CN104209018A - Attapulgite/polyvinylidene fluoride nano-composite ultra-filtration membrane and preparation method thereof - Google Patents
Attapulgite/polyvinylidene fluoride nano-composite ultra-filtration membrane and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an attapulgite/polyvinylidene fluoride nano-composite ultra-filtration membrane and a preparation method thereof. The preparation method comprises the following steps: adding a certain amount of nano attapulgite into triethyl phosphate selected as a solvent; carrying out fierce mechanical agitation and ultrasonic treatment and adding polyvinylidene fluoride powder; agitating until the powder is dissolved; adding polyethylene glycol and agitating uniformly to obtain a membrane casting solution; and preparing the attapulgite/polyvinylidene fluoride nano-composite ultra-filtration membrane by taking water as a condensation bath through the adoption of an immersion precipitated phase conversion method. According to the attapulgite/polyvinylidene fluoride nano-composite ultra-filtration membrane disclosed by the invention, the nano attapulgite is guided into a polyvinylidene fluoride ultra-filtration membrane, and a unique nano fiber structure of the attapulgite and a three-dimensional net-shaped structure formed by the attapulgite and polyvinylidene fluoride are utilized, so that the structure and the strength of the polyvinylidene fluoride ultra-filtration membrane are effectively improved; and meanwhile, the permeability, the hydrophily and the anti-pollution capability of the polyvinylidene fluoride ultra-filtration membrane are improved by utilizing the high hydrophily of the attapulgite.
Description
Technical field
The present invention relates to a kind of attapulgite/polyvinylidene fluoride nanometer composite hyperfiltration membrane and preparation method thereof, belong to separation membrane technical field.
Background technology
Kynoar (PVDF) has the excellent properties such as high-strength corrosion-resisting, chemical resistance, heat-resisting quantity, oxidative resistance, and because PVDF pliability is good, oneself is widely used in preparation hollow fiber ultrafiltration membrane material.But Kynoar has lower surface energy and stronger hydrophobicity, cause its water permeation comparison of resistance high, limit its application in aqueous phase separation system; Hydrophobicity also causes film easily to be polluted simultaneously, its separating property of deterioration, and directly has influence on the economy of membrane separating process.Therefore, carry out hydrophilically modified to polyvinylidene fluoride film, improving its permeance property and suppress pollution capacity, is the simple and effective approach improving Kynoar film properties.
Blending and modifying be a kind of the most frequently used be also the most practical polymeric membrane method of modifying.The early stage film blending and modifying agent mainly water-soluble polymer such as polyethylene glycol and polyvinylpyrrolidone or LiCl, CaCl
2in inorganic salts, because these modifier are soluble in water, not only easily run off being inverted in membrane process, and in use also easily progressively run off from membrane material, thus have a strong impact on its hydrophilic modifying effect, so this type of modifier is mainly used for improving the structure of film and improving the porosity of film, be difficult to obtain good antifouling property.In recent years, by inorganic nano-particle and conventional polymer membrane material blended, the method preparing hydrophily diffusion barrier causes the attention of people, because inorganic nano-particle is hydrophilic but water insoluble, it can be avoided to run off from membrane material, obtain lasting modified effect.Inorganic nano-particle blending and modifying is easy to operate with it, technique is simply also widely used, and improves the hydrophily of film by adding inorganic nano-particle, reduces fouling membrane; In addition, owing to introducing inorganic particle in organic network, improve network structure, enhance the mechanical performance of polymeric membrane, improve heat endurance, made it have concurrently the toughness of polymeric membrane and the heat-resisting quantity of inoranic membrane.
At present, for the inorganic nano-particle of blending and modifying as Al
2o
3, TiO
2, ZrO
2and SiO
2etc. being graininess, these nano level inorganic particles can come off in film preparation and use procedure, and affect performance and the modified effect of film.By contrast, the monodimension nanometer materials such as CNT have superpower mechanical property, high length-width ratio and high-ratio surface, and the monodimension nanometer material be dispersed in polymeric membrane, effectively can improve its stability in membrane material by the spiral winding of macromolecular chain.But the Prof. Du Yucang monodimension nanometer material preparation costs such as CNT are high, purity and yielding poorly down, is difficult to dispersion, which greatly limits its scale application in film blending and modifying.
Summary of the invention
The object of this invention is to provide a kind of high flux attapulgite/polyvinylidene fluoride nanometer composite hyperfiltration membrane, utilize the nanofibrous structures of attapulgite uniqueness and effectively improve structure and the intensity of polyvinylidene fluoride (PVDF) ultrafiltration membrane with the tridimensional network that Kynoar is formed, utilize the permeability of attapulgite height water-wet behavior raising polyvinylidene fluoride (PVDF) ultrafiltration membrane, hydrophily, stability and contamination resistance simultaneously.
According to an aspect of the present invention, a kind of attapulgite/polyvinylidene fluoride nanometer composite hyperfiltration membrane, by weight, its raw materials comprises following component: polyvinylidene fluoride resin 15 ~ 20 parts, organic solvent 80 ~ 85 parts, nano-attapulgite stone, additive; The weight of described nano-attapulgite stone is 0.5 ~ 15% (preferably 6.7 ~ 10%) of polyvinylidene fluoride resin weight, and the weight of described additive is 2 ~ 6% of polyvinylidene fluoride resin and organic solvent gross mass.
Further, described organic solvent is selected from METHYLPYRROLIDONE, oxolane, dimethyl sulfoxide (DMSO), tetramethylurea, amide solvent, esters solvent or lactone solvent.
Further, described amide solvent is selected from dimethylacetylamide, dimethyl formamide etc.; Described esters solvent is selected from trimethyl phosphate or triethyl phosphate etc.; Described lactone solvent is selected from gamma-butyrolacton etc.; Most preferably be triethyl phosphate.
Further, described additive is selected from polyethylene glycol, PVP, polyvinyl alcohol, polyacrylic acid, polyethylene glycol, lithium chloride, sodium chloride, calcium chloride, lithium nitrate, formaldehyde, formamide; Preferred polyethylene glycol.
Further, the fibre length of nano-attapulgite stone is 500 ~ 2000nm, and diameter is 30 ~ 70nm, and attapulgite content is not less than 95%.
Further, nano-attapulgite stone is cationic surfactant modification.
According to another aspect of the present invention, the preparation method of attapulgite/polyvinylidene fluoride nanometer composite hyperfiltration membrane, nano-attapulgite stone is comprised the steps: to add in organic solvent, make mixed system homogenising, casting solution is obtained after adding polyvinylidene fluoride resin and organic additive stirring and dissolving again, standing and defoaming, adopts immersion precipitation phase inversion process to prepare milipore filter.
Further, nano-attapulgite stone is cationic surfactant modification.
Further, water is adopted to be coagulating bath in phase inversion.
Further, spin processes is adopted in phase inversion.
Further, the temperature in the process of homogenising controls at 75 ~ 85 DEG C.
Further, the time of stirring and dissolving is 24 ~ 36 hours.
Further, the time of standing and defoaming is 12 ~ 24 hours; The temperature of standing and defoaming is 75 ~ 85 DEG C.
Further, the technological parameter in spin processes is: it is 0 ~ 30cm that air does journey; Casting solution flow velocity is 2 ~ 10mL/min; Core liquid is deionized water, and its flow velocity is 2 ~ 6mL/min; The water temperature of coagulating bath is at 20 ~ 30 DEG C.
beneficial effect
1. this nano combined hollow fiber ultrafiltration membrane utilizes the nanofibrous structures of attapulgite uniqueness and effectively improves structure and the intensity of polyvinylidene fluoride (PVDF) ultrafiltration membrane with the tridimensional network that Kynoar is formed, and utilizes attapulgite height water-wet behavior effectively to improve the permeability of polyvinylidene fluoride (PVDF) ultrafiltration membrane, hydrophily and contamination resistance simultaneously.
2. compared with particulate inorganic nano particle, attapulgite is that monodimension nanometer material has excellent mechanical property, high length-width ratio, high-ratio surface and nano level structure pore, and the monodimension nanometer material be dispersed in polymeric membrane, effectively can improve its stability in membrane material by the spiral winding of macromolecular chain.
3. compared with unmodified nano-attapulgite stone, by cationic surfactant modification efficient solution from nano-attapulgite stone crystalline substance bundle, improve nano-attapulgite stone dispersiveness and and Kynoar between compatibility and the stability of composite membrane.
4. compared with the nano material of Prof. Du Yucang, natural nano attapulgite clay is huge at China's reserves, cheap, and the process of exploitation energy consumption is extremely low, and do not have the negative effect of environment aspect, its cost performance is obviously better than Prof. Du Yucang nano-fiber material.
Detailed description of the invention
Below by detailed description of the invention, the present invention is described in further detail.But it will be understood to those of skill in the art that the following example only for illustration of the present invention, and should not be considered as limiting scope of the present invention.Unreceipted concrete technology or condition person in embodiment, according to the technology described by the document in this area or condition or carry out according to product description.Agents useful for same or the unreceipted production firm person of instrument, being can by the conventional products of commercial acquisition.
Approximate language used herein can be used for modifying the statement of any quantity in whole description and claims, and it can permit changing under the condition not causing its relevant basic function to change.Therefore, the value of being modified by the term of such as " about " is not limited to specified exact value.In at least some cases, approximate language can be corresponding with the precision of the instrument for measuring this value.Unless separately pointed out in context or statement, otherwise range limit can carry out combining and/or exchanging, and this scope is confirmed as and comprises included all subranges herein.Except in operation embodiment or except indicating in other places, the numeral of the amount, reaction condition etc. of all expression compositions used in description and claims or express the modification that all should be understood to be subject to word " about " in all cases.
The numerical value as range limit not only comprising and clearly listing should be interpreted as in a flexible way using the value that range format is expressed, but also comprise and be encompassed in all single numerical value within the scope of this or subinterval, be expressly recited out just as each numerical value and subinterval.Such as, the concentration range of " about 0.1% to about 5% " should be understood to the concentration not only comprising about 0.1% to about 5% clearly listed, also include single concentration in institute's how (as, 1%, 2%, 3% and 4%) and subinterval (such as, 0.1% to 0.5%, 1% to 2.2%, 3.3% to 4.4%).
Nano-attapulgite stone (nanoattapulgite) is the alumina magnesia silicate of a kind of layer of chain structure, its profile, in threadiness or bar-shaped, has the crystal diameter of nanoscale, diameter 30 ~ 70nm, length about 0.5 ~ 5 μm, belongs to typical monodimension nanometer material.Natural nano attapulgite has the nano-scale structure of one dimension on the external appearance characteristic such as form, size, consistent with the one-dimentional structure nano material of Prof. Du Yucang, this means that they have same or analogous purposes, but compared with the nano material of Prof. Du Yucang, nano-attapulgite stone wide material sources.Attapulgite clay (is called for short recessed soil, its main component is nano-attapulgite stone) huge at China's reserves, only Huai'an, Jiangsu Province Xuyi County has verified recessed native ore resources reserves is 1.03 hundred million tons, account for the whole nation and verify 73% of recessed native reserves, account for that recessed native reserves have been verified in the whole world 44%, prospective reserves reaches 11.7 hundred million tons.The production cost of nano-attapulgite stone is low, be easy to comparatively produce in enormous quantities, exploitation process energy consumption is extremely low, and nano-attapulgite stone has excellent environment compatibility and compatibility, its cost performance is obviously better than Prof. Du Yucang nano-fiber material, can solve little, the high in cost of production problem of artificial nano unit material batch preferably.
The present invention is by introducing polyvinylidene fluoride (PVDF) ultrafiltration membrane by nano-attapulgite stone, utilize the nanofibrous structures of attapulgite uniqueness and effectively improve structure and the intensity of polyvinylidene fluoride (PVDF) ultrafiltration membrane with the tridimensional network that Kynoar is formed, utilize the permeability of attapulgite height water-wet behavior raising polyvinylidene fluoride (PVDF) ultrafiltration membrane, hydrophily and contamination resistance simultaneously, this membrane preparation method is simple, membrane aperture is controlled, is applicable in the practical applications such as sewage disposal of today, Industrial Wastewater Treatment, Treated sewage reusing, rural potable water.The fibre length of the nano-attapulgite stone adopted in following examples is 500 ~ 2000nm, and diameter is 30 ~ 70nm, and attapulgite content is not less than 95%.
Include Kynoar in the raw material of this milipore filter, also include nano-attapulgite stone in addition, be doped in casting solution and can prepare composite hyperfiltration membrane, in casting solution, also include the organic solvent dissolving polyvinylidene fluoride resin.
Herein, organic solvent refers to the material dissolving polyvinylidene fluoride resin, can enumerate: such as, METHYLPYRROLIDONE, oxolane, dimethyl sulfoxide (DMSO), tetramethylurea; The acid amides such as dimethylacetylamide, dimethyl formamide; Ester or the lactones such as trimethyl phosphate, triethyl phosphate, gamma-butyrolacton; And their mixed solvent.
In addition, also can organic additive containing the aperture, porosity, hydrophily, elastic modelling quantity etc. for regulating the micro-porous supporting film of gained in the component of casting solution.As the additive for adjustment aperture and porosity, alcohols can be enumerated, water soluble polymer or their salt such as polyethylene glycol, PVP, polyvinyl alcohol, polyacrylic acid, also have the inorganic salts such as lithium chloride, sodium chloride, calcium chloride, lithium nitrate, formaldehyde, formamide etc., but be not limited thereto.Adopt PEG400 as expanding agent in following examples.
The preparation method of this milipore filter can adopt the method for common inversion of phases to obtain, and after casting solution, in solidification liquid, inversion of phases is occurred, can obtain the milipore filter with microcellular structure.
In said method, solidification liquid, as non-solvent, can be enumerated: such as, water; The aliphatic hydrocarbons such as hexane, pentane, trichloro-ethylene; The aromatic hydrocarbon such as benzene, toluene etc.; And their mixed solvent etc.When by Kynoar be used as polymer raw material, as the non-solvent of coagulating bath, usually preferably use water, as long as but the material of insoluble solution Kynoar, there is no particular limitation.The film form of the micro-porous supporting film obtained changes according to the composition of Polymer Solution, and the film formative of composite semipermeable membrane also changes thereupon.In addition, the temperature of coagulating bath is preferably 10 DEG C ~ 90 DEG C.More preferably 20 ~ 30 DEG C.If the temperature of coagulating bath is higher than this scope, then the vibration in coagulating bath face becomes fierce due to warm-up movement, and the flatness on the film surface after film is formed easily reduces.Otherwise if temperature is too low, then setting rate is slack-off, generation problem in masking.
Next, in order to remove the casting solution of obtained milipore filter, preferably hot water cleaning is carried out to described film.Hot water temperature is now preferably 50 ~ 100 DEG C, more preferably 60 ~ 95 DEG C.If the temperature of hot water is higher than this scope, then the degree of shrinkage of micro-porous supporting film becomes large, and water penetration reduces.Otherwise if the temperature of hot water is low, then cleaning effect is little.
According to an improved procedure of the present invention, nano-attapulgite stone is through cationic surfactant modification, by cationic surfactant modification efficient solution from nano-attapulgite stone crystalline substance bundle, improve nano-attapulgite stone dispersiveness and and Kynoar between compatibility and the stability of composite membrane, and the modification of cationic surfactant to attapulgite carries out exchange by the cation on its attapulgite to carry out, do not affect the hydroxyl on attapulgite surface, after these hydroxyls are retained on attapulgite, more can ensure that it has good hydrophilic modifying effect, improve the stability of compatibility between nano-attapulgite stone and Kynoar and composite membrane.
In the present invention, adopt molecular cut off to characterize milipore filter performance, molecular cut off is the molecular weight of the solute of the clearance of film when can reach 90%.Being determined as follows of molecular cut off.First, filter the weak solution of often kind of water-soluble polymer (glucan etc.) containing multiple different molecular weight as respective solute with film, and try to achieve the clearance to often kind of water-soluble polymer.Next, using the molecular weight of water-soluble polymer as transverse axis, map as the longitudinal axis using clearance, draw curve of approximation, and will be that the molecular weight in the crosspoint of 90% is as molecular cut off with clearance.
In the present invention, fracture strength is adopted to characterize the mechanical performance of milipore filter.Method: cut the long sample of 5 cm from film, this sample is set as on the autoplotter of 2 cm to make mode that the length direction of sample is draw direction be arranged on initial jaw separation, environment temperature be 25 DEG C, till draw speed is stretched to sample breakage under being the condition of 20 cm/ minutes.Fracture strength during working sample fracture.
Film pure water flux measures on self-control milipore filter evaluating apparatus, and operating pressure is 0.1 MPa, and flow velocity is 1 m/s, and running time is 30 min; Under room temperature and 0.1 MPa pressure, deionized water is replaced on film properties evaluating apparatus, to carry out separating property experiment to milipore filter, to measure the contamination resistance of film with bovine serum albumin (BSA) PBS that mass concentration is 50 mg/L.In operation after 120 minutes, measure the attenuation of flux, attenuation=(at the end of 1-filtration flux/initial flux) × 100%.
Dry after membrane sample being soaked in ethanol 48 h, measure the contact angle of deionized water on film surface with contact angle instrument, often kind of film is tested 5 samples and is averaged.
embodiment 1
1 gram of nano-attapulgite stone is joined among 80 grams of triethyl phosphates, after vigorous mechanical agitation and ultrasonic process evenly, add 20 grams of Kynoar powders stirring and dissolving 24 hours at 80 DEG C, add 5 grams of polyethylene glycol again and stir 12 hours to obtain casting solution, standing and defoaming 24 hours at 80 DEG C, adopt immersion precipitation phase inversion process, condition is: it is 0cm that air does journey; Casting solution flow velocity is 2mL/min; Core liquid is deionized water, and its flow velocity is 2mL/min; Coagulating bath is deionized water, and water temperature, at 20 ~ 30 DEG C, obtains attapulgite/polyvinylidene fluoride nanometer composite hollow fibre milipore filter, film thickness about 200 μm, external diameter about 1.0 mm.After measured, the pure water flux at 0.1MPa and 20 DEG C is 160 L/ (m
2h); With glucan be demarcate thing, its molecular cut off is 150000 Da; Film average pore size about 23 nm, water droplet contact angle is 60.3 °; Fracture strength about 3.2 MPa, filters the flux decline about 75% of BSA solution.
reference examples 1
Be with the difference of embodiment 1: in casting solution, do not add nano-attapulgite stone, prepare conventional PVDF ultrafiltration membrane.20 grams of Kynoar powders stirring and dissolving 24 hours at 80 DEG C is added among 80 grams of triethyl phosphates, add 5 grams of polyethylene glycol again and stir 12 hours to obtain casting solution, standing and defoaming 24 hours at 80 DEG C, adopt immersion precipitation phase inversion process, condition is: it is 0cm that air does journey; Casting solution flow velocity is 2mL/min; Core liquid is deionized water, and its flow velocity is 2mL/min; Coagulating bath is deionized water, and water temperature, at 20 ~ 30 DEG C, obtains polyvinylidene fluoride hollow fiber ultrafiltration membrane, film thickness about 200 μm, external diameter about 1.0 mm.After measured, the pure water flux at 0.1MPa and 20 DEG C is 106 L/ (m
2h); With glucan be demarcate thing, its molecular cut off is 200000 Da; Water droplet contact angle is 94.1 °; Fracture strength about 2.8 MPa, filters the flux decline about 89% of BSA solution.Can be found out by embodiment 1 and reference examples 1, by add nano-attapulgite stone in casting solution after, its three-dimensional structure and hydrophily can be utilized to make the surface of milipore filter produce hydrophily, water flux is larger, and its molecular cut off can be reduced significantly, improve separation accuracy, its drawing mechanical performance can also be improved in addition.
embodiment 2
Respectively 0.1,0.5,1,1.5,2 gram of nano-attapulgite stone is joined 85 grams of triethyl phosphates wherein, after vigorous mechanical agitation and ultrasonic process evenly, add 15 grams of Kynoar powders stirring and dissolving 24 hours at 80 DEG C, add 5 grams of polyethylene glycol again and stir 12 hours to obtain casting solution, standing and defoaming 24 hours at 80 DEG C, adopt immersion precipitation phase inversion process, condition is: it is 0cm that air does journey; Casting solution flow velocity is 2mL/min; Core liquid is deionized water, and its flow velocity is 2mL/min; Coagulating bath is deionized water, and water temperature, at 20 ~ 30 DEG C, obtains attapulgite/polyvinylidene fluoride nanometer composite hollow fibre milipore filter.Under the condition of different nano-attapulgite stone additions, film properties data are as shown in the table:
As can be seen from the table, the addition controlling nano-attapulgite stone can obtain the large composite hyperfiltration membrane of flux preferably, and in the scope of the addition of 0.5 ~ 1.5g, flux is more excellent; And there is less molecular cut off, there is good separating property.
embodiment 3
1 gram of nano-attapulgite stone is joined in 80 grams of organic solvents and (adopts METHYLPYRROLIDONE, gamma-butyrolacton, triethyl phosphate, dimethyl formamide respectively), after vigorous mechanical agitation and ultrasonic process evenly, add 20 grams of Kynoar powders stirring and dissolving 24 hours at 80 DEG C, add 4 grams of polyethylene glycol again and stir 12 hours to obtain casting solution, standing and defoaming 24 hours at 80 DEG C, adopt immersion precipitation phase inversion process, condition is: it is 30cm that air does journey; Casting solution flow velocity is 2mL/min; Core liquid is deionized water, and its flow velocity is 6mL/min; Coagulating bath is deionized water, and water temperature, at 20 ~ 30 DEG C, obtains attapulgite/polyvinylidene fluoride nanometer composite hollow fibre milipore filter.Film properties parameter is as follows:
embodiment 4
Be with the difference of embodiment 2: nano-attapulgite stone is before use through cationic surfactant modification, and method of modifying is: the nano-attapulgite stone of 5g is added in the deionized water of 500 ml, stir obtained suspension; The temperature of suspension is adjusted to 80 DEG C, then adds the cationic surfactant of nano-attapulgite stone weight 3%, holding temperature, stir 3h, after reaction bonded, suction filtration, successively respectively washs 3 times with deionized water and absolute ethyl alcohol, dry, pulverize, to obtain final product.
The nano-attapulgite stone of 1 gram of above-mentioned modification is joined 85 grams of triethyl phosphates wherein, after vigorous mechanical agitation and ultrasonic process evenly, add 15 grams of Kynoar powders stirring and dissolving 24 hours at 80 DEG C, add 5 grams of polyethylene glycol again and stir 12 hours to obtain casting solution, standing and defoaming 24 hours at 80 DEG C, adopt immersion precipitation phase inversion process, condition is: it is 30cm that air does journey; Casting solution flow velocity is 2mL/min; Core liquid is deionized water, and its flow velocity is 6mL/min; Coagulating bath is deionized water, and water temperature, at 20 ~ 30 DEG C, obtains high flux attapulgite/polyvinylidene fluoride nanometer composite hollow fibre milipore filter.Film properties parameter is as follows:
As can be seen from the table, after carrying out modification to nano-attapulgite stone, milipore filter flux decline in filter process is less than unmodified, and this may be the compatibility owing to can improve after modification between nano-attapulgite stone and polymer.
reference examples 2
So with the difference of embodiment 3 by the modification of attapulgite Silane coupling reagent KH-570 is obtained, method of modifying is: (at 105 DEG C, predrying 2 h) to add 100 ml toluene, 1 ml water and 3.0 g nano-attapulgite stones in the reactor successively, add 3 ml silane couplers subsequently while stirring, ultrasonic 40 min at 40 ~ 45 DEG C; Then under agitation constant temperature 45 ~ 50 DEG C reaction 4 h, unnecessary silane coupler is removed with the washing of toluene, absolute ethyl alcohol and deionized water successively after product is separated by filtration, dry at 105 DEG C, obtain silane coupler modified nano-attapulgite stone, ground 200 mesh sieves are for subsequent use.The nano-attapulgite stone of 1 gram of above-mentioned modification is joined 85 grams of triethyl phosphates wherein, after vigorous mechanical agitation and ultrasonic process evenly, add 15 grams of Kynoar powders stirring and dissolving 24 hours at 80 DEG C, add 5 grams of polyethylene glycol again and stir 12 hours to obtain casting solution, standing and defoaming 24 hours at 80 DEG C, adopt immersion precipitation phase inversion process, condition is: it is 30cm that air does journey; Casting solution flow velocity is 2mL/min; Core liquid is deionized water, and its flow velocity is 6mL/min; Coagulating bath is deionized water, and water temperature, at 20 ~ 30 DEG C, obtains high flux attapulgite/polyvinylidene fluoride nanometer composite hollow fibre milipore filter.
After measured, the pure water flux at 0.1MPa and 20 DEG C is 230 L/ (m
2h); With glucan be demarcate thing, its molecular cut off is 210000 Da; Film average pore size about 30 nm, water droplet contact angle is 55.7 °; Fracture strength about 3.2 MPa, filters the flux decline about 70% of BSA solution.Compared with silane coupler modified nano-attapulgite stone, the modification of cationic surfactant to attapulgite carries out exchange by the cation on its attapulgite to carry out, do not affect the hydroxyl on attapulgite surface, and silane coupler modified nano-attapulgite stone is undertaken by the hydroxyl reaction on coupling agent and attapulgite surface, cause the flux of final obtained milipore filter, antifouling property all be not so good as the film that the modification of employing cationic surfactant obtains.
Claims (9)
1. attapulgite/polyvinylidene fluoride nanometer composite hyperfiltration membrane, is characterized in that, by weight, its raw materials comprises following component: polyvinylidene fluoride resin 15 ~ 20 parts, organic solvent 85 ~ 80 parts, nano-attapulgite stone, additive; The weight of described nano-attapulgite stone is 0.5 ~ 15% of polyvinylidene fluoride resin weight, and the weight of described additive is 2 ~ 6% of polyvinylidene fluoride resin and organic solvent gross mass.
2. attapulgite according to claim 1/polyvinylidene fluoride nanometer composite hyperfiltration membrane, is characterized in that: described organic solvent is selected from METHYLPYRROLIDONE, oxolane, dimethyl sulfoxide (DMSO), tetramethylurea, amide solvent, esters solvent or lactone solvent; Described amide solvent is selected from dimethylacetylamide, dimethyl formamide; Described esters solvent is selected from trimethyl phosphate or triethyl phosphate etc.; Described lactone solvent is selected from gamma-butyrolacton.
3. attapulgite according to claim 1/polyvinylidene fluoride nanometer composite hyperfiltration membrane, is characterized in that: described additive is selected from polyethylene glycol, PVP, polyvinyl alcohol, polyacrylic acid, polyethylene glycol, lithium chloride, sodium chloride, calcium chloride, lithium nitrate, formaldehyde, formamide.
4. attapulgite according to claim 1/polyvinylidene fluoride nanometer composite hyperfiltration membrane, is characterized in that: the fibre length of nano-attapulgite stone is 500 ~ 2000nm, and diameter is 30 ~ 70nm, and attapulgite content is not less than 95%.
5. attapulgite according to claim 1/polyvinylidene fluoride nanometer composite hyperfiltration membrane, is characterized in that: described nano-attapulgite stone is cationic surfactant modification.
6. the preparation method of attapulgite according to claim 1/polyvinylidene fluoride nanometer composite hyperfiltration membrane, it is characterized in that, nano-attapulgite stone is comprised the steps: to add in organic solvent, make mixed system homogenising, casting solution is obtained after adding polyvinylidene fluoride resin and additive stirring and dissolving again, standing and defoaming, adopts immersion precipitation phase inversion process to prepare milipore filter.
7. the preparation method of attapulgite according to claim 6/polyvinylidene fluoride nanometer composite hyperfiltration membrane, is characterized in that: adopt water to be coagulating bath in phase inversion; Spin processes is adopted in phase inversion.
8. the preparation method of attapulgite according to claim 6/polyvinylidene fluoride nanometer composite hyperfiltration membrane, is characterized in that: the temperature in the process of homogenising controls at 75 ~ 85 DEG C; The time of stirring and dissolving is 24 ~ 36 hours; The time of standing and defoaming is 12 ~ 24 hours; The temperature of standing and defoaming is 75 ~ 85 DEG C.
9. the preparation method of attapulgite according to claim 7/polyvinylidene fluoride nanometer composite hyperfiltration membrane, is characterized in that: the technological parameter in spin processes is: it is 0 ~ 30cm that air does journey; Casting solution flow velocity is 2 ~ 10mL/min; Core liquid is deionized water, and its flow velocity is 2 ~ 6mL/min; The water temperature of coagulating bath is at 20 ~ 30 DEG C.
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| CN115920676A (en) * | 2022-12-07 | 2023-04-07 | 中复新水源科技有限公司 | Preparation method of polyimide composite nanofiltration membrane |
| CN115920676B (en) * | 2022-12-07 | 2023-06-20 | 中复新水源科技有限公司 | Preparation method of polyimide composite nanofiltration membrane |
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