Polyether sulfone resin, polymerization method thereof and polyether sulfone resin composition

Abstract

The invention discloses a polyethersulfone resin which is derived from the following monomers in percentage by mole: 49.9-50.1 mol% of a diol monomer; the preparation method comprises the following steps: adding 49.9 to 50.1 mol% of 4, 4 '-dichlorodiphenyl sulfone; the diol monomer is bisphenol S and other diol, and the other diol accounts for 0.2-10% of the total molar percentage of the diol monomer; and the other diol is selected from at least one of ethylene glycol, diethylene glycol, 1, 4-cyclohexanedimethanol, spirodiol, 1, 2-propylene glycol, 1, 3-propylene glycol, neopentyl glycol, 1, 4-butanediol and 1, 5-pentanediol, and the other diol is selected from at least one of ethylene glycol, diethylene glycol, 1, 4-cyclohexanedimethanol, spirodiol, 1, 2-propylene glycol, 1, 3-propylene glycol, neopentyl glycol, 1, 4-butanediol and 1, 5-pentanediol. According to the invention, by introducing other glycols with a specific content into a repetitive unit of polysulfone, the hydrophilicity of the polyethersulfone resin prepared into a film and the peel strength before and after boiling resistance can be remarkably improved, and the defects of bubbling, cracks and the like of the polysulfone resin after high-temperature boiling are improved.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, in particular to a polyethersulfone resin and a polymerization method thereof, and a polyethersulfone resin composition. Background Art

[0002] Polyethersulfone (PES) boasts excellent properties, including high-temperature resistance, creep resistance, high strength, non-toxicity, chemical resistance, and flame retardancy. Consequently, it has long been widely used in electronics, electrical appliances, machinery, automobiles, medical devices, food processing, and non-stick coatings. The typical preparation method involves the salt polymerization of bisphenol S and 4,4'-dichlorodiphenyl sulfone in an alkaline environment. After post-treatment, the resulting high-temperature-resistant, high-strength PES resin is obtained.

[0003] However, existing polyethersulfone resins in the coating field may cause problems such as shedding and blistering after being boiled in high-temperature water.

[0004] The existing method to improve the above technical defects is to add epoxy resin / initiator for modification. However, on the one hand, this method is complicated in preparation process, and on the other hand, this method will destroy other properties of the resin, making subsequent modification and application difficult. Summary of the Invention

[0005] The purpose of the present invention is to overcome the above technical defects and provide a polyethersulfone resin suitable for the coating field and a polymerization method and composition thereof.

[0006] The present invention is achieved through the following technical solutions: A polyethersulfone resin composition, based on molar percentage, is derived from the following monomers: Diol monomer 49.9-50.1 mol%; 4,4'-dichlorodiphenyl sulfone 49.9-50.1 mol%; The diol monomers are bisphenol S and other diols, wherein the molar percentage of other diols in the total diol monomers is in the range of 0.2-10%; The other diols are selected from at least one of ethylene glycol, diethylene glycol, 1,4-cyclohexanedimethanol, spirodiol, 1,2-propylene glycol, 1,3-propylene glycol, neopentyl glycol, 1,4-butanediol, and 1,5-pentanediol.

[0007] Preferably, when the other diol is selected from ethylene glycol, the molar percentage of ethylene glycol in the total diol monomer is in the range of 8-10 mol%; Preferably, when the other diol is selected from diethylene glycol, the molar percentage of diethylene glycol in the total diol monomer is in the range of 7-10 mol%; Preferably, when the other diol is selected from 1,4-cyclohexanedimethanol, the molar percentage of 1,4-cyclohexanedimethanol in the total diol monomer is in the range of 2-4 mol%; Preferably, when the other diol is selected from spirodiol, the spirodiol accounts for 2-4 mol% of the total mole percentage of the diol monomer; Preferably, when the other diol is selected from 1,2-propylene glycol, the molar percentage of 1,2-propylene glycol in the total diol monomer is in the range of 5-8 mol%; Preferably, when the other diol is selected from 1,3-propylene glycol, the molar percentage of 1,3-propylene glycol in the total diol monomer is in the range of 5-8 mol%; Preferably, when the other diol is selected from neopentyl glycol, the molar percentage of neopentyl glycol in the total diol monomer is in the range of 4-6 mol%; Preferably, when the other diol is selected from 1,4-butanediol, the molar percentage of 1,4-butanediol in the total diol monomer is in the range of 3-5 mol%; Preferably, when the other diol is selected from 1,5-pentanediol, the molar percentage of 1,5-pentanediol in the total diol monomers is in the range of 3-6 mol%.

[0008] Preferably, the other diol is selected from at least one of 1,4-cyclohexanedimethanol, spirodiol, and 1,5-pentanediol.

[0009] The weight average molecular weight of the polyethersulfone resin is in the range of 60,000 to 80,000.

[0010] The polyethersulfone resin polymerization method of the present invention comprises the following steps: adding bisphenol S, 4,4'-dichlorodiphenyl sulfone, other diols, a salt-forming agent, a solvent and a water-separating agent into a reaction container, stirring at 140-180 DEG C, and separating water for 1-3 hours; distilling off the water-separating agent, stirring at 40-70 r / min, heating to 160-250 DEG C, and continuing to keep the temperature for reaction for 10-15 hours; increasing the stirring speed to 80-100 r / min, maintaining the temperature for 0.5-1.5 hours, pouring the reaction solution into distilled water, and cooling, crushing, filtering, washing, drying, etc. to obtain the polyethersulfone resin.

[0011] The salt-forming agent is selected from at least one of sodium carbonate, potassium carbonate, lithium carbonate, sodium hydroxide, potassium hydroxide, and lithium hydroxide; the solvent is selected from at least one of N-methylpyrrolidone, N,N'-dimethylformamide, N,N'-dimethylacetamide, dimethyl sulfoxide, cyclopentane, and diphenyl sulfone; and the water-separating agent is selected from at least one of toluene, xylene, mesitylene, meta-trimethylbenzene, o-trimethylbenzene, ethylbenzene, and ethylidene.

[0012] The present invention also provides a polyethersulfone resin composition using the above-mentioned polyethersulfone resin, which comprises the following components in parts by weight: 70-90 parts of polyethersulfone resin; 9.9-25 parts of silane coupling agent; Additives 0.1-5 parts.

[0013] The silane coupling agent is selected from at least one of γ-glycidyloxypropyltrimethoxysilane, aminopropyltriethoxysilane, vinyltriethoxysilane, vinyltri(β-methoxyethoxy)silane, γ-methacryloxypropyltrimethoxysilane, and γ-aminopropyltrimethoxysilane.

[0014] Additives can be: antioxidants, lubricants, toughening agents, fillers, etc.

[0015] The present invention has the following beneficial effects: The invention introduces other glycols at a specific molar content into the repeating units of polysulfone, thereby significantly improving the hydrophilicity of the polyethersulfone resin after being prepared into a film and the peel strength before and after water boiling, thereby improving the defects of the polysulfone resin such as blistering and cracking under high-temperature water boiling. DETAILED DESCRIPTION

[0016] The present invention will be described in detail below with reference to specific embodiments. The following embodiments will help those skilled in the art to further understand the present invention, but are not intended to limit the present invention in any form. It should be noted that, for those skilled in the art, several variations and improvements can be made without departing from the scope of the present invention. These all fall within the scope of protection of the present invention.

[0017] The sources of experimental raw materials used in the present invention are as follows: Bisphenol S, 4,4'-dichlorodiphenyl sulfone, ethylene glycol, diethylene glycol, 1,4-cyclohexanedimethanol, spirodiol, 1,2-propylene glycol, 1,3-propylene glycol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, organic solvent, water separator, potassium carbonate, etc. were commercially available.

[0018] Silane coupling agent: KBM-403, Shin-Etsu Chemical Co., Ltd., Japan; Examples and Comparative Examples A method for preparing a polyethersulfone resin comprises adding bisphenol S, 4,4'-dichlorodiphenyl sulfone, other glycols, a salt-forming agent, a solvent, and a water-separating agent to a reaction vessel, stirring at 160° C. to separate water for 1-3 hours; distilling off the water-separating agent, stirring at 40-70 r / min, heating to 160-250° C., and continuing to heat and react for 10-15 hours; increasing the stirring speed to 80-100 r / min and maintaining the temperature for 0.5-1.5 hours, pouring the reaction solution into distilled water, and obtaining a polyethersulfone resin by cooling, crushing, filtering, washing, and drying.

[0019] Various test methods: Dissolve polyethersulfone resin in NMP, add zirconium beads, grind thoroughly, and filter to obtain a coating solution. Apply the solution to the treated aluminum plate using a spray gun and evenly spray it onto the plate. The plate is then baked in a 170°C oven for 10 minutes. The thickness is measured and maintained between 10 and 15 microns. If the thickness is not within the specified range, repeat the above steps. If the thickness is within the specified range, bake the plate at 380°C for 10 minutes to obtain a film-coated part. The aluminum plate is treated by baking at 150°C for 10 minutes before use. The following hydrophilicity and boiling water resistance tests are then performed.

[0020] (1) Hydrophilicity: Test its water contact angle.

[0021] (2) Water boiling resistance: Prepare a film in the form of a coating, and test the peel strength of the material after boiling in water (85°C, 12 hours).

[0022] (3) Weight average molecular weight: Take 0.03 g of polyethersulfone resin, add 10 mL of DMF to prepare a solution, and use GPC to test its weight average molecular weight.

[0023] Table 1: Monomer contents and test results of polyethersulfone resins in Examples and Comparative Examples Example A-1 Example A-2 Example A-3 Example A-4 Example A-5 Bisphenol S, mol% 49 46 45.6 45.2 45 4,4'-Dichlorodiphenyl sulfone, mol% 50 50 50 50 50 Ethylene glycol, mol% 1 4 4.4 4.8 5 Weight average molecular weight 65207 71538 70005 68642 67535 Water contact angle, ° 81 75 71 70 68 Peel strength, N / mm 0.71 0.77 0.83 0.80 0.78 From Examples A1 to A5 and Comparative Example 1, it can be seen that as the molar content of ethylene glycol repeating units increases, the hydrophilicity increases, and the peel strength first increases and then decreases. Preferably, the molar percentage of ethylene glycol in the total diol monomers is in the range of 8-10 mol%.

[0024] Continued Table 1: Comparative Example 1 Comparative Example 2 Comparative Example 3 Bisphenol S, mol% 50 44 44 4,4'-Dichlorodiphenyl sulfone, mol% 50 50 50 Ethylene glycol, mol% 0 6 1,4-Cyclohexanedimethanol, mol% 6 Weight average molecular weight 72033 71220 69305 Water contact angle, ° 85 65 72 Peel strength, N / mm 0.65 0.68 0.74 It can be seen from Comparative Example 1 that conventional polyethersulfone has poor hydrophilicity and low peel strength.

[0025] It can be seen from Comparative Examples 2 / 3 that the peel strength decreases significantly when the molar content of ethylene glycol or 1,4-cyclohexanedimethanol increases.

[0026] Continued Table 1: Example B-1 Example B-2 Example B-3 Example B-4 Example B-5 Bisphenol S, mol% 49 46.5 46 45.6 44.9 4,4'-Dichlorodiphenyl sulfone, mol% 50 50 50 50 50.1 Diethylene glycol, mol% 1 3.5 4 4.4 5 Weight average molecular weight 70995 73561 72143 71381 71328 Water contact angle, ° 82 76 72 69 67 Peel strength, N / mm 0.72 0.78 0.79 0.81 0.77 As can be seen from Examples B1 to B5, the preferred molar percentage range of diethylene glycol to the total molar percentage of diol monomers is 7-10 mol%.

[0027] Continued Table 1: Example C-1 Example C-2 Example C-3 Example C-4 Example C-5 Bisphenol S, mol% 49.9 49 48.5 48 45 4,4'-Dichlorodiphenyl sulfone, mol% 50 50 50 50 50 1,4-Cyclohexanedimethanol, mol% 0.1 1 1.5 2 5 Weight average molecular weight 79183 77348 76185 75818 70537 Water contact angle, ° 88 84 82 80 74 Peel strength, N / mm 0.81 0.90 0.99 0.94 0.83 As can be seen from Examples C1 to C5, the preferred molar percentage range of 1,4-cyclohexanedimethanol to the total molar percentage of diol monomers is 2-4 mol%.

[0028] Table 1 continued: Example D-1 Example D-2 Example D-3 Example D-4 Example D-5 Bisphenol S, mol% 49.9 49 48.5 48 45 4,4'-Dichlorodiphenyl sulfone, mol% 50 50 50 50 50 Spirodiol, mol% 0.1 1 1.5 2 5 Weight average molecular weight 78156 78924 79281 80163 74229 Water contact angle, ° 89 82 79 77 72 Peel strength, N / mm 0.82 0.95 1.01 0.97 0.84 As can be seen from Examples D1 to D5, the preferred molar percentage range of spirodiol to the total molar percentage of diol monomers is 2-4 mol%.

[0029] Table 1 continued: Example E-1 Example E-2 Example E-3 Example E-4 Example E-5 Example E-6 Bisphenol S, mol% 49.9 47.5 47 46.5 46 45 4,4'-Dichlorodiphenyl sulfone, mol% 50 50 50 50 50 50 1,3-Propanediol, mol% 0.1 2.5 3 3.5 4 5 Weight average molecular weight 73699 75254 74123 73018 70864 76014 Water contact angle, ° 84 79 77 74 72 68 Peel strength, N / mm 0.70 0.79 0.83 0.86 0.81 0.75 As can be seen from Examples E1 to E5, the preferred molar percentage range of 1,3-propylene glycol to the total molar percentage of diol monomers is 5-8 mol%.

[0030] Table 1 continued: Example F-1 Example F-2 Example F-3 Example F-4 Example F-5 Bisphenol S, mol% 49.9 48 47.6 47 45 4,4'-Dichlorodiphenyl sulfone, mol% 50 50 50 50 50 Neopentyl glycol, mol% 0.1 2 2.4 3 5 Weight average molecular weight 73551 77183 76281 74253 76581 Water contact angle, ° 84 77 75 72 68 Peel strength, N / mm 0.75 0.84 0.89 0.83 0.73 As can be seen from Examples F1 to F5, the preferred molar percentage range of neopentyl glycol to the total molar percentage of diol monomers is 4-6 mol%.

[0031] Table 1 continued: Example G-1 Example G-2 Example G-3 Example G-4 Example G-5 Bisphenol S, mol% 49.9 48.5 48.1 47.5 45 4,4'-Dichlorodiphenyl sulfone, mol% 50 50 50 50 50 1,4-Butanediol, mol% 0.1 1.5 1.9 2.5 5 Weight average molecular weight 74003 78001 77773 76054 77337 Water contact angle, ° 83 77 75 72 67 Peel strength, N / mm 0.76 0.85 0.95 0.88 0.79 As can be seen from Examples G1 to G5, the preferred molar percentage range of 1,4-butanediol to the total molar percentage of diol monomers is 3-5 mol%.

[0032] Table 1 continued: Example H-1 Example H-2 Example H-3 Example H-4 Example H-5 Bisphenol S, mol% 49.9 48.5 47.5 47 45 4,4'-Dichlorodiphenyl sulfone, mol% 50 50 50 50 50 1,5-Pentanediol, mol% 0.1 1.5 2.5 3 5 Weight average molecular weight 76448 78013 75518 74810 70109 Water contact angle, ° 84 80 76 74 70 Peel strength, N / mm 0.74 0.87 0.91 0.84 0.77 As can be seen from Examples H1 to H5, the preferred molar percentage range of 1,5-pentanediol to the total molar percentage of diol monomers is 3-6 mol%.

Claims

1. A polyethersulfone resin composition, characterized in that Derived from the following monomers, measured by mole percentage: Diol monomer 49.9-50.1 mol%; 4,4'-dichlorodiphenyl sulfone 49.9-50.1 mol%; The diol monomers are bisphenol S and other diols, wherein the molar percentage of other diols in the total diol monomers is in the range of 0.2-10%; The other diols are selected from at least one of ethylene glycol, diethylene glycol, 1,4-cyclohexanedimethanol, spirodiol, 1,2-propylene glycol, 1,3-propylene glycol, neopentyl glycol, 1,4-butanediol, and 1,5-pentanediol.

2. The polyethersulfone resin according to claim 1, characterized in that When the other diol is selected from ethylene glycol, the molar percentage of ethylene glycol in the total diol monomer is in the range of 8-10 mol%; When the other diol is selected from diethylene glycol, the molar percentage of diethylene glycol in the total diol monomer is in the range of 7-10 mol%; When the other diol is selected from 1,4-cyclohexanedimethanol, the molar percentage of 1,4-cyclohexanedimethanol in the total diol monomer is in the range of 2-4 mol%; When the other diol is selected from spirodiol, the spirodiol accounts for 2-4 mol% of the total mole percentage of the diol monomer; When the other diol is selected from 1,2-propylene glycol, the molar percentage of 1,2-propylene glycol in the total diol monomers is in the range of 5-8 mol%; When the other diol is selected from 1,3-propylene glycol, the molar percentage of 1,3-propylene glycol in the total diol monomers is in the range of 5-8 mol%; When the other diol is selected from neopentyl glycol, the molar percentage of neopentyl glycol in the total diol monomers is in the range of 4-6 mol%; When the other diol is selected from 1,4-butanediol, the molar percentage of 1,4-butanediol in the total diol monomer is in the range of 3-5 mol%; When the other diol is selected from 1,5-pentanediol, the molar percentage of 1,5-pentanediol in the total diol monomers is in the range of 3-6 mol%.

3. The polyethersulfone resin according to claim 1, characterized in that The other diols are selected from at least one of 1,4-cyclohexanedimethanol, spirodiol, and 1,5-pentanediol.

4. The polyethersulfone resin according to claim 1, characterized in that The weight average molecular weight of the polyethersulfone resin is in the range of 60,000 to 80,000.

5. The method for polymerizing the polyethersulfone resin according to any one of claims 1 to 4, characterized in that: The method comprises the following steps: adding bisphenol S, 4,4'-dichlorodiphenyl sulfone, other glycols, a salt-forming agent, a solvent and a water-separating agent into a reaction container, stirring at 140-180 DEG C, and separating water for 1-3 hours; distilling out the water-separating agent, stirring at 40-70 r / min, heating to 160-250 DEG C, and continuing to keep the temperature and react for 10-15 hours; increasing the stirring speed to 80-100 r / min, maintaining the temperature for 0.5-1.5 hours, pouring the reaction solution into distilled water, and obtaining polyethersulfone resin through cooling, crushing, filtering, washing, drying, etc.

6. The method for polymerizing a polyethersulfone resin according to claim 5, wherein: The salt-forming agent is selected from at least one of sodium carbonate, potassium carbonate, lithium carbonate, sodium hydroxide, potassium hydroxide, and lithium hydroxide; the solvent is selected from at least one of N-methylpyrrolidone, N,N'-dimethylformamide, N,N'-dimethylacetamide, dimethyl sulfoxide, cyclopentane, and diphenyl sulfone; and the water-separating agent is selected from at least one of toluene, xylene, mesitylene, meta-trimethylbenzene, o-trimethylbenzene, ethylbenzene, and ethylidene.

7. A polyethersulfone resin composition, characterized in that Calculated by weight, it includes the following components: 70-90 parts of polyethersulfone resin; 9.9-25 parts of silane coupling agent; Additives 0.1-5 parts.

8. The polyethersulfone resin composition according to claim 7, characterized in that The silane coupling agent is selected from at least one of γ-glycidyloxypropyltrimethoxysilane, aminopropyltriethoxysilane, vinyltriethoxysilane, vinyltri(β-methoxyethoxy)silane, γ-methacryloxypropyltrimethoxysilane, and γ-aminopropyltrimethoxysilane.