors. At room temperature, add 15 kg of N,N-dimethylacetamide to the main reactor. Add a mixture of 15 kg of N,N-dimethylacetamide, 4.66 kg of 4,4'-biphenylhydrazine, 7.25 kg of 4,4'-dichlorodiphenyl sulfone, and 4.15 kg of potassium carbonate to the high-level reactor to obtain a suspension. Close the reactor lid and purge with nitrogen three times, ensuring a nitrogen atmosphere during the reaction process after each purging.

[0035] 2) Set the oil temperature of the main reactor to 180℃ and start heating. When the temperature inside the main reactor reaches 160℃, set the rotation speed of the high-level reactor to 500rpm, open the bottom valve of the high-level reactor, and put the suspension into the main reactor. The internal temperature drops to about 140℃, and then the temperature gradually rises, and the reaction solvent begins to be carried out.

[0036] 3) As the reaction solvent is continuously carried out, water is also carried out. When the water removal rate reaches 80%, the external circulation of the main reactor is turned on. The reaction liquid travels from the bottom of the reactor to the top of the reactor through the external circulation pipeline. The circulation time is 3 hours. At this time, the water removal rate reaches more than 95%. The external circulation of the main reactor is stopped, and the reaction continues for 3 hours.

[0037] 4) Add 10 kg of N,N-dimethylacetamide to the high-temperature reaction solution in the polymerization process to cool and dilute it, thereby stopping the polymerization and obtaining a polymer solution.

[0038] Example 3

[0039] 1) Turn on the main reactor and stir. At room temperature, add 15 kg of N-methylpyrrolidone to the main reactor. Add the remaining 15 kg of N-methylpyrrolidone and a mixture of 4.75 kg of 4,4'-biphenyl, 7.18 kg of 4,4'-dichlorodiphenyl sulfone, and 3.18 kg of sodium carbonate to the high-level reactor to obtain a suspension. Close the reactor lid and perform nitrogen purging three times. After purging, ensure that the reaction process is under a nitrogen atmosphere.

[0040] 2) Set the oil temperature of the main reactor to 220℃ and start heating. When the temperature inside the main reactor reaches 170℃, set the speed of the high-level reactor to 500rpm, open the bottom valve of the high-level reactor, and put the suspension into the main reactor. The internal temperature drops to about 150℃, and then the temperature gradually rises, and the reaction solvent begins to be carried out.

[0041] 3) As the reaction solvent is continuously carried out, water is also carried out. When the water removal rate reaches 80%, the external circulation is turned on. The reaction liquid travels from the bottom of the reactor to the top of the reactor through the external circulation pipeline. The circulation time is 3 hours. At this time, the water removal rate reaches more than 95%. The external circulation is stopped, and the reaction continues for 2 hours.

[0042] 4) Add 10 kg of N-methylpyrrolidone to the high-temperature reaction solution in the polymerization process to cool and dilute it, thereby stopping the polymerization and obtaining a polymer solution.

[0043] Comparative Example 1

[0044] The difference from Example 1 is that: in the one-pot method, all the required mass of N-methylpyrrolidone, 4,4'-biphenyl, 4,4'-dichlorodiphenyl sulfone, and potassium carbonate are added to the reaction vessel without an external circulation pipeline.

[0045] 1) At room temperature, add 4.66 kg of 4,4'-biphenylhydrazine, 7.25 kg of 4,4'-dichlorodiphenyl sulfone, 4.15 kg of potassium carbonate, and 30 kg of N-methylpyrrolidone to the reaction vessel, stir evenly, and then set the temperature of the reaction vessel to 200℃.

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

[0047] 3) Add 10 kg of N-methylpyrrolidone to the high-temperature reaction solution for cooling and dilution. The polymerization is then complete, and the final reaction solution is obtained.

[0048] Comparative Example 2

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

[0050] 1) At room temperature, add 4.66 kg of 4,4'-biphenylhydrazine, 7.25 kg of 4,4'-dichlorodiphenyl sulfone, 4.15 kg of potassium carbonate, and 30 kg of N-methylpyrrolidone to the reaction vessel, stir evenly, and then set the temperature of the reaction vessel to 200℃.

[0051] 2) When the water content reaches 80%, start the external circulation of the reactor. The reaction liquid will flow from the bottom of the reactor to the top of the reactor through the external circulation pipeline. The circulation time is 2 hours. At this time, the water content reaches more than 95%. Stop the external circulation and continue the reaction for 3 hours.

[0052] 3) Add 10 kg of N-methylpyrrolidone to the high-temperature reaction solution for cooling and dilution. The polymerization is then complete, and the final reaction solution is obtained.

[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 and add 15 kg of N-methylpyrrolidone to the main reactor at room temperature; add a mixture of 15 kg of N-methylpyrrolidone, 4.66 kg of 4,4'-biphenylhydrazine, 7.25 kg of 4,4'-dichlorodiphenyl sulfone, and 4.15 kg of potassium carbonate to the high-level reactor to obtain a suspension. Close the reactor lid and perform nitrogen purging three times. After purging, ensure that the reaction process is under a nitrogen atmosphere.

[0056] 2) Set the oil temperature of the main reactor to 200℃ and start heating. When the temperature inside the main reactor reaches 140℃, set the speed of the high-level reactor to 500rpm, open the bottom valve of the high-level reactor, and put the suspension into the main reactor. The internal temperature drops to about 120℃, and then the temperature gradually rises, and the reaction solvent begins to be carried out.

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

[0058] 4) Add 10 kg of N-methylpyrrolidone to the high-temperature reaction solution for cooling and dilution. The polymerization is then complete, and the final reaction solution is obtained.

[0059] Test method:

[0060] Moisture content test: A Karl Fischer moisture titrator was used; less than 0.01g of the distillate was added to the titrator and the moisture content was tested. The moisture content was calculated using the formula: Moisture content = Total amount of distillate * Moisture content. The total moisture content is the sum of the moisture content measured each time.

[0061] GPC test: The instrument model is LC-20AD XR; the mobile phase is DMF containing 20 mmol / L lithium bromide. The test powder is prepared into a 0.1 wt% DMF solution. Take 0.5 to 1 mL of the test solution, filter it to obtain a clear solution, add the solution to the test sample tray for testing, integrate the obtained GPC curve, and calculate the percentage by taking a specific lg(Mw) value.

[0062] Water absorption test: Polyphenylsulfone powder was dissolved in NMP at a certain concentration to prepare a casting solution. The casting solution was spread into a smooth film on a glass plate, dried, demolded, and dried again to obtain a homogeneous film. The film was cut into 20*30mm blocks, dried, and weighed, recorded as W0. The film was immersed at 80℃ for 24 hours, removed, wiped dry, and weighed, which is W1. The water absorption rate was calculated.

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

[0064] Swelling rate test: Cut the membrane into 20*30mm blocks, dry them, and record the length and width values ​​of the membrane as L0; immerse the membrane at 80℃ for 24 hours, remove it, wipe off the surface moisture, and record the length and width values ​​of the membrane as L1. Calculate the swelling rate:

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

[0066] Relevant 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] Based on the performance test results of the examples and comparative examples, we can conclude that:

[0071] Examples 1-3 employ a feeding method of adding solvent first and then monomer, along with an external circulation mixing method. This reduces monomer decomposition, enhances mixing efficiency between monomers, increases reaction rate, and reduces the content of ultra-high molecular weight polyphenylsulfone and oligomers. Consequently, it improves the uniformity of polymer molecular chain length, thereby controlling the diphenyl content in the molecular chain. The absorption rate and swelling rate of the polyphenylsulfone film are reduced, exhibiting excellent dimensional stability.

[0072] Comparative Example 1 did not use the method of adding solvent first and then monomer, and did not use an external circulation pipeline for reaction liquid circulation; this resulted in a higher content of heat-sensitive components such as high and low polymers with uneven molecular chain lengths, significantly increased water absorption and swelling at 80℃, leading to reduced dimensional stability.

[0073] Comparative Example 2 did not use the method of adding solvent first and then monomer, but instead used an external circulation pipeline to circulate the reaction liquid; the molecular weight of polyphenylsulfone is unstable, and the content of high and low polymers increases, which also leads to an increase in absorption rate and swelling rate, and a decrease in dimensional stability.

[0074] Comparative Example 3 uses a method of adding solvent first and then monomer, but does not use an external circulation pipeline for reaction liquid circulation; during the polymerization process, the mixing effect of raw materials and intermediates deteriorates, the polymer molecular chains are shorter, the uniformity decreases, the absorption rate and swelling rate decrease, and the dimensional stability decreases.

[0075] In summary, the combination of adding solvent first and then monomer, along with the external circulation pipeline mixing method, can effectively improve reaction efficiency, enhance the mixing between raw materials and intermediates, and improve the uniformity of polymer molecular chain length, resulting in polyphenylene sulfone resin with excellent dimensional stability. This allows for better application in fields requiring dimensional stability, such as plumbing fittings and electronic appliances.

[0076] Although the present invention has been described in detail through the preferred embodiments described above, it should be understood that the above description should not be considered as a limitation of the present invention. Those skilled in the art will understand that modifications or adjustments can be made to the present invention based on the teachings of this specification. 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 chromatographic curve obtained by gel permeation chromatography, P[lg(Mw1)]+P[lg(Mw2)]<1.2%, where lg(Mw1)>5.3 and lg(Mw2)<3.6; In the above formula, P is a percentage, and Mw1 and Mw2 are mass-average molecular weights; The preparation method of the polyphenylsulfone includes: 1) Turn on the stirring of the two reaction vessels at room temperature, add 50-70% of the total mass of the reaction solvent to the main reaction vessel, and add 30-50% of the total mass of the reaction solvent, along with the prepared mixture of bisphenol, dichlorodiphenyl sulfone, and alkaline catalyst, to the high-level vessel to obtain a suspension. Close the lids of the two reaction vessels and perform nitrogen vacuum purging multiple times. After purging, ensure that the reaction process is in a nitrogen atmosphere. 2) Set the oil temperature of the main reactor to 180-250℃ and start heating. After the temperature inside the main reactor rises to 140-180℃, open the stirrer in the high-level vessel and add the suspension to the main reactor. As the internal temperature gradually rises, the reaction solvent begins to be carried out. 3) As the reaction solvent is continuously carried out, water is also continuously carried out. When the water removal rate reaches more than 80%, the external circulation of the main reactor is turned on. The reaction liquid reaches the top of the reactor from the bottom through the external circulation pipeline. When the water removal rate reaches more than 95%, the external circulation of the main reactor is stopped and the reaction continues. 4) Add the solvent to the high-temperature reaction solution in the polymerization process to cool and dilute it, thereby stopping the polymerization and obtaining a polymer solution.

2. The polyphenylene sulfone according to claim 1, wherein, The bisphenol mentioned in step 1) is 4,4'-biphenyl; 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.

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

4. The polyphenylene sulfone according to claim 1, wherein, The reaction solvent in step 1) 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-imidazolinone.

5. The polyphenylene sulfone according to any one of claims 1-4, wherein, In step 1), the total amount of reaction solvent used is 60-80 wt% of the total amount of the reaction solution.

6. The polyphenylene sulfone according to claim 1, wherein, Add the suspension when the internal temperature is 150-170℃ in step 2).

7. The polyphenylene sulfone according to claim 1, wherein, In step 3), the external circulation is started and the circulation time is 0.5 to 4 hours; after the external circulation is stopped, the reaction time continues for 1 to 3 hours.

8. The polyphenylene sulfone according to claim 1, wherein, In step 3), the external circulation is started and the circulation time is 1 to 3 hours; after the external circulation is stopped, the reaction time continues for 2 to 3 hours.

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