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WO2010078721A1 - Modification method of interpenetrating polymer network on surface of porous polyvinylidene fluoride membrane - Google Patents

Modification method of interpenetrating polymer network on surface of porous polyvinylidene fluoride membrane Download PDF

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Publication number
WO2010078721A1
WO2010078721A1 PCT/CN2009/001609 CN2009001609W WO2010078721A1 WO 2010078721 A1 WO2010078721 A1 WO 2010078721A1 CN 2009001609 W CN2009001609 W CN 2009001609W WO 2010078721 A1 WO2010078721 A1 WO 2010078721A1
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Prior art keywords
polyvinylidene fluoride
mass concentration
amine compound
membrane
hours
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PCT/CN2009/001609
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French (fr)
Chinese (zh)
Inventor
王晓琳
林亚凯
田野
杨健
马文中
马恒宇
唐元晖
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清华大学
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Publication of WO2010078721A1 publication Critical patent/WO2010078721A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/0093—Chemical modification
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/30—Polyalkenyl halides
    • B01D71/32—Polyalkenyl halides containing fluorine atoms
    • B01D71/34—Polyvinylidene fluoride
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/30—Cross-linking

Definitions

  • the invention belongs to the field of separation membrane technology and membrane material, and particularly relates to a modification method for a polyvinylidene fluoride porous membrane surface interpenetrating polymer network. Background technique
  • Polyvinylidene fluoride has excellent thermal stability, corrosion resistance, non-combustibility, anti-UV aging and other properties, and has high strength and wear resistance. Therefore, it has attracted extensive attention in the field of separation membranes in recent years, for example, in microfiltration. In terms of ultrafiltration, a polyvinylidene fluoride film has been used as a film having excellent properties.
  • polyvinylidene fluoride is a hydrophobic polymer, and its hydrophobicity causes two problems: First, the separation process requires a large driving force; ⁇ ⁇ is easy to produce adsorption pollution, causing membrane flux to decrease, membrane The shortened service life limits its application in aqueous systems such as biochemical pharmaceuticals, food and beverage, and water purification. Therefore, the hydrophilization modification of polyvinylidene fluoride has important practical significance.
  • polyvinylidene fluoride is not dissolved in most organic solvents, it is not resistant to some polar solvents.
  • polyvinylidene fluoride can be dissolved in some ketones and amine solvents at normal temperature.
  • fluorenyl-hydrazinopyrrolidone, hydrazine, hydrazine-dimethylformamide, hydrazine, hydrazine-dimercaptoacetamide, and dimethyl sulfoxide Therefore, it is also necessary to further improve the solvent resistance of polyvinylidene fluoride.
  • hydrophilized polymer film To prepare a hydrophilized polymer film, the following three methods are generally employed: (1) polymerizing a small molecule having a hydrophilic group to obtain a hydrophilic polymer; (2) blending with a hydrophilic polymer (3) Surface modification. The first one is the most difficult to implement because it undergoes complex organic synthesis reactions and monomer polymerization to gradually obtain the final product. The second method is relatively easy to implement, and most of the current domestic
  • the method of hydrophilic modification of ethylene is a blending method.
  • Chinese Patent No. CN1 01147848A discloses a method for hydrophilic modification of a polyvinylidene fluoride film, which adopts a modification method of blending polyvinylidene fluoride and polyvinyl alcohol.
  • Chinese patents CN101 190401A and CN101264428A employ polyvinylidene fluoride blended with an amphiphilic polymer. In addition, it is blended with polyvinylidene fluoride and oligosaccharide (Chinese patent CN101234301A), blended with polyvinylidene fluoride and polyvinyl chloride (Chinese patent CN1282498C), blended with polyvinylidene fluoride and titanium dioxide (Chinese patent CN1318502C), Polyvinylidene fluoride blended with nano-alumina (Chinese patent CN1303149C).
  • the essence of the third modification method is to introduce a polar group or a pro-permanent macromolecular chain on the surface of the polymer, and the main ginger is realized by surface chemical treatment, surface grafting and the like.
  • the surface chemical treatment is insufficient in that the initial hydrophilic effect is low, and the polar group may be gradually embedded in the surface layer of the membrane by the rotation of the polyvinylidene fluoride molecule, resulting in gradual degradation of hydrophilicity.
  • the surface grafting mainly generates active centers on the surface of the material by irradiation, photoinitiation, plasma, etc., and then obtains a longer hydrophilic chain on the surface of the film by graft polymerization.
  • the advantages of surface grafting are that the hydrophilization effect is good, the hydrophilicity is long lasting, and the deficiency is complicated by the hydrophilization process.
  • An object of the present invention is to provide a method for modifying a polyvinylidene fluoride porous film which has a long-term hydrophilicity and further improves its resistance to a solvent.
  • the method for modifying the interpenetrating polymer network of the polyvinylidene fluoride porous membrane of the present invention comprises the following steps:
  • An interpenetrating polymer network can be defined as a combination of two or more polymers in a network form, at least one of which is synthesized or cross-linked in the presence of another polymer. United. It differs from the previous blends and graft copolymers in that the network chains of the various component components have a structure of intertwined structure after cross-linking.
  • the IPN method can improve the compatibility of various molecular chains, increase the network lattice density, make the phase structure finer and improve the interphase bonding force.
  • the amine compound is on the surface of the polyvinylidene fluoride porous membrane with polyvinylidene fluoride Cross-linking occurs, and the vinyl alcohol hydrophilic polymer cross-links with the aldehyde compound on the surface of the polyvinylidene fluoride porous membrane, and the two cross-linking reactions which do not interfere with each other are simultaneously performed, and the surface of the polyvinylidene fluoride porous membrane is realized.
  • the inter-molecular entanglement forms a hydrophilized structure with an interpenetrating polymer network.
  • crosslinking reaction of polyvinylidene fluoride with an amine is:
  • the crosslinking reaction between the vinyl alcohol polymer and the aldehyde compound is:
  • the modification method of the interpenetrating polymer network of the invention has the following advantages: 1 after the cross-linking of the polyvinylidene fluoride and the amine compound, the solvent resistance of the surface of the film is enhanced, in N-mercaptopyrrolidone, N, N-difluorene Solvents such as carboxamide, N,N-dimethylacetamide, dimethyl sulfoxide, acetone, butanone, and tetrahydrofuran are also difficult to dissolve.
  • the hydrophilic polymer and polyvinylidene fluoride are simultaneously cross-linked to form an interpenetrating polymer network structure, so that the polyvinylidene fluoride porous film substrate and the hydrophilic polymer are entangled at the molecular level, so that The hydrophilic polymer is firmly fixed on the surface of the membrane to achieve permanent hydrophilicity of the membrane surface, and the purified membrane pure water flux can be stably operated for a long period of time without a decrease in flux, and the modified porous membrane Rehydration immediately after complete drying under heating conditions still has a high flux.
  • the 3 vinyl alcohol hydrophilic polymer is only fixed on the surface of the film, and does not chemically react with the bulk of the polyvinylidene fluoride porous film, so that the physical and chemical properties of the polyvinylidene fluoride porous film are not lowered.
  • 4 molecular entanglement with amines which can immobilize the vinyl alcohol hydrophilic polymer under the premise of greatly reducing the amount of aldehyde crosslinking agent, avoiding excessive crosslinking of vinyl alcohol polymer
  • the blockage of the surface pore structure ensures an increase in the initial flux.
  • the method for modifying the interpenetrating polymer network of the polyvinylidene fluoride porous membrane of the present invention comprises the following steps:
  • the polyvinylidene fluoride porous film is preferably of a flat plate type or a hollow fiber type. It is preferably prepared by melt stretching, non-solvent induced phase separation, or thermally induced phase separation.
  • the vinyl alcohol-based polymer is preferably polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyvinyl acetal, polyvinyl acetal, polyvinyl acetal, polyvinyl butyral, and Any one of polyethylene glycols or a mixture thereof.
  • the aldehyde compound is preferably any one of formaldehyde, butyl ketone and glutaraldehyde or a mixture thereof.
  • the contacting in the step 1) can be preferably carried out by immersing the film in a solution of a vinyl alcohol polymer and an aldehyde compound, or in contact with a vapor of the two types of materials.
  • the solution is preferably an aqueous solution of the above substances.
  • the mass concentration of the vinyl alcohol polymer in the aqueous solution is preferably 0.1% to 5%, and most preferably the mass concentration is 0.2% to 1%.
  • the mass concentration of the aldehyde compound in the aqueous solution is preferably 0.05%. - 2%, most preferably the mass concentration is from 0.1% to 0.5%.
  • the contact time is preferably from 5 minutes to 2 hours.
  • the amine compound preferably consists of a polyamine or a mixture of a polyamine and a monoamine.
  • the polyamine is preferably ethylenediamine, propylenediamine, hexamethylenediamine, p-phenylenediamine, N,N,N,N,-tetradecyl-1,6-diaminohexane and 1, 2, Any one of 2-triaminopropane or a mixture thereof.
  • the monoamine is preferably any one of decylamine, ethylamine, aniline and benzylamine or a mixture thereof.
  • the percentage by mass of the polyamine in the amine compound is preferably from 10% to 100%, and most preferably the percentage by mass is from 20% to 90%.
  • the contacting in step 2) can preferably be achieved by immersing the membrane in a solution of the amine compound or in contact with its vapor.
  • the solution is preferably an aqueous solution of an amine compound, and the amine compound is excellent in mass concentration in an aqueous solution. It is selected from 40% to 95%, and the most preferred mass concentration is from 50% to 90%.
  • the time of the contacting is preferably from 5 minutes to 2 hours.
  • Step 2) and step 3) can be performed simultaneously or sequentially.
  • the crosslinking reaction is preferably carried out under the catalysis of phosphoric acid.
  • the phosphoric acid is preferably used in the form of an aqueous solution, preferably a solution having a mass concentration of 0.1% to 2%.
  • the crosslinking reaction temperature is preferably 20" - 60 C, and the reaction time is preferably from 1 hour to 24 hours.
  • the crosslinked porous film is immersed in deionized water, and the soaking time is preferably from 12 hours to 48 hours, and the temperature of the deionized water is preferably from 30 C to 60.
  • the technical solutions of the present invention are further described below with reference to the embodiments, but the examples of the embodiments do not constitute a limitation of the present invention.
  • the pure water flux of the prepared sample was determined by the following method: Applying with a pump 0. The pressure of IMPa allowed pure water to pass through the sample, and the volume of water per unit area of the sample per unit time was measured.
  • the polyvinylidene fluoride N,N-didecylacetamide solution having a polymer weight percentage of 25% by weight is cast on a glass plate, and water is used as a coagulation bath to prepare a polyvinylidene fluoride porous flat membrane by dry-wet method.
  • the pure water flux is 600 ⁇ 700L / m 2 ⁇ h ⁇ 0. lMPa.
  • the obtained polyvinylidene fluoride porous flat membrane is first immersed in an aqueous solution containing polyvinyl alcohol having a shield concentration of 1% and glutaraldehyde having a mass concentration of 0.2% for 10 minutes; then, polyvinyl alcohol and glutaraldehyde are adsorbed.
  • the polyvinylidene fluoride porous membrane is immersed in an aqueous solution containing an amine compound, wherein the aqueous solution containing the amine compound contains ethylene diamine and 1% phosphoric acid at a mass concentration of 50%.
  • the water temperature was controlled at 40", and after 10 hours of reaction, the membrane was immersed in 30 deionized water for 12 hours to obtain a porous polyvinylidene fluoride membrane modified by a surface interpenetrating polymer network.
  • the measured pure water flux was 650. ⁇ 750L/m 2 . h ⁇ 0. lMPa. After 120 hours of continuous use, the pure water flux is still kept at 650 ⁇ 750L/m 2 . 0 . lMPa.
  • the prepared film is placed at 50 ⁇ . The drying was carried out for 24 hours in an oven, and the water was directly rehydrated, and the pure water flux was measured to be 550 - 600 L/m 2 ⁇ h ⁇ 0. lMPa.
  • the inner diameter is 0. 6mm, the inner diameter is 0.
  • the outer diameter is 1. 6mm, the inner diameter is 0.
  • the outer diameter is 1. 6mm, the inner diameter is 0. MPa ⁇
  • the 9mm hollow fiber membrane, the hollow fiber membrane pure water flux is 600 ⁇ 700L / m 2 ⁇ h ⁇ 0. lMPa.
  • the mass concentration of 0.2% by mass of polyvinyl alcohol having a mass concentration of 1% is immersed in a polyvinyl alcohol having a mass concentration of 1%.
  • the time in the aqueous solution of glutaraldehyde was 2 hours, and the aqueous solution containing the amine compound contained ethylenediamine and 2% phosphoric acid having a mass concentration of 90%.
  • the pure water flux of the crosslinked hollow fiber membrane is 650 ⁇ 750L/m 2 ⁇ h ⁇ 0. IMPa, after 120 hours of continuous use, the pure water flux is still kept at 650 ⁇ 750L / m 2 ⁇ h 0. lMPa.
  • the obtained film was dried in a 50-mesh oven for 24 hours, and then directly rehydrated after taking out, and the pure water flux was measured to be 550 - 600 L/m 2 ⁇ h ⁇ 0. lMPa.
  • crosslinked polyvinylidene fluoride porous film was no longer dissolved in N,N-dimethylformamide, N,N-dimethylacetamide, N-decylpyrrolidone and dimethyl sulfoxide.
  • the polyvinylidene fluoride resin and the diphenyl fluorenone-polyvinylidene fluoride resin are 35% by weight, and the dimercapto ketone is 65% by weight, which is heated to 200 in a high temperature stirred tank. A homogeneous solution of the polymer. Then, it is spun through a ring-shaped spinneret, the core liquid is glycerin, and water is used as a coagulation bath.
  • MPa The hollow fiber membrane having an outer diameter of 1. 6mm, the hollow fiber membrane having a pure water flux of 800 - lOOOL / m 2 ⁇ h ⁇ 0. lMPa.
  • the hollow fiber membrane was subjected to a crosslinking reaction in the same manner as in Example 1, except that the aqueous solution containing the amine compound contained hexamethylenediamine having a mass concentration of 50%, 40% of decylamine and 1 .5% phosphoric acid.
  • the pure water flux of the crosslinked hollow fiber membrane is 850 - 1100L/m 2 - h ⁇ 0. IMPa , after 120 hours of continuous use, the pure water flux is still kept at 850 ⁇ 1100L/m 2 ⁇ h 0. lMPa.
  • the prepared film was dried in a 50-inch oven for 24 hours, and directly rehydrated after taking out, and the pure water flux was measured to be 750 ⁇ 900 L/m 2 -h -0. IMPa.
  • crosslinked polyvinylidene fluoride porous film was no longer dissolved in N,N-dimethylformamide, hydrazine, hydrazine-dimethylacetamide, hydrazine-methylpyrrolidone and dimethyl sulfoxide.
  • the polyvinylidene fluoride resin is extruded from a spinneret having an annular hole through a single screw extruder, and The heat treatment was rapidly performed at 180 Torr for 60 minutes, and then stretched, the draw ratio was 3 times, and finally heat set at 1851 C for 10 minutes, and the obtained pure fiber membrane was measured to have a pure water flux of 300-400 L/m 2 ⁇ h. ⁇ 0. lMPa.
  • the obtained film was subjected to a crosslinking reaction in the same manner as in Example 1, except that the polyvinylidene fluoride porous film was immersed in an aqueous solution containing polyvinyl alcohol and glutaraldehyde for 5 minutes, and The mass concentration of polyvinyl alcohol is 2%, and the mass concentration of glutaraldehyde is 1%.
  • the pure water flux of the crosslinked hollow fiber membrane is 300-400L/m 2 ⁇ h ⁇ 0. IMPa , after 120 hours of continuous use, the pure water flux is still maintained at 300 ⁇ 400L/m 2 -h 0. IMPa.
  • the prepared film was dried in a 50-inch oven for 24 hours, and then directly rehydrated after taking out, and the pure water flux was measured to be 300 - 400 L / m 2 ⁇ h ⁇ 0. lMPa.
  • crosslinked polyvinylidene fluoride porous film was no longer dissolved in N,N-dimercaptophthalamide, N,N-dimethylacetamide, N-methylpyrrolidone and dimercaptosulfoxide.
  • a hollow fiber membrane was obtained in the same manner as in Example 3.
  • the hollow fiber membrane has a pure water flux of 800 to 1000 L/m 2 ⁇ h ⁇ 0. lMPa.
  • the concentration of the glutaraldehyde is 0.05%
  • the aqueous solution of the amine compound is an aqueous solution of the amine compound.
  • the mass concentration of ethylene diamine is 4%
  • the concentration of ethylamine shield is 36%
  • the mass concentration of phosphoric acid is 0.1%.
  • the pure water flux of the crosslinked hollow fiber membrane is 1000 ⁇ 1200L / m 2 ⁇ h ⁇ 0. IMPa , after 120 hours of continuous use, the pure water flux is still maintained at 1000 ⁇ 1200L / m 2 ⁇ h ⁇ 0. lMPa.
  • the film was dried in a 50 oven for 24 hours, and then directly rehydrated after taking out, and the pure water flux was measured to be 700-800 L/m 2 . h ⁇ 0. lMPa.
  • crosslinked polyvinylidene fluoride porous film was no longer dissolved in N,N-dimercaptocarboxamide, N,N-dimercaptoacetamide, N-methylpyrrolidone and dimethyl sulfoxide.
  • a hollow fiber membrane was obtained in the same manner as in Example 3.
  • the hollow fiber membrane has a pure water flux of 800 to 1000 L/m 2 ⁇ h ⁇ 0. lMPa.
  • the hollow fiber membrane was crosslinked in a manner similar to that in Example 1, except that the polyvinyl alcohol had a mass concentration of 5% and the glutaraldehyde had a mass concentration of 2%, in an aqueous solution of an amine compound.
  • the mass concentration of p-phenylenediamine was 86%
  • the mass concentration of aniline was 9%
  • the mass concentration of phosphoric acid was 2%.
  • the pure water flux of the crosslinked hollow fiber membrane is 600 - 800L/m 2 ⁇ h ⁇ 0. IMPa
  • the pure water flux is still measured to be 600 - 800L / m 2 -h ⁇ 0. lMPa.
  • the prepared film was dried in a 50*C oven for 24 hours, and then directly rehydrated after taking out, and the pure water flux was measured to be 600 ⁇ 750 L / m 2 ⁇ h ⁇ 0. lMPa.
  • crosslinked polyvinylidene fluoride porous film was no longer dissolved in N,N-dimercaptocarboxamide, N,N-dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide.
  • a hollow fiber membrane was obtained in the same manner as in Example 3.
  • the hollow fiber membrane has a pure water flux of 800 - 1000 L/m 2 . h . 0, IMPa.
  • the hollow fiber membrane was crosslinked in a manner similar to that in Example 1, except that polyvinyl alcohol was changed to polyvinyl butyral at a mass concentration of 3 %, and glutaraldehyde was changed to formaldehyde. , the mass concentration is 2%, ethylenediamine is changed to propylenediamine, and the mass concentration is 50%.
  • the pure water flux of the crosslinked hollow fiber membrane is 800 ⁇ 1000L/m 2 - h - 0. IMPa , after 120 hours of continuous use, the pure water flux is still maintained at 800 - 1000L / m 2 . 0. lMPa.
  • the obtained film was dried in a 50-inch oven for 24 hours, and then directly rehydrated after taking out, and the pure water flux was measured to be 700-800 L/m 2 ⁇ h ⁇ 0. lMPa.
  • the crosslinked polyvinylidene fluoride porous film was no longer dissolved in hydrazine, hydrazine-dimethylformamide, hydrazine, hydrazine-dimethylacetamide, fluorenyl-pyridylpyrrolidone and dimethyl sulfoxide.
  • a hollow fiber membrane was obtained in the same manner as in Example 3.
  • the hollow fiber membrane has a pure water flux of 800 ⁇ 1000 L / m 2 ⁇ h ⁇ 0. IMPa.
  • the hollow fiber membrane was crosslinked in a manner similar to that in Example 1, except that the crosslinking time was extended to 24 hours, the crosslinking temperature was changed to 60 TC, the deionized water temperature was 601 C, and the immersion was carried out for 48 hours. .
  • the pure water flux of the crosslinked hollow fiber membrane is 500 ⁇ 600L/m 2 ⁇ h ⁇ 0. IMPa, after 120 hours of continuous use, the pure water flux is still maintained at 500 ⁇ 600L / m 2 -h ⁇ 0. IMPa.
  • the prepared film was dried in a 50 oven for 24 hours, and directly rehydrated after taking out, and the pure water flux was measured to be 500 - 600 L/m 2 ⁇ h ⁇ 0. IMPa.
  • crosslinked polyvinylidene fluoride porous film was no longer dissolved in N,N-dimethylformamide, N,N-dimercaptoacetamide, N-decylpyrrolidone and dimercaptosulfoxide.
  • a hollow fiber membrane was obtained in the same manner as in Example 3.
  • the hollow fiber membrane has a pure water flux of 800 - 1000 L/m 2 ⁇ h ⁇ 0. IMPa, g
  • the hollow fiber membrane was crosslinked in a manner similar to that in Example 1, except that the crosslinking time was changed to 1 hour, the crosslinking temperature was 20*C, the deionized water temperature was 30, and the immersion was carried out for 12 hours.
  • the pure water flux of the crosslinked hollow fiber membrane is 1000 - 1200L/m 2 ⁇ h ⁇ 0. IMPa , after 120 hours of continuous use, the pure water flux is 700 ⁇ 800L / m 2 ⁇ h ⁇ 0 . lMPa.
  • the prepared film was dried in a 50" C oven for 24 hours, and then directly rehydrated after taking out, and the pure water flux was measured to be 300 ⁇ 400 L / m 2 ⁇ h ⁇ 0. lMPa.
  • crosslinked polyvinylidene fluoride membrane is still soluble in N,N-dimethylformamide, N,N-dimethylacetamide, N-decylpyrrolidone and dimethyl sulfoxide, but the dissolution rate obviously decased.
  • the weight percent of polyvinylidene fluoride resin and benzophenone monovinylidene fluoride resin is 35%, and the weight percentage of benzophenone is 65% - it is heated to 200 ⁇ in a high temperature stirred tank. A homogeneous solution of the polymer. Then, it is spun through a ring-shaped spinneret, the core liquid is glycerin, and water is used as a coagulation bath.
  • the hollow fiber membrane having an outer diameter of 1. 6 mm and an inner diameter of 0.9 mm was obtained.
  • the hollow fiber membrane was made into a small membrane module, the pure water flux was measured to be 800 ⁇ 1000L / m 2 ⁇ h ⁇ 0. lMPa. After continuous operation for 120 hours, the pure water flux was measured to be 500 ⁇ 600 L / m 2 ⁇ h ⁇ 0. lMPa.
  • the prepared film was dried in a 50-inch oven for 24 hours, and directly rehydrated after taking out, and the pure water flux was measured to be zero.
  • the polyvinylidene fluoride porous film is easily dissolved in N,N-dimethylformamide, N,N-dimethylacetamide, N-decylpyrrolidone and dimethyl sulfoxide.

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

A modification method of interpenetrating polymer network on the surface of a porous polyvinylidene fluoride membrane, characterized in that, contacting the porous polyvinylidene fluoride membrane with a vinyl alcohol polymer and an aldehyde compound, then contacting it with an amine compound. The amine compound is crosslinked with the polyvinylidene fluoride on the surface of the porous polyvinylidene fluoride membrane, while the hydrophilic vinyl alcohol polymer is crosslinked with the aldehyde compound on the surface of the porous polyvinylidene fluoride membrane. The two non-interfering crosslinking reactions are performed at the same time to interweave, realizing the entanglement of molecules on the surface of the porous polyvinylidene fluoride membrane, and forming a hydrophilic structure with interpenetrating polymer network, thereby achieving the permanent hydrophilicity and solvent tolerance of the porous polyvinylidene fluoride membrane.

Description

聚偏氟乙烯多孔膜表面互穿聚合物网络的改性方法 技术领域  Method for modifying interpenetrating polymer network of polyvinylidene fluoride porous membrane surface
本发明属于分离膜技术与膜材料领域，具体涉及一种聚偏氟乙烯多 孔膜表面互穿聚合物网络的改性方法。 背景技术  The invention belongs to the field of separation membrane technology and membrane material, and particularly relates to a modification method for a polyvinylidene fluoride porous membrane surface interpenetrating polymer network. Background technique
聚偏氟乙烯具有优良的热稳定性、 耐腐蚀性、 不燃性、 抗紫外线老 化等性能， 并具有高强度和耐磨性， 因此近年来在分离膜领域引起了广 泛的重视， 例如在微滤和超滤方面， 聚偏氟乙烯膜一直作为性能优异的 膜被应用。 然而聚偏氟乙烯是一种疏水性的聚合物， 其疏水性会导致两 个问题： 一是分离过程需要较大的驱动力； ·Π是容易产生吸附污染， 使 膜通量下降， 膜的使用寿命缩短， 制约了其在生化制药、 食品饮料和水 体净化等水相体系中的应用。 因此， 聚偏氟乙烯的亲水化改性具有重要 的实际意义。  Polyvinylidene fluoride has excellent thermal stability, corrosion resistance, non-combustibility, anti-UV aging and other properties, and has high strength and wear resistance. Therefore, it has attracted extensive attention in the field of separation membranes in recent years, for example, in microfiltration. In terms of ultrafiltration, a polyvinylidene fluoride film has been used as a film having excellent properties. However, polyvinylidene fluoride is a hydrophobic polymer, and its hydrophobicity causes two problems: First, the separation process requires a large driving force; · Π is easy to produce adsorption pollution, causing membrane flux to decrease, membrane The shortened service life limits its application in aqueous systems such as biochemical pharmaceuticals, food and beverage, and water purification. Therefore, the hydrophilization modification of polyvinylidene fluoride has important practical significance.
另外， 虽然聚偏氟乙烯在大部分有机溶剂中都不溶解， 但对部分极 性溶剂耐受性不强，例如聚偏氟乙烯在常温下就能溶解在部分酮类与胺 类溶剂中， 例如 Ν-曱基吡咯烷酮、 Ν，Ν-二甲基甲酰胺， Ν，Ν-二曱基乙酰 胺和二曱基亚砜等。因此进一步提高聚偏氟乙烯的耐溶剂性也是十分必 须的。  In addition, although polyvinylidene fluoride is not dissolved in most organic solvents, it is not resistant to some polar solvents. For example, polyvinylidene fluoride can be dissolved in some ketones and amine solvents at normal temperature. For example, fluorenyl-hydrazinopyrrolidone, hydrazine, hydrazine-dimethylformamide, hydrazine, hydrazine-dimercaptoacetamide, and dimethyl sulfoxide. Therefore, it is also necessary to further improve the solvent resistance of polyvinylidene fluoride.
制备亲水化的高分子膜， 一般采用以下三种方法： （1 )将具有亲 水基团的小分子进行聚合反应得到亲水性高分子； （2 ) 与亲水性的聚 合物共混； （ 3 )表面改性。 第一种实现起来最为困难， 因为它要经过 复杂的有机合成反应和单体的聚合反应，逐步得到最终产物； 第二种方 法工艺相对筒单， 比较容易实现， 目前国内大部分关于聚偏氟乙烯亲水 改性的方法为共混法。例如中国专利 CN1 01147848A公开了一种聚偏氟乙 烯膜亲水改性的方法， 采用了聚偏氟乙烯与聚乙烯醇共混的改性方法。 中国专利 CN101 190401A与 CN101264428A采用了聚偏氟乙烯与两亲性聚 合物共混。 另外还有采用聚偏氟乙烯与低聚糖共混 （ 中国专利 CN101234301A ) ,聚偏氟乙烯与聚氯乙烯共混（中国专利 CN1282498C )、 聚偏氟乙烯与二氧化钛共混（中国专利 CN1318502C )、 聚偏氟乙烯与纳 米氧化铝共混（中国专利 CN1303149C )。 但由于共混的亲水性聚合物或 其它添加剂与聚偏氟乙烯的相容性， 以及混合不均匀等问题的存在，共 混改性后的亲水效果并不是特别明显， 并且难以实现长久亲水。 第三种 改性方法的本质是在聚合物表面引入极性基团或亲永性大分子链，主姜 通过表面化学处理、表面接枝等方法来实现。表面化学处理不足的地方 是起始亲水效果低，极性基团也可能通过聚偏氟乙烯分子的旋转逐渐被 包埋到膜表层内导致亲水性逐渐退化。表面接枝主要是通过辐照、光引 发、等离子等技术在材料表面生成活性中心，再通过接枝聚合反应的方 法在膜表面得到较长的亲水性链。表面接枝的优点是亲水化效杲好， 亲 水性持久， 不足是亲水化过程复杂。 To prepare a hydrophilized polymer film, the following three methods are generally employed: (1) polymerizing a small molecule having a hydrophilic group to obtain a hydrophilic polymer; (2) blending with a hydrophilic polymer (3) Surface modification. The first one is the most difficult to implement because it undergoes complex organic synthesis reactions and monomer polymerization to gradually obtain the final product. The second method is relatively easy to implement, and most of the current domestic The method of hydrophilic modification of ethylene is a blending method. For example, Chinese Patent No. CN1 01147848A discloses a method for hydrophilic modification of a polyvinylidene fluoride film, which adopts a modification method of blending polyvinylidene fluoride and polyvinyl alcohol. Chinese patents CN101 190401A and CN101264428A employ polyvinylidene fluoride blended with an amphiphilic polymer. In addition, it is blended with polyvinylidene fluoride and oligosaccharide (Chinese patent CN101234301A), blended with polyvinylidene fluoride and polyvinyl chloride (Chinese patent CN1282498C), blended with polyvinylidene fluoride and titanium dioxide (Chinese patent CN1318502C), Polyvinylidene fluoride blended with nano-alumina (Chinese patent CN1303149C). But due to the blended hydrophilic polymer or The compatibility of other additives with polyvinylidene fluoride, and the problem of uneven mixing, the hydrophilic effect after blending modification is not particularly obvious, and it is difficult to achieve long-lasting hydrophilicity. The essence of the third modification method is to introduce a polar group or a pro-permanent macromolecular chain on the surface of the polymer, and the main ginger is realized by surface chemical treatment, surface grafting and the like. The surface chemical treatment is insufficient in that the initial hydrophilic effect is low, and the polar group may be gradually embedded in the surface layer of the membrane by the rotation of the polyvinylidene fluoride molecule, resulting in gradual degradation of hydrophilicity. The surface grafting mainly generates active centers on the surface of the material by irradiation, photoinitiation, plasma, etc., and then obtains a longer hydrophilic chain on the surface of the film by graft polymerization. The advantages of surface grafting are that the hydrophilization effect is good, the hydrophilicity is long lasting, and the deficiency is complicated by the hydrophilization process.
关于提高聚偏氟乙婦多孔膜耐溶剂性的研究， 目前国内也还没有相 应的专利报道。因此，寻找一种简便快捷的聚偏氟乙烯多孔膜改性方法， 使得在不改变聚偏氟乙烯多孔膜性质甚至能改善其物化特性的前提下， 能显著提高聚偏氟乙烯多孔膜的亲水性能和对溶剂的耐受性就变得十 分有意义。 发明内容  There is no corresponding patent report on improving the solvent resistance of polyvinylidene fluoride porous membranes. Therefore, a simple and rapid modification method of polyvinylidene fluoride porous membrane is found, so that the polyvinylidene fluoride porous membrane can be significantly improved without changing the properties of the polyvinylidene fluoride porous membrane or even improving its physicochemical properties. Water performance and resistance to solvents make sense. Summary of the invention
本发明的目的是提供一种聚偏氟乙烯多孔膜的改性方法，使聚偏氟 乙烯多孔膜在具有长久亲水性的同时， 进一步提高其对溶剂的耐受性。  SUMMARY OF THE INVENTION An object of the present invention is to provide a method for modifying a polyvinylidene fluoride porous film which has a long-term hydrophilicity and further improves its resistance to a solvent.
本发明的聚偏氟乙烯多孔膜表面互穿聚合物网络的改性方法包括 如下步骤：  The method for modifying the interpenetrating polymer network of the polyvinylidene fluoride porous membrane of the present invention comprises the following steps:
1 )使聚偏氟乙烯多孔膜与乙烯醇类聚合物和醛类化合物相接触； 1) contacting the polyvinylidene fluoride porous film with a vinyl alcohol polymer and an aldehyde compound;
2 )使步骤 1 )获得的聚偏氟乙烯多孔膜与胺类化合物相接触； 3 )使聚偏氟乙烯以及所述乙烯醇类聚合物、 醛类化合物和胺类 化合物进行交联反应， 形成表面互穿聚合物网络结构。 2) contacting the polyvinylidene fluoride porous film obtained in the step 1) with the amine compound; 3) crosslinking the polyvinylidene fluoride and the vinyl alcohol polymer, the aldehyde compound and the amine compound to form Surface interpenetrating polymer network structure.
互穿聚合物网络（Interpenetrat ing Polymer Network, 简称 IPN) 可以定义为两种或多种聚合物以网络形式的结合，其中至少有一种聚合 物是在另外一种聚合物直接存在下进行合成或交联的。它与以前的共混 物、接枝共聚物不同之处在于， 各种成分聚合物交联后， 其网链具有互 相缠结的结构。用 IPN法可提高各种分子链的相容性，增加网络格密度， 使相组织微细化及提高相间结合力。  An interpenetrating polymer network (IPN) can be defined as a combination of two or more polymers in a network form, at least one of which is synthesized or cross-linked in the presence of another polymer. United. It differs from the previous blends and graft copolymers in that the network chains of the various component components have a structure of intertwined structure after cross-linking. The IPN method can improve the compatibility of various molecular chains, increase the network lattice density, make the phase structure finer and improve the interphase bonding force.
在本发明中，胺类化合物在聚偏氟乙烯多孔膜的表面与聚偏氟乙烯 发生交联，同时乙烯醇类亲水性聚合物在聚偏氟乙烯多孔膜表面与醛类 化合物发生交联， 两个互不干扰的交联反应同时进行，在聚偏氟乙烯多 孔膜表面实现分子间的缠结， 形成了具有互穿聚合物网络的亲水化结 构。 In the present invention, the amine compound is on the surface of the polyvinylidene fluoride porous membrane with polyvinylidene fluoride Cross-linking occurs, and the vinyl alcohol hydrophilic polymer cross-links with the aldehyde compound on the surface of the polyvinylidene fluoride porous membrane, and the two cross-linking reactions which do not interfere with each other are simultaneously performed, and the surface of the polyvinylidene fluoride porous membrane is realized. The inter-molecular entanglement forms a hydrophilized structure with an interpenetrating polymer network.
本发明的方法中， 聚偏氟乙烯与胺的交联反应为：  In the method of the present invention, the crosslinking reaction of polyvinylidene fluoride with an amine is:
Figure imgf000005_0001
Figure imgf000005_0001
乙烯醇类聚合物与醛类化合物的交联反应为：  The crosslinking reaction between the vinyl alcohol polymer and the aldehyde compound is:
Figure imgf000005_0002
Figure imgf000005_0002
本发明的互穿聚合物网络的改性方法具有如下优点：①聚偏氟乙烯 与胺类化合物交联后， 膜表面的耐溶剂性增强， 在 N-曱基吡咯烷酮， N，N-二曱基甲酰胺、 N，N-二甲基乙酰胺、 二甲基亚砜、 丙酮、 丁酮、 四 氢呋喃等溶剂中也难以溶解。 ②亲水性聚合物、聚偏氟乙烯分别同时发 生交联反应， 形成互穿聚合物网络结构， 使得聚偏氟乙烯多孔膜基体与 亲水性聚合物在分子级别上缠结在一起，这样就将亲水性聚合物牢牢地 固定在膜表面， 实现了膜表面的永久性亲水， 改性后的膜纯水通量能长 期稳定运行而通量不降低，并且改性后多孔膜在加热条件下完全变干后 立即复水，仍然具有较高的通量。 ③乙烯醇类亲水性聚合物只是被固定 在膜表面， 而未与聚偏氟乙烯多孔膜本体发生化学反应， 这样就未降低 聚偏氟乙烯多孔膜的物理化学性能。 ④与胺类物质发生了分子缠结， 这 样可在大大降低醛类交联剂的用量的前提下，将乙烯醇类亲水性聚合物 固定住，避免了因乙烯醇类聚合物的过度交联对表面孔结构的堵塞，从 而保证了初始通量的提高。 具体实施方式 The modification method of the interpenetrating polymer network of the invention has the following advantages: 1 after the cross-linking of the polyvinylidene fluoride and the amine compound, the solvent resistance of the surface of the film is enhanced, in N-mercaptopyrrolidone, N, N-difluorene Solvents such as carboxamide, N,N-dimethylacetamide, dimethyl sulfoxide, acetone, butanone, and tetrahydrofuran are also difficult to dissolve. 2 The hydrophilic polymer and polyvinylidene fluoride are simultaneously cross-linked to form an interpenetrating polymer network structure, so that the polyvinylidene fluoride porous film substrate and the hydrophilic polymer are entangled at the molecular level, so that The hydrophilic polymer is firmly fixed on the surface of the membrane to achieve permanent hydrophilicity of the membrane surface, and the purified membrane pure water flux can be stably operated for a long period of time without a decrease in flux, and the modified porous membrane Rehydration immediately after complete drying under heating conditions still has a high flux. The 3 vinyl alcohol hydrophilic polymer is only fixed on the surface of the film, and does not chemically react with the bulk of the polyvinylidene fluoride porous film, so that the physical and chemical properties of the polyvinylidene fluoride porous film are not lowered. 4 molecular entanglement with amines, which can immobilize the vinyl alcohol hydrophilic polymer under the premise of greatly reducing the amount of aldehyde crosslinking agent, avoiding excessive crosslinking of vinyl alcohol polymer The blockage of the surface pore structure ensures an increase in the initial flux. detailed description
本发明的聚偏氟乙烯多孔膜表面互穿聚合物网络的改性方法包括 以下步骤：  The method for modifying the interpenetrating polymer network of the polyvinylidene fluoride porous membrane of the present invention comprises the following steps:
1 )使聚偏氟乙烯多孔膜与乙烯醇类聚合物和醛类化合物相接触； 1) contacting the polyvinylidene fluoride porous film with a vinyl alcohol polymer and an aldehyde compound;
2)使步骤 1)获得的聚偏氟乙烯多孔膜与胺类化合物相接触；2) contacting the polyvinylidene fluoride porous film obtained in the step 1) with an amine compound;
3)使聚偏氟乙烯以及所述乙烯醇类聚合物、 醛类化合物和胺类 化合物进行交联反应， 形成表面互穿聚合物网络结构。 3) Cross-linking reaction of polyvinylidene fluoride and the vinyl alcohol-based polymer, aldehyde compound and amine compound to form a surface interpenetrating polymer network structure.
本发明方法中，所述的聚偏氟乙烯多孔膜优选是平板式或中空纤维 式的。 其优选是用熔融拉伸法、 非溶剂致相分离法、 或热致相分离法所 制备的。  In the method of the present invention, the polyvinylidene fluoride porous film is preferably of a flat plate type or a hollow fiber type. It is preferably prepared by melt stretching, non-solvent induced phase separation, or thermally induced phase separation.
所述的乙烯醇类聚合物优选为聚乙烯醇、 乙烯-乙烯醇共聚物、 聚 乙烯醇缩曱醛、 聚乙烯醇缩乙醛、 聚乙烯醇缩甲乙醛、 聚乙烯醇缩丁醛 和聚乙二醇中的任一种或它们的混合物。  The vinyl alcohol-based polymer is preferably polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyvinyl acetal, polyvinyl acetal, polyvinyl acetal, polyvinyl butyral, and Any one of polyethylene glycols or a mixture thereof.
所述的醛类化合物优选为甲醛、乙二酪和戊二醛中的任一种或它们 的混合物。  The aldehyde compound is preferably any one of formaldehyde, butyl ketone and glutaraldehyde or a mixture thereof.
步骤 1 )中所述接触可优选通过将膜浸泡在乙烯醇类聚合物和醛类 化合物的溶液中、或与这两类物质的蒸气接触而实现。 当通过浸泡实现 所述接触时， 所述溶液优选为上述物质的水溶液。 并且所述的乙烯醇类 聚合物在水溶液中的质量浓度优选为 0.1% ~5%, 最优选质量浓度为 0.2% ~ 1%„ 所述的醛类化合物在水溶液中的质量浓度优选为 0.05 % - 2 % , 最优选质量浓度为 0.1% ~ 0.5%。 所述接触的时间优选为 5 分钟至 2小时。  The contacting in the step 1) can be preferably carried out by immersing the film in a solution of a vinyl alcohol polymer and an aldehyde compound, or in contact with a vapor of the two types of materials. When the contact is achieved by soaking, the solution is preferably an aqueous solution of the above substances. And the mass concentration of the vinyl alcohol polymer in the aqueous solution is preferably 0.1% to 5%, and most preferably the mass concentration is 0.2% to 1%. The mass concentration of the aldehyde compound in the aqueous solution is preferably 0.05%. - 2%, most preferably the mass concentration is from 0.1% to 0.5%. The contact time is preferably from 5 minutes to 2 hours.
所述的胺类化合物优选由多元胺或由多元胺与单胺的混合物组成。 所述的多元胺优选为乙二胺、 丙二胺、 己二胺、 对苯二胺、 N,N，N，N， - 四曱基 -1,6-二氨基己烷和 1， 2， 2-三氨基丙烷中的任一种或它们的混 合物。 所述的单胺优选为曱胺、 乙胺、 苯胺和苯甲胺中的任一种或它们 的混合物。 所述的多元胺在胺类化合物中的质量百分比例优选为 10 % - 100% , 最优选质量百分比例为 20% ~ 90%。  The amine compound preferably consists of a polyamine or a mixture of a polyamine and a monoamine. The polyamine is preferably ethylenediamine, propylenediamine, hexamethylenediamine, p-phenylenediamine, N,N,N,N,-tetradecyl-1,6-diaminohexane and 1, 2, Any one of 2-triaminopropane or a mixture thereof. The monoamine is preferably any one of decylamine, ethylamine, aniline and benzylamine or a mixture thereof. The percentage by mass of the polyamine in the amine compound is preferably from 10% to 100%, and most preferably the percentage by mass is from 20% to 90%.
步骤 2) 中所述接触可优选通过将膜浸泡在胺类化合物的溶液中、 或与其蒸气接触而实现。 当通过浸泡实现所述接触时， 所述溶液优选为 胺类化合物的水溶液，并且所述的胺类化合物在水溶液中的质量浓度优 选为 40% ~ 95%， 最优选质量浓度为 50% ~ 90%。 所述接触的时间优 选为 5分钟至 2小时。 The contacting in step 2) can preferably be achieved by immersing the membrane in a solution of the amine compound or in contact with its vapor. When the contact is achieved by immersion, the solution is preferably an aqueous solution of an amine compound, and the amine compound is excellent in mass concentration in an aqueous solution. It is selected from 40% to 95%, and the most preferred mass concentration is from 50% to 90%. The time of the contacting is preferably from 5 minutes to 2 hours.
步骤 2 )和步骤 3 )可同时进行或依次进行。  Step 2) and step 3) can be performed simultaneously or sequentially.
交联反应优选在磷酸的催化下进行。所述磷酸优选以水溶液的形式 使用， 优选其为质量浓度为 0.1% ~ 2%的溶液。 所述的交联反应温度 优选为 20" -60 C, 反应时间优选为 1小时 ~24小时。  The crosslinking reaction is preferably carried out under the catalysis of phosphoric acid. The phosphoric acid is preferably used in the form of an aqueous solution, preferably a solution having a mass concentration of 0.1% to 2%. The crosslinking reaction temperature is preferably 20" - 60 C, and the reaction time is preferably from 1 hour to 24 hours.
优选将交联后的多孔膜在去离子水中浸泡， 浸泡时间优选为 12小 时~48小时， 去离子水的温度优选为 30 C ~ 60 。 下面结合实施例对本发明的技术方案进行进一步的说明，但是对所 述实施方式举例不构成对本发明的限制。  Preferably, the crosslinked porous film is immersed in deionized water, and the soaking time is preferably from 12 hours to 48 hours, and the temperature of the deionized water is preferably from 30 C to 60. The technical solutions of the present invention are further described below with reference to the embodiments, but the examples of the embodiments do not constitute a limitation of the present invention.
以下各实施例中， 所制得的样品的纯水通量通过以下方法测定： 用泵施加 0. IMPa的压力使纯水透过样品， 测量单位时间内透过单 位面积样品的水体积。 实施例 1  In the following examples, the pure water flux of the prepared sample was determined by the following method: Applying with a pump 0. The pressure of IMPa allowed pure water to pass through the sample, and the volume of water per unit area of the sample per unit time was measured. Example 1
把聚合物重量百分数为 25%的聚偏氟乙烯的 N，N-二曱基乙酰胺溶 液浇铸在玻璃板上， 以水为凝固浴， 用干湿法制备成聚偏氟乙烯多孔平 板膜， 纯水通量为 600 ~ 700L/m2 · h · 0. lMPa。 The polyvinylidene fluoride N,N-didecylacetamide solution having a polymer weight percentage of 25% by weight is cast on a glass plate, and water is used as a coagulation bath to prepare a polyvinylidene fluoride porous flat membrane by dry-wet method. The pure water flux is 600 ~ 700L / m 2 · h · 0. lMPa.
将得到的聚偏氟乙烯多孔平板膜先浸泡在含有盾量浓度为 1 %的聚 乙烯醇和质量浓度为 0.2%的戊二醛的水溶液中 10分钟； 然后将吸附 了聚乙烯醇与戊二醛的聚偏氟乙烯多孔膜浸泡在含胺类化合物的水溶 液中， 其中， 含胺类化合物的水溶液中含有质量浓度为 50%的乙二胺 和 1%的磷酸。 水温控制在 40" ， 反应 10小时后， 将膜放入 30 的去 离子水中浸泡 12小时， 即得到表面互穿聚合物网络改性的聚偏氟乙烯 多孔膜。 测得纯水通量为 650 ~ 750L/m2. h · 0. lMPa。 连续使用 120小 时后， 再测其纯水通量仍保持为 650 ~ 750L/m2. h . 0. lMPa。 将所制得 的膜置于 50Ό烘箱中干燥 24小时， 取出后直接复水， 测得其纯水通量 为 550 - 600L/m2 · h · 0. lMPa。 The obtained polyvinylidene fluoride porous flat membrane is first immersed in an aqueous solution containing polyvinyl alcohol having a shield concentration of 1% and glutaraldehyde having a mass concentration of 0.2% for 10 minutes; then, polyvinyl alcohol and glutaraldehyde are adsorbed. The polyvinylidene fluoride porous membrane is immersed in an aqueous solution containing an amine compound, wherein the aqueous solution containing the amine compound contains ethylene diamine and 1% phosphoric acid at a mass concentration of 50%. The water temperature was controlled at 40", and after 10 hours of reaction, the membrane was immersed in 30 deionized water for 12 hours to obtain a porous polyvinylidene fluoride membrane modified by a surface interpenetrating polymer network. The measured pure water flux was 650. ~ 750L/m 2 . h · 0. lMPa. After 120 hours of continuous use, the pure water flux is still kept at 650 ~ 750L/m 2 . 0 . lMPa. The prepared film is placed at 50Ό. The drying was carried out for 24 hours in an oven, and the water was directly rehydrated, and the pure water flux was measured to be 550 - 600 L/m 2 · h · 0. lMPa.
交联后的聚偏氟乙烯多孔膜在 N，N -二曱基甲酰胺、 N，N-二甲基乙 酰胺、 N-甲基吡咯烷酮和二甲基亚砜中不再溶解。 实施例 2 The crosslinked polyvinylidene fluoride porous film was no longer dissolved in N,N-dimercaptocarboxamide, N,N-dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide. Example 2
把实施例 1 中使用的聚偏氟乙烯的 N，N-二曱基乙酰胺溶液通过环 状喷丝板纺丝， 用水作为芯液和凝固浴， 得到了外径为 1. 6mm 内径为 0. 9mm 的 中 空纤维膜， 该 中 空纤维膜纯水通量为 600 ~ 700L/m2 · h · 0. lMPa。 The inner diameter is 0. 6mm, the inner diameter is 0. The outer diameter is 1. 6mm, the inner diameter is 0. The outer diameter is 1. 6mm, the inner diameter is 0. MPa。 The 9mm hollow fiber membrane, the hollow fiber membrane pure water flux is 600 ~ 700L / m 2 · h · 0. lMPa.
然后，把该中空纤维膜按与实施例 1中同样的方式进行交联， 不同 之处在于聚偏氟乙烯多孔膜浸泡在含有质量浓度为 1 %的聚乙烯醇和 质量浓度为 0. 2 %的戊二醛的水溶液中的时间为 2小时， 且含胺类化合 物的水溶液中含有质量浓度为 90 %的乙二胺和 2 %的磷酸。交联后的中 空纤维膜的纯水通量为 650 ~ 750L/m2 · h · 0. IMPa, 连续使用 120小时 后， 再测其纯水通量仍保持为 650 ~ 750L/m2 · h . 0. lMPa。 将所制得的 膜置于 50 烘箱中干燥 24 小时， 取出后直接复水， 测得纯水通量为 550 - 600L/m2■ h · 0. lMPa。 And the mass concentration of 0.2% by mass of polyvinyl alcohol having a mass concentration of 1% is immersed in a polyvinyl alcohol having a mass concentration of 1%. The time in the aqueous solution of glutaraldehyde was 2 hours, and the aqueous solution containing the amine compound contained ethylenediamine and 2% phosphoric acid having a mass concentration of 90%. The pure water flux of the crosslinked hollow fiber membrane is 650 ~ 750L/m 2 · h · 0. IMPa, after 120 hours of continuous use, the pure water flux is still kept at 650 ~ 750L / m 2 · h 0. lMPa. The obtained film was dried in a 50-mesh oven for 24 hours, and then directly rehydrated after taking out, and the pure water flux was measured to be 550 - 600 L/m 2 ■ h · 0. lMPa.
交联后的聚偏氟乙烯多孔膜在 N，N-二甲基甲酰胺、 N，N-二甲基乙 酰胺、 N-曱基吡咯烷酮和二甲基亚砜中不再溶解。  The crosslinked polyvinylidene fluoride porous film was no longer dissolved in N,N-dimethylformamide, N,N-dimethylacetamide, N-decylpyrrolidone and dimethyl sulfoxide.
实施例 3  Example 3
将聚偏氟乙烯树脂与二苯曱酮一一聚偏氟乙烯树脂的重量百分含 量为 35 %、 二笨甲酮重量百分含量为 65 %——放入高温搅拌釜中加热 至 200 成为聚合物均相溶液。 然后通过环状喷丝板纺丝， 芯液为丙三 醇， 水作为凝固浴。 得到了外径为 1. 6mm内径为 0. 9mm的中空纤维膜， 该中空纤维膜纯水通量为 800 - lOOOL/m2 · h · 0. lMPa。 The polyvinylidene fluoride resin and the diphenyl fluorenone-polyvinylidene fluoride resin are 35% by weight, and the dimercapto ketone is 65% by weight, which is heated to 200 in a high temperature stirred tank. A homogeneous solution of the polymer. Then, it is spun through a ring-shaped spinneret, the core liquid is glycerin, and water is used as a coagulation bath. MPa。 The hollow fiber membrane having an outer diameter of 1. 6mm, the hollow fiber membrane having a pure water flux of 800 - lOOOL / m 2 · h · 0. lMPa.
然后， 把该中空纤维膜按与实施例 1中同样的方式进行交联反应， 不同之处在于含胺类化合物的水溶液中含有质量浓度为 50 %的己二 胺、 40 %的曱胺和 1. 5%的磷酸。 交联后的中空纤维膜的纯水通量为 850 - 1100L/m2 - h · 0. IMPa , 连续使用 120小时后， 再测其纯水通量仍 保持为 850 ~ 1100L/m2 · h . 0. lMPa。 将所制得的膜置于 50Ό烘箱中干 燥 24小时，取出后直接复水，测得纯水通量为 750 ~ 900L/m2 -h -0. IMPa. Then, the hollow fiber membrane was subjected to a crosslinking reaction in the same manner as in Example 1, except that the aqueous solution containing the amine compound contained hexamethylenediamine having a mass concentration of 50%, 40% of decylamine and 1 .5% phosphoric acid. The pure water flux of the crosslinked hollow fiber membrane is 850 - 1100L/m 2 - h · 0. IMPa , after 120 hours of continuous use, the pure water flux is still kept at 850 ~ 1100L/m 2 · h 0. lMPa. The prepared film was dried in a 50-inch oven for 24 hours, and directly rehydrated after taking out, and the pure water flux was measured to be 750 ~ 900 L/m 2 -h -0. IMPa.
交联后的聚偏氟乙烯多孔膜在 N，N-二甲基曱酰胺、 Ν, Ν-二甲基乙 酰胺、 Ν-甲基吡咯烷酮和二甲基亚砜中不再溶解。  The crosslinked polyvinylidene fluoride porous film was no longer dissolved in N,N-dimethylformamide, hydrazine, hydrazine-dimethylacetamide, hydrazine-methylpyrrolidone and dimethyl sulfoxide.
实施例 4  Example 4
将聚偏氟乙烯树脂通过单螺杆挤出器从带环状孔的喷丝头挤出，并 迅速于 180Ό下热处理 60分钟， 然后进行拉伸， 拉伸倍数为 3倍， 最 后于 1851C下热定形处理 10 分钟， 测得所得的中空纤维膜纯水通量为 300-400L/m2 · h · 0. lMPa。 The polyvinylidene fluoride resin is extruded from a spinneret having an annular hole through a single screw extruder, and The heat treatment was rapidly performed at 180 Torr for 60 minutes, and then stretched, the draw ratio was 3 times, and finally heat set at 1851 C for 10 minutes, and the obtained pure fiber membrane was measured to have a pure water flux of 300-400 L/m 2 · h. · 0. lMPa.
然后，将制得的膜按与实施例 1中同样的方式进行交联反应， 不同 之处在于聚偏氟乙烯多孔膜浸泡在含有聚乙烯醇和戊二醛的水溶液中 的时间为 5分钟， 且聚乙烯醇的质量浓度为 2 % , 戊二醛的质量浓度为 1 %。 交联后的中空纤维膜的纯水通量为 300-400L/m2 · h · 0. IMPa , 连 续使用 120小时后，再测其纯水通量仍保持为 300 ~ 400L/m2 -h ·0. IMPa. 将所制得的膜置于 50Ό烘箱中干燥 24小时， 取出后直接复水， 测得纯 水通量为 300 - 400L/m2 · h · 0. lMPa。 Then, the obtained film was subjected to a crosslinking reaction in the same manner as in Example 1, except that the polyvinylidene fluoride porous film was immersed in an aqueous solution containing polyvinyl alcohol and glutaraldehyde for 5 minutes, and The mass concentration of polyvinyl alcohol is 2%, and the mass concentration of glutaraldehyde is 1%. The pure water flux of the crosslinked hollow fiber membrane is 300-400L/m 2 · h · 0. IMPa , after 120 hours of continuous use, the pure water flux is still maintained at 300 ~ 400L/m 2 -h 0. IMPa. The prepared film was dried in a 50-inch oven for 24 hours, and then directly rehydrated after taking out, and the pure water flux was measured to be 300 - 400 L / m 2 · h · 0. lMPa.
交联后的聚偏氟乙烯多孔膜在 N，N-二曱基曱酰胺、 N，N-二甲基乙 酰胺、 N-甲基吡咯烷酮和二曱基亚砜中不再溶解。  The crosslinked polyvinylidene fluoride porous film was no longer dissolved in N,N-dimercaptophthalamide, N,N-dimethylacetamide, N-methylpyrrolidone and dimercaptosulfoxide.
实施例 5  Example 5
按与实施例 3相同的方法得到中空纤维膜。该中空纤维膜纯水通量 为 800 ~ 1000L/m2 · h · 0. lMPa。 A hollow fiber membrane was obtained in the same manner as in Example 3. The hollow fiber membrane has a pure water flux of 800 to 1000 L/m 2 · h · 0. lMPa.
然后，把该中空纤维膜按与实施例 1中类似的方式进行交联， 不同 之处在于聚乙烯醇浓度为 0. 1 % , 戊二醛的浓度为 0. 05 %， 胺类化合物 的水溶液中， 乙二胺的质量浓度为 4 % , 乙胺的盾量浓度为 36 %， 磷酸 的质量浓度为 0. 1 %。 交联后的中空纤维膜的純水通量为 1000 ~ 1200L/m2 · h■ 0. IMPa , 连续使用 120 小时后， 再测其纯水通量仍保持 为 1000 ~ 1200L/m2■ h · 0. lMPa。 将所制得的膜置于 50 烘箱中干燥 24 小时， 取出后直接复水， 测得纯水通量为 700 ~ 800L/m2 . h · 0. lMPa。 And the concentration of the glutaraldehyde is 0.05%, and the aqueous solution of the amine compound is an aqueous solution of the amine compound. 1重量。 The mass concentration of ethylene diamine is 4%, the concentration of ethylamine shield is 36%, the mass concentration of phosphoric acid is 0.1%. The pure water flux of the crosslinked hollow fiber membrane is 1000 ~ 1200L / m 2 · h ■ 0. IMPa , after 120 hours of continuous use, the pure water flux is still maintained at 1000 ~ 1200L / m 2 ■ h · 0. lMPa. The film was dried in a 50 oven for 24 hours, and then directly rehydrated after taking out, and the pure water flux was measured to be 700-800 L/m 2 . h · 0. lMPa.
交联后的聚偏氟乙烯多孔膜在 N，N-二曱基甲酰胺、 N，N-二曱基乙 酰胺、 N-甲基吡咯烷酮和二甲基亚砜中不再溶解。  The crosslinked polyvinylidene fluoride porous film was no longer dissolved in N,N-dimercaptocarboxamide, N,N-dimercaptoacetamide, N-methylpyrrolidone and dimethyl sulfoxide.
实施例 6  Example 6
按与实施例 3相同的方法得到中空纤维膜。该中空纤维膜纯水通量 为 800 ~ 1000L/m2 · h · 0. lMPa。 A hollow fiber membrane was obtained in the same manner as in Example 3. The hollow fiber membrane has a pure water flux of 800 to 1000 L/m 2 · h · 0. lMPa.
然后，把该中空纤维膜按与实施例 1中类似的方式进行交联， 不同 之处在于聚乙烯醇质量浓度为 5%， 戊二醛的质量浓度为 2 %， 胺类化合 物的水溶液中， 对苯二胺的质量浓度为 86 % , 苯胺的质量浓度为 9 % , 磷酸的质量浓度为 2 %。 交联后的中空纤维膜的纯水通量为 600 - 800L/m2 · h · 0. IMPa, 连续使用 120小时后， 再测其纯水通量仍保持为 600 - 800L/m2 -h · 0. lMPa。将所制得的膜置于 50*C烘箱中干燥 24小时， 取出后直接复水， 测得纯水通量为 600 ~ 750L/m2 · h · 0. lMPa。 Then, the hollow fiber membrane was crosslinked in a manner similar to that in Example 1, except that the polyvinyl alcohol had a mass concentration of 5% and the glutaraldehyde had a mass concentration of 2%, in an aqueous solution of an amine compound. The mass concentration of p-phenylenediamine was 86%, the mass concentration of aniline was 9%, and the mass concentration of phosphoric acid was 2%. The pure water flux of the crosslinked hollow fiber membrane is 600 - 800L/m 2 · h · 0. IMPa, after continuous use for 120 hours, the pure water flux is still measured to be 600 - 800L / m 2 -h · 0. lMPa. The prepared film was dried in a 50*C oven for 24 hours, and then directly rehydrated after taking out, and the pure water flux was measured to be 600 ~ 750 L / m 2 · h · 0. lMPa.
交联后的聚偏氟乙烯多孔膜在 N，N-二曱基甲酰胺、 N，N-二甲基乙 酰胺、 N-甲基吡咯烷酮和二甲基亚砜中不再溶解。  The crosslinked polyvinylidene fluoride porous film was no longer dissolved in N,N-dimercaptocarboxamide, N,N-dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide.
实施例 7  Example 7
按与实施例 3相同的方法得到中空纤维膜。该中空纤维膜纯水通量 为 800 - 1000L/m2 . h . 0, IMPa. A hollow fiber membrane was obtained in the same manner as in Example 3. The hollow fiber membrane has a pure water flux of 800 - 1000 L/m 2 . h . 0, IMPa.
然后， 把该中空纤维膜按与实施例 1中类似的方式进行交联， 不同 之处在于将聚乙烯醇换为聚乙烯醇缩丁醛， 质量浓度为 3 % , 将戊二醛 换为甲醛， 质量浓度为 2 %， 乙二胺换为丙二胺， 质量浓度为 50 %。 交 联后的中空纤维膜的纯水通量为 800 ~ 1000L/m2 - h - 0. IMPa , 连续使用 120小时后， 再测其纯水通量仍保持为 800 - 1000L/m2 . h . 0. lMPa。 将 所制得的膜置于 50Ό烘箱中干燥 24小时， 取出后直接复水， 测得纯水 通量为 700 ~ 800L/m2 · h · 0. lMPa。 Then, the hollow fiber membrane was crosslinked in a manner similar to that in Example 1, except that polyvinyl alcohol was changed to polyvinyl butyral at a mass concentration of 3 %, and glutaraldehyde was changed to formaldehyde. , the mass concentration is 2%, ethylenediamine is changed to propylenediamine, and the mass concentration is 50%. The pure water flux of the crosslinked hollow fiber membrane is 800 ~ 1000L/m 2 - h - 0. IMPa , after 120 hours of continuous use, the pure water flux is still maintained at 800 - 1000L / m 2 . 0. lMPa. The obtained film was dried in a 50-inch oven for 24 hours, and then directly rehydrated after taking out, and the pure water flux was measured to be 700-800 L/m 2 · h · 0. lMPa.
交联后的聚偏氟乙烯多孔膜在 Ν, Ν-二甲基甲酰胺、 Ν，Ν-二甲基乙 酰胺、 Ν-曱基吡咯烷酮和二甲基亚砜中不再溶解。  The crosslinked polyvinylidene fluoride porous film was no longer dissolved in hydrazine, hydrazine-dimethylformamide, hydrazine, hydrazine-dimethylacetamide, fluorenyl-pyridylpyrrolidone and dimethyl sulfoxide.
实施例 8  Example 8
按与实施例 3相同的方法得到中空纤维膜。该中空纤维膜纯水通量 为 800 ~ 1000L/m2 · h■ 0. IMPa. A hollow fiber membrane was obtained in the same manner as in Example 3. The hollow fiber membrane has a pure water flux of 800 ~ 1000 L / m 2 · h ■ 0. IMPa.
然后，把该中空纤维膜按与实施例 1中类似的方式进行交联， 不同 之处在于将交联时间延长至 24小时， 交联温度变为 60TC , 去离子水温 度为 601C， 浸泡 48 小时。 交联后的中空纤维膜的纯水通量为 500 ~ 600L/m2 · h · 0. IMPa, 连续使用 120小时后， 再测其纯水通量仍保持为 500 ~ 600L/m2 -h · 0. IMPa。将所制得的膜置于 50 烘箱中干燥 24小时， 取出后直接复水， 测得纯水通量为 500 - 600L/m2 · h · 0. IMPa. Then, the hollow fiber membrane was crosslinked in a manner similar to that in Example 1, except that the crosslinking time was extended to 24 hours, the crosslinking temperature was changed to 60 TC, the deionized water temperature was 601 C, and the immersion was carried out for 48 hours. . The pure water flux of the crosslinked hollow fiber membrane is 500 ~ 600L/m 2 · h · 0. IMPa, after 120 hours of continuous use, the pure water flux is still maintained at 500 ~ 600L / m 2 -h · 0. IMPa. The prepared film was dried in a 50 oven for 24 hours, and directly rehydrated after taking out, and the pure water flux was measured to be 500 - 600 L/m 2 · h · 0. IMPa.
交联后的聚偏氟乙烯多孔膜在 N，N-二甲基甲跣胺、 N，N-二曱基乙 酰胺、 N-曱基吡咯烷酮和二曱基亚砜中不再溶解。  The crosslinked polyvinylidene fluoride porous film was no longer dissolved in N,N-dimethylformamide, N,N-dimercaptoacetamide, N-decylpyrrolidone and dimercaptosulfoxide.
实施例 9  Example 9
按与实施例 3相同的方法得到中空纤维膜。该中空纤维膜纯水通量 为 800 - 1000L/m2 · h · 0. IMPa, g 然后，把该中空纤维膜按与实施例 1中类似的方式进行交联， 不同 之处在于将交联时间变 1小时， 交联温度为 20*C , 去离子水温度为 30 , 浸泡 12 小时。 交联后的中空纤维膜的纯水通量为 1000 - 1200L/m2 · h · 0. IMPa , 连续使用 120小时后， 再其纯水测通量为 700 ~ 800L/m2 · h · 0. lMPa。 将所制得的膜置于 50"C烘箱中干燥 24小时， 取 出后直接复水， 测得纯水通量为 300 ~ 400L/m2 · h · 0. lMPa。 A hollow fiber membrane was obtained in the same manner as in Example 3. The hollow fiber membrane has a pure water flux of 800 - 1000 L/m 2 · h · 0. IMPa, g Then, the hollow fiber membrane was crosslinked in a manner similar to that in Example 1, except that the crosslinking time was changed to 1 hour, the crosslinking temperature was 20*C, the deionized water temperature was 30, and the immersion was carried out for 12 hours. . The pure water flux of the crosslinked hollow fiber membrane is 1000 - 1200L/m 2 · h · 0. IMPa , after 120 hours of continuous use, the pure water flux is 700 ~ 800L / m 2 · h · 0 . lMPa. The prepared film was dried in a 50" C oven for 24 hours, and then directly rehydrated after taking out, and the pure water flux was measured to be 300 ~ 400 L / m 2 · h · 0. lMPa.
交联后的聚偏氟乙烯多孔膜在 N，N-二甲基甲酰胺、 N，N-二甲基乙 酰胺、 N-曱基吡咯烷酮和二甲基亚砜中仍然可溶，但溶解速率明显降低。  The crosslinked polyvinylidene fluoride membrane is still soluble in N,N-dimethylformamide, N,N-dimethylacetamide, N-decylpyrrolidone and dimethyl sulfoxide, but the dissolution rate obviously decased.
比较例 1  Comparative example 1
将聚偏氟乙烯树脂与二苯甲酮一一聚偏氟乙烯树脂的重量百分含 量为 35 %、 二苯曱酮重量百分含量为 65 % —―放入高温搅拌釜中加热 至 200Ό成为聚合物均相溶液。 然后通过环状喷丝板纺丝， 芯液为丙三 醇， 水作为凝固浴。 得到了外径为 1. 6mm内径为 0. 9mm的中空纤维膜。  The weight percent of polyvinylidene fluoride resin and benzophenone monovinylidene fluoride resin is 35%, and the weight percentage of benzophenone is 65% - it is heated to 200 放入 in a high temperature stirred tank. A homogeneous solution of the polymer. Then, it is spun through a ring-shaped spinneret, the core liquid is glycerin, and water is used as a coagulation bath. The hollow fiber membrane having an outer diameter of 1. 6 mm and an inner diameter of 0.9 mm was obtained.
将该中空纤维膜制成小型膜组件， 测得其纯水通量为 800 ~ 1000L/m2 · h · 0. lMPa。 连续运行 120小时后， 再测其纯水通量为 500 ~ 600L/m2 · h · 0. lMPa。 将所制得的膜置于 50Ό烘箱中干燥 24小时， 取 出后直接复水， 测得纯水通量为零。 MPa。 The hollow fiber membrane was made into a small membrane module, the pure water flux was measured to be 800 ~ 1000L / m 2 · h · 0. lMPa. After continuous operation for 120 hours, the pure water flux was measured to be 500 ~ 600 L / m 2 · h · 0. lMPa. The prepared film was dried in a 50-inch oven for 24 hours, and directly rehydrated after taking out, and the pure water flux was measured to be zero.
该聚偏氟乙烯多孔膜在 N，N-二甲基曱酰胺、 N，N-二甲基乙酰胺、 N-曱基吡咯烷酮和二甲基亚砜中很容易就被溶解掉了。  The polyvinylidene fluoride porous film is easily dissolved in N,N-dimethylformamide, N,N-dimethylacetamide, N-decylpyrrolidone and dimethyl sulfoxide.

Claims

权利要求书 Claim
1、 聚偏氟乙烯多孔膜表面互穿聚合物网络的改性方法， 该方法包 括如下步骤：  1. A method for modifying a polyvinylidene fluoride porous membrane surface interpenetrating polymer network, the method comprising the steps of:
1 H吏聚偏氟乙烯多孔膜与乙烯醇类聚合物和醛类化合物相接触； 1 H吏 polyvinylidene fluoride porous membrane is contacted with a vinyl alcohol polymer and an aldehyde compound;
2 )使步骤 1 )获得的聚偏氟乙烯多孔膜与胺类化合物相接触；2) contacting the polyvinylidene fluoride porous film obtained in the step 1) with an amine compound;
3 )使聚偏氟乙烯以及所述乙烯醇类聚合物、 醛类化合物和胺类 化合物进行交联反应， 形成表面互穿聚合物网络结构。 3) Cross-linking reaction of polyvinylidene fluoride and the vinyl alcohol-based polymer, aldehyde compound and amine compound to form a surface interpenetrating polymer network structure.
2、 根据权利要求 1所述的方法， 其特征在于： 所述的聚偏氟乙烯 多孔膜是用熔融拉伸法、非溶剂致相分离法或热致相分离法所制备的平 板膜或中空纤维膜。  2. The method according to claim 1, wherein: the polyvinylidene fluoride porous membrane is a flat membrane or hollow prepared by melt stretching, non-solvent phase separation or thermal phase separation. Fiber membrane.
3、 根据权利要求 1所述的方法， 其特征在于： 所述的乙烯醇类聚 合物为聚乙烯醇、 乙浠-乙烯醇共聚物、 聚乙烯醇缩曱窿、 聚乙烯醇缩 乙醛、聚乙烯醇缩曱乙醛、聚乙烯醇缩丁醛和聚乙二醇中的任一种或它 们的混合物， 所述的醛类化合物为甲醛、 乙二醛和戊二醛中的任一种或 它们的混合物。  3. The method according to claim 1, wherein: the vinyl alcohol polymer is polyvinyl alcohol, acetonitrile-vinyl alcohol copolymer, polyvinyl acetal, polyvinyl acetal, Any one or a mixture of polyvinyl acetal, polyvinyl butyral, and polyethylene glycol, and the aldehyde compound is any one of formaldehyde, glyoxal, and glutaraldehyde. Or a mixture of them.
4、 根据权利要求 1 所述的方法， 其特征在于： 步骤 1 ) 中所述接 触通过将膜浸泡在乙烯醇类聚合物和醛类化合物的溶液中、或与这两类 物质的蒸气接触而实现， 其中所述溶液优选为上述物盾的水溶液； 所述 接触的时间为 5分钟至 2小时。  4. The method according to claim 1, wherein: the contacting in step 1) is performed by immersing the film in a solution of a vinyl alcohol polymer and an aldehyde compound, or in contact with vapors of the two types of substances. It is achieved that the solution is preferably an aqueous solution of the above shield; the contact time is from 5 minutes to 2 hours.
5、 根据权利要求 4所述的方法， 其特征在于： 在所述水溶液中， 所述的乙烯醇类聚合物的质量浓度为 0. 1 % ~ 5 %，优选质量浓度为 0. 2 % ~ 1 %； 所迷的 ^类化合物的质量浓度为 0. 05 % ~ 2 %， 优选质量浓 度为 0. 1 % ~ 0. 5 %。  2 % ~ The mass concentration is 0.2% ~ 5%, preferably the mass concentration is 0. 2 % ~ 1 %〜 0. 5 %。 The mass concentration of the compound is 0. 05% ~ 2%, preferably the mass concentration is 0.1% ~ 0. 5 %.
6、 根据权利要求 1所述的方法， 其特征在于： 步骤 2 ) 中所述接 触通过将膜浸泡在胺类化合物的溶液中、或与其蒸气接触而实现， 其中 所述溶液优选为胺类化合物的水溶液；所述接触的时间为 5分钟至 2小 时。  6. The method according to claim 1, wherein: the contacting in step 2) is achieved by immersing the membrane in a solution of an amine compound or in contact with a vapor thereof, wherein the solution is preferably an amine compound. An aqueous solution; the contact time is from 5 minutes to 2 hours.
7、 根据权利要求 1所述的方法， 其特征在于： 所述的胺类化合物 由多元胺或由多元胺与单胺的混合物组成；胺类化合物在水溶液中的质 量浓度为 40 % ~ 95 %， 优选质量浓度为 50 % ~ 90 %。  7. The method according to claim 1, wherein: the amine compound is composed of a polyamine or a mixture of a polyamine and a monoamine; and the mass concentration of the amine compound in the aqueous solution is 40% to 95%. Preferably, the mass concentration is from 50% to 90%.
8、 根据权利要求 7所述的方法， 其特征在于： 所述的多元胺为乙 二胺、 丙二胺、 己二胺、 对苯二胺、 N，N，N，N， -四曱基- 1， 6-二氨基己 烷和 1， 2， 2-三氨基丙烷中的任一种或它们的混合物； 所述的单胺为甲 胺、 乙胺、 苯胺和苯甲胺中的任一种或它们的混合物； 多元胺在胺类 ¾ 合物中的质量百分比例为 10% - 100%, 优选为 20% ~90%。 8. The method according to claim 7, wherein: the polyamine is B Any of diamine, propylenediamine, hexamethylenediamine, p-phenylenediamine, N,N,N,N,-tetradecyl-1,6-diaminohexane and 1,2,2-triaminopropane One or a mixture thereof; the monoamine is any one of methylamine, ethylamine, aniline and benzylamine or a mixture thereof; and the mass percentage of the polyamine in the amine compound is 10% - 100%, preferably 20% to 90%.
9、 根据权利要求 1所述的方法， 其特征在于： 所述交联反应在磷 酸的催化下进行， 所述磷酸以水溶液的形式使用， 其质量浓度为 0.1 % - 2 %； 所述的交联反应温度为 20~60 ， 反应时间为 1 小时 ~24 小时。  9. The method according to claim 1, wherein: the crosslinking reaction is carried out under the catalysis of phosphoric acid, and the phosphoric acid is used in the form of an aqueous solution having a mass concentration of 0.1% to 2%; The reaction temperature is 20~60, and the reaction time is 1 hour~24 hours.
10、 根据权利要求 1所述的方法， 其特征在于： 将交联后的聚偏氟 乙晞多孔膜在去离子水中浸泡， 浸泡时间为 12小时 ~ 48小时， 去离子 水的温度为 30 ~60匸。  10. The method according to claim 1, wherein: the crosslinked polyvinylidene fluoride porous membrane is immersed in deionized water for a immersion time of 12 hours to 48 hours, and the temperature of the deionized water is 30 ～. 60匸.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015500907A (en) * 2011-12-09 2015-01-08 ナンヤン テクノロジカル ユニヴァーシティー Graft copolymer of poly (vinylidene fluoride) -based polymer and at least one conductive polymer, and method for forming the graft copolymer
US20200287187A1 (en) * 2018-04-13 2020-09-10 Lg Chem, Ltd. Method for improving physical properties of separator by post-treatment crosslinking and separator prepared thereby
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Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101485960B (en) * 2009-01-09 2011-08-17 清华大学 Method for modifying interpenetrating polymer network on surface of polyvinylidene fluoride porous membrane
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JP6688702B2 (en) * 2016-08-17 2020-04-28 株式会社バルカー Method for producing new hydrophilic porous fluororesin membrane
CN108043248B (en) * 2017-12-06 2019-04-26 南京工业大学 PVA-PVDF hollow fiber ultrafiltration membrane, preparation method, preparation device and application
CN111249919B (en) * 2020-02-19 2021-09-24 天津工业大学 A kind of surface modification method of hydrophobic membrane
CN111659267A (en) * 2020-07-23 2020-09-15 天津海龙津阳材料科技有限公司 Pollution-resistant modified porous membrane and preparation method thereof
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0430082A2 (en) * 1989-11-30 1991-06-05 Millipore Corporation Porous membrane formed from an interpenetrating polymer network having hydrophilic surface
CN1986038A (en) * 2006-11-28 2007-06-27 浙江大学 Surface hydrophilicity modification process for separating fluoric polymer film
WO2008012909A1 (en) * 2006-07-28 2008-01-31 Toray Industries, Inc. Interpenetrating polymer network structure and polishing pad and processes for producing them
CN101485960A (en) * 2009-01-09 2009-07-22 清华大学 Method for modifying interpenetrating polymer network on surface of polyvinylidene fluoride porous membrane

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2841807B2 (en) 1990-09-21 1998-12-24 ダイキン工業株式会社 Solid polymer substance and its use
JPH05148400A (en) 1991-11-27 1993-06-15 Asahi Glass Co Ltd Fliororubber composition and its preparation
CN1554690A (en) * 2003-12-26 2004-12-15 中山大学 Preparation method of solvent-resistant semi-interpenetrating network membrane
JP5224504B2 (en) * 2005-12-15 2013-07-03 独立行政法人理化学研究所 Thin film having interpenetrating polymer network layer and method for producing the thin film

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0430082A2 (en) * 1989-11-30 1991-06-05 Millipore Corporation Porous membrane formed from an interpenetrating polymer network having hydrophilic surface
WO2008012909A1 (en) * 2006-07-28 2008-01-31 Toray Industries, Inc. Interpenetrating polymer network structure and polishing pad and processes for producing them
CN1986038A (en) * 2006-11-28 2007-06-27 浙江大学 Surface hydrophilicity modification process for separating fluoric polymer film
CN101485960A (en) * 2009-01-09 2009-07-22 清华大学 Method for modifying interpenetrating polymer network on surface of polyvinylidene fluoride porous membrane

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015500907A (en) * 2011-12-09 2015-01-08 ナンヤン テクノロジカル ユニヴァーシティー Graft copolymer of poly (vinylidene fluoride) -based polymer and at least one conductive polymer, and method for forming the graft copolymer
US20200287187A1 (en) * 2018-04-13 2020-09-10 Lg Chem, Ltd. Method for improving physical properties of separator by post-treatment crosslinking and separator prepared thereby
US12054595B2 (en) * 2018-04-13 2024-08-06 Lg Energy Solution, Ltd. Method for improving physical properties of separator by post-treatment crosslinking and separator prepared thereby
CN115364686A (en) * 2021-12-24 2022-11-22 浙江理工大学 A durable hydrophilic nanofibrous membrane based on crosslinking and curing
CN115364686B (en) * 2021-12-24 2024-02-20 浙江理工大学 Durable hydrophilic nanofiber membrane based on crosslinking curing

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