CN109364773A - A kind of CNTs/PSMA/ fluorocarbon surfactant composite material and preparation method for water-oil separating - Google Patents
A kind of CNTs/PSMA/ fluorocarbon surfactant composite material and preparation method for water-oil separating Download PDFInfo
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Abstract
The invention discloses a kind of CNTs/PSMA/ fluorocarbon surfactant composite material and preparation methods for water-oil separating.CNTs/PSMA/ fluorocarbon surfactant composite material of the invention has fluorocarbon surfactant in the adsorption of the PSMA of the CNTs/PSMA including the CNTs/PSMA that there is the modification CNTs of carboxyl and/or hydroxyl to polymerize with PSMA on surface.PSMA is grafted on the surface CNTs by in-situ polymerization, CNTs is dispersed in PSMA, solve the problems, such as that CNTs is difficult to evenly spread in polymer by the present invention；The mechanical strength for increasing high molecular material has widened its application range；PSMA/CNTs and fluorocarbon surfactant are subjected to intermolecular self assembly by electrostatic force etc. and reset, it forms hydrophilic nano channel and assigns the good oil-water separation of film, to in the antifouling property for completing to improve material while water-oil separating, PSMA is increased a possibility that the fields such as water-oil separating are applied, there is huge application prospect in fields such as water process.
Description
Technical field
The present invention relates to technical field of composite materials more particularly to a kind of CNTs/PSMA/ fluorine carbon tables for water-oil separating
Face activating agent composite material.
Background technique
Carbon nanotube (CNTs) be a kind of size be in nano-scale range, the novel carbon materials with complete molecular structure
Material.Carbon nanotube has excellent mechanics, electrical and optical performance and excellent transmission characteristic, is filling with carbon nanotube
The polymer composites of material have become an important research direction of Material Field.But carbon nanotube and basis material phase
Capacitive is poor, and therefore, it is difficult to evenly dispersed in a polymer matrix, excellent performances to be unable to get effective performance.
In numerous high molecular materials, styrene-maleic anhydride copolymer (PSMA) is a kind of amphiphilic polymers.It is this kind of
Polymer not only has thickening property possessed by general polymerization object, and has the surface-active of traditional low-molecular-weight surfactant, makes it
With unique physics and chemical property.The anhydride group provided in especially PSMA by maleic anhydride, under given conditions can
A variety of reactions occur and connect specific function group, assign material special performance, this is also a big advantage of PSMA material；Separately
On the one hand, since it is with amphipathic, oil water mixture can not be made to separate, the intensity of PSMA itself is not high, has certain
Brittleness.
Traditional water-oil separating material such as organic clay, zeolite, polypropylene non-woven fabric etc. can absorb water while oil suction,
Make that separation process is cumbersome, low efficiency；Membrane material with lipophilic-hydrophobic property will cause film and is polluted by the oil and leads again in use
The separative efficiency of cause reduces.When handling oily wastewater, generally more demanding to film strength, single polymer film or Nanowire
The problems such as generally existing poor mechanical property when tieing up film as separation material, surface is in hydrophobicity, pollution resistance is weak, it is used for water-oil separating
Excellent membrane material should have good hydrophily and oleophobic property.
Summary of the invention
It is an object of the present invention to be directed to the above-mentioned deficiency of the prior art, propose that a kind of mechanical strength is big, water-oil separating effect
The good CNTs/PSMA/ fluorocarbon surfactant composite material and preparation method for water-oil separating of fruit.
A kind of CNTs/PSMA/ fluorocarbon surfactant composite material for water-oil separating of the invention, including surface tool
The CNTs/PSMA for thering is the modification CNTs of carboxyl and/or hydroxyl to polymerize with PSMA, in the table of the PSMA of the CNTs/PSMA
Face is adsorbed with fluorocarbon surfactant.
Preferably, the mass ratio of the CNTs and PSMA is 0.1~1:1, the matter of CNTs/PSMA and fluorocarbon surfactant
Amount is than being 2:1~10.
Preferably, the acidified processing of the CNTs.Acidified treated CNTs has a large amount of carboxyl and hydroxyl
Polar group, the effect of PSMA grafting can be more preferable.
Preferably, fluorocarbon surfactant is cation or amphoteric ion.
Preferably, the molecular weight of PSMA is 30,000~300,000.
Preferably, the diameter of CNTs is 10~60nm, and length is 5 μm~15 μm.
A kind of preparation method of the CNTs/PSMA/ fluorocarbon surfactant composite material for water-oil separating, including it is as follows
Step:
1) carbon nanotube is added in the mix acid liquor of 98% concentrated sulfuric acid and 68% concentrated nitric acid, then passes through ultrasound
And/or be heated to reflux and acidification is carried out to carbon nano tube surface, by filtering and being dried to obtain acidification CNTs；
2) by the CNTs, monomer styrene and maleic anhydride of the obtained acidification of step 1) by following mass ratio 0.002~
0.03:1~2:1 is reacted to obtain CNTs/PSMA in solvent toluene and two isobutyl of initiator azo are fine；
3) CNTs/PSMA for obtaining step 2) is dissolved in n,N-Dimethylformamide, solution concentration be 0.02~
0.05g/ml；
It 4) be 0.01~0.1g/ml by solution concentration is that fluorocarbon surfactant is added to centrifugal drying in 3) solution and obtains
CNTs/PSMA/ fluorocarbon surfactant composite material.
The reaction wherein carried out in step 2) is that the polymerization of monomer styrene and maleic anhydride generates PSMA and PSMA
It is grafted on the CNTs of acidification, generates PSMA relative to first polymerization and be grafted again, situ-formed graft is completed to connect while polymerization
Branch, step is simple, and at low cost, graft effect is good.
Preferably, the volume ratio of the concentrated sulfuric acid and concentrated nitric acid is 0~3:1 in step 1).
Preferably, in step 1) volume of nitration mixture and CNTs 50~200ml:1g of mass ratio.
Preferably, ultrasonic time is 0~2 hour in step 1).
If it is heat reflux in step 1), the reflux temperature of heat reflux is 65~75 DEG C；Return time is 1~10 small
When.
PSMA is grafted on the surface CNTs by in-situ polymerization, CNTs is dispersed in by the present invention
In PSMA, solve the problems, such as that CNTs is difficult to evenly spread in polymer；The mechanical strength for increasing high molecular material, is widened
Its application range；By PSMA/CNTs and fluorocarbon surfactant by electrostatic force etc. carry out intermolecular self assembly with
It resets, forms hydrophilic nano channel and assign the good oil-water separation of film, to improve while completing water-oil separating
The antifouling property of material, increases PSMA a possibility that the fields such as water-oil separating are applied, and has in fields such as water process
There is huge application prospect.
Detailed description of the invention
Fig. 1 is the TEM figure of acidification carbon nanotube prepared by embodiment 1；
Fig. 2 is the TEM figure of PSMA grafting carbon nanotube composite material made from embodiment 1；
Fig. 3 is the laser Raman spectroscopy figure of PSMA grafting carbon nanotube composite material prepared by embodiment 2；
Fig. 4 is that the SEM of blank steel mesh schemes；
The SEM figure of the coating film forming steel mesh of CNTs/PSMA/FCS composite material prepared by Fig. 5 embodiment 1.
Specific embodiment
Following is a specific embodiment of the present invention in conjunction with the accompanying drawings, technical scheme of the present invention will be further described,
However, the present invention is not limited to these examples.
Embodiment 1
A kind of CNTs/PSMA/ fluorocarbon surfactant composite material for water-oil separating, it is that PSMA is grafted on acid
Change the surface CNTs, then is obtained with fluorocarbon surfactant FS-510 by the way that self assembly between interface and molecular rearrangement are compound.Acid
The mass ratio for changing CNTs and PSMA is 0.005:1；The diameter of carbon nanotube is 40~60nm, length is 5 μm~10 μm；Fluorine carbon table
The mass ratio of face activating agent FS-510 and CNTs/PSMA are 1:1；The relative molecular mass of PSMA is 30,000~90,000.
The preparation method of above-mentioned CNTs/PSMA/ fluorocarbon surfactant composite material passes through original on the surface of carbon nanotube
The mode of position polymerization is grafted one layer of PSMA, the specific steps are as follows:
1) 1g carbon nanotube is poured into the mix acid liquor of the concentrated nitric acid of 50ml68% and the concentrated sulfuric acid of 150ml98%, is surpassed
It flows back 3 hours at 75 DEG C again after sonication two hours, suction filtration is dried to obtain acidification carbon nanotube, tests its microcosmic shape with TEM
Caliber is 50nm or so to looks as shown in Figure 1:, and outermost layer has slight destruction；
2) 0.05g is acidified carbon nanotube ultrasonic disperse in 100ml toluene in three-necked flask, 4.9g maleic acid is added
Acid anhydride, 20ml toluene, 9.8g styrene and 0.09gAIBN are in constant pressure funnel.After reacting 0.5 hour at 75 DEG C, start to be added dropwise
Styrene mixed solution is warming up to filtration drying after 85 DEG C of reactions 1 hour after reacting half an hour after being added dropwise at 75 DEG C again
PSMA grafting carbon nanotube composite material (CNTs/PSMA) is obtained, the microcosmic shape of the carbon nanotube of TEM test PSMA grafting is utilized
Looks are as shown in Figure 2: average caliber is 100nm or so；
3) 2g CNTs/PSMA is dissolved in 100mlDMF, (active constituent is 5ml fluorocarbon surfactant FS-510
40%) it is added dropwise in above-mentioned DMF solution again after being dissolved in 95ml deionized water, centrifugal drying obtains CNTs/PSMA/
FCS composite material.
The reaction process that PSMA is grafted on the acidification surface CNTs is as follows:
It is compared by Fig. 1, Fig. 2 it is found that carbon nanotube is coated in PSMA well by surface grafting in composite material；
By the dissolution of CNTs/PSMA/ fluorocarbon surfactant composite material in DMF after, 100 mesh steel wires are soaked respectively to be applied to PSMA molten
Liquid, PSMA/FS-510 solution and CNTs/PSMA/FCS-510 solution film forming, and make comparisons with blank steel mesh, different films for
The contact angular data of water and two different oil is listed in table 1.
Contact angle of the different film of table 1 for water and two different oil
As known from Table 1, oily contact angle before film less than 30 ° from becoming after coating CNTs/PSMA/FCS-510 film
Greater than 76 °, water contact angle becomes after film 100 ° from 49 ° before film.It is carried out with the steel wire for applying CNTs/PSMA/FCS-510 film
Water-oil separating experiment, separative efficiency are up to 90% or more.
Fig. 4 is that the SEM of blank steel mesh schemes；Fig. 5 is that CNTs/PSMA/FCS composite material prepared by embodiment 1 is applied as
The SEM of film steel mesh schemes.From Fig. 4, Fig. 5 it can be seen that blank steel wire net surface there are what is formed in molding process to be parallel to
The gully in steel wire direction, the steel mesh surface after coating film forming smooth out, and be respectively formed between steel wire surface and hole one layer it is compound
The film of object.
Embodiment 2
A kind of CNTs/PSMA/ fluorocarbon surfactant composite material for water-oil separating, it is that PSMA is passed through original position
Graft polymerization is multiple by self assemblies such as intermolecular electrostatic power in acidification carbon nano tube surface, then with fluorocarbon surfactant FS-51
What conjunction obtained.The mass ratio for being acidified carbon nanotube and PSMA is 0.008:1；The diameter of carbon nanotube is 30~50nm, length 7
μm~10 μm；The mass ratio of fluorocarbon surfactant FS-51 and CNTs/PSMA are 1.2:2；The relative molecular mass of PSMA is 10
Ten thousand~150,000.
The preparation method of the above-mentioned CNTs/PSMA/FCS composite material for water-oil separating, it is logical on the surface of carbon nanotube
It crosses in-situ polymerization and is grafted one layer of PSMA, the specific steps are as follows:
1) 1g carbon nanotube is poured into 50ml concentrated nitric acid, ultrasonic treatment flows back 3 hours at 75 DEG C again after 1 hour, takes out
Filter is dried to obtain acidification carbon nanotube；
2) in the 100ml toluene by 0.08g acidification carbon nanotube ultrasonic disperse in three-necked flask, 4.9g maleic acid is added
Acid anhydride, 20ml toluene, 4.9g styrene and 0.05g AIBN are in constant pressure funnel.After reacting 0.5 hour at 70 DEG C, start to be added dropwise
Styrene and AIBN mixed solution, after being warming up to 80 DEG C of reactions 1.5 hours after reaction half an hour at 70 DEG C again after being added dropwise
Filtration drying obtains PSMA grafting carbon nanotube composite material (CNTs/PSMA).
Fig. 3 is the laser Raman spectroscopy figure of CNTs/PSMA composite material prepared by embodiment 2.It can be apparent from Fig. 3
Find out, D the and G band of blank MWNT is observed at 1350.5cm-1 and 1583.9cm-1 respectively.Carbon nanotube (α-after acidification
MWCNT the center of D band and G band) becomes larger, and ID/IG also becomes larger.This means that the integrality and order of carbon nanotube exist
Acid is mixed in a way to destroy.When a-MWCNT is covered by PSMA, so that the construction of α-MWCNT becomes more unordered.
3) 2g CNTs/PSMA is dissolved in 100ml DMF, 3ml fluorocarbon surfactant FS-51 is dissolved in 97ml and goes
It is added dropwise in DMF solution again after in ionized water, centrifugal drying obtains CNTs/PSMA/FCS composite material.
The CNTs/PSMA/FCS composite material of above-mentioned preparation is dissolved in DMF (concentration 2%wt), by 200 mesh steel wires
Net dip-coating spontaneously dries after taking-up in solution.Contact angle variation before and after the dip-coating of measuring steel wire net, before oily contact angle is by dip-coating
0 ° of 113 ± 3 ° become after dip-coating, before dip-coating water contact angle be 130 ± 5 °, become 85 ± 4 ° after dip-coating.It is carried out with steel wire
Water-oil separating experiment, separative efficiency are up to 85% or more.
Embodiment 3
A kind of CNTs/PSMA/ fluorocarbon surfactant composite material for water-oil separating, it is that PSMA is passed through original position
Graft polymerization in acidification carbon nano tube surface, then with fluorocarbon surfactant FS-500 is compound obtains.Be acidified carbon nanotube with
The mass ratio of PSMA is 0.01:1；The diameter of carbon nanotube is 10~20nm, length is 10 μm~15 μm；Fluorocarbon surfactant
The mass ratio of FS-500 (amphoteric surfactant, effective component 27%) and CNTs/PSMA is 1.62:2；The average molecular of PSMA
Quality is 200,000~250,000.
The preparation method of above-mentioned CNTs/PSMA/FCS composite material passes through in-situ polymerization on the surface of acidification carbon nanotube
It is grafted one layer of PSMA, the specific steps are as follows:
1) 1g carbon nanotube is poured into 50ml concentrated nitric acid and the 50ml concentrated sulfuric acid, ultrasonic treatment is after 1.5 hours again at 75 DEG C
Lower reflux 5 hours, suction filtration is dried to obtain acidification carbon nanotube；
2) in the 100ml toluene by 0.1g acidification carbon nanotube ultrasonic disperse in three-necked flask, 4.9g maleic acid is added
Acid anhydride, 20ml toluene, 5.4g styrene and 0.02gAIBN are in constant pressure funnel.After reacting 0.5 hour at 75 DEG C, start to be added dropwise
Styrene and initiator mixed solution are warming up to 85 DEG C of reactions 2.5 hours after reacting half an hour at 75 DEG C again after being added dropwise
Filtration drying obtains PSMA grafting carbon nanotube (CNTs/PSMA) afterwards；
3) 2g CNTs/PSMA is dissolved in 100mlDMF, 6ml fluorocarbon surfactant FS-500 is dissolved in 94ml and goes
It is added dropwise in DMF solution again after in ionized water, centrifugal drying obtains CNTs/PSMA/FCS composite material later.
After dissolving the material in DMF, 100 mesh steel wire dip-coatings are spontaneously dried in solution.Measuring steel wire net dip-coating
The variation of front and back contact angle, oily contact angle become 133 ± 3 ° from 0 °, and water contact angle becomes 75 ± 4 ° from 130 ± 5 °.Use steel wire
Water-oil separating experiment is carried out, separative efficiency is up to 85% or more.
Embodiment 4
A kind of CNTs/PSMA/ fluorocarbon surfactant composite material for water-oil separating, it is that PSMA is passed through original position
Graft polymerization acidification carbon nano tube surface, then with fluorocarbon surfactant FS-50 (amphoteric surfactant, effective component
27%) reaction obtains.The mass ratio of carbon nanotube and PSMA are 0.005:1；The diameter of carbon nanotube is 20~40nm, length
It is 5 μm~7 μm；The mass ratio of fluorocarbon surfactant FS-50 and PSAM are 2.16:2；The relative molecular mass of PSMA is 250,000
~30 ten thousand.
The preparation method of the above-mentioned CNTs/PSMA/FCS composite material for water-oil separating, in the table of acidification carbon nanotube
Face is grafted one layer of PSMA by in-situ polymerization, the specific steps are as follows:
1) 1g carbon nanotube is poured into 50ml concentrated nitric acid and the 100ml concentrated sulfuric acid, ultrasonic treatment is after 0.5 hour again at 75 DEG C
Lower reflux 4 hours, suction filtration is dried to obtain acidification carbon nanotube；
2) in the 100ml toluene by 0.1g acidification carbon nanotube ultrasonic disperse in three-necked flask, 4.9g maleic acid is added
Acid anhydride, 20ml toluene, 5.4g styrene and 0.01gAIBN are in constant pressure funnel.After reacting 0.5 hour at 75 DEG C, start to be added dropwise
Styrene mixed solution is warming up to filtration drying after 85 DEG C of reactions 5 hours after reacting half an hour after being added dropwise at 75 DEG C again
Obtain PSMA grafting carbon nanotube composite material (CNTs/PSMA)；
3) 2g CNTs/PSMA is dissolved in 100mlDMF, 8ml fluorocarbon surfactant FS-50 be dissolved in 92ml go from
It is added dropwise in DMF solution again after in sub- water, centrifugal drying obtains CNTs/PSMA/FCS composite material later.
After CNTs/PSMA/FCS composite material is dissolved in DMF, 300 mesh steel wire dip-coatings are done naturally in solution
It is dry.Contact angle variation before and after the dip-coating of measuring steel wire net, oily contact angle become 135 ± 2 ° from 0 °, and water contact angle is become by 132 ± 3 °
It is 72 ± 2 °.Water-oil separating experiment is carried out with steel wire, separative efficiency is up to 95% or more.
It is not directed to place above, is suitable for the prior art.
Although some specific embodiments of the invention are described in detail by example, the skill of this field
Art personnel it should be understood that above example merely to be illustrated, the range being not intended to be limiting of the invention, belonging to the present invention
Those skilled in the art can make various modifications or additions to described specific embodiment or using class
As mode substitute, but without departing from direction of the invention or beyond the scope of the appended claims.Ability
Domain it is to be understood by the skilled artisans that according to the technical essence of the invention to made by embodiment of above it is any modification, etc.
With replacement, improvement etc., protection scope of the present invention should be included in.
Claims (10)
1. a kind of CNTs/PSMA/ fluorocarbon surfactant composite material for water-oil separating, it is characterised in that: including surface
CNTs/PSMA that modification CNTs with carboxyl and/or hydroxyl polymerize with PSMA, in the PSMA of the CNTs/PSMA
Adsorption has fluorocarbon surfactant.
2. a kind of CNTs/PSMA/ fluorocarbon surfactant composite material for water-oil separating as described in claim 1,
Be characterized in that: the mass ratio of the CNTs and PSMA is 0.1~1:1, is grafted with the CNTs and and fluorocarbon surfactant of PSMA
Mass ratio be 2:1~10.
3. a kind of CNTs/PSMA/ fluorocarbon surfactant composite material for water-oil separating as described in claim 1,
It is characterized in that: the acidified modification of CNTs.
4. a kind of CNTs/PSMA/ fluorocarbon surfactant composite material for water-oil separating as described in claim 1,
Be characterized in that: fluorocarbon surfactant is cationic surfactant or amphoteric surfactant.
5. a kind of CNTs/PSMA/ fluorocarbon surfactant composite material for water-oil separating as described in claim 1,
Be characterized in that: the molecular weight of PSMA is 30,000~300,000.
6. a kind of CNTs/PSMA/ fluorocarbon surfactant composite material for water-oil separating as described in claim 1,
Be characterized in that: the diameter of CNTs is 10~60nm, and length is 5 μm~15 μm.
7. a kind of CNTs/PSMA/ fluorocarbon surfactant for water-oil separating as described in any one of claims 1 to 6 is multiple
The preparation method of condensation material, characterized by the following steps:
1) carbon nanotube is added in the mix acid liquor of 98% concentrated sulfuric acid and 68% concentrated nitric acid, then by ultrasound and/
Or be heated to reflux and acidification is carried out to the surface CNTs, by the CNTs for filtering and being dried to obtain acidification；
2) by CNTs, monomer styrene and maleic anhydride 0.002~0.03:1 in mass ratio of the obtained acidification of step 1)~
2:1 is in solvent and initiator, and filtration drying obtains CNTs/PSMA after being reacted；
3) CNTs/PSMA for obtaining step 2) is dissolved in n,N-Dimethylformamide, and solution concentration is 0.02~0.05g/mL；
4) fluorocarbon surfactant that solution concentration is 0.01~0.1g/mL is added in 3) solution, centrifugal drying obtains
CNTs/PSMA/ fluorocarbon surfactant composite material.
8. a kind of system of the CNTs/PSMA/ fluorocarbon surfactant composite material for water-oil separating as claimed in claim 7
Preparation Method, it is characterised in that: in step 1) 98% concentrated sulfuric acid and 68% concentrated nitric acid volume ratio be 0~3:1.
9. a kind of system of the CNTs/PSMA/ fluorocarbon surfactant composite material for water-oil separating as claimed in claim 7
Preparation Method, it is characterised in that: 50~200mL:1g of mass ratio of the volume of nitration mixture and CNTs in step 1).
10. a kind of CNTs/PSMA/ fluorocarbon surfactant composite material for water-oil separating as claimed in claim 7
Preparation method, it is characterised in that: the reflux temperature that step 1) is heated to reflux is 65~75 DEG C；Return time is 1~10 hour.
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| CN111978856A (en) * | 2020-07-20 | 2020-11-24 | 华南理工大学 | Super-hydrophilic/underwater super-oleophobic copper mesh, preparation method thereof and application of copper mesh in separation of emulsified oil-in-water |
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| CN111978856B (en) * | 2020-07-20 | 2021-12-17 | 华南理工大学 | Super-hydrophilic/underwater super-oleophobic copper mesh, preparation method thereof and application of copper mesh in separation of emulsified oil-in-water |
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| CN109364773B (en) | 2021-09-10 |
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