CN106310967B - A method of preparing hydrophilic nano hybrid reinforcement type hollow-fibre membrane - Google Patents

A method of preparing hydrophilic nano hybrid reinforcement type hollow-fibre membrane Download PDF

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CN106310967B
CN106310967B CN201610708369.7A CN201610708369A CN106310967B CN 106310967 B CN106310967 B CN 106310967B CN 201610708369 A CN201610708369 A CN 201610708369A CN 106310967 B CN106310967 B CN 106310967B
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reactor
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CN106310967A (en
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陈亦力
代攀
石月荣
李新涛
孟莎莎
彭兴峥
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Beijing Originwater Membrane Technology Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/08—Hollow fibre membranes
    • 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
    • B01D67/0002—Organic membrane manufacture
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/36—Hydrophilic membranes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds

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  • Life Sciences & Earth Sciences (AREA)
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  • Manufacturing & Machinery (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

The invention belongs to polymeric hollow fiber microporous modification and preparation and the field of chemical synthesis, it is related to the preparation method and application that nano-functional material is supported on enhancement type hollow fiber film by a kind of method by click chemistry.There is excellent modification performance by the hydrophilic nano hybrid reinforcement type hollow-fibre membrane that the method for the present invention is prepared, such as the hydrophily of membrane material, the adsorption rate etc. of heavy metal ion.

Description

A method of preparing hydrophilic nano hybrid reinforcement type hollow-fibre membrane
Technical field
The invention belongs to polymeric hollow fiber microporous modifications and preparation and the field of chemical synthesis, are related to one kind and pass through a little Nano-functional material is supported on the preparation method and application on enhancement type hollow fiber film by the method for hitting chemistry.
Background technology
Continuous with industrialization degree is promoted and the worsening of all kinds of accurate water qualities, a huge sum of money in the daily drinking water of the mankind Belong to the exceeded phenomenon getting worse of ion, heavy metal ion has a serious harm to human body, wherein the heavy metals such as lead, arsenic, cadmium and mercury from Son can lead to a series of generation of cancers such as leukaemia, septicemia.Therefore a kind of chemical stability is good, high mechanical strength, anti-pollution The membrane material of the strong oriented attachment heavy metal ion of energy again of dye ability becomes the ideal target of water treatment field.This membrane material Be not limited only to common filtering core of domestic water filter, used in the initial stage processing MBR system for also including industrial wastewater it is enhanced in Empty fiber membrane.
The available membrane material of enhancement type hollow fiber film surface separation layer includes polyacrylonitrile (PAN), polyether sulfone (PES) Or Kynoar (PVDF) etc..PVDF is a kind of those semi-crystalline materials, and -39 DEG C of glass transition temperature, crystalline melt point is about 170 DEG C, Heat decomposition temperature has many advantages, such as excellent chemical stability, thermal stability and easily forms a film, be widely used at 316 DEG C or more Prepare membrane material.Patent US7,306,105, it is enhanced disclosed in CN1864828A, CN1281299C, CN101254420A etc. in Empty fiber membrane element is using PVDF as surface separation material.But since its surface energy is low, hydrophobicity is strong, and the film prepared is hydrophilic Property it is poor, in the aqueous phase separations system application process such as bio-pharmaceuticals, food and drink and Water warfare, film be easy absorption organic solute and It is contaminated, so it is very necessary to improve film properties that pvdf membrane is carried out hydrophilic modification.
Mainly there are blending and modifying, surface coating modified and chemical modification etc., surface coating to the hydrophilic modification method of PVDF Modification occurs mainly in film surface, and durability cannot ensure, chemical modifying process complexity, performance difficulty are not easy industrialization and put Big production.And blending and modifying is relatively easy, and the basic performance improvement of material can be played.Inorganic on a small quantity receive is added in the base Rice material becomes the main method being blended, it had not only maintained the flexibility and low cost of organic matter, but also the chemistry with inorganic matter Stability and high mechanical properties, while also will produce very high interface interaction between the two, to make polymer performance be carried Height shows mechanics, calorifics and wellability etc. different from general composite material.Nano silicon dioxide is that current research is the widest One of general inorganic nano material, it have high activity and selectivity, have stable chemical property, hydrophily and corrosion resistance, The advantages that nontoxic, inexpensive.
But inorganic nano material it is organic at film liquid in be difficult to be uniformly dispersed the problem of be current organic-inorganic blend film system A standby big resistance, research, which is concentrated mainly on, at present is modified inorganic nano material using modifying agent such as silane coupling agents, Make it while there is the performance with organic-inorganic double combination.Yang Zhenglong of Tongji University et al. (" mercaptan-alkenes/alkynes click chemistry system Standby organic/inorganic hybridization material " Progress in Chemistry, 2014,26 (6), 996-1004) using click chemistry Method is prepared for organic-inorganic hybrid material；Click chemistry is also known as click chemistry, since Hawker, Sharpless and Fokin etc. Will click on for the first time in 2004 chemistry be successfully introduced into the synthesis of dendritic macromole since, this method has been developed as synthesizing The topological structures such as linear, scopiform, star, ring-type and dendritic macromole polymer (topological polymers) and special A kind of important means of functional material, click chemistry have following notable feature:(1) reaction process is simple, efficiently and has It is selective；(2) reaction condition is mild, need not generally carry out radical protection；(3) starting material is easier to obtain；(4) anti- It should post-process and product separation simplicity, by-product are environmentally friendly；(5) reaction meets Atom economy requirement, and yield almost may be used Up to 100%；(6) reaction can carry out in water phase, be suitable for biosystem and be modified.Its is important to be divided into following four mode：End The cycloaddition reaction of alkynyl and nitrine；The cycloaddition reaction of cycloalkynyl radical and nitrine；The condensation reaction of non-alcohol aldehyde carbonyl groups compound；Mercapto The addition reaction of base and carbon carbon multikey.
Comprehensive literature and related patents, the present invention utilize the addition of sulfydryl and carbon carbon multikey from click chemistry angle The nano silicon dioxide of sulfhydrylation is supported on hydrophily organic monomer chain by reaction method by way of click chemistry, and will It is blended in polyvinylidene fluoride film, improves the hydrophily of film wire and the oriented attachment to mercury ion.
Invention content
The purpose of the present invention is to provide a kind of hydrophilic nano hybrid reinforcement type doughnut is prepared using click chemistry The method of film.
The present invention is achieved through the following technical solutions.
One aspect of the present invention is related to a kind of preparation method of hydrophilic nano hybrid reinforcement type hollow-fibre membrane, this method packet Include following steps：
(1) preparation of the poly hydroxy ethyl acrylate (PHEMA) of alkynyl
Solvent 1 is added in the reactor, and reaction is added in poly hydroxy ethyl acrylate, catalyst, 4- pentinoic acids later In device, it is put into 0 DEG C of ice bath and reacts, and be passed through nitrogen protection；After reaction carries out 20-50min, dehydrating agent is dissolved in molten It in agent 1, and is added in reactor in 50-80min, stirs 10-16h at room temperature；Wherein, poly hydroxy ethyl acrylate, de- Aqua, catalyst, 4- pentinoic acid dosages weight ratio be 3-8: 5-10: 3-7: 4-10；Total use of the solvent 1 in terms of parts by volume The ratio of amount and poly hydroxy ethyl acrylate in parts by weight is 10-20: 1；
Later, it by reaction solution pure water 3-6 times, filters, obtains the poly hydroxy ethyl acrylate of alkynyl, it is standby With；
In the present invention, unless otherwise specified, parts by weight are calculated with gram (g), and parts by volume is calculated with milliliter (ml) , w/v is calculated with g/ml.
The specific reaction route of the step is as follows：
(2) Nano-meter SiO_2 of sulfhydrylation2Preparation
Nano particle has big specific surface area, and resulting in nano-particle has high surface-active, is dispersed in neutral water Nanometer silicon dioxide particle in solution forms the surface rich in hydroxyl functional group.Nanometer silicon dioxide particle surface is a large amount of Hydroxyl, condensation reaction occurs for the hydroxyl that is formed after being hydrolyzed with silylating reagent, achievees the purpose that surface sulfhydrylation modification.
The present invention is used as silylating reagent using 3- mercaptopropyl trimethoxysilanes (TMMPS).In addition, to improve sulfhydrylation Ammonium hydroxide is added as catalyst in efficiency, the present invention.As catalyst, mass percentage concentration is that this hair can be achieved in 25%-28% Bright, the ammonium hydroxide of the concentration is commercially available, and the ammonium hydroxide for being slightly above and below the range nor affects on the implementation of technical solution.
Weigh the Nano-meter SiO_2 of 0.1-1 parts by weight2It is scattered in the reactor of the pure water of parts by volume containing 5-15,11- is then added The ethyl alcohol of 25 parts by volume after ultrasonic disperse 15-30min, is passed through nitrogen to remove the air in reactor；Measure 0.1-1 volumes The ethyl alcohol of the 3- mercaptopropyl trimethoxysilanes and 10-30 parts by volume of part is added in reactor after mixing, and while stirring The ammonium hydroxide of 2-8 parts by volume is added, 5-12h is stirred to react at 50-90 DEG C；
Liquid in reactor is poured out, centrifugation after being cleaned 3-8 times with ethyl alcohol takes out supernatant, by sediment in baking oven Middle drying, oven temperature are set as 40-70 DEG C, obtain the Nano-meter SiO_2 of sulfhydrylation2, spare；
The specific reaction route of the step is as follows：
(3) preparation of hydrophilic nano hybrid reinforcement type hollow-fibre membrane
According to polyvinylidene fluoride resin: solvent 2: polyethylene glycol additive: polyvinylpyrrolidone additive is by weight 12-25: 50-80: 5-15: 7-18 mixed ingredients, are stirred evenly using machine mixer, add the alkynyl of step (1) preparation The Nano-meter SiO_2 of sulfhydrylation prepared by the poly hydroxy ethyl acrylate and step (2) of change2, the wherein polymethyl of alkynyl The Nano-meter SiO_2 of sour hydroxyl ethyl ester, sulfhydrylation2Weight ratio with polyvinylidene fluoride resin is 1-6: 0.2-2.5: 2-15；
Then deaeration is carried out by the way of negative pressure, manufactured casting solution is positioned in batch can after deaeration, in 50-80 DEG C of guarantor Temperature；Use the solvent 2 that weight ratio is 5-15: 70-95: water mixed solvent is recycled as coagulating bath, then by the following method Prepare hydrophilic nano hybrid reinforcement type hollow-fibre membrane：
1) the doughnut internal lining pipe pulled in fiber roller is passed sequentially through into coating device and gel slot, is then wound in receipts On silk wheel；
2) wire-feed motor and receive silk machine are opened, adjusting the two rotating speed makes equipment run, and the speed of the two is 6-25 ms/min, Feed liquid is added in reaction kettle, is then pressurizeed into reaction kettle, so that feed liquid is passed through expects pipe and is conveyed to coating device；
3) fiber internal lining pipe is under the traction of receive silk machine, enters coagulation bath after coating device coats feeding, in fiber Immersion inversion of phases occurs for the feed liquid on bushing pipe outer surface and gel is shaped, and loses flowability, and forms film wire, is received by wire drawing wheel Collection；
4) film wire is irradiated in the case where wavelength is the ultraviolet light of 200-400nm, so that sulfhydryl cleavage is generated Thiyl Radical, causes and add At reaction.Sulfydryl is excited under ultraviolet lighting, and cracking generates Thiyl Radical；Thiyl Radical attack carbon carbon multikey, activated centre It shifts and generates alkyl diradical；Alkyl diradical captures the hydrogen atom of sulfydryl on sulfhydryl compound, generates Thiyl Radical again, Continue to react, these free radicals can both cause chain growth, and biradical termination can also occur.Reaction is as follows：
5) film wire after causing completely is put into sink and impregnates 10-30h, thoroughly displace solvent and additive；
6) by film wire be dried processing to get to the present invention hydrophilic nano hybrid reinforcement type hollow-fibre membrane.
In a kind of preferred embodiment of the present invention, wherein in above-mentioned steps (1),
Solvent 1 is added in the reactor, later adds poly hydroxy ethyl acrylate (PHEMA), catalyst, 4- pentinoic acids Enter in reactor, is put into 0 DEG C of ice bath and reacts, and be passed through nitrogen protection；It, will after reaction carries out 25-40, preferably 30min Dehydrating agent is dissolved in solvent 1, and is added in reactor in 55-70, preferably 60min, stirs 12-16h, preferably at room temperature 15h；Wherein, poly hydroxy ethyl acrylate (PHEMA), dehydrating agent, catalyst, 4- pentinoic acid dosages weight ratio be 4-6: 6- 9: 4-6: 5-8, preferably 5: 7: 5: 6；The envelope-bulk to weight ratio of the solvent 1 and poly hydroxy ethyl acrylate is 11-15: 1, preferably 12∶1；
Later, it by reaction solution pure water 4-5 times, filters, obtains the poly hydroxy ethyl acrylate of alkynyl (PHEMA), spare.
Wherein,
The dehydrating agent is selected from dicyclohexylcarbodiimide (DCC), dichloroethanes (EDC)；It is preferred that dicyclohexyl carbon two is sub- Amine (DCC)；
The catalyst is selected from 4-dimethylaminopyridine (DMAP), n-Hydroxyphthalimide (NOP)；It is preferred that 4- bis- Methylamino pyridine (DMAP)；
The solvent 1 is selected from N,N-dimethylformamide (DMF), DMAC N,N' dimethyl acetamide (DMAC), dimethyl sulfoxide (DMSO) (DMSO)；It is preferred that N,N-dimethylformamide (DMF)；
The weight average molecular weight of the poly hydroxy ethyl acrylate (PHEMA) is 10,000-9 ten thousand, preferably 1.5-5 ten thousand, more preferably 20000；
In the above-mentioned steps of the present invention, wherein the poly hydroxy ethyl acrylate (PHEMA) of the molecular weight ranges is more Be conducive to the generation of reaction；And poly hydroxy ethyl acrylate (PHEMA), dehydrating agent, catalyst, 4- pentinoic acids are in the ratio Under example, reaction is well on, and can improve the utilization rate of raw material to greatest extent, reduce cost, while reducing side reaction.
In another preferred embodiment of the present invention, wherein in above-mentioned steps (2),
Weigh 0.3-0.7, preferably 0.5 parts by weight Nano-meter SiO_22It is scattered in containing 8-12, preferably 10 parts by volume pure water is anti- Answer in device, be then added 15-22, preferably 20 parts by volume ethyl alcohol, after ultrasonic disperse 18-25, preferably 20min, be passed through nitrogen with Remove the air in reactor；Measure 0.3-0.8, preferably 0.5 parts by volume 3- mercaptopropyl trimethoxysilanes (TMMPS) with The ethyl alcohol of 15-25, preferably 15 parts by volume is added in reactor after mixing, and 3-6, preferably 5 parts by volume are added while stirring Ammonium hydroxide as catalyst, be stirred to react 6-10h, preferably 8h in 65-85, at preferably 80 DEG C；
Liquid in reactor is poured out, is centrifuged after cleaning 4-6, preferably 4 times with ethyl alcohol, supernatant is taken out, by sediment It dries in an oven, oven temperature is set as 45-60 DEG C, preferably 50 DEG C, obtains the Nano-meter SiO_2 of sulfhydrylation2, spare.
In this step, it needs to control Nano-meter SiO_22, 3- mercaptopropyl trimethoxysilanes (TMMPS) and ammonium hydroxide addition Amount, it is ensured that reaction is smoothed out, and improves the utilization rate of raw material to greatest extent.
In another preferred embodiment of the present invention, wherein in above-mentioned steps (3),
According to polyvinylidene fluoride resin (PVDF): solvent 2: polyethylene glycol additive: polyvinylpyrrolidone additive is pressed Weight ratio 15-20: 55-70: 8-12: 10-15, preferably 18: 60: 10: 12 mixed ingredients, are stirred evenly using machine mixer, The sulfhydrylation of the poly hydroxy ethyl acrylate (PHEMA) and step (2) preparation that add the alkynyl of step (1) preparation is received Rice SiO2, the wherein Nano-meter SiO_2 of the poly hydroxy ethyl acrylate (PHEMA) of alkynyl, sulfhydrylation2With polyvinylidene fluoride resin (PVDF) weight ratio is 2-5: 0.7-1.5: 5-12, preferably 3: 1: 9；
Then deaeration is carried out by the way of negative pressure, manufactured casting solution is positioned in batch can after deaeration, in 65-75, excellent Select 70 DEG C of heat preservations；It is 6-12: 80-92, preferably 10: 90 solvent 2 to use weight ratio: water mixed solvent is followed as coagulating bath Then ring prepares hydrophilic nano hybrid reinforcement type hollow-fibre membrane by the following method：
1) the doughnut internal lining pipe pulled in fiber roller is passed sequentially through into coating device and gel slot, is then wound in receipts On silk wheel；
2) wire-feed motor and receive silk machine are opened, both adjusting rotating speed makes equipment run, and the speed of the two is 10-20, preferably 15 ms/min, feed liquid is added in reaction kettle, is then pressurizeed into reaction kettle, so that feed liquid is passed through expects pipe and conveyed to coating device；
3) fiber internal lining pipe is under the traction of receive silk machine, enters coagulation bath after coating device coats feeding, in fiber Immersion inversion of phases occurs for the feed liquid on bushing pipe outer surface and gel is shaped, and loses flowability, and forms film wire, is received by wire drawing wheel Collection；
4) film wire is irradiated in the case where wavelength is the ultraviolet light of 280-380nm, preferably 365nm, sulfhydryl cleavage is made to generate sulphur certainly By base, cause addition reaction；
5) film wire after causing completely is put into sink and impregnates 15-28h, preferably for 24 hours, thoroughly displaced solvent 2 and add Add agent；
6) processing is dried in film wire, dry temperature is 18-30 DEG C, and drying time is 8-15h (more preferably dry Temperature be 22-28 DEG C, drying time 10-15h) to get to the present invention hydrophilic nano hybrid reinforcement type doughnut Film.
Wherein,
The solvent 2 is selected from dimethylacetylamide (DMAC), dimethyl sulfoxide (DMSO) (DMSO), N-Methyl pyrrolidone (NMP)； It is preferred that dimethylacetylamide (DMAC)；
The weight average molecular weight of the polyvinylidene fluoride resin (PVDF) is 420,000-90 ten thousand, preferably 50-80 ten thousand, more preferable 60 Ten thousand；
The preparation facilities of enhancement type hollow fiber film used in the step is known in the art, such as can pass through city Acquisition is sold, can also be obtained by making by oneself, the present invention has no special requirements to the preparation facilities.
In this step, it is the modified effect for ensuring excellent, poly hydroxy ethyl acrylate (PHEMA), the mercapto of alkynyl The Nano-meter SiO_2 of base2Stringent control is needed with polyvinylidene fluoride resin (PVDF) adding proportion, the present inventor by trying repeatedly It tests, it was demonstrated that within the scope of the adding proportion defined by the present invention, it can realize best modified effect, it is hydrophilic such as membrane material Property, adsorption rate of heavy metal ion etc..
Another aspect of the present invention is related to the hydrophilic nano hybrid reinforcement type doughnut being prepared by the above method Film.
There is excellent modification by the hydrophilic nano hybrid reinforcement type hollow-fibre membrane that the method for the present invention is prepared Performance, such as the hydrophily of membrane material, adsorption rate of heavy metal ion etc..It specifically, can be by the contact of hollow-fibre membrane Angle is down to 50 degree hereinafter, and can be more than 28mg/g, adsorption rate to the saturated extent of adsorption of heavy metal ion in water such as lead and mercury More than 80%.
Various reagents, test apparatus and preparation facilities and/or equipment used in the implementation present invention are the prior arts Known, those skilled in the art can be readily by commercially available acquisition, or laboratory provides where inventor.Such as this The used various chemical raw materials of invention and reagent can be purchased from Chinese reagent net, or the laboratory where inventor carries For.Laboratory apparatus such as reactor (such as three-necked flask), centrifugation apparatus, drying equipment, press device etc. can be purchased from Ah Li Baba, or laboratory provides where inventor.Enhancement type hollow fiber film preparation facilities and/or equipment can pass through city Acquisition is sold, or laboratory provides where inventor.
[advantageous effect]
Beneficial effects of the present invention are embodied in：
(1) present invention is using sulfydryl and carbon carbon multikey addition reaction, feature be it is easy to operate, be not easy by oxygen and water The features such as influencing, and avoiding toxic metallic catalyst.
(2) the hydrophilic nano hybrid reinforcement type hollow-fibre membrane that the method for the present invention is prepared has excellent hydrophilic Property, the contact angle of hollow-fibre membrane can be down to 50 degree or less.
(3) the hydrophilic nano hybrid reinforcement type hollow-fibre membrane that the method for the present invention is prepared has excellent adsorptivity Can, 28mg/g is more than to the saturated extent of adsorption of heavy metal ion such as lead and mercury, adsorption rate is more than 80%, can be effectively used for water The fields such as matter purification.
【Description of the drawings】
Fig. 1 is the hydrophilic nano hybrid reinforcement type hollow-fibre membrane outer surface structure that the embodiment of the present invention 1 is prepared Scanning electron microscopic picture.
Fig. 2 is the hydrophilic nano hybrid reinforcement type hollow-fibre membrane section structure that the embodiment of the present invention 1 is prepared Scanning electron microscopic picture.
Fig. 3 is the scanning electricity for the hydrophilic nano hybrid reinforcement type hollow-fibre membrane section structure that reference examples 1 are prepared Mirror picture.
【Specific implementation mode】
The present invention is will be better understood that by following embodiments, but the present invention is not limited by following embodiments.
Used test equipment is provided by laboratory in following embodiments, and operating method is those skilled in the art Known.
Embodiment 1
(1) preparation of the poly hydroxy ethyl acrylate (PHEMA) of alkynyl
50ml solvents n,N-Dimethylformamide (DMF) is added in three-necked flask, later by 5g polymethylacrylic acid hydroxyls Ethyl ester (PHEMA, weight average molecular weight be 2 ten thousand), the 4- pentinoic acids of 5g catalyst 4-dimethylaminopyridine (DMAP) and 6g are added In three-necked flask, it is put into 0 DEG C of ice bath and reacts, and be passed through nitrogen protection；After reaction carries out 30min, by 7g dehydrating agents two Carbodicyclo hexylimide (DCC) is dissolved in 10ml solvents n,N-Dimethylformamide (DMF), and three mouthfuls are added in 60min In flask, 15h is stirred at room temperature.
Later, rear to filter by reaction solution pure water 4 times, obtain the poly hydroxy ethyl acrylate of alkynyl (PHEMA), spare.
(2) Nano-meter SiO_2 of sulfhydrylation2Preparation
Weigh the Nano-meter SiO_2 of 0.5g2It is scattered in the three-necked flask of the pure water containing 10ml, the ethyl alcohol of 20ml is then added, surpass After sound disperses 20min, nitrogen is passed through to remove the air in reactor；Measure the 3- mercaptopropyl trimethoxysilanes of 0.5ml (TMMPS) it with the ethyl alcohol of 15ml, is added in three-necked flask after mixing, and the mass concentration that 5ml is added while stirring is 25% ammonium hydroxide is stirred to react 8h as catalyst at 80 DEG C.
Liquid in reactor is poured out, is centrifuged after cleaning 4 times with ethyl alcohol, takes out supernatant, in an oven by sediment Drying, oven temperature are set as 50 DEG C, you can obtain the Nano-meter SiO_2 of sulfhydrylation2, spare.
(3) preparation of hydrophilic nano hybrid reinforcement type hollow-fibre membrane
Weigh 18g polyvinylidene fluoride resins (PVDF, weight average molecular weight be 60 ten thousand), 60g solvent dimethylacetylamides (DMAC), 10g polyethylene glycol additive and 12g polyvinylpyrrolidone additives are added mixed ingredients in three-necked flask, make Stirred evenly with machine mixer, add 6g steps (1) preparation alkynyl poly hydroxy ethyl acrylate (PHEMA) and The Nano-meter SiO_2 of sulfhydrylation prepared by 2g steps (2)2；Then deaeration is carried out by the way of negative pressure, manufactured casting solution after deaeration It is positioned in batch can, in 70 DEG C of heat preservations；It is 10: 90 dimethylacetylamide (DMAC) to use weight ratio: water is mixed as coagulating bath It is recycled, then prepares hydrophilic nano hybrid reinforcement type hollow-fibre membrane by the following method：
1) the doughnut internal lining pipe pulled in fiber roller is passed sequentially through into coating device and gel slot, is then wound in receipts On silk wheel；
2) wire-feed motor and receive silk machine are opened, adjusting the two rotating speed makes equipment run, and the speed of the two is 15 ms/min, will Feed liquid is added in reaction kettle, then pressurizes into reaction kettle, so that feed liquid is passed through expects pipe and is conveyed to coating device；
3) fiber internal lining pipe is under the traction of receive silk machine, enters coagulation bath after coating device coats feeding, in fiber Immersion inversion of phases occurs for the feed liquid on bushing pipe outer surface and gel is shaped, and loses flowability, and forms film wire, is received by wire drawing wheel Collection；
4) film wire is irradiated in the case where wavelength is the ultraviolet light of 365nm, so that sulfhydryl cleavage is generated Thiyl Radical, it is anti-causes addition It answers；
5) film wire after initiation 18h is put into sink and is impregnated for 24 hours, thoroughly displace solvent and additive；
6) film wire is dried processing, drying temperature is 25 DEG C, and drying time is 15h to get to the hydrophilic of the present invention Property nano hybridization enhancement type hollow fiber film.
Following performance measurement is carried out to the film being prepared：
1. using the obtained nano hybridization of solution-air and the double method of testing pore-size distribution analysis-e/or determinings of liquid-liquid enhanced The average pore size of hollow-fibre membrane is 0.08 micron, and internal diameter is 1.0 millimeters, and outer diameter is 2.0 millimeters.
2. the nano hybridization enhancement type hollow fiber film measured at 0.1MPa and 25 DEG C using flux detector Pure water flux is 2650L/m2.h。
3. the contact angle of the nano hybridization enhancement type hollow fiber film is measured using dynamic contact angle analyzer, wherein selecting It takes 5 different locations of same root nano hybridization enhancement type hollow fiber film to measure contact angle, is averaged, time of contact setting For 20s.After measured, contact angle is 45 degree.
4. to the nano hybridization enhancement type hollow fiber film heavy metal ion adsorbed measurement is carried out to test, the results show that It is 31mg/g, adsorption rate 92% to the saturated extent of adsorption of lead ion；Saturated extent of adsorption to mercury ion is 32mg/g, absorption Rate is 92%.
5. being observed by scanning electron microscope, surface texture and section structure are as illustrated in fig. 1 and 2, it can be seen that film table Micro-nano bulge-structure is presented in face, and hydrophilic nano material enrichment is more advantageous to the hydrophily and antipollution for improving film in film surface Property.There is the supporting layer of sponge and uniform finger-like pore structure in film wire section structure, this structure is conducive to improve film wire flux, subtract Blocking of the small pollutant to fenestra.
Embodiment 2
(1) preparation of the poly hydroxy ethyl acrylate (PHEMA) of alkynyl
70ml solvents n,N-dimethylacetamide (DMAC) is added in three-necked flask, later by 6g polymethylacrylic acid hydroxyls Ethyl ester (PHEMA, weight average molecular weight be 4 ten thousand), the 4- pentynes of 4g catalyst ns-hydroxyl phthalic amide imines (NOP) and 7g Acid is added in three-necked flask, is put into 0 DEG C of ice bath and reacts, and is passed through nitrogen protection；After reaction carries out 30min, 8g is taken off Aqua dicyclohexylcarbodiimide (DCC) is dissolved in 20ml solvents n,N-dimethylacetamide (DMAC), and is added in 70min Enter in three-necked flask, stirs 12h at room temperature.
Later, rear to filter by reaction solution pure water 5 times, obtain the poly hydroxy ethyl acrylate of alkynyl (PHEMA), spare.
(2) Nano-meter SiO_2 of sulfhydrylation2Preparation
Weigh the Nano-meter SiO_2 of 0.7g2It is scattered in the three-necked flask of the pure water containing 12ml, the ethyl alcohol of 16ml is then added, surpass After sound disperses 25min, nitrogen is passed through to remove the air in reactor；Measure the 3- mercaptopropyl trimethoxysilanes of 0.8ml (TMMPS) it with the ethyl alcohol of 25ml, is added in three-necked flask after mixing, and a concentration of 25% ammonia of 6ml is added while stirring Water is stirred to react 10h as catalyst at 85 DEG C.
Liquid in reactor is poured out, is centrifuged after cleaning 5 times with ethyl alcohol, takes out supernatant, in an oven by sediment Drying, oven temperature are set as 55 DEG C, you can obtain the Nano-meter SiO_2 of sulfhydrylation2, spare.
(3) preparation of hydrophilic nano hybrid reinforcement type hollow-fibre membrane
Weigh 20g polyvinylidene fluoride resins (PVDF, weight average molecular weight be 80 ten thousand), 70g solvent N-methyl pyrilidones (NMP), 12g polyethylene glycol additive and 15g polyvinylpyrrolidone additives are added mixed ingredients in three-necked flask, make Stirred evenly with machine mixer, add 8g steps (1) preparation alkynyl poly hydroxy ethyl acrylate (PHEMA) and The Nano-meter SiO_2 of sulfhydrylation prepared by 2.5g steps (2)2；Then deaeration is carried out by the way of negative pressure, manufactured casting film after deaeration Liquid is positioned in batch can, in 65 DEG C of heat preservations；It is 6: 80 N-Methyl pyrrolidone (NMP) to use weight ratio: water is mixed as solidification Bath is recycled, and then prepares hydrophilic nano hybrid reinforcement type hollow-fibre membrane by the following method：
1) the doughnut internal lining pipe pulled in fiber roller is passed sequentially through into coating device and gel slot, is then wound in receipts On silk wheel；
2) wire-feed motor and receive silk machine are opened, adjusting the two rotating speed makes equipment run, and the speed of the two is 20 ms/min, will Feed liquid is added in reaction kettle, then pressurizes into reaction kettle, so that feed liquid is passed through expects pipe and is conveyed to coating device；
3) fiber internal lining pipe is under the traction of receive silk machine, enters coagulation bath after coating device coats feeding, in fiber Immersion inversion of phases occurs for the feed liquid on bushing pipe outer surface and gel is shaped, and loses flowability, and forms film wire, is received by wire drawing wheel Collection；
4) film wire is irradiated in the case where wavelength is the ultraviolet light of 365nm, so that sulfhydryl cleavage is generated Thiyl Radical, it is anti-causes addition It answers；
5) film wire after initiation 20h is put into sink and impregnates 30h, thoroughly displace solvent and additive；
6) film wire is dried processing, drying temperature is 22 DEG C, and drying time is 13h to get to the hydrophilic of the present invention Property nano hybridization enhancement type hollow fiber film.
Following performance measurement is carried out to the film being prepared：
1. with the obtained nano hybridization of the double method of testing pore-size distribution analysis-e/or determinings of solution-air and liquid-liquid it is enhanced in The average pore size of empty fiber membrane is 0.1 micron, and internal diameter is 1.0 millimeters, and outer diameter is 2.0 millimeters.
2. the nano hybridization enhancement type hollow fiber film measured at 0.1MPa and 25 DEG C with flux detector is pure Water flux is 2080L/m2.h。
3. the contact angle of the nano hybridization enhancement type hollow fiber film is measured with dynamic contact angle analyzer, wherein choosing 5 different locations of same root nano hybridization enhancement type hollow fiber film measure contact angle, are averaged, time of contact is set as 20s.After measured, contact angle is 46 degree.
4. to the nano hybridization enhancement type hollow fiber film heavy metal ion adsorbed measurement is carried out to test, the results show that It is 30mg/g, adsorption rate 90% to the saturated extent of adsorption of lead ion；Saturated extent of adsorption to mercury ion is 31mg/g, absorption Rate is 91%.
Embodiment 3
(1) preparation of the poly hydroxy ethyl acrylate (PHEMA) of alkynyl
60ml solvents n,N-Dimethylformamide (DMF) is added in three-necked flask, later by 4g polymethylacrylic acid hydroxyls Ethyl ester (PHEMA, weight average molecular weight be 3 ten thousand), the 4- pentinoic acids of 6g catalyst ns-hydroxyphthalimide (NOP) and 8g It is added in three-necked flask, is put into 0 DEG C of ice bath and reacts, and be passed through nitrogen protection；After reaction carries out 30min, 6g is dehydrated Agent dichloroethanes (EDC) is dissolved in 20ml solvents n,N-Dimethylformamide (DMF), and three-necked flask is added in 55min In, 75h is stirred at room temperature.
Later, rear to filter by reaction solution pure water 3 times, obtain the poly hydroxy ethyl acrylate of alkynyl (PHEMA), spare.
(2) Nano-meter SiO_2 of sulfhydrylation2Preparation
Weigh the Nano-meter SiO_2 of 0.3g2It is scattered in the three-necked flask of the pure water containing 8ml, the ethyl alcohol of 15ml, ultrasound is then added After disperseing 18min, nitrogen is passed through to remove the air in reactor；Measure the 3- mercaptopropyl trimethoxysilanes of 0.3ml (TMMPS) it with the ethyl alcohol of 12ml, is added in three-necked flask after mixing, and 28% ammonium hydroxide that 3ml is added while stirring is made For catalyst, 6h is stirred to react at 65 DEG C.
Liquid in reactor is poured out, is centrifuged after cleaning 6 times with ethyl alcohol, takes out supernatant, in an oven by sediment Drying, oven temperature are set as 45 DEG C, you can obtain the Nano-meter SiO_2 of sulfhydrylation2, spare.
(3) preparation of hydrophilic nano hybrid reinforcement type hollow-fibre membrane
Weigh 15g polyvinylidene fluoride resins (PVDF, weight average molecular weight be 70 ten thousand), 55g solvent dimethylacetylamides (DMAC), 8g polyethylene glycol additive and 10g polyvinylpyrrolidone additives are added mixed ingredients in three-necked flask, make Stirred evenly with machine mixer, add 6g steps (1) preparation alkynyl poly hydroxy ethyl acrylate (PHEMA) and The Nano-meter SiO_2 of sulfhydrylation prepared by 2.1g steps (2)2；Then deaeration is carried out by the way of negative pressure, manufactured casting film after deaeration Liquid is positioned in batch can, in 60 DEG C of heat preservations；The solvent dimethylacetylamide (DMAC) for being 10: 80 with weight ratio: water mixed solvent It is recycled as coagulating bath, then prepares hydrophilic nano hybrid reinforcement type hollow-fibre membrane by the following method：
1) the doughnut internal lining pipe pulled in fiber roller is passed sequentially through into coating device and gel slot, is then wound in receipts On silk wheel；
2) wire-feed motor and receive silk machine are opened, adjusting the two rotating speed makes equipment run, and the speed of the two is 15 ms/min, will Feed liquid is added in reaction kettle, then pressurizes into reaction kettle, so that feed liquid is passed through expects pipe and is conveyed to coating device；
3) fiber internal lining pipe is under the traction of receive silk machine, enters coagulation bath after coating device coats feeding, in fiber Immersion inversion of phases occurs for the feed liquid on bushing pipe outer surface and gel is shaped, and loses flowability, and forms film wire, is received by wire drawing wheel Collection；
4) film wire is irradiated in the case where wavelength is the ultraviolet light of 365nm, so that sulfhydryl cleavage is generated Thiyl Radical, it is anti-causes addition It answers；
5) film wire after initiation 16h is put into sink and impregnates 20h, thoroughly displace solvent and additive；
6) film wire is dried processing, drying temperature is 28 DEG C, and drying time is 12h to get to the hydrophilic of the present invention Property nano hybridization enhancement type hollow fiber film.
Following performance measurement is carried out to the film being prepared：
1. using the obtained nano hybridization of solution-air and the double method of testing pore-size distribution analysis-e/or determinings of liquid-liquid enhanced The average pore size of hollow-fibre membrane is 0.15 micron, and internal diameter is 1.0 millimeters, and outer diameter is 2.0 millimeters.
2. the nano hybridization enhancement type hollow fiber film measured at 0.1MPa and 25 DEG C using flux detector Pure water flux is 2200L/m2.h。
3. the contact angle of the nano hybridization enhancement type hollow fiber film is measured using dynamic contact angle analyzer, wherein selecting It takes 5 different locations of same root nano hybridization enhancement type hollow fiber film to measure contact angle, is averaged, time of contact setting For 20s.After measured, contact angle is 47 degree.
4. to the nano hybridization enhancement type hollow fiber film heavy metal ion adsorbed measurement is carried out to test, the results show that It is 29mg/g, adsorption rate 86% to the saturated extent of adsorption of lead ion；Saturated extent of adsorption to mercury ion is 30mg/g, absorption Rate is 90%.
Embodiment 4
(1) preparation of the poly hydroxy ethyl acrylate (PHEMA) of alkynyl
40ml solvents n,N-dimethylacetamide (DMAC) is added in three-necked flask, later by 7g polymethylacrylic acid hydroxyls Ethyl ester (PHEMA, weight average molecular weight be 5 ten thousand), the 4- pentinoic acids of 3g catalyst 4-dimethylaminopyridine (DMAP) and 9g are added In three-necked flask, it is put into 0 DEG C of ice bath and reacts, and be passed through nitrogen protection；After reaction carries out 40min, by 5g dehydrating agents two Carbodicyclo hexylimide (DCC) is dissolved in 10ml solvents n,N-dimethylacetamide (DMAC), and three mouthfuls are added in 50min In flask, 14h is stirred at room temperature.
Later, rear to filter by reaction solution pure water 6 times, obtain the poly hydroxy ethyl acrylate of alkynyl (PHEMA), spare.
(2) Nano-meter SiO_2 of sulfhydrylation2Preparation
Weigh the Nano-meter SiO_2 of 0.9g2It is scattered in the three-necked flask of the pure water containing 14ml, the ethyl alcohol of 24ml is then added, surpass After sound disperses 16min, nitrogen is passed through to remove the air in reactor；Measure the 3- mercaptopropyl trimethoxysilanes of 0.9ml (TMMPS) it with the ethyl alcohol of 28ml, is added in three-necked flask after mixing, and the ammonium hydroxide of 7ml is added while stirring as catalysis Agent is stirred to react 10h at 75 DEG C.
Liquid in reactor is poured out, is centrifuged after cleaning 5 times with ethyl alcohol, takes out supernatant, in an oven by sediment Drying, oven temperature are set as 45 DEG C, you can obtain the Nano-meter SiO_2 of sulfhydrylation2, spare.
(3) preparation of hydrophilic nano hybrid reinforcement type hollow-fibre membrane
Weigh 12g polyvinylidene fluoride resins (PVDF, weight average molecular weight be 55 ten thousand), 75g solvent N-methyl pyrilidones (NMP), mixed ingredients in three-necked flask are added in 6g polyethylene glycol additive and 8g polyvinylpyrrolidone additives, use Machine mixer stirs evenly, add 4.8g steps (1) preparation alkynyl poly hydroxy ethyl acrylate (PHEMA) and The Nano-meter SiO_2 of sulfhydrylation prepared by 2.4g steps (2)2；Then deaeration is carried out by the way of negative pressure, manufactured casting film after deaeration Liquid is positioned in batch can, in 75 DEG C of heat preservations；The solvent N-methyl pyrilidone (NMP) for being 10: 85 with weight ratio: water mixed solvent It is recycled as coagulating bath, then prepares hydrophilic nano hybrid reinforcement type hollow-fibre membrane by the following method：
1) the doughnut internal lining pipe pulled in fiber roller is passed sequentially through into coating device and gel slot, is then wound in receipts On silk wheel；
2) wire-feed motor and receive silk machine are opened, adjusting the two rotating speed makes equipment run, and the speed of the two is 20 ms/min, will Feed liquid is added in reaction kettle, then pressurizes into reaction kettle, so that feed liquid is passed through expects pipe and is conveyed to coating device；
3) fiber internal lining pipe is under the traction of receive silk machine, enters coagulation bath after coating device coats feeding, in fiber Immersion inversion of phases occurs for the feed liquid on bushing pipe outer surface and gel is shaped, and loses flowability, and forms film wire, is received by wire drawing wheel Collection；
4) film wire is irradiated in the case where wavelength is the ultraviolet light of 365nm, so that sulfhydryl cleavage is generated Thiyl Radical, it is anti-causes addition It answers；
5) film wire after initiation 18h is put into sink and impregnates 25h, thoroughly displace solvent and additive；
6) film wire is dried processing, drying temperature is 20 DEG C, and drying time is 14h to get to the hydrophilic of the present invention Property nano hybridization enhancement type hollow fiber film.
Following performance measurement is carried out to the film being prepared：
1. with the obtained nano hybridization of the double method of testing pore-size distribution analysis-e/or determinings of solution-air and liquid-liquid it is enhanced in The average pore size of empty fiber membrane is 0.09 micron, and internal diameter is 1.0 millimeters, and outer diameter is 2.0 millimeters.
2. the nano hybridization enhancement type hollow fiber film measured at 0.1MPa and 25 DEG C with flux detector is pure Water flux is 2250L/m2.h。
3. the contact angle of the nano hybridization enhancement type hollow fiber film is measured with dynamic contact angle analyzer, wherein choosing 5 different locations of same root nano hybridization enhancement type hollow fiber film measure contact angle, are averaged, time of contact is set as 20s.After measured, contact angle is 48 degree.
4. to the nano hybridization enhancement type hollow fiber film heavy metal ion adsorbed measurement is carried out to test, the results show that It is 29mg/g, adsorption rate 90% to the saturated extent of adsorption of lead ion；Saturated extent of adsorption to mercury ion is 29mg/g, absorption Rate is 89%.
Comparative example 1
Relative to embodiment 1, do not add modified component (i.e. step 1 and 2 component), while do not use ultraviolet light, Rest part is identical.
Weigh 18g polyvinylidene fluoride resins (PVDF, weight average molecular weight be 60 ten thousand), 60g solvent dimethylacetylamides (DMAC), 10g polyethylene glycol additive and 12g polyvinylpyrrolidone additives are added mixed ingredients in three-necked flask, make It is stirred evenly with machine mixer；Then deaeration is carried out by the way of negative pressure, manufactured casting solution is positioned over batch can after deaeration In, in 70 DEG C of heat preservations；Use weight ratio be 10: 90 solvent dimethylacetylamide (DMAC): water mixed solvent as coagulating bath into Row cycle, then prepares hollow-fibre membrane by the following method：
1) the doughnut internal lining pipe pulled in fiber roller is passed sequentially through into coating device and gel slot, is then wound in receipts On silk wheel；
2) wire-feed motor and receive silk machine are opened, adjusting the two rotating speed makes equipment run, and the speed of the two is 15 ms/min, will Feed liquid is added in reaction kettle, then pressurizes into reaction kettle, so that feed liquid is passed through expects pipe and is conveyed to coating device；
3) fiber internal lining pipe is under the traction of receive silk machine, enters coagulation bath after coating device coats feeding, in fiber Immersion inversion of phases occurs for the feed liquid on bushing pipe outer surface and gel is shaped, and loses flowability, and forms film wire, is received by wire drawing wheel Collection；
4) film wire of collection is put into sink and is impregnated for 24 hours, thoroughly displace solvent and additive；
5) film wire is dried processing, drying temperature is 25 DEG C, and drying time is 15h to get to hollow-fibre membrane.
Following performance measurement is carried out to the film being prepared：
1. with being averaged for obtained hollow-fibre membrane of the double method of testing pore-size distribution analysis-e/or determinings of solution-air and liquid-liquid Aperture is 0.15 micron, and internal diameter is 1.0 millimeters, and outer diameter is 2.0 millimeters.
2. the pure water flux of the hollow-fibre membrane measured at 0.1MPa and 25 DEG C with flux detector is 980L/ m2.h。
3. the contact angle of the hollow-fibre membrane is measured with dynamic contact angle analyzer, wherein choosing same root doughnut 5 different locations of film measure contact angle, are averaged, time of contact is set as 20s.After measured, contact angle is 80 degree.
4. carrying out heavy metal ion adsorbed measurement to the hollow-fibre membrane to test, the results show that it satisfies to lead ion It is 5mg/g, adsorption rate 25% with adsorbance；Saturated extent of adsorption to mercury ion is 8mg/g, adsorption rate 30%.
5. being observed by scanning electron microscope, section structure is as shown in Figure 3, it can be seen that does not carry out the film of nano modification Fine and close sponge pore structure is presented in silk section, and pollutant is easily blocked in fenestra intracavitary to such structure in the process of running, it is difficult to clear Wash recovery.
Relative to embodiment 1, with the Nano-meter SiO_2 of equivalent2In alternate embodiment 1 modified component (i.e. step 1 and 2 group Point), rest part is identical.
Weigh 18g polyvinylidene fluoride resins (PVDF, weight average molecular weight be 60 ten thousand), 60g solvent dimethylacetylamides (DMAC), 10g polyethylene glycol additive and 12g polyvinylpyrrolidone additives are added mixed ingredients in three-necked flask, make It is stirred evenly with machine mixer, adds 8g Nano-meter SiO_2s2；Then deaeration is carried out by the way of negative pressure, it is manufactured after deaeration Casting solution is positioned in batch can, in 70 DEG C of heat preservations；The solvent dimethylacetylamide (DMAC) for being 10: 90 with weight ratio: water mixing Solvent is recycled as coagulating bath, then prepares hollow-fibre membrane by the following method：
1) the doughnut internal lining pipe pulled in fiber roller is passed sequentially through into coating device and gel slot, is then wound in receipts On silk wheel；
2) wire-feed motor and receive silk machine are opened, adjusting the two rotating speed makes equipment run, and the speed of the two is 15 ms/min, will Feed liquid is added in reaction kettle, then pressurizes into reaction kettle, so that feed liquid is passed through expects pipe and is conveyed to coating device；
3) fiber internal lining pipe is under the traction of receive silk machine, enters coagulation bath after coating device coats feeding, in fiber Immersion inversion of phases occurs for the feed liquid on bushing pipe outer surface and gel is shaped, and loses flowability, and forms film wire, is received by wire drawing wheel Collection；
4) film wire is irradiated in the case where wavelength is the ultraviolet light of 365nm；
5) after irradiating when 18h, film wire is put into sink and is impregnated for 24 hours, solvent and additive are thoroughly displaced；
6) film wire is dried processing, drying temperature is 25 DEG C, and drying time is 15h to get to hollow-fibre membrane.
Following performance measurement is carried out to the film being prepared：
1. with being averaged for obtained hollow-fibre membrane of the double method of testing pore-size distribution analysis-e/or determinings of solution-air and liquid-liquid Aperture is 0.2 micron, and internal diameter is 1.0 millimeters, and outer diameter is 2.0 millimeters.
2. the pure water flux of the hollow-fibre membrane measured at 0.1MPa and 25 DEG C with flux detector is 1500L/ m2.h。
3. the contact angle of the hollow-fibre membrane is measured with dynamic contact angle analyzer, wherein choosing same root doughnut 5 different locations of film measure contact angle, are averaged, time of contact is set as 20s.After measured, contact angle is 65 degree.
4. carrying out heavy metal ion adsorbed measurement to the hollow-fibre membrane to test, the results show that it satisfies to lead ion It is 10mg/g, adsorption rate 30% with adsorbance；Saturated extent of adsorption to mercury ion is 9mg/g, adsorption rate 44%.
From the data of 1-4 of the embodiment of the present invention and comparative example 1-2 can be seen that material modification through the invention after receive Rice hybrid reinforcement type hollow-fibre membrane performance in terms of hydrophily and to the adsorption capacity of heavy metal ion is substantially better than control Tunica fibrosa.

Claims (10)

1. a kind of preparation method of hydrophilic nano hybrid reinforcement type hollow-fibre membrane, described method includes following steps：
(1) preparation of the poly hydroxy ethyl acrylate of alkynyl
Solvent 1 is added in the reactor, and poly hydroxy ethyl acrylate, catalyst, 4- pentinoic acids are added in reactor later, It is put into 0 DEG C of ice bath and reacts, and be passed through nitrogen protection；After reaction carries out 20-50min, dehydrating agent is dissolved in solvent 1 In, and be added in reactor in 50-80min, 10-16h is stirred at room temperature；Wherein, poly hydroxy ethyl acrylate, dehydration Agent, catalyst, 4- pentinoic acid dosages weight ratio be 3-8: 5-10: 3-7: 4-10；Total dosage of the solvent 1 in terms of parts by volume And the ratio of poly hydroxy ethyl acrylate in parts by weight is 10-20: 1；
Later, it by reaction solution pure water 3-6 times, filters, obtains the poly hydroxy ethyl acrylate of alkynyl, it is spare；
(2) Nano-meter SiO_2 of sulfhydrylation2Preparation
Weigh the Nano-meter SiO_2 of 0.1-1 parts by weight2It is scattered in the reactor of the pure water of parts by volume containing 5-15,11-25 bodies is then added The ethyl alcohol of product part, after ultrasonic disperse 15-30min, is passed through nitrogen to remove the air in reactor；Measure 0.1-1 parts by volume The ethyl alcohol of 3- mercaptopropyl trimethoxysilanes and 10-30 parts by volume is added in reactor, and is added while stirring after mixing The ammonium hydroxide of 2-8 parts by volume is stirred to react 5-12h at 50-90 DEG C；
Liquid in reactor is poured out, centrifugation after being cleaned 3-8 times with ethyl alcohol takes out supernatant, sediment is dried in an oven Dry, oven temperature is set as 40-70 DEG C, obtains the Nano-meter SiO_2 of sulfhydrylation2, spare；
(3) preparation of hydrophilic nano hybrid reinforcement type hollow-fibre membrane
According to polyvinylidene fluoride resin: solvent 2: polyethylene glycol additive: polyvinylpyrrolidone additive is by weight 12-25 : 50-80: 5-15: 7-18 mixed ingredients stir evenly, and add the polymethylacrylic acid hydroxyl second of the alkynyl of step (1) preparation The Nano-meter SiO_2 of sulfhydrylation prepared by ester and step (2)2, the wherein nanometer of the poly hydroxy ethyl acrylate of alkynyl, sulfhydrylation SiO2Weight ratio with polyvinylidene fluoride resin is 1-6: 0.2-2.5: 2-15；
Then deaeration is carried out by the way of negative pressure, manufactured casting solution is positioned in batch can after deaeration, in 50-80 DEG C of heat preservation； Use the solvent 2 that weight ratio is 5-15: 70-95: water mixed solvent is recycled as coagulating bath, is then prepared by the following method Hydrophilic nano hybrid reinforcement type hollow-fibre membrane：
1) doughnut internal lining pipe is passed sequentially through into coating device and gel slot, be then wound on wire drawing wheel；
2) wire-feed motor and receive silk machine are opened, adjusting the two rotating speed makes equipment run, and the speed of the two is 6-25 ms/min, will be expected Liquid is added in reaction kettle, then pressurizes into reaction kettle, so that feed liquid is passed through expects pipe and is conveyed to coating device；
3) fiber internal lining pipe enters coagulation bath, fiber liner under the traction of receive silk machine after coating device coats casting solution Immersion inversion of phases occurs for the feed liquid on tube outer surface and gel is shaped, and loses flowability, and forms film wire, is received by wire drawing wheel Collection；
4) film wire is irradiated in the case where wavelength is the ultraviolet light of 200-400nm, so that sulfhydryl cleavage is generated Thiyl Radical, it is anti-causes addition It answers；
5) film wire after causing completely is put into sink and impregnates 10-30h, thoroughly displace solvent and additive；
6) processing is dried in film wire, obtains the hydrophilic nano hybrid reinforcement type hollow-fibre membrane.
2. the preparation method of hydrophilic nano hybrid reinforcement type hollow-fibre membrane according to claim 1, which is characterized in that In step (1),
Solvent 1 is added in the reactor, and poly hydroxy ethyl acrylate, catalyst, 4- pentinoic acids are added in reactor later, It is put into 0 DEG C of ice bath and reacts, and be passed through nitrogen protection；After reaction carries out 25-40min, dehydrating agent is dissolved in solvent 1 In, and be added in reactor in 55-70min, 12-16h is stirred at room temperature；Wherein, poly hydroxy ethyl acrylate, dehydration Agent, catalyst, 4- pentinoic acid dosages weight ratio be 4-6: 6-9: 4-6: 5-8；Total dosage of the solvent 1 in terms of parts by volume with The ratio of poly hydroxy ethyl acrylate in parts by weight is 11-15: 1；
Later, it by reaction solution pure water 4-5 times, filters, obtains the poly hydroxy ethyl acrylate of alkynyl.
3. the preparation method of hydrophilic nano hybrid reinforcement type hollow-fibre membrane according to claim 1 or 2, feature exist In, in step (1),
The dehydrating agent is selected from dicyclohexylcarbodiimide or dichloroethanes；
The catalyst is selected from 4-dimethylaminopyridine or n-Hydroxyphthalimide；
The solvent 1 is selected from N,N-dimethylformamide, DMAC N,N' dimethyl acetamide or dimethyl sulfoxide (DMSO).
4. the preparation method of hydrophilic nano hybrid reinforcement type hollow-fibre membrane according to claim 3, which is characterized in that In step (1),
The dehydrating agent is dicyclohexylcarbodiimide；
The catalyst is 4-dimethylaminopyridine；
The solvent 1 is N,N-dimethylformamide；
The poly hydroxy ethyl acrylate, dehydrating agent, catalyst, 4- pentinoic acids weight ratio be 5:7:5:6.
5. the preparation method of hydrophilic nano hybrid reinforcement type hollow-fibre membrane according to claim 1, which is characterized in that In step (2),
Weigh the Nano-meter SiO_2 of 0.3-0.7 parts by weight2It is scattered in the reactor of the pure water of parts by volume containing 8-12,15-22 is then added The ethyl alcohol of parts by volume after ultrasonic disperse 18-25min, is passed through nitrogen to remove the air in reactor；Measure 0.3-0.8 volumes The ethyl alcohol of the 3- mercaptopropyl trimethoxysilanes and 15-25 parts by volume of part is added in reactor after mixing, and while stirring The ammonium hydroxide of 3-6 parts by volume is added, 6-10h is stirred to react at 65-85 DEG C；
Liquid in reactor is poured out, centrifugation after being cleaned 4-6 times with ethyl alcohol takes out supernatant, sediment is dried in an oven Dry, oven temperature is set as 45-60 DEG C, obtains the Nano-meter SiO_2 of sulfhydrylation2, spare.
6. a kind of preparation method of hydrophilic nano hybrid reinforcement type hollow-fibre membrane according to claim 1 or 5, special Sign is, in step (2),
Weigh the Nano-meter SiO_2 of 0.5 parts by weight2It is scattered in the reactor containing 10 parts by volume pure water, the second of 20 parts by volume is then added Alcohol after ultrasonic disperse 20min, is passed through nitrogen to remove the air in reactor；Measure the 3- mercapto propyl trimethoxies of 0.5 parts by volume The ethyl alcohol of base silane and 15 parts by volume is added in reactor, and the ammonium hydroxide conduct of 5 parts by volume is added while stirring after mixing Catalyst is stirred to react 8h at 80 DEG C；
Liquid in reactor is poured out, is centrifuged after cleaning 4 times with ethyl alcohol, supernatant is taken out, sediment is dried in an oven, Oven temperature is set as 50 DEG C, you can obtains the Nano-meter SiO_2 of sulfhydrylation2, spare.
7. a kind of preparation method of hydrophilic nano hybrid reinforcement type hollow-fibre membrane according to claim 1, feature It is, in step (3),
According to polyvinylidene fluoride resin: solvent 2: polyethylene glycol additive: polyvinylpyrrolidone additive is by weight 15-20 : 55-70: 8-12: 10-15 mixed ingredients are stirred evenly using machine mixer, add the alkynyl of step (1) preparation The Nano-meter SiO_2 of sulfhydrylation prepared by poly hydroxy ethyl acrylate and step (2)2, the wherein polymethylacrylic acid hydroxyl of alkynyl The Nano-meter SiO_2 of ethyl ester, sulfhydrylation2Weight ratio with polyvinylidene fluoride resin is 2-5: 0.7-1.5: 5-12；
Then deaeration is carried out by the way of negative pressure, manufactured casting solution is positioned in batch can after deaeration, in 65-75 DEG C of heat preservation； Use the solvent 2 that weight ratio is 6-12: 80-92: water mixed solvent is recycled as coagulating bath, is then prepared by the following method Hydrophilic nano hybrid reinforcement type hollow-fibre membrane：
1) the doughnut internal lining pipe pulled in fiber roller is passed sequentially through into coating device and gel slot, is then wound in wire drawing wheel On；
2) wire-feed motor and receive silk machine are opened, adjusting the two rotating speed makes equipment run, and the speed of the two is 10-20 ms/min, will be expected Liquid is added in reaction kettle, then pressurizes into reaction kettle, so that feed liquid is passed through expects pipe and is conveyed to coating device；
3) fiber internal lining pipe enters coagulation bath, fiber internal lining pipe under the traction of receive silk machine after coating device coats feeding Immersion inversion of phases occurs for the feed liquid on outer surface and gel is shaped, and loses flowability, and forms film wire, is collected by wire drawing wheel；
4) film wire is irradiated in the case where wavelength is the ultraviolet light of 280-380nm, so that sulfhydryl cleavage is generated Thiyl Radical, it is anti-causes addition It answers；
5) film wire after causing completely is put into sink and impregnates 15-28h, thoroughly displace solvent and additive；
6) film wire is dried processing, dry temperature is 18-30 DEG C, and drying time is 8-15h to get to the hydrophily Nano hybridization enhancement type hollow fiber film.
8. a kind of preparation method of hydrophilic nano hybrid reinforcement type hollow-fibre membrane according to claim 1 or claim 7, special Sign is, in step (3),
The solvent 2 is selected from dimethylacetylamide, dimethyl sulfoxide (DMSO) or N-Methyl pyrrolidone.
9. a kind of preparation method of hydrophilic nano hybrid reinforcement type hollow-fibre membrane according to claim 8, feature It is, in step (3),
According to polyvinylidene fluoride resin: dimethylacetylamide: polyethylene glycol additive: polyvinylpyrrolidone additive is by weight It than 18: 60: 10: 12 mixed ingredients, is stirred evenly using machine mixer, adds the poly- first of the alkynyl of step (1) preparation The Nano-meter SiO_2 of sulfhydrylation prepared by base hydroxy-ethyl acrylate and step (2)2, wherein the poly hydroxy ethyl acrylate of alkynyl, The Nano-meter SiO_2 of sulfhydrylation2Weight ratio with polyvinylidene fluoride resin is 3: 1: 9；
Then deaeration is carried out by the way of negative pressure, manufactured casting solution is positioned in batch can after deaeration, in 70 DEG C of heat preservations；With weight Amount is than the dimethylacetylamide for 10: 90: water mixed solvent is recycled as coagulating bath, then prepares parent by the following method Water nano hybrid reinforcement type hollow-fibre membrane：
1) the doughnut internal lining pipe pulled in fiber roller is passed sequentially through into coating device and gel slot, is then wound in wire drawing wheel On；
2) wire-feed motor and receive silk machine are opened, adjusting the two rotating speed makes equipment run, and the speed of the two is 15 ms/min, by feed liquid It is added in reaction kettle, then pressurizes into reaction kettle, so that feed liquid is passed through expects pipe and conveyed to coating device；
3) fiber internal lining pipe enters coagulation bath, fiber internal lining pipe under the traction of receive silk machine after coating device coats feeding Immersion inversion of phases occurs for the feed liquid on outer surface and gel is shaped, and loses flowability, and forms film wire, is collected by wire drawing wheel；
4) film wire is irradiated in the case where wavelength is the ultraviolet light of 365nm, so that sulfhydryl cleavage is generated Thiyl Radical, causes addition reaction；
5) film wire after causing completely is put into sink and is impregnated for 24 hours, thoroughly displace solvent and additive；
6) film wire is dried processing, dry temperature is 22-28 DEG C, and drying time is 10-15h to get to described hydrophilic Property nano hybridization enhancement type hollow fiber film.
10. the hydrophilic nano hybrid reinforcement type doughnut being prepared according to claim 1-9 any one of them methods Film.
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CN203227420U (en) * 2013-05-08 2013-10-09 浙江师范大学 Novel antibacterial anti-pollution composite ultrafiltration membrane
CN103480278A (en) * 2013-09-06 2014-01-01 烟台绿水赋膜材料有限公司 Preparation method and application of anti-pollution hydrophilic separating membrane
WO2014023379A1 (en) * 2012-08-09 2014-02-13 Helmholtz-Zentrum Geesthacht Zentrum Für Material- Und Kuestenforschung Gmbh Membrane with isoporous, active separation layer and method for producing a membrane

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WO2014023379A1 (en) * 2012-08-09 2014-02-13 Helmholtz-Zentrum Geesthacht Zentrum Für Material- Und Kuestenforschung Gmbh Membrane with isoporous, active separation layer and method for producing a membrane
CN203227420U (en) * 2013-05-08 2013-10-09 浙江师范大学 Novel antibacterial anti-pollution composite ultrafiltration membrane
CN103480278A (en) * 2013-09-06 2014-01-01 烟台绿水赋膜材料有限公司 Preparation method and application of anti-pollution hydrophilic separating membrane

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