CN103785304B - A kind of hydrophilic grafts multi-walled carbon nano-tubes modified polyvinilidene fluoride film and preparation method thereof - Google Patents
A kind of hydrophilic grafts multi-walled carbon nano-tubes modified polyvinilidene fluoride film and preparation method thereof Download PDFInfo
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- CN103785304B CN103785304B CN201410025347.1A CN201410025347A CN103785304B CN 103785304 B CN103785304 B CN 103785304B CN 201410025347 A CN201410025347 A CN 201410025347A CN 103785304 B CN103785304 B CN 103785304B
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Abstract
The invention provides a kind of hydrophilic grafts multi-walled carbon nano-tubes modified polyvinilidene fluoride film and preparation method thereof.First the peg molecule chain of low polymerization degree is grafted on multi-walled carbon nano-tubes, then the CNT of hydrophilic grafts is evenly spread in PVDF casting solutions, using immersion precipitation phase inversion process film forming.The polyglycol chain of the low polymerization degree being grafted on CNT is on the one hand as hydrophilic radical, the hydrophily of film, and then the contamination resistance of raising film can be improved, on the other hand as polymer, there can be good compatibility with PVDF matrixes, be conducive to CNT dispersion in the base, improve the contact area between CNT and matrix, increase film-strength, in addition, preparation process is simple of the present invention, it is workable, it is easy to accomplish.
Description
Technical field
The invention belongs to seperation film technical field of modification, more particularly to a kind of multi-walled carbon nano-tubes of employing hydrophilic grafts
Modified seperation film and preparation method thereof.
Background technology
Kynoar (PVDF) is a kind of polymer of semicrystalline, due to C-F bond distance it is short, the big (486kJ/ of bond energy
Mo1), thus with good heat endurance, chemical stability, radiation resistance and high mechanical strength, it is a kind of combination property
Excellent separation membrane material.However, as a kind of very strong macromolecular material of hydrophobicity, PVDF in use, its film surface and
Easy cooperating microorganisms in duct, absorption inorganic matter, colloidal solid thing, protein etc., some for causing film properties can not inversion
Change, such as membrane aperture diminish or block the film permeation flux that causes decline, it is selective reduce, service life shortening etc., i.e. fouling membrane.
Increase the hydrophily of film, film surface can be made the orderly layer of hydrogen bond to be formed with hydrone, absorption pollution is just not susceptible to, so as to increase
The resistance tocrocking of film itself.Therefore, how effective and easy the hydrophily and antibiotic property of raising film, extend the use of seperation film
Life-span, it has also become improve an important directions of fouling membrane.
At present, by inorganic filler and high-molecular organic material blending and modifying, the resistance tocrocking and antibiotic property of film are improved, is to grind
Study carefully one of more modified direction, inorganic filler mainly has the A1 of three-dimensional2O3、SiO2、TiO2, Nano Silver etc., the Graphene of two dimension
And one-dimensional CNT etc..As inorganic three-dimensional manometer packing specific area is little, and it is difficult to carry out effectively with polymer matrix
Combination, cause which poor to high molecular hydrophilic modifying effect, be also easy to become stress concentration point and destroyed material.
Therefore, increasing researcher is introduced into after being processed Graphene and CNT in PVDF, to increase the strong of film simultaneously
Degree and hydrophily.
Patent 201210096520.8 discloses a kind of method for preparing polyvinylidene fluoride-carbon nano tube composite separation film,
It is CNT is evenly spread in PVDF using ultrasound plus churned mechanically method, by prepared by wet method phase inversion being combined
Seperation film.As the addition of CNT enhances the hydrophily of film, the resistance tocrocking of film is improve.Patent
201310014691.6 disclosing a kind of preparation method of the modified seperation film of hydrophilicity kynoar, it is while by graphite oxide
Alkene, CNT and pore-foaming agent are added in PVDF, and the oxygen-containing functional group on filler can strengthen the hydrophily of seperation film, and carbon
Nanotube and Graphene mutually suppress respective reunion, but all to there is modified effect not notable for both method of modifying, by
Very big in the specific surface area of nano level Graphene and CNT, simple oxidation processes can not make the fully homogeneous dispersion of carbon pipe
And be easier to reunite, and then affect film-strength and separating property and resistance tocrocking.This is accomplished by us and attempts significantly more efficient process
Method carries out hydrophilic modifying to carbon pipe so as to is easier to disperse in polymer matrix, improves the resistance tocrocking of seperation film.
The content of the invention
It is an object of the present invention to provide it is a kind of effectively can strengthen dispersiveness of the CNT in polymer matrix,
The hydrophily and resistance tocrocking of film are improved, while the simple hydrophilic grafts carbon nano-tube modification Kynoar of filming technology
Film and preparation method thereof.
To solve above-mentioned technical problem, the technical solution used in the present invention is：
A kind of hydrophilic grafts carbon nano-tube modification polyvinylidene fluoride film, percentage are made up of the following raw material：
Kynoar 5%-15%
N-N dimethyl acetamides 85%-95%
Hydrophilic grafts multi-walled carbon nano-tubes accounts for Kynoar 0.1%-3% (by weight)；
The overall weight percent of above-mentioned raw materials is 100%；
The Kynoar refers to the Kynoar that molecular weight ranges are 400000-900000, in changing for the present invention
In property film as film material of main part.
The hydrophilic grafts multi-walled carbon nano-tubes is obtained by the following raw material reaction：
Functionalized multi-wall carbonnanotubes purity >=95wt% 1.0g ± 0.001g
Thionyl chloride purity >=99.5% 200mL ± 1mL
The chemical pure 150mL ± 1mL of polyethylene glycol (200g/mo1)
The diameter range of described functionalized multi-wall carbonnanotubes is that, less than 8nm, length range is 10-30 μm, specific surface
More than 500m2/g, the draw ratio of the functionalized multi-wall carbonnanotubes is 1250-3750: 1 to product.Compared with SWCN,
There are more defects in the tube wall of multi-walled carbon nano-tubes, thus reactivity increases, it is easy to possess more work by being modified
Property group.
The preparation method of hydrophilic grafts multi-walled carbon nano-tubes of the present invention, comprises the steps：
(1) reaction is carried out in there-necked flask, and the functionalized multi-wall carbonnanotubes weighed according to above-mentioned weight are added to
In thionyl chloride, in 20 DEG C of ultrasound 0.5-1h, make functionalized multi-wall carbonnanotubes carry out preliminary dispersion and be beneficial to reaction；
(2) condensation reflux unit is assembled, opens stirring and heat, at 60-70 DEG C, flow back controlling reaction temperature 10h；
(3) stop heating, temperature be slowly decreased to into room temperature, stir 3h, be again turned on heating, be to slowly warm up to 60-70 DEG C,
It is stirred at reflux 40h；
(4) by mixture suction filtration, it is dried at room temperature for, obtains the multi-walled carbon nano-tubes of chloride；
(5) take acyl chlorides multi-walled carbon nano-tube and polyethylene glycol (200g/mo1) is added in there-necked flask, control reaction
Temperature at 120-150 DEG C, stirring reaction 36h；
(6) (5) reacted suspended mixture suction filtration, ethanol are washed, drying at room temperature obtains many wall carbon of hydrophilic grafts
Nanotube.
Present invention also offers a kind of preparation method of hydrophilic grafts multi-walled carbon nano-tubes modified polyvinilidene fluoride film, including
The following steps for carrying out in order：
(1) the hydrophilic grafts multi-walled carbon nano-tubes weighed according to above-mentioned percetage by weight is added to into N-N dimethylacetamides
In amine, at 50-60 DEG C, heating stirring 2-4h in preferably 60 DEG C of water-bath, preferably 2 hours, then be placed in ultrasonic washing instrument super
Sound disperses 1-2h, preferably 1 hour, hydrophilic grafts multi-walled carbon nano-tubes is tentatively disperseed in casting solution；
(2) Kynoar is added in above-mentioned dispersion liquid, solution is placed in into heating stirring in 55-60 DEG C of water-bath and is extremely polymerized
Thing is completely dissolved, and then transfers the solution into strength ultrasound in ultrasonic cell disruptor, until obtaining many wall carbon of hydrophilic grafts
The finely dispersed casting solution of nanotube；
(3) above-mentioned casting solution is stood into placement deaeration at room temperature；
(4) at ambient temperature, take casting solution and certain thickness homogeneous membrane is made with knifing rod on a glass, in air
In immerse film forming in coagulating bath (deionized water) after pre- volatilization 30-50s；
(5) water is changed repeatedly to above-mentioned film to deviate from solvent N-N dimethyl acetamides, finally film is taken out from coagulating bath is
Hydrophilic grafts multi-walled carbon nano-tubes modified polyvinilidene fluoride film is obtained.
The hydrophilic grafts multi-walled carbon nano-tubes modified polyvinilidene fluoride film is Flat Membrane.
Described modified seperation film is microfiltration membranes and milipore filter.
The invention provides a kind of basement membrane film strength that neither reduces can improve the side of polyvinylidene fluoride film hydrophilically again
Method, i.e., be first grafted to the peg molecule chain of low polymerization degree on multi-walled carbon nano-tubes, then by the CNT of hydrophilic grafts
Evenly spread in PVDF casting solutions, using immersion precipitation phase inversion process film forming.The low polymerization degree being grafted on CNT
Polyglycol chain can improve the hydrophily of film, and then the contamination resistance of raising film, the opposing party on the one hand as hydrophilic radical
Face can have good compatibility with PVDF matrixes as polymer, be conducive to CNT distribution in the base, improve carbon
Contact area between nanotube and matrix, increases film-strength, carbon nano-tube filled inclined to gathering with simply acidified process
It is modified in fluoride separation membrane and compares, the present invention is adopted first carries out hydrophilic polymer grafting to multi-walled carbon nano-tubes, then altogether
The method of film is blended, CNT can not only be solved and be difficult to a scattered difficult problem, and CNT and polymer matrix can also be made
There is more preferable compatibility, additionally, preparation process is simple of the present invention, workable, it is easy to accomplish.
Specific embodiment
With reference to the polyethylene glycol grafted multi-wall CNT that specific embodiment is provided to the present invention, and hydrophilic grafts carbon
The preparation method of nanotube modified polyvinilidene fluoride film is described in detail.
Embodiment 1：
Above-mentioned functionalized multi-wall carbonnanotubes 1.0g ± 0.001g and thionyl chloride 200mL ± 1mL are weighed, three are added to
In mouth flask, jump a queue, in 20 DEG C of water-baths after ultrasound 40min, assemble condensation reflux unit, while open stirring and heat,
65 DEG C are to slowly warm up to, flow back 10h, then stop heating and temperature is slowly dropped to into room temperature, after stirring 3h, be again turned on heating
65 DEG C are warming up to, the lower backflow 40h of stirring, then by mixture room temperature suction filtration, drying, obtain black powder, i.e. chloride carbon nanometer
Pipe.Then the polyethylene glycol (200g/mo1) of the acyl chlorides carbon nano tube for obtaining and 150mL ± 1mL is added to into there-necked flask
In, unlatching is stirred and is heated, and is warming up to 130 DEG C of reaction 36h, by reacted suspended mixture room temperature suction filtration, ethanol washing, is done
It is dry, that is, obtain the multi-walled carbon nano-tubes of PEG hydrophilic grafts.
Polyethylene glycol hydrophilic grafts multi-walled carbon nano-tubes to preparing should be stored in water white glass container, sealed
Preserve, waterproof, sun-proof, anti-chemical medicine to corrode, 20 DEG C ± 2 DEG C of storage temperature.
Embodiment 2：
The multi-walled carbon nano-tubes of the hydrophilic grafts that 0.02g embodiments 1 are prepared is added to 23g N-N dimethylacetamides
In amine, heating stirring 2h in 60 DEG C of water-baths, then ultrasonic disperse 1h in ultrasonic washing instrument is placed in, 2g polyvinylidene fluorides are added afterwards
Alkene, in 60 DEG C of water-baths, heating stirring 8h then carries out strength ultrasound (100W) 30min to being completely dissolved to which, is stored at room temperature de-
Bubble, using the knifing rod of the certain thickness knifing on clean glass plate is controlled, makes the casting solution after knifing through pre- volatilization 30s
Afterwards, in rapid immersion deionized water coagulating bath, after film forming, water abjection solvent N-N dimethyl acetamides are changed repeatedly to which, is finally made
Obtain the polyvinylidene fluoride film of hydrophilic grafts carbon nano-tube modification.
In order to the hydrophily for characterizing modified seperation film changes, above-mentioned hydrophilic grafts modified polyvinilidene fluoride film is vacuum dried
The contact angle to water is carried out afterwards to test, and the contact angle of water is contrasted with pure polyvinylidene fluoride film.Experimental result shows,
Pure polyvinylidene fluoride film is 79.6 ° to the contact angle of water, and the modified polyvinilidene fluoride film that the present embodiment is provided, it is being added without
In the case of hydrophilic additive so as to be 60.3 ° to the contact angle of water, show the modified polyvinilidene fluoride film that the present invention is prepared
Hydrophily significantly improve, the contamination resistance of corresponding film is also improved.
Embodiment 3：
The CNT of the hydrophilic grafts that 0.04g embodiments 1 are prepared is added to 24g N-N dimethyl acetamides
In, heating stirring 3h in 55 DEG C of water-baths, then ultrasonic disperse 1h in ultrasonic washing instrument is placed in, 2g Kynoar is added afterwards,
In 55 DEG C of water-baths, heating stirring 8h is to being completely dissolved, then strength ultrasound (100W) 30min is carried out to which, is stored at room temperature deaeration,
Using the knifing rod of the certain thickness knifing on clean glass plate is controlled, the casting solution after knifing is made after pre- volatilization 30s,
In rapid immersion deionized water coagulating bath, after film forming, water abjection solvent N-N dimethyl acetamides are changed repeatedly to which, is finally obtained
The polyvinylidene fluoride film of hydrophilic grafts carbon nano-tube modification.
Carry out the contact angle to water to test after above-mentioned hydrophilic grafts modified polyvinilidene fluoride film is vacuum dried, experimental result
Show, pure polyvinylidene fluoride film is 79.6 ° to the contact angle of water, and the modified polyvinilidene fluoride film that the present embodiment is provided,
In the case of being added without hydrophilic additive so as to be 55.7 ° to the contact angle of water, show the modified polyvinilidene fluorine that the present invention is prepared
The hydrophily of vinyl film is significantly improved, and the contamination resistance of corresponding film is also improved.
Embodiment 4：
The CNT that 0.096g embodiments 1 prepare hydrophilic grafts is added in 55g N-N dimethyl acetamides,
Heating stirring 3h in 60 DEG C of water-baths, then ultrasonic disperse 2h in ultrasonic washing instrument is placed in, 9.6g Kynoar is added afterwards,
In 60 DEG C of water-baths, heating stirring 10h is to being completely dissolved, then strength ultrasound (200W) 1h is carried out to which, and room temperature vacuumizing and defoaming is adopted
With the knifing rod of the certain thickness knifing on clean glass plate is controlled, the casting solution after knifing is made after pre- volatilization 30s, it is fast
In speed immersion deionized water coagulating bath, after film forming, water abjection solvent N-N dimethyl acetamides are changed repeatedly to which, parent is finally obtained
The modified polyvinylidene fluoride film of water grafting carbon nanotube.
Carry out the contact angle to water to test after above-mentioned hydrophilic grafts modified polyvinilidene fluoride film is vacuum dried, experimental result
Show, pure polyvinylidene fluoride film is 79.6 ° to the contact angle of water, and the modified polyvinilidene fluoride film that the present embodiment is provided,
In the case of being added without hydrophilic additive so as to be 50.6 ° to the contact angle of water, show the modified polyvinilidene fluorine that the present invention is prepared
The hydrophily of vinyl film is significantly improved, and the contamination resistance of corresponding film is also improved.
Above presently preferred embodiments of the present invention is described in detail, but the content has been only the preferable enforcement of the present invention
Example, it is impossible to be considered as limiting practical range of the invention.All impartial changes made according to the present patent application scope and improvement
Deng, still all should belong to the present invention patent covering scope within.
Claims (6)
1. a kind of hydrophilic grafts multi-walled carbon nano-tubes modified polyvinilidene fluoride film, it is characterised in that：Percentage, it is described
Modified polyvinilidene fluoride film be made up of following raw materials according：
Kynoar 5%-15%
N-N dimethyl acetamides 85%-95%
Hydrophilic grafts multi-walled carbon nano-tubes accounts for Kynoar 0.1%-3%；
The overall weight percent of above-mentioned raw materials is 100%；
The Kynoar refers to the Kynoar that molecular weight ranges are 400000-900000；
First the peg molecule of low polymerization degree is linked on multi-walled carbon nano-tubes, then will be the CNT of hydrophilic grafts uniform
It is distributed in PVDF casting solutions, using immersion precipitation phase inversion process film forming；
The hydrophilic grafts multi-walled carbon nano-tubes is obtained by the reaction of functionalized multi-wall carbonnanotubes, thionyl chloride and polyethylene glycol,
The molal weight concentration of the polyethylene glycol is 200g/mol；
In hydrophilic grafts multi-walled carbon nano-tubes, the weight of each raw material is：
Functionalized multi-wall carbonnanotubes 1.0g ± 0.001g
Oxidation sulfoxide 200mL ± 1mL
Polyethylene glycol 150mL ± 1mL.
2. a kind of hydrophilic grafts multi-walled carbon nano-tubes modified polyvinilidene fluoride film according to claim 1, it is characterised in that：
The draw ratio of the functionalized multi-wall carbonnanotubes is 1250-3750: 1.
3. a kind of hydrophilic grafts multi-walled carbon nano-tubes modified polyvinilidene fluoride film according to any one of claim 1-2, its
It is characterised by：The membrane aperture of described hydrophilic grafts multi-walled carbon nano-tubes modified polyvinilidene fluoride film is applied to micro-filtration and ultra filtration
Journey.
4. a kind of hydrophilic grafts multi-walled carbon nano-tubes modified polyvinilidene fluoride film according to claim 3, it is characterised in that：
Hydrophilic grafts multi-walled carbon nano-tubes modified polyvinilidene fluoride film is Flat Membrane.
5. a kind of side of the hydrophilic grafts multi-walled carbon nano-tubes modified polyvinilidene fluoride film prepared described in any one of claim 1-4
Method, it is characterised in that：Including the following steps for carrying out in order：
(1) hydrophilic grafts multi-walled carbon nano-tubes is added in N-N dimethyl acetamides, the heating stirring in 50-60 DEG C of water-bath
2-4 hours, then it is placed in ultrasonic disperse 1-2 hours in ultrasonic washing instrument；
(2) Kynoar is added in above-mentioned dispersion liquid, solution is placed in into heating stirring in 55-60 DEG C of water-bath complete to polymer
CL, then transfers the solution into strength ultrasound in ultrasonic cell disruptor, until obtaining hydrophilic grafts multi-wall carbon nano-tube
Manage finely dispersed casting solution；
(3) above-mentioned casting solution is stood into placement deaeration at room temperature；
(4) at ambient temperature, take casting solution and certain thickness homogeneous membrane is made with knifing rod on a glass, in atmosphere in advance
Film forming in coagulating bath is immersed after volatilization 30-50s；
(5) water is changed repeatedly to above-mentioned film to deviate from solvent N-N dimethyl acetamides, finally film is taken out from coagulating bath and can be obtained
To hydrophilic grafts multi-walled carbon nano-tubes modified polyvinilidene fluoride film.
6. method according to claim 5, it is characterised in that：The preparation of the hydrophilic grafts multi-walled carbon nano-tubes include as
Lower step：
(1) functionalized multi-wall carbonnanotubes are added in thionyl chloride, in 20 DEG C of ultrasound 0.5-1h；
(2) reaction temperature of (1) is controlled at 60-70 DEG C, flow back 10h；
(3) stop heating, temperature is slowly decreased to into room temperature, stir 3h, be again turned on heating, be to slowly warm up to 60-70 DEG C, stir
Backflow 40h；
(4) the mixture suction filtration for obtaining (3), is dried at room temperature for, and obtains the multi-walled carbon nano-tubes of chloride；
(5) acyl chlorides multi-walled carbon nano-tube and polyethylene glycol reaction are taken, controlling reaction temperature at 120-150 DEG C, stirring reaction
36h；
(6) (5) reacted suspended mixture suction filtration, ethanol are washed, drying at room temperature obtains hydrophilic grafts multi-wall carbon nano-tube
Pipe.
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| CN106607012B (en) * | 2015-10-23 | 2019-12-13 | 北京中科艾加科技有限公司 | Polyvinylidene fluoride nano composite material and preparation method and application thereof |
| CN105327624A (en) * | 2015-11-30 | 2016-02-17 | 上海应用技术学院 | Preparation method of modified polyvinylidene fluoride-polyvinyl alcohol binary composite ultrafiltration membrane |
| CN106964264A (en) * | 2017-04-27 | 2017-07-21 | 苏州捷尔沃科技有限公司 | Self-supporting with superhydrophobic breathable property and the pvdf membrane containing substrate |
| CN107325319B (en) * | 2017-07-13 | 2020-07-24 | 中国人民解放军第三军医大学第一附属医院 | Preparation method and application of porous polyvinylidene fluoride composite nano-silver film |
| CN109621756A (en) * | 2019-01-28 | 2019-04-16 | 沈阳建筑大学 | The preparation method of high-throughput resistant to pollution PVDF ultrafiltration membrane |
| CN110252155A (en) * | 2019-06-20 | 2019-09-20 | 西华大学 | A kind of pollution-resistant multi-walled carbon nano-tube composite membrane and preparation method thereof |
| CN112516817B (en) * | 2020-11-03 | 2022-10-11 | 贵州省材料产业技术研究院 | Polyvinylidene fluoride loose nanofiltration membrane and preparation method and application thereof |
| CN112473376B (en) * | 2020-12-11 | 2021-07-23 | 江苏泷膜环境科技有限公司 | Functional carbon nanowire ultrafiltration membrane and preparation method thereof |
| CN113713628B (en) * | 2021-04-20 | 2023-09-19 | 保定源汉升新材料科技有限公司 | Hg in waste water is adsorbed to composite film 2+ Applications of (2) |
| CN113578067B (en) * | 2021-07-23 | 2023-09-15 | 哈尔滨工业大学 | Method for preparing oil-water separation film based on heterogeneous carbon nano tube self-assembly |
| CN115799610B (en) * | 2023-02-06 | 2023-05-02 | 星源材质(南通)新材料科技有限公司 | Composite membrane and preparation method thereof, PVDF microporous membrane coated with lithium salt grafted carbon nano tube and solid-state battery |
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