High performance polyphenylsulfone and method for its synthesis

Abstract

The application relates to the technical field of high polymer material synthesis, and discloses high-performance polyphenyl sulfone and a synthesis method thereof, wherein the synthesis method is as follows: 4,4'-diphenol, 4,4'-dichlorodiphenyl sulfone, modified 2,6-difluorobenzene hydrazine and a polar aprotic solvent are mixed and dissolved, a salting agent and a water-carrying agent are added, a salting reaction and a polymerization reaction are carried out under an inert gas atmosphere, after the reaction is completed, precipitation, washing and drying are carried out, and high-performance polyphenyl sulfone is obtained. The high-performance polyphenyl sulfone has good impact resistance and high-temperature stability.

Description

Technical Field

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

[0002] Polyphenylsulfone (PPS) is a high-performance special engineering plastic composed of benzene rings and sulfone groups linked by ether bonds or aryl groups. It possesses excellent chemical corrosion resistance, flame retardancy, and low smoke toxicity, making it widely used in medical devices, the automotive industry, aerospace, and other fields. Currently, with changing societal demands, industries such as automotive and aerospace are pursuing energy conservation and emission reduction. To reduce energy consumption, plastics are being used to replace metals, and "replacing steel with plastics" has become a trend. While PPS on the market exhibits good overall performance in many practical applications, its impact resistance and high-temperature stability still need improvement. Therefore, avoiding this issue is key to solving the problem. The literature "Preparation and Performance Study of Polyphenylsulfone-based Antifouling Ultrafiltration Membranes" provides a copolymerization method for PPS. Patent CN117229637A discloses a PPS composite material, comprising the following components by weight percentage: 95-99% PPS resin; 1-5% fluorinated siloxane; and 0.1-0.5 parts silane coupling agent. The invention has excellent stain resistance and oil resistance, but its impact resistance and high temperature stability still need to be improved. Summary of the Invention

[0003] (a) Technical problems to be solved

[0004] To address the shortcomings of existing technologies, this invention provides a high-performance polyphenylene sulfone and its synthesis method. The high-performance polyphenylene sulfone of this invention exhibits excellent impact resistance and high-temperature stability.

[0005] (II) Technical Solution

[0006] To achieve the above objectives, the present invention provides the following technical solution: a method for synthesizing high-performance polyphenylsulfone, characterized in that, by molar percentage, it comprises structural units derived from the following monomers:

[0007] 4,4'-Biphenyldiol: 20-35 mol%

[0008] 4,4'-Dichlorodiphenyl sulfone: 40-45 mol%

[0009] Modified 2,6-difluorophenylhydrazine: 20-30 mol%.

[0010] Furthermore, the preparation method of the modified 2,6-difluorophenylhydrazine is as follows:

[0011] Step 1: Add 2,6-difluorophenylhydrazine and 4-vinylbenzoyl chloride to toluene solvent, stir well, add triethylamine dropwise, and react at 50-70℃ for 3-5 h. After the reaction is complete, wash and dry, concentrate, and purify by column chromatography to obtain intermediate 1.

[0012] Step 2: Under inert gas protection, intermediate 1 and heptane-4-thiol were added to N,N-dimethylformamide solvent, followed by the addition of benzoin dimethyl ether photoinitiator. The mixture was then irradiated with 365nm ultraviolet light at 30-36℃ for 2-4 hours. After the reaction was completed, the mixture was centrifuged, washed, and dried to obtain modified 2,6-difluorophenylhydrazine.

[0013] Furthermore, in step one, the ratio of toluene, 2,6-difluorophenylhydrazine, 4-vinylbenzoyl chloride, and triethylamine is 13-15 mL: 0.8-1 mmol: 1-1.1 mmol: 0.02-0.04 mmol.

[0014] Furthermore, in step two, the ratio of intermediate 1, heptane-4-thiol, N,N-dimethylformamide, and benzoin dimethyl ether photoinitiator is 0.9-1.1 mmol: 1.1-1.2 mmol: 10-12 mL: 0.03-0.05 mmol.

[0015] Furthermore, the method for synthesizing the high-performance polyphenylsulfone includes the following steps:

[0016] 4,4'-Biphenylhydrazine, 4,4'-dichlorodiphenyl sulfone, modified 2,6-difluorophenylhydrazine, and a polar aprotic solvent were mixed and dissolved. A salt-forming agent and a dehydrating agent were added, and the salt-forming reaction and polymerization reaction were carried out under an inert gas atmosphere. After the reaction was completed, the precipitate was collected, washed, and dried to obtain high-performance polyphenylsulfone.

[0017] Furthermore, the ratio of the polar aprotic solvent, salt-forming agent, and dehydrating agent is 8-10 mL: 2.2-2.5 g: 25-28 g.

[0018] Furthermore, the polar aprotic solvent is at least one of N-methylpyrrolidone, sulfolane, and dimethyl sulfoxide.

[0019] Furthermore, the salt-forming agent is one of sodium carbonate or potassium carbonate.

[0020] Furthermore, the water-removing agent is one of toluene and xylene.

[0021] Furthermore, the salt formation reaction temperature is 120-140℃, and the polymerization reaction temperature is 220-250℃.

[0022] (III) Beneficial Technical Effects

[0023] This invention involves mixing and dissolving 4,4'-biphenylhydrazine, 4,4'-dichlorodiphenyl sulfone, modified 2,6-difluorophenylhydrazine, and a polar aprotic solvent, adding a salt-forming agent and a dehydrating agent, and carrying out a salt-forming reaction and a polymerization reaction under an inert gas atmosphere. After the reaction is completed, the precipitate is collected, washed, and dried to obtain high-performance polyphenylsulfone.

[0024] 2,6-Difluorophenylhydrazine, as a structural unit of polyphenylsulfone, introduces a secondary amino group. The benzene ring structure of the aromatic secondary amino group forms a conjugated system with the phenylsulfone unit of the polyphenylsulfone main chain, which significantly improves the rigidity of the chain segments and inhibits the molecular chain movement at high temperatures, thereby improving the high-temperature stability of polyphenylsulfone. Then, 2,6-difluorophenylhydrazine and 4-vinylbenzoyl chloride are added to toluene solvent to react and obtain intermediate 1, which introduces an amide group. The amide bond is more flexible than the rigid sulfone group of polyphenylsulfone, giving the chain segments a higher degree of freedom of movement. This allows the impact energy to be converted into heat energy dissipation through chain segment movement, rather than directly causing fracture, thereby improving the impact resistance of polyphenylsulfone. Attached Figure Description

[0025] Figure 1 This is the 1H NMR spectrum of intermediate 1 in Example 1.

[0026] Figure 2 This is the 1H NMR spectrum of the modified 2,6-difluorophenylhydrazine in Example 1. Detailed Implementation

[0027] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are described clearly and completely. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention through further extension or optimization are also within the scope of protection of the present invention.

[0028] To better understand the above technical solutions, the following will provide a detailed explanation of the technical solutions in conjunction with the accompanying drawings and specific embodiments.

[0029] Example 1

[0030] This embodiment provides a high-performance polyphenylsulfone, comprising, by molar percentage, structural units derived from the following monomers: 4,4'-biphenylhydrazine: 35 mol%, 4,4'-dichlorodiphenylsulfone: 45 mol%, and modified 2,6-difluorophenylhydrazine: 20 mol%. The specific steps are as follows:

[0031] (1) Add 0.8 mmol of 2,6-difluorophenylhydrazine and 1 mmol of 4-vinylbenzoyl chloride to 13 mL of toluene solvent, stir well, add 0.02 mmol of triethylamine dropwise, and react at 50 °C for 3 h. After the reaction is complete, wash and dry, concentrate, and purify by column chromatography to obtain intermediate 1; the reaction process is as follows.

[0032]

[0033] (2) Under nitrogen protection, 0.9 mmol of intermediate 1 and 1.1 mmol of heptane-4-thiol were added to 10 mL of N,N-dimethylformamide solvent, followed by the addition of 0.03 mmol of benzoin dimethyl ether photoinitiator. The mixture was irradiated with 365 nm ultraviolet light at 30 °C for 2 h. After the reaction was complete, the mixture was centrifuged, washed, and dried to obtain modified 2,6-difluorophenylhydrazine. The reaction process is as follows:

[0034]

[0035] (3) 3.25 g of 4,4'-biphenylhydrazine, 6.46 g of 4,4'-dichlorodiphenyl sulfone, 3.84 g of modified 2,6-difluorophenylhydrazine, and 8 mL of N-methylpyrrolidone were mixed and dissolved. 2.2 g of sodium carbonate and 25 g of toluene were added, and a salt-forming reaction was carried out under a nitrogen atmosphere at 120 °C. Then, a polymerization reaction was carried out under a nitrogen atmosphere at 220 °C. After the reaction, the precipitate was collected, washed, and dried to obtain high-performance polyphenylsulfone. The reaction process is as follows:

[0036]

[0037] Example 2

[0038] This embodiment provides a high-performance polyphenylsulfone, comprising, by molar percentage, structural units derived from the following monomers: 4,4'-biphenylhydrazine: 30 mol%, 4,4'-dichlorodiphenylsulfone: 45 mol%, and modified 2,6-difluorophenylhydrazine: 25 mol%. The specific steps are as follows:

[0039] (1) Add 1 mmol of 2,6-difluorophenylhydrazine and 1.1 mmol of 4-vinylbenzoyl chloride to 15 mL of toluene solvent, stir well, add 0.04 mmol of triethylamine dropwise, and react at 70 °C for 5 h. After the reaction is complete, wash and dry, concentrate, and purify by column chromatography to obtain intermediate 1.

[0040] (2) Under nitrogen protection, 1.1 mmol of intermediate 1 and 1.2 mmol of heptane-4-thiol were added to 12 mL of N,N-dimethylformamide solvent, and then 0.05 mmol of benzoin dimethyl ether photoinitiator was added. The mixture was irradiated with 365 nm ultraviolet light at 36 °C for 4 h. After the reaction was completed, the mixture was centrifuged, washed and dried to obtain modified 2,6-difluorophenylhydrazine.

[0041] (3) 2.79 g of 4,4'-biphenylhydrazine, 6.46 g of 4,4'-dichlorodiphenyl sulfone, 4.8 g of modified 2,6-difluorophenylhydrazine and 10 mL of sulfolane were mixed and dissolved. 2.5 g of potassium carbonate and 28 g of xylene were added. The salt formation reaction was carried out under a nitrogen atmosphere at a reaction temperature of 140 °C. Then, the polymerization reaction was carried out under a nitrogen atmosphere at a reaction temperature of 250 °C. After the reaction was completed, the precipitate was collected, washed and dried to obtain high-performance polyphenylsulfone.

[0042] Example 3

[0043] This embodiment provides a high-performance polyphenylsulfone, comprising, by molar percentage, structural units derived from the following monomers: 4,4'-biphenylhydrazine: 35 mol%, 4,4'-dichlorodiphenylsulfone: 40 mol%, and modified 2,6-difluorophenylhydrazine: 25 mol%. The specific steps are as follows:

[0044] (1) Add 0.9 mmol of 2,6-difluorophenylhydrazine and 1 mmol of 4-vinylbenzoyl chloride to 14 mL of toluene solvent, stir well, add 0.03 mmol of triethylamine dropwise, and react at 60 °C for 4 h. After the reaction is complete, wash and dry, concentrate, and purify by column chromatography to obtain intermediate 1.

[0045] (2) Under nitrogen protection, 1 mmol of intermediate 1 and 1.1 mmol of heptane-4-thiol were added to 11 mL of N,N-dimethylformamide solvent, and then 0.04 mmol of benzoin dimethyl ether photoinitiator was added. The mixture was irradiated with 365 nm ultraviolet light at 33 °C for 3 h. After the reaction was completed, the mixture was centrifuged, washed and dried to obtain modified 2,6-difluorophenylhydrazine.

[0046] (3) Mix and dissolve 3.25g of 4,4'-biphenylhydrazine, 5.74g of 4,4'-dichlorodiphenyl sulfone, 4.8g of modified 2,6-difluorophenylhydrazine and 9mL of dimethyl sulfoxide, add 2.3g of potassium carbonate and 26g of toluene, and carry out a salt formation reaction under a nitrogen atmosphere at a reaction temperature of 130℃. Then carry out a polymerization reaction under a nitrogen atmosphere at a reaction temperature of 230℃. After the reaction is completed, precipitate, wash and dry to obtain high-performance polyphenylsulfone.

[0047] Example 4

[0048] This embodiment provides a high-performance polyphenylsulfone, comprising, by molar percentage, structural units derived from the following monomers: 4,4'-biphenylhydrazine: 25 mol%, 4,4'-dichlorodiphenylsulfone: 45 mol%, and modified 2,6-difluorophenylhydrazine: 30 mol%. The specific steps are as follows:

[0049] (1) Add 0.9 mmol of 2,6-difluorophenylhydrazine and 1 mmol of 4-vinylbenzoyl chloride to 13 mL of toluene solvent, stir well, add 0.03 mmol of triethylamine dropwise, and react at 60 °C for 4 h. After the reaction is complete, wash and dry, concentrate, and purify by column chromatography to obtain intermediate 1.

[0050] (2) Under nitrogen protection, 1 mmol of intermediate 1 and 1.1 mmol of heptane-4-thiol were added to 11 mL of N,N-dimethylformamide solvent, and then 0.04 mmol of benzoin dimethyl ether photoinitiator was added. The mixture was irradiated with 365 nm ultraviolet light at 33 °C for 2 h. After the reaction was completed, the mixture was centrifuged, washed and dried to obtain modified 2,6-difluorophenylhydrazine.

[0051] (3) 2.33 g of 4,4'-biphenylhydrazine, 6.46 g of 4,4'-dichlorodiphenyl sulfone, 5.76 g of modified 2,6-difluorophenylhydrazine and 9 mL of N-methylpyrrolidone were mixed and dissolved. 2.3 g of potassium carbonate and 27 g of xylene were added. The salt formation reaction was carried out under a nitrogen atmosphere at a reaction temperature of 120 °C. Then, the polymerization reaction was carried out under a nitrogen atmosphere at a reaction temperature of 230 °C. After the reaction was completed, the precipitate was collected, washed and dried to obtain high-performance polyphenylsulfone.

[0052] Example 5

[0053] This embodiment provides a high-performance polyphenylsulfone, comprising, by molar percentage, structural units derived from the following monomers: 4,4'-biphenylhydrazine: 30 mol%, 4,4'-dichlorodiphenylsulfone: 40 mol%, and modified 2,6-difluorophenylhydrazine: 30 mol%. The specific steps are as follows:

[0054] (1) Add 1 mmol of 2,6-difluorophenylhydrazine and 1.1 mmol of 4-vinylbenzoyl chloride to 14 mL of toluene solvent, stir well, add 0.04 mmol of triethylamine dropwise, and react at 70 °C for 4 h. After the reaction is complete, wash and dry, concentrate, and purify by column chromatography to obtain intermediate 1.

[0055] (2) Under nitrogen protection, 1 mmol of intermediate 1 and 1.2 mmol of heptane-4-thiol were added to 12 mL of N,N-dimethylformamide solvent, and then 0.05 mmol of benzoin dimethyl ether photoinitiator was added. The mixture was irradiated with 365 nm ultraviolet light at 36 °C for 3 h. After the reaction was completed, the mixture was centrifuged, washed and dried to obtain modified 2,6-difluorophenylhydrazine.

[0056] (3) 2.79 g of 4,4'-biphenylhydrazine, 5.74 g of 4,4'-dichlorodiphenyl sulfone, 5.76 g of modified 2,6-difluorophenylhydrazine and 10 mL of sulfolane were mixed and dissolved. 2.4 g of potassium carbonate and 27 g of toluene were added. The salt formation reaction was carried out under a nitrogen atmosphere at a reaction temperature of 140 °C. Then, the polymerization reaction was carried out under a nitrogen atmosphere at a reaction temperature of 240 °C. After the reaction was completed, the precipitate was collected, washed and dried to obtain high-performance polyphenylsulfone.

[0057] Comparative Example 1

[0058] The difference between this comparative example and Example 5 is that intermediate 1 was used instead of modified 2,6-difluorophenylhydrazine.

[0059] Comparative Example 2

[0060] The difference between this comparative example and Example 5 is that modified 2,6-difluorophenylhydrazine was not added, and the molar percentages were 4,4'-biphenylhydrazine: 50 mol%, 4,4'-dichlorodiphenyl sulfone: 50 mol%.

[0061] Result detection:

[0062] Impact strength and heat distortion temperature tests were performed on the high-performance polyphenylsulfone obtained in the above embodiments and comparative examples.

[0063] Test method:

[0064] (1) Impact strength test: The test method refers to standard ISO 179 / 1eA.

[0065] (2) Heat distortion temperature test: The test method refers to standard ISO 75-2:2013.

[0066] The test results are shown in Table 1.

[0067] Table 1:

[0068]

[0069]

[0070] As can be seen from Table 1, the impact strength of the high-performance polyphenylene sulfone obtained in Examples 1-5 of the present invention is all greater than 25 kJ / m. 2Furthermore, the heat distortion temperature of all of them is greater than 230℃, indicating that the high-performance polyphenylsulfone of the present invention has good impact resistance and high-temperature stability.

[0071] It should be noted that, in this document, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Unless otherwise specified, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes said element.

[0072] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A high-performance polyphenylsulfone, characterized in that, Mole percentage meter, comprising structural units derived from the following monomers: 4,4'-Biphenyldiol: 20-35 mol% 4,4'-Dichlorodiphenyl sulfone: 40-45 mol% Modified 2,6-difluorophenylhydrazine: 20-30 mol% The preparation method of the modified 2,6-difluorophenylhydrazine is as follows: Step 1: Add 2,6-difluorophenylhydrazine and 4-vinylbenzoyl chloride to toluene solvent, stir well, add triethylamine dropwise, and react at 50-70℃ for 3-5 h. After the reaction is complete, wash and dry, concentrate, and purify by column chromatography to obtain intermediate 1. Step 2: Under inert gas protection, intermediate 1 and heptane-4-thiol were added to N,N-dimethylformamide solvent, followed by the addition of benzoin dimethyl ether photoinitiator. The mixture was then irradiated with 365nm ultraviolet light at 30-36℃ for 2-4 hours. After the reaction was completed, the mixture was centrifuged, washed, and dried to obtain modified 2,6-difluorophenylhydrazine.

2. The high-performance polyphenylsulfone according to claim 1, characterized in that, In step one, the ratio of toluene, 2,6-difluorophenylhydrazine, 4-vinylbenzoyl chloride, and triethylamine is 13-15 mL: 0.8-1 mmol: 1-1.1 mmol: 0.02-0.04 mmol.

3. The high-performance polyphenylene sulfone according to claim 1, characterized in that, In step two, the ratio of intermediate 1, heptane-4-thiol, N,N-dimethylformamide, and benzoin dimethyl ether photoinitiator is 0.9-1.1 mmol: 1.1-1.2 mmol: 10-12 mL: 0.03-0.05 mmol.

4. A method for synthesizing high-performance polyphenylsulfone as described in any one of claims 1-3, characterized in that, The method for synthesizing the high-performance polyphenylsulfone includes the following steps: 4,4'-Biphenylhydrazine, 4,4'-dichlorodiphenyl sulfone, modified 2,6-difluorophenylhydrazine, and a polar aprotic solvent were mixed and dissolved. A salt-forming agent and a dehydrating agent were added, and the salt-forming reaction and polymerization reaction were carried out under an inert gas atmosphere. After the reaction was completed, the precipitate was collected, washed, and dried to obtain high-performance polyphenylsulfone.

5. The method for synthesizing high-performance polyphenylsulfone according to claim 4, characterized in that, The ratio of the polar aprotic solvent, salt-forming agent, and dehydrating agent is 8-10 mL: 2.2-2.5 g: 25-28 g.

6. The method for synthesizing high-performance polyphenylsulfone according to claim 4, characterized in that, The polar aprotic solvent is at least one of N-methylpyrrolidone, sulfolane, and dimethyl sulfoxide.

7. The method for synthesizing high-performance polyphenylsulfone according to claim 4, characterized in that, The salt-forming agent is either sodium carbonate or potassium carbonate.

8. The method for synthesizing high-performance polyphenylsulfone according to claim 4, characterized in that, The water-removing agent is one of toluene and xylene.

9. The method for synthesizing high-performance polyphenylsulfone according to claim 4, characterized in that, The salt formation reaction temperature is 120-140℃, and the polymerization reaction temperature is 220-250℃.

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