CN106310967A - Method for preparing hydrophilic nanohybrid enhancement type hollow fiber membrane - Google Patents

Method for preparing hydrophilic nanohybrid enhancement type hollow fiber membrane Download PDF

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CN106310967A
CN106310967A CN201610708369.7A CN201610708369A CN106310967A CN 106310967 A CN106310967 A CN 106310967A CN 201610708369 A CN201610708369 A CN 201610708369A CN 106310967 A CN106310967 A CN 106310967A
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reactor
nano
solvent
type hollow
fibre membrane
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CN106310967B (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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  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
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  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

The invention belongs to the field of modification and preparation and chemical analysis of a macromolecular hollow fiber microporous membrane, relates to a preparation method and application of loading nano functional materials onto the enhanced hollow fiber membrane by adopting a click chemistry method. The obtained hydrophilic nanohybrid enhancement type hollow fiber membrane prepared by adopting the method has excellent modification performance, such as the hydrophilicity of the membrane materials, the adsorption rate of heavy metal ions and the like.

Description

A kind of method preparing hydrophilic nano hybrid reinforcement type hollow-fibre membrane
Technical field
The invention belongs to polymeric hollow fiber microporous modification and preparation and the field of chemical synthesis, relate to one and pass through a little Hit the preparation method and application that nano-functional material is supported on enhancement type hollow fiber film by the method for chemistry.
Background technology
Along with constantly promoting of industrialization degree and going from bad to worse of all kinds of accurate water quality, a huge sum of money in the daily drunk water of the mankind Belonging to the ion phenomenon that exceeds standard day by day serious, heavy metal ion has serious harm to human body, the heavy metal such as Qi Zhongqian, arsenic, cadmium and hydrargyrum from Son may result in the generation of a series of cancer such as leukemia, septicemia.It is therefore a kind of that chemical stability is good, mechanical strength is high, anti-soil Dye ability the membrane material of oriented adsorption heavy metal ion can become the target that water treatment field is ideal the most again.This membrane material Being not limited only to the filtering core of domestic water filter commonly used, the initial stage also comprising industrial wastewater processes in the enhancement mode used in MBR system Hollow fiber film.
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, vitrification point-39 DEG C, and crystalline melt point is about 170 DEG C, Heat decomposition temperature, more than 316 DEG C, has the advantages such as excellent chemical stability, heat stability and easy film forming, is widely used in Prepare membrane material.Patent US7,306,105, in the disclosed enhancement mode such as CN1864828A, CN1281299C, CN101254420A Hollow fiber membrane component is all with PVDF for surface separation material.But owing to its surface can be low, hydrophobicity is strong, and the film prepared is hydrophilic Property is poor, in the aqueous phase separation system application processes such as bio-pharmaceuticals, food and drink and Water warfare, film easily adsorb organic solute and It is contaminated, so it is the most necessary to improve film properties that pvdf membrane carries out hydrophilic modification.
The hydrophilic modification method of PVDF is mainly had blending and modifying, surface coating modified and chemical modification etc., surface-coated Modification occurs mainly in film surface, and durability can not get ensureing, chemical modifying process is complicated, performance difficulty, is difficult to industrialization and puts Big production.And blending and modifying is relatively easy, and the basic performance improvement of material can be played.Add the most inorganic receiving in the base Rice material becomes blended main method, and it had both maintained organic pliability and low cost, and had had again the chemistry of inorganic matter Stability and high mechanical properties, the most also can produce the highest interface interaction, so that polymer performance is carried simultaneously Height, presents and is different from the mechanics of general composite, calorifics and wellability etc..Nano silicon is that research is the widest at present One of general inorganic nano material, it has high activity and selectivity, have stable chemical property, hydrophilic and corrosion resistance, The advantages such as nontoxic, low cost.
But it is current organic-inorganic blend film system that inorganic nano material is difficult to finely dispersed problem in organic film forming liquid The big resistance of standby one, research at present is concentrated mainly on modifying agent such as utilizing silane coupler and is modified inorganic nano material, Make it have and the performance of organic-inorganic double combination simultaneously.Yang Zhenglong of Tongji University et al. (" mercaptan-alkene/alkynes click chemistry system Standby organic/inorganic hybridization material " Progress in Chemistry, 2014,26 (6), 996-1004) use click chemistry Method is prepared for organic-inorganic hybrid material；Click chemistry is also known as click chemistry, since Hawker, Sharpless and Fokin etc. Since 2004 will click on the synthesis that chemistry is successfully introduced into dendritic macromole first, this method has been developed as synthesis Topological structure polymer (topological polymers) such as linear, scopiform, star, ring-type and dendritic macromole and special A kind of important means of functional material, click chemistry has following marked feature: (1) course of reaction is simple, efficient and has Selective；(2) reaction condition is gentle, is typically made without radical protection；(3) initiation material is easier to obtain；(4) anti- Answer post processing and product separation is easy, by-product is environmentally friendly；(5) reaction meets Atom economy requirement, and productivity almost may be used Reach 100%；(6) reaction can be carried out in aqueous phase, it is adaptable to living things system is modified.It is important is divided into following four mode: end Alkynyl and the cycloaddition reaction of nitrine；Cycloalkynyl radical and the cycloaddition reaction of nitrine；The condensation reaction of non-alcohol aldehyde carbonyl groups compound；Mercapto Base and the additive reaction of carbon carbon multikey.
Comprehensive literature and Patents, the present invention, from click chemistry angle, utilizes the addition of sulfydryl and carbon carbon multikey The nano silicon of sulfhydrylation is supported on hydrophilic organic monomer chain by the way of click chemistry by reaction method, and will It is blended in polyvinylidene fluoride film, improves the hydrophilic of film silk and the oriented adsorption to mercury ion.
Summary of the invention
It is an object of the invention to provide one utilizes click chemistry to prepare hydrophilic nano hybrid reinforcement type doughnut The method of film.
The present invention is achieved through the following technical solutions.
One aspect of the present invention relates to the preparation method of a kind of hydrophilic nano hybrid reinforcement type hollow-fibre membrane, the method bag Include following steps:
(1) preparation of the poly hydroxy ethyl acrylate (PHEMA) of alkynyl
Add solvent 1 in the reactor, afterwards poly hydroxy ethyl acrylate, catalyst, 4-pentinoic acid are added reaction In device, put in the ice bath of 0 DEG C and react, and be passed through nitrogen protection；After reaction carries out 20-50min, dehydrant is dissolved in molten In agent 1, and add in 50-80min in reactor, under room temperature, stir 10-16h；Wherein, poly hydroxy ethyl acrylate, de- Water preparation, catalyst, the weight ratio of 4-pentinoic acid consumption are 3-8: 5-10: 3-7: 4-10；The described solvent 1 total use in terms of parts by volume Amount is 10-20: 1 with poly hydroxy ethyl acrylate ratio in parts by weight；
Afterwards, by reactant liquor pure water 3-6 time, sucking filtration, obtain the poly hydroxy ethyl acrylate of alkynyl, standby With；
In the present invention, if no special instructions, weight portion calculates with gram (g), and parts by volume is to calculate with milliliter (ml) , w/v calculates with g/ml.
The concrete reaction scheme of this step is as follows:
(2) Nano-meter SiO_2 of sulfhydrylation2Preparation
Nano-particle has big specific surface area, result in nanoparticle and has high surface activity, is dispersed in neutral water Nanometer silicon dioxide particle in solution, defines the surface rich in hydroxyl functional group.Nanometer silicon dioxide particle surface is a large amount of Hydroxyl, the hydroxyl generation condensation reaction formed after hydrolyzing with silylating reagent, reach the purpose that surface sulfhydrylation is modified.
The present invention uses 3-mercaptopropyl trimethoxysilane (TMMPS) as silylating reagent.It addition, for improving sulfhydrylation Efficiency, the present invention adds ammonia as catalyst.As catalyst, mass percentage concentration is that 25%-28% all can realize this Bright, the ammonia of this concentration is commercially available, and the ammonia being slightly above and below this scope nor affects on the enforcement of technical scheme.
Weigh the Nano-meter SiO_2 of 0.1-1 weight portion2It is scattered in the reactor containing 5-15 parts by volume pure water, is subsequently adding 11- The ethanol of 25 parts by volume, after ultrasonic disperse 15-30min, is passed through nitrogen to remove the air in reactor；Measure 0.1-1 volume The 3-mercaptopropyl trimethoxysilane of part and the ethanol of 10-30 parts by volume, add in reactor after mix homogeneously, and while stirring Add the ammonia of 2-8 parts by volume, stirring reaction 5-12h at 50-90 DEG C；
Liquid in reactor is poured out, is centrifuged afterwards for 3-8 time with ethanol purge, takes out supernatant, by precipitate at baking oven Middle drying, oven temperature is set as 40-70 DEG C, obtains the Nano-meter SiO_2 of sulfhydrylation2, standby；
The concrete reaction scheme of this 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 mix, uses machine mixer to stir, adds alkynyl prepared by step (1) The Nano-meter SiO_2 of sulfhydrylation prepared by the poly hydroxy ethyl acrylate changed and step (2)2, the wherein polymethyl of alkynyl Acid hydroxyl ethyl ester, the Nano-meter SiO_2 of sulfhydrylation2It is 1-6: 0.2-2.5: 2-15 with the weight ratio of polyvinylidene fluoride resin；
Then the mode using negative pressure carries out deaeration, and the casting solution made after deaeration is positioned in batch can, in 50-80 DEG C of guarantor Temperature；Solvent 2 with weight ratio is 5-15: 70-95: water mixed solvent is circulated as coagulating bath, then according to 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 coating device and gel groove, be then around in receipts On silk wheel；
2) opening wire-feed motor and receive silk machine, the two rotating speed of regulation makes equipment run, and the speed of the two is 6-25 m/min, Feed liquid is added in reactor, then pressurize in reactor, make feed liquid lead to charge tube and carry to coating device；
3) fiber internal lining pipe is under the traction receiving silk machine, enters coagulation bath, in fiber after coating device coating feeding Feed liquid generation immersion inversion of phases on bushing pipe outer surface and gel sizing, lost flowability, form film silk, received by wire drawing wheel Collection；
4) by film silk irradiation under the ultraviolet light that wavelength is 200-400nm, making sulfhydryl cleavage produce Thiyl Radical, initiation adds Become reaction.Sulfydryl is excited under ultraviolet lighting, and cracking produces Thiyl Radical；Thiyl Radical attack carbon carbon multikey, active center Shift and produce alkyl diradical；Alkyl diradical captures the hydrogen atom of sulfydryl on sulfhydryl compound, again produces Thiyl Radical, Proceeding reaction, these free radicals both can cause chain to increase, it is also possible to occurs double-basis to terminate.React as follows:
5) immersion 10-30h in tank put into by the film silk after causing completely, thoroughly displaces solvent and additive；
6) film silk is dried process, i.e. obtains the hydrophilic nano hybrid reinforcement type hollow-fibre membrane of the present invention.
One of the present invention preferred embodiment in, wherein, in above-mentioned steps (1),
Add solvent 1 in the reactor, afterwards poly hydroxy ethyl acrylate (PHEMA), catalyst, 4-pentinoic acid are added Enter in reactor, put in the ice bath of 0 DEG C and react, and be passed through nitrogen protection；After reaction carries out 25-40, preferred 30min, will Dehydrant is dissolved in solvent 1, and adds in reactor in 55-70, preferred 60min, stirs 12-16h, preferably under room temperature 15h；Wherein, poly hydroxy ethyl acrylate (PHEMA), dehydrant, catalyst, the weight ratio of 4-pentinoic acid consumption are 4-6: 6- 9: 4-6: 5-8, preferably 5: 7: 5: 6；Described solvent 1 is 11-15: 1 with the envelope-bulk to weight ratio of poly hydroxy ethyl acrylate, preferably 12∶1；
Afterwards, by reactant liquor pure water 4-5 time, sucking filtration, the poly hydroxy ethyl acrylate of alkynyl is obtained (PHEMA), standby.
Wherein,
Described dehydrant is selected from dicyclohexylcarbodiimide (DCC), dichloroethanes (EDC)；Preferably dicyclohexyl carbon two is sub- Amine (DCC)；
Described catalyst is selected from DMAP (DMAP), HP (NOP)；Preferably 4-bis- Methylamino pyridine (DMAP)；
Described solvent 1 is selected from N,N-dimethylformamide (DMF), DMAC N,N' dimethyl acetamide (DMAC), dimethyl sulfoxide (DMSO)；Preferably N,N-dimethylformamide (DMF)；
The weight average molecular weight of described poly hydroxy ethyl acrylate (PHEMA) is 10,000-9 ten thousand, preferred 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 described molecular weight ranges is more Be conducive to the generation of reaction；And poly hydroxy ethyl acrylate (PHEMA), dehydrant, catalyst, 4-pentinoic acid are at described ratio Under example, reaction is well on, it is possible to improve the utilization rate of raw material to greatest extent, reduces cost, reduces side reaction simultaneously and occurs.
In another preferred embodiment of the present invention, wherein, in above-mentioned steps (2),
Weigh 0.3-0.7, the Nano-meter SiO_2 of preferably 0.5 weight portion2Be scattered in containing 8-12, preferably 10 parts by volume pure water anti- Answer in device, be subsequently adding 15-22, the ethanol of preferably 20 parts by volume, after ultrasonic disperse 18-25, preferred 20min, be passed through nitrogen with Remove the air in reactor；Measure 0.3-0.8, preferably 0.5 parts by volume 3-mercaptopropyl trimethoxysilane (TMMPS) with 15-25, the ethanol of preferably 15 parts by volume, add in reactor after mix homogeneously, and add 3-6, preferably 5 parts by volume while stirring Ammonia as catalyst, at 65-85, preferably 80 DEG C stirring reaction 6-10h, preferred 8h；
Liquid in reactor is poured out, with centrifugal after ethanol purge 4-6, preferably 4 times, takes out supernatant, by precipitate Drying in an oven, oven temperature is set as 45-60 DEG C, preferably 50 DEG C, obtains the Nano-meter SiO_2 of sulfhydrylation2, standby.
In this step, need to control Nano-meter SiO_22, 3-mercaptopropyl trimethoxysilane (TMMPS) and the addition of ammonia 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 mix, uses machine mixer to stir, Add the poly hydroxy ethyl acrylate (PHEMA) of alkynyl prepared by step (1) and the receiving of sulfhydrylation prepared by step (2) Rice SiO2, the wherein poly hydroxy ethyl acrylate (PHEMA) of alkynyl, the Nano-meter SiO_2 of sulfhydrylation2With polyvinylidene fluoride resin (PVDF) weight ratio is 2-5: 0.7-1.5: 5-12, preferably 3: 1: 9；
Then the mode using negative pressure carries out deaeration, and the casting solution made after deaeration is positioned in batch can, in 65-75, excellent Select 70 DEG C of insulations；Solvent 2 with weight ratio is 6-12: 80-92, preferably 10: 90: water mixed solvent follows as coagulating bath Ring, then according to following method prepares hydrophilic nano hybrid reinforcement type hollow-fibre membrane:
1) the doughnut internal lining pipe pulled in fiber roller is passed sequentially through coating device and gel groove, be then around in receipts On silk wheel；
2) opening wire-feed motor and receive silk machine, the two rotating speed of regulation makes equipment run, and the speed of the two is 10-20, preferred 15 ms/min, feed liquid is added in reactor, then pressurize in reactor, make feed liquid lead to charge tube and carry to coating device；
3) fiber internal lining pipe is under the traction receiving silk machine, enters coagulation bath, in fiber after coating device coating feeding Feed liquid generation immersion inversion of phases on bushing pipe outer surface and gel sizing, lost flowability, form film silk, received by wire drawing wheel Collection；
4) by film silk wavelength be 280-380nm, irradiation under the ultraviolet light of preferred 365nm, make sulfhydryl cleavage produce sulfur from By base, cause additive reaction；
5) immersion 15-28h, preferred 24h in tank put into by the film silk after causing completely, thoroughly displaces solvent 2 and adds Add agent；
6) film silk being dried process, dry temperature is 18-30 DEG C, and drying time is that 8-15h is (the driest Temperature be 22-28 DEG C, drying time is 10-15h), i.e. obtain the hydrophilic nano hybrid reinforcement type doughnut of the present invention Film.
Wherein,
Described solvent 2 is selected from dimethyl acetylamide (DMAC), dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone (NMP)； Preferably dimethyl acetylamide (DMAC)；
The weight average molecular weight of described polyvinylidene fluoride resin (PVDF) is 420,000-90 ten thousand, preferred 50-80 ten thousand, more preferably 60 Ten thousand；
The preparation facilities of the enhancement type hollow fiber film used in this step is to it known in the art, such as to pass through city Selling acquisition, it is also possible to obtained by self-control, described preparation facilities is had no special requirements by the present invention.
In this step, for guaranteeing the modified effect of excellence, the poly hydroxy ethyl acrylate (PHEMA) of alkynyl, mercapto The Nano-meter SiO_2 of base2Needing strict control with polyvinylidene fluoride resin (PVDF) adding proportion, the present inventor is through repeatedly trying Test, it was demonstrated that in the range of the adding proportion that the present invention is limited, it is possible to realize best modified effect, hydrophilic such as membrane material Property, adsorption rate of heavy metal ion etc..
Another aspect of the present invention relates to the hydrophilic nano hybrid reinforcement type doughnut prepared by said method Film.
The hydrophilic nano hybrid reinforcement type hollow-fibre membrane prepared through the inventive method has excellent modification Performance, such as the hydrophilic of membrane material, adsorption rate of heavy metal ion etc..Specifically, can be by the contact of hollow-fibre membrane Angle is down to less than 50 degree, and can be to the saturated extent of adsorption of heavy metal ion in water such as lead and hydrargyrum more than 28mg/g, adsorption rate More than 80%.
Implement various reagent, test apparatus and the preparation facilities used in the present invention and/or equipment is all prior art Known, those skilled in the art readily by commercially available acquisition, or can be provided by inventor place laboratory.Such as originally Various chemical raw materials and reagent used in invention purchased from China's reagent net, or can be carried by inventor place laboratory Supply.Experimental apparatus such as reactor (such as there-necked flask etc.), centrifugation apparatus, drying equipment, press device etc. all can purchased from Ah Li Baba, or provided by inventor place laboratory.Enhancement type hollow fiber film preparation facilities and/or equipment can pass through city Sell acquisition, or provided by inventor place laboratory.
[beneficial effect]
Beneficial effects of the present invention is embodied in:
(1) present invention utilize sulfydryl and carbon carbon multikey additive reaction, its feature be easy and simple to handle, be susceptible to oxygen and water Impact, and avoid the features such as poisonous metallic catalyst.
(2) the hydrophilic nano hybrid reinforcement type hollow-fibre membrane that the inventive method prepares has the hydrophilic of excellence Property, the contact angle of hollow-fibre membrane can be down to less than 50 degree.
(3) the hydrophilic nano hybrid reinforcement type hollow-fibre membrane that the inventive method prepares has the adsorptivity of excellence Can, the saturated extent of adsorption of heavy metal ion such as lead and hydrargyrum is more than 28mg/g, and adsorption rate is more than 80%, it is possible to be effectively used for water The fields such as matter purification.
[accompanying drawing explanation]
Fig. 1 is the hydrophilic nano hybrid reinforcement type hollow-fibre membrane outer surface structure that the embodiment of the present invention 1 prepares 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 prepares Scanning electron microscopic picture.
Fig. 3 is the scanning electricity of the hydrophilic nano hybrid reinforcement type hollow-fibre membrane section structure that reference examples 1 prepares Mirror picture.
[detailed description of the invention]
Will be better understood that the present invention by following embodiment, but the present invention is not limited by following embodiment.
Test instrunment used in following embodiment is provided by laboratory, and its operational approach is those skilled in the art Known.
Embodiment 1
(1) preparation of the poly hydroxy ethyl acrylate (PHEMA) of alkynyl
50ml solvent DMF (DMF) is added, afterwards by 5g polymethylacrylic acid hydroxyl in there-necked flask Ethyl ester (PHEMA, weight average molecular weight is 20,000), the 4-pentinoic acid of 5g catalyst DMAP (DMAP) and 6g add In there-necked flask, put in the ice bath of 0 DEG C and react, and be passed through nitrogen protection；After reaction carries out 30min, by 7g dehydrant two Carbodicyclo hexylimide (DCC) is dissolved in 10ml solvent DMF (DMF), and adds three mouthfuls in 60min In flask, under room temperature, stir 15h.
Afterwards, by reactant liquor pure water 4 times, rear sucking filtration, the poly hydroxy ethyl acrylate of alkynyl is obtained (PHEMA), standby.
(2) Nano-meter SiO_2 of sulfhydrylation 2 Preparation
Weigh the Nano-meter SiO_2 of 0.5g2It is scattered in the there-necked flask containing 10ml pure water, is subsequently adding the ethanol of 20ml, super After sound dispersion 20min, it is passed through nitrogen to remove the air in reactor；Measure the 3-mercaptopropyl trimethoxysilane of 0.5ml (TMMPS) with the ethanol of 15ml, add in there-necked flask after mix homogeneously, and the mass concentration adding 5ml while stirring is 25% ammonia is as catalyst, and at 80 DEG C, 8h is reacted in stirring.
Liquid in reactor is poured out, with centrifugal after ethanol purge 4 times, takes out supernatant, by precipitate in an oven Drying, oven temperature is set as 50 DEG C, i.e. can get the Nano-meter SiO_2 of sulfhydrylation2, standby.
(3) preparation of hydrophilic nano hybrid reinforcement type hollow-fibre membrane
Weigh 18g polyvinylidene fluoride resin (PVDF, weight average molecular weight is 600,000), 60g solvent dimethyl acetylamide (DMAC), 10g Polyethylene Glycol additive and 12g polyvinylpyrrolidone additive, add mix in there-necked flask, make Stir with machine mixer, add alkynyl prepared by 6g step (1) poly hydroxy ethyl acrylate (PHEMA) and The Nano-meter SiO_2 of sulfhydrylation prepared by 2g step (2)2；Then the mode using negative pressure carries out deaeration, the casting solution made after deaeration It is positioned in batch can, in 70 DEG C of insulations；Dimethyl acetylamide (DMAC) with weight ratio is 10: 90: water mixes as coagulating bath It is circulated, then according to following method prepares hydrophilic nano hybrid reinforcement type hollow-fibre membrane:
1) the doughnut internal lining pipe pulled in fiber roller is passed sequentially through coating device and gel groove, be then around in receipts On silk wheel；
2) opening wire-feed motor and receive silk machine, the two rotating speed of regulation makes equipment run, and the speed of the two is 15 ms/min, will Feed liquid adds in reactor, then pressurizes in reactor, makes feed liquid lead to charge tube and carries to coating device；
3) fiber internal lining pipe is under the traction receiving silk machine, enters coagulation bath, in fiber after coating device coating feeding Feed liquid generation immersion inversion of phases on bushing pipe outer surface and gel sizing, lost flowability, form film silk, received by wire drawing wheel Collection；
4) by film silk irradiation under the ultraviolet light that wavelength is 365nm, make sulfhydryl cleavage produce Thiyl Radical, cause addition anti- Should；
5) immersion 24h in tank put into by the film silk after causing 18h, thoroughly displaces solvent and additive；
6) film silk being dried process, baking temperature is 25 DEG C, and drying time is 15h, i.e. obtains the hydrophilic of the present invention Property nano hybridization enhancement type hollow fiber film.
The film prepared is carried out following performance measurement:
1. the nano hybridization enhancement mode obtained by solution-air and the double method of testing pore-size distribution analysis-e/or determining of liquid-liquid is used The average pore size of hollow-fibre membrane is 0.08 micron, and internal diameter is 1.0 millimeters, and external diameter is 2.0 millimeters.
2. the described nano hybridization enhancement type hollow fiber film that use flux detector measures at 0.1MPa and 25 DEG C Pure water flux is 2650L/m2.h。
3. dynamic contact angle analyzer is used to measure the contact angle of described nano hybridization enhancement type hollow fiber film, Qi Zhongxuan 5 diverse locations taking same nano hybridization enhancement type hollow fiber film record contact angle, average, and time of contact sets For 20s.After measured, contact angle is 45 degree.
4. described nano hybridization enhancement type hollow fiber film being carried out heavy metal ion adsorbed determination test, result shows, It is 31mg/g to the saturated extent of adsorption of lead ion, and adsorption rate is 92%；Saturated extent of adsorption to mercury ion is 32mg/g, absorption Rate is 92%.
5. being observed by scanning electron microscope, its surface texture and section structure are as illustrated in fig. 1 and 2, it can be seen that film table Face presents micro-nano bulge-structure, and the enrichment of hydrophilic nano material is more beneficial for improving hydrophilic and the antipollution of film on film surface Property.There is the supporting layer of sponge and uniform finger-like pore structure in film silk section structure, and this structure is conducive to improving film silk flux, subtracts The blocking to fenestra of the little pollutant.
Embodiment 2
(1) preparation of the poly hydroxy ethyl acrylate (PHEMA) of alkynyl
70ml solvent N,N-dimethylacetamide (DMAC) is added, afterwards by 6g polymethylacrylic acid hydroxyl in there-necked flask Ethyl ester (PHEMA, weight average molecular weight is 40,000), 4g catalyst n-hydroxyl phthalic amide imines (NOP) and the 4-pentyne of 7g Acid adds in there-necked flask, puts in the ice bath of 0 DEG C and reacts, and is passed through nitrogen protection；After reaction carries out 30min, 8g is taken off Water preparation dicyclohexylcarbodiimide (DCC) is dissolved in 20ml solvent N,N-dimethylacetamide (DMAC), and adds in 70min Enter in there-necked flask, under room temperature, stir 12h.
Afterwards, by reactant liquor pure water 5 times, rear sucking filtration, the poly hydroxy ethyl acrylate of alkynyl is obtained (PHEMA), standby.
(2) Nano-meter SiO_2 of sulfhydrylation 2 Preparation
Weigh the Nano-meter SiO_2 of 0.7g2It is scattered in the there-necked flask containing 12ml pure water, is subsequently adding the ethanol of 16ml, super After sound dispersion 25min, it is passed through nitrogen to remove the air in reactor；Measure the 3-mercaptopropyl trimethoxysilane of 0.8ml (TMMPS) with the ethanol of 25ml, add in there-necked flask after mix homogeneously, and the concentration adding 6ml while stirring is 25% ammonia Water is as catalyst, and at 85 DEG C, 10h is reacted in stirring.
Liquid in reactor is poured out, with centrifugal after ethanol purge 5 times, takes out supernatant, by precipitate in an oven Drying, oven temperature is set as 55 DEG C, i.e. can get the Nano-meter SiO_2 of sulfhydrylation2, standby.
(3) preparation of hydrophilic nano hybrid reinforcement type hollow-fibre membrane
Weigh 20g polyvinylidene fluoride resin (PVDF, weight average molecular weight is 800,000), 70g solvent N-methyl pyrilidone (NMP), 12g Polyethylene Glycol additive and 15g polyvinylpyrrolidone additive, add mix in there-necked flask, make Stir with machine mixer, add alkynyl prepared by 8g step (1) poly hydroxy ethyl acrylate (PHEMA) and The Nano-meter SiO_2 of sulfhydrylation prepared by 2.5g step (2)2；Then the mode using negative pressure carries out deaeration, the casting film made after deaeration Liquid is positioned in batch can, in 65 DEG C of insulations；N-Methyl pyrrolidone (NMP) with weight ratio is 6: 80: water mixing is as solidification Bath is circulated, then according to following method prepares hydrophilic nano hybrid reinforcement type hollow-fibre membrane:
1) the doughnut internal lining pipe pulled in fiber roller is passed sequentially through coating device and gel groove, be then around in receipts On silk wheel；
2) opening wire-feed motor and receive silk machine, the two rotating speed of regulation makes equipment run, and the speed of the two is 20 ms/min, will Feed liquid adds in reactor, then pressurizes in reactor, makes feed liquid lead to charge tube and carries to coating device；
3) fiber internal lining pipe is under the traction receiving silk machine, enters coagulation bath, in fiber after coating device coating feeding Feed liquid generation immersion inversion of phases on bushing pipe outer surface and gel sizing, lost flowability, form film silk, received by wire drawing wheel Collection；
4) by film silk irradiation under the ultraviolet light that wavelength is 365nm, make sulfhydryl cleavage produce Thiyl Radical, cause addition anti- Should；
5) immersion 30h in tank put into by the film silk after causing 20h, thoroughly displaces solvent and additive；
6) film silk being dried process, baking temperature is 22 DEG C, and drying time is 13h, i.e. obtains the hydrophilic of the present invention Property nano hybridization enhancement type hollow fiber film.
The film prepared is carried out following performance measurement:
1. use in the nano hybridization enhancement mode obtained by solution-air and the double method of testing pore-size distribution analysis-e/or determining of liquid-liquid The average pore size of hollow fiber film is 0.1 micron, and internal diameter is 1.0 millimeters, and external diameter is 2.0 millimeters.
2. the described nano hybridization enhancement type hollow fiber film measured at 0.1MPa and 25 DEG C by flux detector pure Water flux is 2080L/m2.h。
3. measure the contact angle of described nano hybridization enhancement type hollow fiber film with dynamic contact angle analyzer, wherein choose 5 diverse locations of same nano hybridization enhancement type hollow fiber film record contact angle, average, and time of contact is set as 20s.After measured, contact angle is 46 degree.
4. described nano hybridization enhancement type hollow fiber film being carried out heavy metal ion adsorbed determination test, result shows, It is 30mg/g to the saturated extent of adsorption of lead ion, and adsorption rate is 90%；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 solvent DMF (DMF) is added, afterwards by 4g polymethylacrylic acid hydroxyl in there-necked flask Ethyl ester (PHEMA, weight average molecular weight is 30,000), 6g catalyst n-hydroxyphthalimide (NOP) and the 4-pentinoic acid of 8g Add in there-necked flask, put in the ice bath of 0 DEG C and react, and be passed through nitrogen protection；After reaction carries out 30min, 6g is dehydrated Agent dichloroethanes (EDC) is dissolved in 20ml solvent DMF (DMF), and adds there-necked flask in 55min In, stir 75h under room temperature.
Afterwards, by reactant liquor pure water 3 times, rear sucking filtration, the poly hydroxy ethyl acrylate of alkynyl is obtained (PHEMA), standby.
(2) Nano-meter SiO_2 of sulfhydrylation 2 Preparation
Weigh the Nano-meter SiO_2 of 0.3g2It is scattered in the there-necked flask containing 8ml pure water, is subsequently adding the ethanol of 15ml, ultrasonic After dispersion 18min, it is passed through nitrogen to remove the air in reactor；Measure the 3-mercaptopropyl trimethoxysilane of 0.3ml (TMMPS) with the ethanol of 12ml, add in there-necked flask after mix homogeneously, and add while stirring 3ml 28% ammonia make For catalyst, stirring reaction 6h at 65 DEG C.
Liquid in reactor is poured out, with centrifugal after ethanol purge 6 times, takes out supernatant, by precipitate in an oven Drying, oven temperature is set as 45 DEG C, i.e. can get the Nano-meter SiO_2 of sulfhydrylation2, standby.
(3) preparation of hydrophilic nano hybrid reinforcement type hollow-fibre membrane
Weigh 15g polyvinylidene fluoride resin (PVDF, weight average molecular weight is 700,000), 55g solvent dimethyl acetylamide (DMAC), 8g Polyethylene Glycol additive and 10g polyvinylpyrrolidone additive, add mix in there-necked flask, make Stir with machine mixer, add alkynyl prepared by 6g step (1) poly hydroxy ethyl acrylate (PHEMA) and The Nano-meter SiO_2 of sulfhydrylation prepared by 2.1g step (2)2；Then the mode using negative pressure carries out deaeration, the casting film made after deaeration Liquid is positioned in batch can, in 60 DEG C of insulations；Solvent dimethyl acetylamide (DMAC) with weight ratio is 10: 80: water mixed solvent It is circulated as coagulating bath, then according to following method prepares hydrophilic nano hybrid reinforcement type hollow-fibre membrane:
1) the doughnut internal lining pipe pulled in fiber roller is passed sequentially through coating device and gel groove, be then around in receipts On silk wheel；
2) opening wire-feed motor and receive silk machine, the two rotating speed of regulation makes equipment run, and the speed of the two is 15 ms/min, will Feed liquid adds in reactor, then pressurizes in reactor, makes feed liquid lead to charge tube and carries to coating device；
3) fiber internal lining pipe is under the traction receiving silk machine, enters coagulation bath, in fiber after coating device coating feeding Feed liquid generation immersion inversion of phases on bushing pipe outer surface and gel sizing, lost flowability, form film silk, received by wire drawing wheel Collection；
4) by film silk irradiation under the ultraviolet light that wavelength is 365nm, make sulfhydryl cleavage produce Thiyl Radical, cause addition anti- Should；
5) immersion 20h in tank put into by the film silk after causing 16h, thoroughly displaces solvent and additive；
6) film silk being dried process, baking temperature is 28 DEG C, and drying time is 12h, i.e. obtains the hydrophilic of the present invention Property nano hybridization enhancement type hollow fiber film.
The film prepared is carried out following performance measurement:
1. the nano hybridization enhancement mode obtained by solution-air and the double method of testing pore-size distribution analysis-e/or determining of liquid-liquid is used The average pore size of hollow-fibre membrane is 0.15 micron, and internal diameter is 1.0 millimeters, and external diameter is 2.0 millimeters.
2. the described nano hybridization enhancement type hollow fiber film that use flux detector measures at 0.1MPa and 25 DEG C Pure water flux is 2200L/m2.h。
3. dynamic contact angle analyzer is used to measure the contact angle of described nano hybridization enhancement type hollow fiber film, Qi Zhongxuan 5 diverse locations taking same nano hybridization enhancement type hollow fiber film record contact angle, average, and time of contact sets For 20s.After measured, contact angle is 47 degree.
4. described nano hybridization enhancement type hollow fiber film being carried out heavy metal ion adsorbed determination test, result shows, It is 29mg/g to the saturated extent of adsorption of lead ion, and adsorption rate is 86%；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 solvent N,N-dimethylacetamide (DMAC) is added, afterwards by 7g polymethylacrylic acid hydroxyl in there-necked flask Ethyl ester (PHEMA, weight average molecular weight is 50,000), the 4-pentinoic acid of 3g catalyst DMAP (DMAP) and 9g add In there-necked flask, put in the ice bath of 0 DEG C and react, and be passed through nitrogen protection；After reaction carries out 40min, by 5g dehydrant two Carbodicyclo hexylimide (DCC) is dissolved in 10ml solvent N,N-dimethylacetamide (DMAC), and adds three mouthfuls in 50min In flask, under room temperature, stir 14h.
Afterwards, by reactant liquor pure water 6 times, rear sucking filtration, the poly hydroxy ethyl acrylate of alkynyl is obtained (PHEMA), standby.
(2) Nano-meter SiO_2 of sulfhydrylation 2 Preparation
Weigh the Nano-meter SiO_2 of 0.9g2It is scattered in the there-necked flask containing 14ml pure water, is subsequently adding the ethanol of 24ml, super After sound dispersion 16min, it is passed through nitrogen to remove the air in reactor；Measure the 3-mercaptopropyl trimethoxysilane of 0.9ml (TMMPS) with the ethanol of 28ml, add in there-necked flask after mix homogeneously, and add the ammonia of 7ml while stirring as catalysis Agent, stirring reaction 10h at 75 DEG C.
Liquid in reactor is poured out, with centrifugal after ethanol purge 5 times, takes out supernatant, by precipitate in an oven Drying, oven temperature is set as 45 DEG C, i.e. can get the Nano-meter SiO_2 of sulfhydrylation2, standby.
(3) preparation of hydrophilic nano hybrid reinforcement type hollow-fibre membrane
Weigh 12g polyvinylidene fluoride resin (PVDF, weight average molecular weight is 550,000), 75g solvent N-methyl pyrilidone (NMP), 6g Polyethylene Glycol additive and 8g polyvinylpyrrolidone additive, mix in addition there-necked flask, use Machine mixer stirs, add alkynyl prepared by 4.8g step (1) poly hydroxy ethyl acrylate (PHEMA) and The Nano-meter SiO_2 of sulfhydrylation prepared by 2.4g step (2)2；Then the mode using negative pressure carries out deaeration, the casting film made after deaeration Liquid is positioned in batch can, in 75 DEG C of insulations；Solvent N-methyl pyrilidone (NMP) with weight ratio is 10: 85: water mixed solvent It is circulated as coagulating bath, then according to following method prepares hydrophilic nano hybrid reinforcement type hollow-fibre membrane:
1) the doughnut internal lining pipe pulled in fiber roller is passed sequentially through coating device and gel groove, be then around in receipts On silk wheel；
2) opening wire-feed motor and receive silk machine, the two rotating speed of regulation makes equipment run, and the speed of the two is 20 ms/min, will Feed liquid adds in reactor, then pressurizes in reactor, makes feed liquid lead to charge tube and carries to coating device；
3) fiber internal lining pipe is under the traction receiving silk machine, enters coagulation bath, in fiber after coating device coating feeding Feed liquid generation immersion inversion of phases on bushing pipe outer surface and gel sizing, lost flowability, form film silk, received by wire drawing wheel Collection；
4) by film silk irradiation under the ultraviolet light that wavelength is 365nm, make sulfhydryl cleavage produce Thiyl Radical, cause addition anti- Should；
5) immersion 25h in tank put into by the film silk after causing 18h, thoroughly displaces solvent and additive；
6) film silk being dried process, baking temperature is 20 DEG C, and drying time is 14h, i.e. obtains the hydrophilic of the present invention Property nano hybridization enhancement type hollow fiber film.
The film prepared is carried out following performance measurement:
1. use in the nano hybridization enhancement mode obtained by solution-air and the double method of testing pore-size distribution analysis-e/or determining of liquid-liquid The average pore size of hollow fiber film is 0.09 micron, and internal diameter is 1.0 millimeters, and external diameter is 2.0 millimeters.
2. the described nano hybridization enhancement type hollow fiber film measured at 0.1MPa and 25 DEG C by flux detector pure Water flux is 2250L/m2.h。
3. measure the contact angle of described nano hybridization enhancement type hollow fiber film with dynamic contact angle analyzer, wherein choose 5 diverse locations of same nano hybridization enhancement type hollow fiber film record contact angle, average, and time of contact is set as 20s.After measured, contact angle is 48 degree.
4. described nano hybridization enhancement type hollow fiber film being carried out heavy metal ion adsorbed determination test, result shows, It is 29mg/g to the saturated extent of adsorption of lead ion, and adsorption rate is 90%；Saturated extent of adsorption to mercury ion is 29mg/g, absorption Rate is 89%.
Comparative example 1
Relative to embodiment 1, without modified component (i.e. step 1 and the component of 2), do not use ultraviolet light to irradiate simultaneously, Remainder is identical.
Weigh 18g polyvinylidene fluoride resin (PVDF, weight average molecular weight is 600,000), 60g solvent dimethyl acetylamide (DMAC), 10g Polyethylene Glycol additive and 12g polyvinylpyrrolidone additive, add mix in there-necked flask, make Stir with machine mixer；Then the mode using negative pressure carries out deaeration, and the casting solution made after deaeration is positioned over batch can In, in 70 DEG C of insulations；Solvent dimethyl acetylamide (DMAC) with weight ratio is 10: 90: water mixed solvent enters as coagulating bath Row circulation, then according to following method prepares hollow-fibre membrane:
1) the doughnut internal lining pipe pulled in fiber roller is passed sequentially through coating device and gel groove, be then around in receipts On silk wheel；
2) opening wire-feed motor and receive silk machine, the two rotating speed of regulation makes equipment run, and the speed of the two is 15 ms/min, will Feed liquid adds in reactor, then pressurizes in reactor, makes feed liquid lead to charge tube and carries to coating device；
3) fiber internal lining pipe is under the traction receiving silk machine, enters coagulation bath, in fiber after coating device coating feeding Feed liquid generation immersion inversion of phases on bushing pipe outer surface and gel sizing, lost flowability, form film silk, received by wire drawing wheel Collection；
4) the film silk of collection is put into immersion 24h in tank, thoroughly displaces solvent and additive；
5) film silk being dried process, baking temperature is 25 DEG C, and drying time is 15h, i.e. obtains hollow-fibre membrane.
The film prepared is carried out following performance measurement:
1. the average of the obtained hollow-fibre membrane of solution-air and the double method of testing pore-size distribution analysis-e/or determining of liquid-liquid is used Aperture is 0.15 micron, and internal diameter is 1.0 millimeters, and external diameter is 2.0 millimeters.
The pure water flux of the described hollow-fibre membrane 2. measured at 0.1MPa and 25 DEG C by flux detector is 980L/ m2.h。
3. measure the contact angle of described hollow-fibre membrane with dynamic contact angle analyzer, wherein choose same doughnut 5 diverse locations of film record contact angle, average, and time of contact is set as 20s.After measured, contact angle is 80 degree.
4. described hollow-fibre membrane being carried out heavy metal ion adsorbed determination test, result shows, lead ion is satisfied by it Being 5mg/g with adsorbance, adsorption rate is 25%；Saturated extent of adsorption to mercury ion is 8mg/g, and adsorption rate is 30%.
5. being observed by scanning electron microscope, its section structure is as shown in Figure 3, it can be seen that do not carry out the film of nano modification Silk section presents the sponge pore structure of densification, and this kind of structure pollutant in running are easily blocked in fenestra intracavity, it is difficult to clear Wash recovery.
Relative to embodiment 1, with the Nano-meter SiO_2 of equivalent2Modified component (i.e. step 1 and the group of 2 in alternate embodiment 1 Point), remainder is identical.
Weigh 18g polyvinylidene fluoride resin (PVDF, weight average molecular weight is 600,000), 60g solvent dimethyl acetylamide (DMAC), 10g Polyethylene Glycol additive and 12g polyvinylpyrrolidone additive, add mix in there-necked flask, make Stir with machine mixer, add 8g Nano-meter SiO_22；Then the mode using negative pressure carries out deaeration, makes after deaeration Casting solution is positioned in batch can, in 70 DEG C of insulations；Solvent dimethyl acetylamide (DMAC) with weight ratio is 10: 90: water mixes Solvent is circulated as coagulating bath, then according to following method prepares hollow-fibre membrane:
1) the doughnut internal lining pipe pulled in fiber roller is passed sequentially through coating device and gel groove, be then around in receipts On silk wheel；
2) opening wire-feed motor and receive silk machine, the two rotating speed of regulation makes equipment run, and the speed of the two is 15 ms/min, will Feed liquid adds in reactor, then pressurizes in reactor, makes feed liquid lead to charge tube and carries to coating device；
3) fiber internal lining pipe is under the traction receiving silk machine, enters coagulation bath, in fiber after coating device coating feeding Feed liquid generation immersion inversion of phases on bushing pipe outer surface and gel sizing, lost flowability, form film silk, received by wire drawing wheel Collection；
4) by film silk irradiation under the ultraviolet light that wavelength is 365nm；
5), after irradiation during 18h, film silk is put into immersion 24h in tank, thoroughly displaces solvent and additive；
6) film silk being dried process, baking temperature is 25 DEG C, and drying time is 15h, i.e. obtains hollow-fibre membrane.
The film prepared is carried out following performance measurement:
1. the average of the obtained hollow-fibre membrane of solution-air and the double method of testing pore-size distribution analysis-e/or determining of liquid-liquid is used Aperture is 0.2 micron, and internal diameter is 1.0 millimeters, and external diameter is 2.0 millimeters.
The pure water flux of the described hollow-fibre membrane 2. measured at 0.1MPa and 25 DEG C by flux detector is 1500L/ m2.h。
3. measure the contact angle of described hollow-fibre membrane with dynamic contact angle analyzer, wherein choose same doughnut 5 diverse locations of film record contact angle, average, and time of contact is set as 20s.After measured, contact angle is 65 degree.
4. described hollow-fibre membrane being carried out heavy metal ion adsorbed determination test, result shows, lead ion is satisfied by it Being 10mg/g with adsorbance, adsorption rate is 30%；Saturated extent of adsorption to mercury ion is 9mg/g, and adsorption rate is 44%.
From the data of embodiment of the present invention 1-4 and comparative example 1-2 it can be seen that by receiving after material modification of the present invention Rice hybrid reinforcement type hollow-fibre membrane performance in terms of the absorbability of hydrophilic and heavy metal ion is substantially better than comparison Fibrous membrane.

Claims (10)

1. a preparation method for hydrophilic nano hybrid reinforcement type hollow-fibre membrane, described method comprises the steps:
(1) preparation of the poly hydroxy ethyl acrylate of alkynyl
Add solvent 1 in the reactor, afterwards poly hydroxy ethyl acrylate, catalyst, 4-pentinoic acid added in reactor, Put in the ice bath of 0 DEG C and react, and be passed through nitrogen protection；After reaction carries out 20-50min, dehydrant is dissolved in solvent 1 In, and add in 50-80min in reactor, stir 10-16h under room temperature；Wherein, poly hydroxy ethyl acrylate, dehydration Agent, catalyst, the weight ratio of 4-pentinoic acid consumption are 3-8: 5-10: 3-7: 4-10；The described solvent 1 total consumption in terms of parts by volume It is 10-20: 1 with poly hydroxy ethyl acrylate ratio in parts by weight；
Afterwards, by reactant liquor pure water 3-6 time, sucking filtration, obtain the poly hydroxy ethyl acrylate of alkynyl, standby；
(2) Nano-meter SiO_2 of sulfhydrylation2Preparation
Weigh the Nano-meter SiO_2 of 0.1-1 weight portion2It is scattered in the reactor containing 5-15 parts by volume pure water, is subsequently adding 11-25 body The ethanol of long-pending part, after ultrasonic disperse 15-30min, is passed through nitrogen to remove the air in reactor；Measure 0.1-1 parts by volume 3-mercaptopropyl trimethoxysilane and the ethanol of 10-30 parts by volume, add in reactor after mix homogeneously, and add while stirring The ammonia of 2-8 parts by volume, stirring reaction 5-12h at 50-90 DEG C；
Liquid in reactor is poured out, is centrifuged afterwards for 3-8 time with ethanol purge, takes out supernatant, precipitate is dried in an oven Dry, oven temperature is set as 40-70 DEG C, obtains the Nano-meter SiO_2 of sulfhydrylation2, standby；
(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 mix, stir, add the polymethylacrylic acid hydroxyl second of alkynyl prepared by step (1) 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 SiO2It is 1-6: 0.2-2.5: 2-15 with the weight ratio of polyvinylidene fluoride resin；
Then the mode using negative pressure carries out deaeration, and the casting solution made after deaeration is positioned in batch can, in 50-80 DEG C of insulation； Solvent 2 with weight ratio is 5-15: 70-95: water mixed solvent is circulated as coagulating bath, then according to prepared by following method Hydrophilic nano hybrid reinforcement type hollow-fibre membrane:
1) doughnut internal lining pipe is passed sequentially through coating device and gel groove, be then around on wire drawing wheel；
2) opening wire-feed motor and receive silk machine, the two rotating speed of regulation makes equipment run, and the speed of the two is 6-25 m/min, will material Liquid adds in reactor, then pressurizes in reactor, makes feed liquid lead to charge tube and carries to coating device；
3) fiber internal lining pipe is under the traction receiving silk machine, enters coagulation bath, fiber liner after coating device coating casting solution Feed liquid generation immersion inversion of phases on tube outer surface and gel sizing, lost flowability, form film silk, received by wire drawing wheel Collection；
4) by film silk irradiation under the ultraviolet light that wavelength is 200-400nm, make sulfhydryl cleavage produce Thiyl Radical, cause addition anti- Should；
5) immersion 10-30h in tank put into by the film silk after causing completely, thoroughly displaces solvent and additive；
6) film silk is dried process, obtains described hydrophilic nano hybrid reinforcement type hollow-fibre membrane.
The preparation method of hydrophilic nano hybrid reinforcement type hollow-fibre membrane the most according to claim 1, it is characterised in that In step (1),
Add solvent 1 in the reactor, afterwards poly hydroxy ethyl acrylate, catalyst, 4-pentinoic acid added in reactor, Put in the ice bath of 0 DEG C and react, and be passed through nitrogen protection；After reaction carries out 25-40min, dehydrant is dissolved in solvent 1 In, and add in 55-70min in reactor, stir 12-16h under room temperature；Wherein, poly hydroxy ethyl acrylate, dehydration Agent, catalyst, the weight ratio of 4-pentinoic acid consumption are 4-6: 6-9: 4-6: 5-8；The described solvent 1 total consumption in terms of parts by volume with Poly hydroxy ethyl acrylate ratio in parts by weight is 11-15: 1；
Afterwards, by reactant liquor pure water 4-5 time, sucking filtration, the poly hydroxy ethyl acrylate of alkynyl is obtained.
The preparation method of hydrophilic nano hybrid reinforcement type hollow-fibre membrane the most according to claim 1 and 2, its feature exists In, in step (1),
Described dehydrant is selected from dicyclohexylcarbodiimide or dichloroethanes；
Described catalyst is selected from DMAP or HP；
Described solvent 1 is selected from N,N-dimethylformamide, DMAC N,N' dimethyl acetamide or dimethyl sulfoxide.
The preparation method of hydrophilic nano hybrid reinforcement type hollow-fibre membrane the most according to claim 3, it is characterised in that In step (1),
Described dehydrant is dicyclohexylcarbodiimide；
Described catalyst is DMAP；
Described solvent 1 is N,N-dimethylformamide；
Described poly hydroxy ethyl acrylate, dehydrant, catalyst, the weight ratio of 4-pentinoic acid are 5:7:5:6.
The preparation method of hydrophilic nano hybrid reinforcement type hollow-fibre membrane the most according to claim 1, it is characterised in that In step (2),
Weigh the Nano-meter SiO_2 of 0.3-0.7 weight portion2It is scattered in the reactor containing 8-12 parts by volume pure water, is subsequently adding 15-22 The ethanol of parts by volume, after ultrasonic disperse 18-25min, is passed through nitrogen to remove the air in reactor；Measure 0.3-0.8 volume The 3-mercaptopropyl trimethoxysilane of part and the ethanol of 15-25 parts by volume, add in reactor after mix homogeneously, and while stirring Add the ammonia of 3-6 parts by volume, stirring reaction 6-10h at 65-85 DEG C；
Liquid in reactor is poured out, is centrifuged afterwards for 4-6 time with ethanol purge, takes out supernatant, precipitate is dried in an oven Dry, oven temperature is set as 45-60 DEG C, obtains the Nano-meter SiO_2 of sulfhydrylation2, standby.
The preparation method of a kind of hydrophilic nano hybrid reinforcement type hollow-fibre membrane, it is special Levy and be, in step (2),
Weigh the Nano-meter SiO_2 of 0.5 weight portion2It is scattered in the reactor containing 10 parts by volume pure water, is subsequently adding the second of 20 parts by volume Alcohol, after ultrasonic disperse 20min, is passed through nitrogen to remove the air in reactor；Measure the 3-mercapto propyl group trimethoxy of 0.5 parts by volume Base silane and the ethanol of 15 parts by volume, add in reactor after mix homogeneously, and add the ammonia conduct of 5 parts by volume while stirring Catalyst, stirring reaction 8h at 80 DEG C.
Liquid in reactor is poured out, with centrifugal after ethanol purge 4 times, take out supernatant, precipitate is dried in an oven, Oven temperature is set as 50 DEG C, i.e. can get the Nano-meter SiO_2 of sulfhydrylation2, standby.
The preparation method of a kind of hydrophilic nano hybrid reinforcement type hollow-fibre membrane the most according to claim 1, its 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 mix, use machine mixer to stir, add alkynyl prepared by step (1) The Nano-meter SiO_2 of sulfhydrylation prepared by poly hydroxy ethyl acrylate and step (2)2, the wherein polymethylacrylic acid hydroxyl of alkynyl Ethyl ester, the Nano-meter SiO_2 of sulfhydrylation2It is 2-5: 0.7-1.5: 5-12 with the weight ratio of polyvinylidene fluoride resin；
Then the mode using negative pressure carries out deaeration, and the casting solution made after deaeration is positioned in batch can, in 65-75 DEG C of insulation； Solvent 2 with weight ratio is 6-12: 80-92: water mixed solvent is circulated as coagulating bath, then according to prepared by following method Hydrophilic nano hybrid reinforcement type hollow-fibre membrane:
1) the doughnut internal lining pipe pulled in fiber roller is passed sequentially through coating device and gel groove, be then around in wire drawing wheel On；
2) opening wire-feed motor and receive silk machine, the two rotating speed of regulation makes equipment run, and the speed of the two is 10-20 m/min, will material Liquid adds in reactor, then pressurizes in reactor, makes feed liquid lead to charge tube and carries to coating device；
3) fiber internal lining pipe is under the traction receiving silk machine, enters coagulation bath, fiber internal lining pipe after coating device coating feeding Feed liquid generation immersion inversion of phases on outer surface and gel sizing, lost flowability, form film silk, collected by wire drawing wheel；
4) by film silk irradiation under the ultraviolet light that wavelength is 280-380nm, make sulfhydryl cleavage produce Thiyl Radical, cause addition anti- Should；
5) immersion 15-28h in tank put into by the film silk after causing completely, thoroughly displaces solvent and additive；
6) film silk being dried process, dry temperature is 18-30 DEG C, and drying time is 8-15h, i.e. obtains described hydrophilic Nano hybridization enhancement type hollow fiber film.
8., according to the preparation method of a kind of hydrophilic nano hybrid reinforcement type hollow-fibre membrane described in claim 1 or 7, it is special Levy and be, in step (3),
Described solvent 2 is selected from dimethyl acetylamide, dimethyl sulfoxide or N-Methyl pyrrolidone.
9. according to the preparation side of a kind of hydrophilic nano hybrid reinforcement type hollow-fibre membrane described in claim 1, any one of 7-8 Method, it is characterised in that in step (3),
According to polyvinylidene fluoride resin: dimethyl acetylamide: Polyethylene Glycol additive: polyvinylpyrrolidone additive is by weight Ratio 18: 60: 10: 12 mixes, use machine mixer to stir, add the poly-first of alkynyl prepared by step (1) The Nano-meter SiO_2 of sulfhydrylation prepared by base 2-(Acryloyloxy)ethanol and step (2)2, wherein alkynyl poly hydroxy ethyl acrylate, The Nano-meter SiO_2 of sulfhydrylation2It is 3: 1: 9 with the weight ratio of polyvinylidene fluoride resin；
Then the mode using negative pressure carries out deaeration, and the casting solution made after deaeration is positioned in batch can, in 70 DEG C of insulations；With weight Amount is than the dimethyl acetylamide being 10: 90: water mixed solvent is circulated as coagulating bath, then according to following method preparation parent Water nano hybrid reinforcement type hollow-fibre membrane:
1) the doughnut internal lining pipe pulled in fiber roller is passed sequentially through coating device and gel groove, be then around in wire drawing wheel On；
2) opening wire-feed motor and receive silk machine, the two rotating speed of regulation makes equipment run, and the speed of the two is 15 ms/min, by feed liquid Add in reactor, then pressurize in reactor, make feed liquid lead to charge tube and carry to coating device；
3) fiber internal lining pipe is under the traction receiving silk machine, enters coagulation bath, fiber internal lining pipe after coating device coating feeding Feed liquid generation immersion inversion of phases on outer surface and gel sizing, lost flowability, form film silk, collected by wire drawing wheel；
4) by film silk irradiation under the ultraviolet light that wavelength is 365nm, make sulfhydryl cleavage produce Thiyl Radical, cause additive reaction；
5) immersion 24h in tank put into by the film silk after causing completely, thoroughly displaces solvent and additive；
6) film silk being dried process, dry temperature is 22-28 DEG C, and drying time is 10-15h, i.e. obtains described hydrophilic Property nano hybridization enhancement type hollow fiber film.
10. the hydrophilic nano hybrid reinforcement type doughnut prepared according to the method described in any one of claim 1-9 Film.
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CN117942426A (en) * 2024-03-22 2024-04-30 四川大学 Multi-stage porous material with oriented pore structure, and preparation method and application thereof

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CN112827367A (en) * 2021-01-22 2021-05-25 武汉钜能科技有限责任公司 Diatomite modified polyvinyl chloride composite separation membrane with high thermal stability and preparation method thereof
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CN117942426B (en) * 2024-03-22 2024-05-31 四川大学 Multi-stage porous material with oriented pore structure, and preparation method and application thereof

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