Method for preparing hydrophilic PVDF hollow fiber membrane by high energy electron beam mutual irradiation grafting

A high-energy electron beam and hydrophilic technology, applied in chemical instruments and methods, membrane technology, semi-permeable membrane separation, etc., can solve the problems of flux attenuation, seriousness, high driving pressure, etc., and achieve the increase of active sites and the surface Strong activation and simple operation

Inactive Publication Date: 2012-08-08
TIANJIN POLYTECHNIC UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

But this is also the main factor that restricts the large-scale application of PVDF membranes in many fields, especially when it is used in oil-water separation, protein drug separation, water treatment, etc., its strong hydrophobicity will cause two problems: (1) In order to maintain a certain The permeation flux of the membrane requires a high driving pressure; (2) the flux attenuation is serious after the membrane is polluted by proteins, etc.
There are relatively few studies on the improvement of membrane properties by high-energy electron beam irradiation, and the use of high-energy electron beam co-irradiation grafting to improve hydrophilicity has not been seen.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0015] The basement membrane with an average pore diameter of 0.15 μm is soaked and shaken with ultrapure water for 3 to 5 times until the liquid becomes clear, and then soaked and shaken with 5% to 20% ethanol aqueous solution for 2 to 3 times, each time for 3 to 4 hours. After cleaning, soak the hollow fiber membrane in an ethanol aqueous solution with a concentration of 0.5% by mass of acrylic acid and 2% by mass of copper sulfate (the volume ratio of ethanol to water is 1 / 9), feed nitrogen for 15 minutes, and then use high-energy electron Co-irradiate the base film and monomer solution with beam radiation source, and the irradiation dose is 40kGy. After the irradiation, soak the obtained grafted film in ultrapure water for 12h-24h to remove unreacted monomer and homopolymer That is, the modified PVDF hollow fiber membrane is obtained. The permeation flux of the membrane is 748.3 m -2 h -1 , the rejection rate of 1g / L BSA is 74.7%. The water contact angle is 44.7°.

Embodiment 2

[0017] The basement membrane with an average pore diameter of 0.15 μm is soaked and shaken with ultrapure water for 3 to 5 times until the liquid becomes clear, and then soaked and shaken with 5% to 20% ethanol aqueous solution for 2 to 3 times, each time for 3 to 4 hours. After cleaning, soak the hollow fiber membrane in an ethanol aqueous solution with a concentration of 0.5% by mass of acrylic acid and 2% by mass of copper sulfate (the volume ratio of ethanol to water is 1 / 9), feed nitrogen for 15 minutes, and then use high-energy electron Co-irradiate the base film and monomer solution with beam radiation source, the irradiation dose is 60kGy, after the irradiation, soak the obtained grafted film in ultrapure water for 12h~24h to remove unreacted monomer and homopolymer That is, the modified PVDF hollow fiber membrane is obtained. The permeation flux of the membrane is 744.2 m -2 h -1 , the rejection rate of 1g / L BSA is 89.2%. The water contact angle was 40.1°.

Embodiment 3

[0019] The basement membrane with an average pore diameter of 0.15 μm is soaked and shaken with ultrapure water for 3 to 5 times until the liquid becomes clear, and then soaked and shaken with 5% to 20% ethanol aqueous solution for 2 to 3 times, each time for 3 to 4 hours. After cleaning, soak the hollow fiber membrane in an ethanol aqueous solution with a concentration of 0.5% by mass of acrylic acid and 2% by mass of copper sulfate (the volume ratio of ethanol to water is 1 / 9), feed nitrogen for 15 minutes, and then use high-energy electron Co-irradiate the base film and the monomer solution with beam radiation source, and the irradiation dose is 80kGy. After the irradiation, soak the obtained grafted film in ultrapure water for 12h-24h to remove unreacted monomer and homopolymer That is, the modified PVDF hollow fiber membrane is obtained. The permeation flux of the membrane is 913.5 m -2 h -1 , The rejection rate of 1g / L BSA is 84.4%. The water contact angle is 32.9°. ...

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PUM

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Abstract

The invention provides a method for preparing a hydrophilic PVDF hollow fiber membrane by high energy electron beam mutual irradiation grafting. By the mutual irradiation method of a grafting monomer and a base membrane by high energy electron beam, graft modification of the PVDF hollow fiber membrane having average pore size of 0.15-0.45 micrometer is carried out to improve its hydrophilicity. The concrete process is as follows: firstly cleaning the base membrane to remove an additive adhered to the base membrane, then immersing the treated base membrane in a monomer solution, carrying out mutual irradiation under high energy electron beam, and grafting the monomer onto the surface of the base membrane through free radical graft copolymerization so as to improve its hydrophilicity. After improvement of hydrophilicity, the pure water contact angle of the PVDF hollow fiber membrane, flux is increased and retention rate is raised. The monomer used is convenient and easy to obtain and requires low cost. The high energy electron beam only modifies the surface of the base membrane without influencing material performance. In addition, the method provided by the invention is simple and convenient to operate and can be completed at room temperature.

Description

technical field [0001] The invention belongs to the field of membrane material modification, and in particular relates to a method for hydrophilic modification of membrane materials, specifically a method for preparing hydrophilic PVDF hollow fiber membranes by high-energy electron beam co-irradiation grafting. Background technique [0002] Hollow fiber membrane is a membrane material with a fiber-like shape and a hollow pore structure inside. Compared with other structural membrane materials, the hollow fiber membrane has good pressure resistance, no support, large membrane area and flux per unit volume, not only as a separation membrane for the separation of gas and liquid mixtures, but also in catalytic reactions, biological In the field of reaction, it is used as a catalytic reactor, membrane fermenter, membrane tissue culture device, etc. [0003] At present, hollow fiber membranes are mainly based on polymer materials, and the selected substrates include polyvinyliden...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01D69/08
Inventor 魏俊富赵孔银罗子安杨亮李东英
Owner TIANJIN POLYTECHNIC UNIV
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