Polyether sulfone resin and polymerization method thereof

Abstract

The invention discloses a polyethersulfone resin which is derived from the following monomers in percentage by mole: 48-52 mol% of a dihydroxyl monomer and 48-52 mol% of 4, 4 '-dichlorodiphenyl sulfone, wherein in the dihydroxy monomer, the molar ratio of 4, 4 '-dihydroxy diphenyl sulfone to a bisphenol S type diether glycol monomer to other glycol monomers is equal to (1.5-2.5): (0.5-1.5): 1. The polyether sulfone resin with high light transmittance and low haze can be obtained by introducing a specific content of other diol monomers into a polyether sulfone resin repeating unit and designing the molecular structure of the bisphenol S monomer.

Description

Technical Field

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

[0002] Polyethersulfone is a type of thermoplastic amorphous polymer material containing sulfone groups in the repeating units of the polymer. Due to the effects of the sulfone groups and benzene rings in their molecular chains, polyarylethersulfone materials have excellent properties such as high glass transition temperature, good mechanical properties, outstanding heat resistance and flame retardancy, and excellent biocompatibility. They are widely used in electronic appliances, medical devices, non-stick pan coatings, baby and child products, and food.

[0003] Polyethersulfone is a polymer material with excellent thermal stability, chemical stability and mechanical properties, and is widely used in aerospace, automobile, electronics and other fields. However, traditional polyethersulfone has deficiencies in light transmittance and haze, which limits its application in high-end fields such as medical devices, aerospace and other fields. Summary of the invention

[0004] The object of the present invention is to overcome the above technical defects and provide a polyphenylene ether sulfone resin and a polymerization method thereof.

[0005] The present invention is achieved through the following technical solutions:

[0006] A polyethersulfone resin, measured by mole percentage, comprises the following monomers:

[0007] Dihydroxy monomer 48-52 mol%;

[0008] 4,4-dichlorodiphenyl sulfone 48-52 mol%;

[0009] The molar ratio of each monomer in the dihydroxy monomer is: 4,4-'dihydroxydiphenyl sulfone: bisphenol S type diether diol monomer: other diol monomers = (1.5-2.5): (0.5-1.5): 1;

[0010] The molecular formula of the bisphenol S type diether diol monomer is as follows:

[0011]

[0012] Among them, R is Any one of, wherein n is a positive integer from 1 to 6;

[0013] The other monomers 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.

[0014] Preferably, the molar ratio of each monomer in the dihydroxy monomer is: 4,4-dihydroxydiphenyl sulfone: bisphenol S type diether diol monomer: other diol monomers = (1.8-2.2): (0.8-1.2): 1.

[0015] Optionally, the bisphenol S type diether diol monomer is selected from

[0016]

[0017] At least one of .

[0018] Preferably, the bisphenol S type diether diol monomer is selected from dihydroxyphenyl-diol ether sulfonate.

[0019] Preferably, the other monomers are selected from ethylene glycol.

[0020] The weight average molecular weight of the polyethersulfone resin of the present invention is in the range of 45,000-80,000 Daltons.

[0021] The polymerization method of polyethersulfone resin comprises the following steps:

[0022] Salt-forming reaction: add solvent to the reaction kettle, stir and heat to 50-70°C, add dihydroxy monomer, 4,4-'dichlorodiphenyl sulfone, salt-forming agent, water-separating agent, continue stirring and heat to 130-170°C, and salt-forming reaction for 1-4h;

[0023] Polymerization reaction: evaporate the water-separating agent, raise the temperature to 150-200°C, stir at a speed of 40-70r / min, keep the constant temperature for 9-15h, increase the stirring speed to 80-100r / min to the set viscosity, and obtain polyethersulfone resin viscous liquid. After cooling, crushing, filtering, washing and drying, polyethersulfone resin is obtained.

[0024] The solvent is selected from at least one of N-methylpyrrolidone, N,N'-dimethylformamide, N,N'-dimethylacetamide, diphenyl sulfone, dimethyl sulfoxide, and cyclopentane; the salt-forming agent is selected from at least one of potassium hydroxide, potassium carbonate, sodium hydroxide, and sodium carbonate; the molar amount of the salt-forming agent is 1.05-1.5 times the molar amount of 4,4-dichlorodiphenyl sulfone; the water-separating agent is selected from at least one of toluene, xylene, mesitylene, o-trimethylbenzene, m-trimethylbenzene, ethylbenzene, ethylbenzene, and ethylidene.

[0025] The present invention has the following beneficial effects:

[0026] The present invention can obtain a polyethersulfone resin with high light transmittance and low haze by introducing other diol monomers with specific contents into the polyethersulfone resin repeating unit and designing the molecular structure of bisphenol S monomer. The presence of ether bonds can enhance the chemical stability and thermal stability of the material, and help reduce the degradation of optical properties caused by thermal degradation. In addition, ether bonds can form a more uniform network structure, which can reduce light scattering, thereby improving the light transmittance of the material, and the haze of the material is usually related to the uniformity of its internal structure. By introducing ether bonds, a more uniform polymer network can be formed, thereby reducing the scattering interface and reducing the haze. Especially in transparent polymers, the uniform distribution of ether bonds can help reduce microscopic inhomogeneity, reduce light scattering, and cause a reduction in haze. DETAILED DESCRIPTION

[0027] The present invention is described in detail below in conjunction with 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 of ordinary skill in the art, several variations and improvements may be made without departing from the concept of the present invention. These all belong to the protection scope of the present invention.

[0028] The raw materials used in the embodiments and comparative examples are derived from the following sources:

[0029] Monomers such as 4,4-'dichlorodiphenyl sulfone, 4,4-'dihydroxydiphenyl sulfone, ethylene glycol, diethylene glycol, 1,4-cyclohexanedimethanol, spirodiol, 1,2-propylene glycol, 1,3-propylene glycol, neopentyl glycol, 1,4-butylene glycol, and 1,5-pentanediol are commercially available.

[0030] Bisphenol S diether glycol A:

[0031] Commercially available.

[0032] Bisphenol S diether glycol B:

[0033] Commercially available.

[0034] Bisphenol S diether glycol C:

[0035] Commercially available.

[0036] Bisphenol S diether diol D:

[0037] Commercially available.

[0038] Other S-type diether diols:

[0039] Commercially available.

[0040] Embodiment and comparative example Preparation method of polyethersulfone resin: add N-methylpyrrolidone to a reaction kettle, stir and heat to 50-70°C, add dihydroxy monomer, 4,4-'dichlorodiphenyl sulfone, salt-forming agent (potassium carbonate, 1.2 times the molar amount of 4,4-dichlorodiphenyl sulfone), water-separating agent (toluene), continue stirring and heat to 130-170°C, and react for 2.5h; evaporate the water-separating agent, heat to 150-200°C, stir at a speed of 40-70r / min, keep the temperature constant for 9-15h, increase the stirring speed to 80-100r / min to the set viscosity, and obtain polyethersulfone resin viscous liquid, which is cooled, crushed, filtered, washed and dried to obtain polyethersulfone resin.

[0041] Various test methods:

[0042] (1) Transmittance / haze: GB / T 2410 Transparent Plastics and Transmittance and Haze Determination Test Methods are used.

[0043] (2) Weight average molecular weight: measured by gel permeation chromatography (GPC).

[0044] Table 1: Composition and test results of each unit of polyethersulfone resin in Examples 1-8

[0045]

[0046]

[0047] It can be seen from Examples 1-4 that the transparency of bisphenol S-type diether diol is better when it is preferably dihydroxyphenyl-diol ether sulfonate.

[0048] It can be seen from Examples 1 / 5-8 that other diol is preferably ethylene glycol.

[0049] Table 2: Composition and test results of each unit of polyethersulfone resin in Examples 9-14

[0050]

[0051] It can be seen from Examples 1 / 9-14 that the polyethersulfone resin with the preferred dihydroxy monomer molar ratio has higher transparency.

[0052] Table 3: Composition and test results of each unit of comparative polyethersulfone resin

[0053]

[0054]

[0055] It can be seen from the comparative examples that the transparency of the polyethersulfone resin composed of other monomers is not high.

Claims

1. A polyethersulfone resin, characterized in that Derived from monomers including the following, by mole percentage: Dihydroxy monomer 48-52 mol%; 4,4-dichlorodiphenyl sulfone 48-52 mol%; The molar ratio of each monomer in the dihydroxy monomer is: 4,4-'dihydroxydiphenyl sulfone: bisphenol S type diether diol monomer: other diol monomers = (1.5-2.5): (0.5-1.5): 1; The molecular formula of the bisphenol S type diether diol monomer is as follows: Among them, R is Any one of, wherein n is a positive integer from 1 to 6; The other monomers 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 The molar ratio of each monomer in the dihydroxy monomer is: 4,4-dihydroxydiphenyl sulfone: bisphenol S type diether diol monomer: other diol monomers = (1.8-2.2): (0.8-1.2):

1.

3. The polyethersulfone resin according to claim 1, characterized in that The bisphenol S type diether diol monomer is selected from At least one of .

4. The polyethersulfone resin according to claim 3, characterized in that The bisphenol S type diether diol monomer is selected from dihydroxyphenyl-diol ether sulfonate.

5. The polyethersulfone resin according to claim 1, characterized in that The other monomers are selected from ethylene glycol.

6. The polyethersulfone resin according to claim 1, characterized in that The weight average molecular weight of the polyethersulfone resin is in the range of 45,000-80,000 Daltons.

7. The method for polymerizing the polyethersulfone resin according to any one of claims 1 to 6, characterized in that: The following steps are involved: Salt-forming reaction: add solvent to the reaction kettle, stir and heat to 50-70°C, add dihydroxy monomer, 4,4-'dichlorodiphenyl sulfone, salt-forming agent, water-separating agent, continue stirring and heat to 130-170°C, and salt-forming reaction for 1-4h; Polymerization reaction: evaporate the water-separating agent, raise the temperature to 150-200°C, stir at a speed of 40-70r / min, keep the constant temperature for 9-15h, increase the stirring speed to 80-100r / min to the set viscosity, and obtain polyethersulfone resin viscous liquid. After cooling, crushing, filtering, washing and drying, polyethersulfone resin is obtained.

8. The method for polymerizing a polyethersulfone resin according to claim 7, characterized in that: The solvent is selected from at least one of N-methylpyrrolidone, N,N'-dimethylformamide, N,N'-dimethylacetamide, diphenyl sulfone, dimethyl sulfoxide, and cyclopentane; the salt-forming agent is selected from at least one of potassium hydroxide, potassium carbonate, sodium hydroxide, and sodium carbonate; the molar amount of the salt-forming agent is 1.05-1.5 times the molar amount of 4,4-dichlorodiphenyl sulfone; the water-separating agent is selected from at least one of toluene, xylene, mesitylene, o-trimethylbenzene, m-trimethylbenzene, ethylbenzene, ethylbenzene, and ethylidene.

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