CN106178599A - A kind of automatically cleaning polybenzoxazine super-hydrophobic super-oleophylic fiber web material and preparation thereof and application in oil-water separation - Google Patents
A kind of automatically cleaning polybenzoxazine super-hydrophobic super-oleophylic fiber web material and preparation thereof and application in oil-water separation Download PDFInfo
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Abstract
The present invention relates to a kind of automatically cleaning polybenzoxazine super-hydrophobic super-oleophylic fiber web material and preparation thereof and the application in oil-water separation.Consisting of of the super-hydrophobic super-oleophylic fiber web material of the present invention: benzimidazole dihydrochloride 1 weight portion, nanoparticle 0.001～60 weight portion, solvent 1～100 weight portion；Its preparation technology: being added by nanoparticle in benzimidazole dihydrochloride solution, mixing is uniformly dispersed；Polymer fiber filter cloth or metal screen are placed in blends described above, prepare automatically cleaning polybenzoxazine super-hydrophobic super-oleophylic fiber web material by lifting coating method and further thermal curing method.The present invention provide a kind of raw material inexpensive, without fluorochemical additive, technique is simple, be suitable to the super-hydrophobic super-oleophylic fiber web material with excellent oil-water separation characteristic and the preparation of continuous industrial production, this oil-water separation material acid and alkali-resistance, resistance to ultra-vioket radiation, high temperature resistant, can be recycled for multiple times, and under the common effect of illumination and heat treated, there is good automatically cleaning characteristic.
Description
Technical field
The invention belongs to chemical, material surface modifying technology field, be specifically related to a kind of automatically cleaning polyphenyl
And piperazine super-hydrophobic super-oleophylic fiber web material and preparation method thereof, and the application in oil-water separation.
Background technology
Oil-water separation all has at daily life and field of industrial production and is of great significance, membrane separation technique
It is a kind of effective ways processing oily water.But, fouling membrane is the matter of utmost importance nowadays needing to solve, it
Oil-water separation membrane flux can be reduced, reduce separation efficiency, the oil reducing final generation or water quality.Therefore,
It is necessary to prepare a kind of oil-water separation membrane material with automatically cleaning characteristic, improves or solve oil-water separation material
Pollution problem, effectively to carry out oil-water separation.
Publication No. CN102925877A (invention entitled " one have special infiltrating hollowed-out vessel and
Its preparation method and application ", Application No. CN201210454486.7), CN102961893A (invention name
It is referred to as " oil-water separation mesh film of a kind of super-hydrophobic super-oleophylic and preparation method thereof ", Application No.
CN201210440282.8), (invention entitled " one has super-hydrophobic super-oleophylic character to CN103157392A
And degradable oil-water separation mesh film and preparation method thereof ", Application No. CN201310093434.6),
CN104117287A (invention entitled " a kind of response oil-water separation mesh film with superhydrophobic property and
Preparation method ", Application No. CN201410315799.3) Chinese patent (application) individually disclose and have
The oil-water separation mesh film of super-hydrophobic super-oleophylic characteristic or oil-water separation hollowed-out vessel.Publication No.
CN104193999A (invention entitled " preparation method of a kind of fluorine silicon benzimidazole dihydrochloride copolymer ", application number
For CN201410454287.5) Chinese patent application disclose a kind of fluorine silicon polybenzoxazine copolymer
Preparation method and the application in oil-water separation thereof.Although these five kinds of technology all have the effect of oil-water separation,
But in the processing procedure of oil-polluted water, nethike embrane or container have suffered from a certain degree of greasy dirt dye, and this makes
Membrane flux reduces, separation efficiency reduces, profit quality declines, materials'use lifetime.And, open
Number it is that the Chinese patent of CN104193999A uses in the preparation process of fluorine silicon polybenzoxazine copolymer
Platinum-type catalyst, containing fluorine atom in molecule, adds production cost.
It addition, Publication No. CN1387932A (invention entitled " nano-interface with self-cleaning function divides
Off-network and preparation method thereof and purposes ", Application No. CN01118387.X) open being doped with of Chinese patent have
Titanium dioxide (the TiO of photocatalytic self-cleaning character2) monolayer net, although the oil-water separating net prepared by this technology
There is photic automatic cleaning action, but its manufacture process is complicated, raw material forms numerous and diverse, fluorochemical usage amount
Greatly.Additionally, Publication No. CN102764536A (invention entitled " a kind of oil-polluted water purify nethike embrane and
Preparation method and application ", Application No. CN201210241886.X) Chinese patent disclose photic from clear
Clean oil-water separating net, but its manufacture process is the longest, as being accomplished by soaking more than 48h when hydrophobization processes.
Its manufacture process is loaded down with trivial details, needs to prepare two-layer filter screen, and one layer has TiO for deposition2Photic automatically cleaning filter screen,
Another layer is hydrophobic screen.
Carry out oil-water separation based on the special wettability of material and be always the research and development focus of this area, how to ensure
Oil-water separating net membrane material not only has super-hydrophobic super-oleophylic characteristic but also has automatically cleaning characteristic, can lack again
The technology to be solved with or without fluorine compounds, reduction cost and manufacturing process difficulty, always this area is asked
Topic.
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art, it is provided that a kind of automatically cleaning polybenzoxazine is super thin
Water surpasses oleophylic fiber web material；Another object of the present invention is to provide a kind of automatically cleaning polybenzoxazine super-hydrophobic
The preparation method of super oleophylic fiber web material；The third object of the present invention is to provide a kind of automatically cleaning polyphenyl also
The application in oil-water separation of the piperazine super-hydrophobic super-oleophylic fiber web material.
The main technical schemes of the present invention is as follows: a kind of automatically cleaning polybenzoxazine super-hydrophobic super-oleophylic membrane material
Technology of preparing, its raw material consists of: benzimidazole dihydrochloride 1 weight portion, nanoparticle 0.001～20 weight portion,
Solvent 1～100 weight portion.Concrete preparation technology: nanoparticle is added benzimidazole dihydrochloride solution, mixing dispersion
Uniformly；Clean polymer fiber filter cloth or metal screen are placed in blends described above, by lifting film
Automatically cleaning polybenzoxazine super-hydrophobic super-oleophylic nethike embrane is prepared in method and further heat cure.Described benzimidazole dihydrochloride
There are H, C in amine source and the main substituent groups group in phenol source in monomer and polybenzoxazine1～C18Alkyl, C1～C4Hydroxyl
Base, C6～C10Aromatic ring yl, substituted aromatic ring yl, siloxy group.
A first aspect of the present invention, it is provided that a kind of automatically cleaning polybenzoxazine super-hydrophobic super-oleophylic fiber web material,
Described automatically cleaning polybenzoxazine super-hydrophobic super-oleophylic fiber web material is by following raw material shape by weight percentage
One-tenth blend:
Benzoxazine monomer 1
Nanoparticle 0.001～60
Solvent 1～100；
The chemical structural formula of described benzoxazine monomer is shown in formula I:
In Formulas I, X, Y can be identical or different, and X is selected from H, C1～C4Alkyl, C1～C4Hydroxyl, C6～C10
One in aromatic ring yl or substituted aromatic ring yl；Y is selected from H, C1～C18Alkyl, C1～C4Hydroxyl, C6～C10
One in aromatic ring yl or siloxy group；
Described benzoxazine monomer, when X is selected from substituted aromatic ring yl, its chemical structural formula is selected from following
Abc is arbitrary:
The chemical structural formula of the polybenzoxazine of the present invention is as follows, wherein n >=2:
Preferably, described benzoxazine monomer, compound I-1 in embodiment, I-2, I-3, I-4,
I-5, I-6, I-7, I-8, I-9 etc..
Described nanoparticle is titanium dioxide (TiO2) or TiO2And during alloy, described doping
Thing is selected from silicon dioxide, zinc oxide, ferroso-ferric oxide, silver phosphate, CNT, nanoclay, graphite
One or more in alkene.
Preferably, described nanoparticle is TiO2, or described nanoparticle be TiO2And SiO2's
Mixture.
When described nanoparticle is TiO2And during alloy, wherein TiO2The ratio of nanoparticle should be
Weight ratio more than 50%.
Described solvent selected from chloroform, toluene, dichloromethane, ethanol, dimethylbenzene, oxolane, two
One or more in alkane, pyridine, ethyl acetate.
Preferably, benzoxazine monomer, nanoparticle, the weight ratio of solvent are 1:0.1～5:5～50；More
Excellent, benzoxazine monomer, nanoparticle, the weight ratio of solvent are 1:1:25.
A second aspect of the present invention, it is provided that a kind of automatically cleaning polybenzoxazine super-hydrophobic super-oleophylic nethike embrane, institute
The automatically cleaning polybenzoxazine super-hydrophobic super-oleophylic nethike embrane stated is polymer fiber filter cloth or metal screen to be dipped in
In automatically cleaning polybenzoxazine super-hydrophobic super-oleophylic fiber web material described above, by lifting coating method and entering
One step heat cure prepares.
Described lifting coating method, can use this area routine techniques, such as list of references: Tang X, Si Y, Ge
J,Ding B,Liu L,Zheng G,Luo W,Yu J.In Situ Polymerized Superhydrophobic and
Superoleophilic Nanofibrous Membranes for Gravity Driven Oil-Water Separation[J].
Nanoscale,2013,5(23):11657-11664.
Described heat cure, can use benzimidazole dihydrochloride to be polymerized routine techniques, such as list of references: Liu J, Lu X, Xin
Z,Zhou C.Synthesis and Surface Properties of Low Surface Free Energy
Silane-Functional Polybenzoxazine Films[J].Langmuir,2013,29(1):411-416.
Preferably, described lifting coating method and further heat cure condition be: soak time is 5～300s；
Pull rate is 40～120mm/min；Heat curing temperature is 120～300 DEG C；Thermal curing time is 0.1～24h.
Invention further provides the preparation side of above-mentioned automatically cleaning polybenzoxazine super-hydrophobic super-oleophylic nethike embrane
Method, described preparation method comprises the following steps:
A, benzoxazine monomer is dissolved in solvent；Nanoparticle adds above-mentioned solution, and ultrasonic mixing divides
Benzimidazole dihydrochloride and nanoparticle blend is obtained after dissipating uniformly；
B, the benzimidazole dihydrochloride that clean polymer fiber filter cloth or metal screen immersion step A are obtained and nanometer
In particle blend 5～300s, the speed with 40～120mm/min is dried after lifting, then is placed in
Cross-linking reaction 0.1～24h at 120～300 DEG C.
Described preparation method comprises the following steps:
In step B, clean polymer fiber filter cloth or metal screen, be by polymer fiber filter cloth/film
Or metal screen dries through water, ethanol, washing with acetone room temperature；
In step B, preferably, described pull rate 60mm/min, 160 DEG C are carried out in solidification case
Cross-linking reaction.
A third aspect of the present invention, it is provided that above-mentioned automatically cleaning polybenzoxazine super-hydrophobic super-oleophylic nethike embrane material
Material, nethike embrane application in oil-water separation.
In the oil-water separation of the present invention, oil water mixture is vegetable oil and the mixture of water, industry oil and water
Mixture, or organic solvent and the mixture of water.
Described oil water mixture is vegetable oil and the mixture of the mixture of water, industry oil and water, You Jirong
Agent and the mixture of water；Described vegetable oil is selected from Semen Maydis oil, soybean oil, Oleum Arachidis hypogaeae semen, olive oil, Oleum sesami
In one；Described industry oil one in diesel oil, kerosene, gasoline；Described organic solvent is selected from C6～C16
Alkane, the C of halogen substiuted6～C16Alkane, C6～C10One in aromatic hydrocarbon.
Beneficial effects of the present invention:
The surface of described super-hydrophobic super-oleophylic polybenzoxazine fiber web material is twin-stage composite construction, is specially
The photocatalytic nanometer particle of the fiber of micro-meter scale or mesh and nanoscale or and alloy.
The surface water contact angle of described super-hydrophobic super-oleophylic polybenzoxazine fiber web material more than 150 °, oil connects
Feeler is less than 5 °.
After described super-hydrophobic super-oleophylic fiber web material soaks in strong acid, highly basic, still possesses super-hydrophobic super parent
Oil characteristic, described soak pH scope is 1～13, and soak time is more than 1h；Described super-hydrophobic super parent
After oil network membrane material exposes under ultraviolet light, still possessing super-hydrophobic super-oleophylic characteristic, described open-assembly time is big
In 10h；Described super-hydrophobic super-oleophylic fiber web material, after high-temperature process, still possesses super-hydrophobic super-oleophylic special
Property, described temperature is 250～300 DEG C, and the time that processes is more than 1h.
The present invention is technically characterized in that use novel polyphenyl cheap and easy to get piperazine hydrophobic material substitute fluorine-containing
Hydrophobic agents, reduces cost.Secondly, the technical matters of the present invention is simple, by lifting film and follow-up
Directly solidification can prepare functional oil-water separation mesh film, and this substantially reduces process time, reduces
Cost, is more suitable for industrial continuous production.Again, the super-hydrophobic super-oleophylic nethike embrane of the present invention has automatically cleaning
Characteristic, is possible not only to realize the automatically cleaning of oil-water separation mesh film, improves the service life of oil-water separation mesh film,
And water body can will not be produced secondary pollution with organic pollution solvable in degradation water.Finally, the present invention
Super-hydrophobic super-oleophylic nethike embrane have excellent acid and alkali-resistance, resistance to ultra-vioket radiation, high-temperature stability it can also be used to
The oil-water separation of the extreme environment such as strong acid and strong base, high temperature.
Accompanying drawing explanation
Fig. 1 is the surface of the automatically cleaning polybenzoxazine super-hydrophobic super-oleophylic fiber web material of the embodiment of the present invention 1 preparation
Topography scan electron microscopic picture.
Fig. 2 is that the automatically cleaning polybenzoxazine super-hydrophobic super-oleophylic fiber web material profit of the embodiment of the present invention 1 preparation divides
Experimental provision picture from application.
Fig. 3 is that the automatically cleaning polybenzoxazine super-hydrophobic super-oleophylic fiber web material of the embodiment of the present invention 1 preparation is in simulation
Before oil (a) pollutes, after (b) pollution and after (c) illumination heating, its surface water droplet aerial contact angle picture.
Detailed description of the invention
In conjunction with embodiment and accompanying drawing, the present invention is described in detail, but the enforcement of the present invention is not limited only to this.
The experimental technique of unreceipted actual conditions in the following example, generally according to normal condition, or according to system
Make the condition proposed by manufacturer.
Embodiment 1
(1) by the polyster fibre non-woven fabrics (Shanghai Tian Lve new textile material company limited) of 4 × 5cm through water,
Ethanol, acetone ultrasonic cleaning 15min, at room temperature dry standby；
(2) by 1g benzoxazine monomer (3-(3-trimethoxy silane) n-pro-pyl-6-methyl-3,4-dihydro
-2H-1,3-benzimidazole dihydrochloride, MP-aptms, such as Formulas I-1) be dissolved in 25g chloroform；By 1g TiO2Nanometer
Particle (particle diameter 25-70nm) adds above-mentioned solution, obtains benzimidazole dihydrochloride/nanometer after ultrasonic mixing dispersion 2h
Particle blend；
(3), under room temperature, clean fabrics of polyester is immersed benzimidazole dihydrochloride/nanoparticle blend 30s
After, pull it with the pull rate of 60mm/min, with binder clip, it is vertically picked up, the most immediately
Put in 160 DEG C of solidification casees and solidify 2h.
Its surface topography scanning electron microscopic picture is as shown in Figure 1, it is known that this surface has by the fiber of micro-meter scale
Photocatalytic nanometer grain molecular twin-stage composite construction with nanoscale；Test through contact angle measurement, on
Oil-water separation mesh film prepared by the method for stating is 156 ° to the contact angle of water, and the contact angle to oil is 0 °.Preparating acid
Aqueous slkali and after prepared material is immersed in wherein 1h room temperature dry and test connecing of its surface water and oil
Feeler；Prepared material is placed under 250～450 DEG C of high temperature and after 1h, tests its surface water and the contact of oil
Angle.Prepared super-hydrophobic super-oleophylic oil-water separation material is resistant to 300 DEG C of high temperature above, strong acid (as
Highly basic (such as pH=13) pH=1), soaks rear surface wettability stable.
Utilize the device shown in Fig. 2 to carry out oil-water separation application experiment, polybenzoxazine obtained above is surpassed
Hydrophobic super oleophylic nethike embrane is clipped in and is lined with between the bottle,suction of annular gasket and feed glass container, by dichloromethane
Directly poured into by the feed containers of top with the mixture (volume ratio is 1:1) of water.Real under gravity
Existing oil-water separation, the oil water mixture of i.e. separable 100ml in 25s.Above-mentioned nethike embrane is placed in 1-100ppm
In the aqueous solution of methylene blue, irradiate under 100W Hg lamp, photocatalyst TiO2In catalytic degradation water
Soluble dye, the colourless pure water after being purified.Finally, use in oleic acid simulating pollution experimentation
State the photic automatically cleaning characteristic of nethike embrane, above-mentioned nethike embrane is soaked in oleic acid solutions and takes out room temperature after 15min and dry in the air
Dry.Heat treated 30min at 100 DEG C again after irradiating under 100W Hg lamp.From the figure 3, it may be seen that
After greasy dirt dye, nethike embrane no longer possesses super-hydrophobic super-oleophylic characteristic；After illumination and heat treated, nethike embrane is again
Recover its super-hydrophobic super-oleophylic characteristic, can again carry out oil-water separation, show photic automatically cleaning characteristic.
Embodiment 2
(1) by the stainless steel metal filter screen of 200 mesh, 4 × 5cm, (the sapphire blue experimental apparatus in Shanghai manufactures limited public affairs
Department) through water, ethanol, acetone ultrasonic cleaning 15min, dry standby at normal temperatures；
(2) by 1g benzoxazine monomer (6-methyl-3-phenyl-3,4-dihydro-2H-1,3-benzimidazole dihydrochloride, MP-a,
Such as Formulas I-2) it is dissolved in 10g oxolane；By 0.5g TiO2Nanoparticle (particle diameter 25-70nm) adds
Enter above-mentioned solution, after ultrasonic mixing dispersion 2h, obtain benzimidazole dihydrochloride/nanoparticle blend；
(3) under room temperature, after clean stainless steel filtering net is immersed benzimidazole dihydrochloride/nanoparticle blend 30s,
Pull it with the pull rate of 100mm/min, with binder clip, it is vertically picked up, be immediately placed in after drying
210 DEG C of solidification casees solidify 1h.
Oil water mixture all with embodiment 1, is only changed to the mixing of diesel oil and water by its operating procedure and implementation
Thing.
Embodiment 3
(1) by the nylon fibre filter cloth (Shanghai Tian Lve new textile material company limited) of 4 × 5cm through water,
Ethanol, acetone ultrasonic cleaning 15min, dry standby at normal temperatures；
(2) by 1g benzoxazine monomer (3-ethoxy-6-methyl-3,4-dihydro-2H-1,3-benzimidazole dihydrochloride,
MP-eta, such as Formulas I-3) it is dissolved in 15g ethanol；By 0.7g TiO2Nanoparticle (particle diameter 50-60nm)
Add above-mentioned solution, after ultrasonic mixing dispersion 2h, obtain benzimidazole dihydrochloride/nanoparticle blend；
(3), under room temperature, clean nylon fibre filter cloth is immersed benzimidazole dihydrochloride/nanoparticle blend 60s
After, pull it with the pull rate of 120mm/min, with binder clip, it is vertically picked up, the most immediately
Put in 150 DEG C of solidification casees and solidify 1h.
Oil water mixture all with embodiment 1, is only changed to the mixing of toluene and water by its operating procedure and implementation
Thing.
Embodiment 4
(1) by the vinylon fibre filter cloth (Shanghai Tian Lve new textile material company limited) of 4 × 5cm through water,
Ethanol, acetone ultrasonic cleaning 15min, dry standby at normal temperatures；
(2) by the 1g benzoxazine monomer (double (3-trimethoxy silane-3,4-dihydro-2H-1,3-benzo of 2,2-
Piperazine base) isopropyl alkane, BA-aptms, such as Formulas I-4) be dissolved in 5g toluene；By 0.2g TiO2Nanoparticle
Son (particle diameter 25-70nm) adds above-mentioned solution, obtains benzimidazole dihydrochloride/nanoparticle after ultrasonic mixing dispersion 2h
Sub-blend；
(3), under room temperature, clean vinylon fibre filter cloth is immersed benzimidazole dihydrochloride/nanoparticle blend 60s
After, pull it with the pull rate of 120mm/min, with binder clip, it is vertically picked up, the most immediately
Put in 160 DEG C of solidification casees and solidify 2h.
Oil water mixture, all with embodiment 1, is only changed to the mixed of normal hexane and water by its operating procedure and implementation
Compound.
Embodiment 5
(1) by the polypropylene fiber filter cloth (Shanghai Tian Lve new textile material company limited) of 4 × 5cm through water,
Ethanol, acetone ultrasonic cleaning 15min, dry standby at normal temperatures；
(2) by 1g benzoxazine monomer, (2,2-is double (3-phenyl-3,4-dihydro-2H-1,3-benzimidazole dihydrochloride base)
Isopropyl alkane, BA-a, such as Formulas I-5) be dissolved in 20g dioxane；By 1g TiO2Nanoparticle (particle diameter 25-70
Nm) add above-mentioned solution, after ultrasonic mixing dispersion 2h, obtain benzimidazole dihydrochloride/nanoparticle blend；
(3), under room temperature, clean polypropylene fiber filter cloth is immersed benzimidazole dihydrochloride/nanoparticle blend 210s
After, pull it with the pull rate of 120mm/min, with binder clip, it is vertically picked up, the most immediately
Put in 150 DEG C of solidification casees and solidify 1.5h.
Oil water mixture, all with embodiment 1, is only changed to the mixed of hexadecane and water by its operating procedure and implementation
Compound.
Embodiment 6
(1) by 600 mesh, the copper mesh (Shanghai sapphire blue experimental apparatus Manufacturing Co., Ltd) of 4 × 5cm, through water,
Ethanol, acetone ultrasonic cleaning 15min, dry standby at normal temperatures；
(2) by 1g benzoxazine monomer (double (3-(trimethoxy silane) n-pro-pyl-3,4-dihydro-2H-1,3-
Benzimidazole dihydrochloride base) Ketene dimethyl, BN-aptms, such as Formulas I-6) be dissolved in 50g ethyl acetate；By 5g TiO2
Nanoparticle (particle diameter 25-70nm) adds above-mentioned solution, obtain after ultrasonic mixing dispersion 2h benzimidazole dihydrochloride/
Nanoparticle blend；
(3) under room temperature, after clean copper mesh is immersed benzimidazole dihydrochloride/nanoparticle blend 90s, with 100
The pull rate of mm/min pulls it, and it is vertically picked up with binder clip, is immediately placed in 180 DEG C after drying
Solidification case solidifies 1h.
Oil water mixture, all with embodiment 1, is only changed to the mixed of Semen Maydis oil and water by its operating procedure and implementation
Compound.
Embodiment 7
(1) by the polypropylene fiber filter cloth (Shanghai Tian Lve new textile material company limited) of 4 × 5cm through water,
Ethanol, acetone ultrasonic cleaning 15min, dry standby at normal temperatures；
(2) by 1g benzoxazine monomer (double (3-ethoxy-3,4-dihydro-2H-1,3-benzimidazole dihydrochloride bases) two
Ketone, BN-eta, such as Formulas I-7) be dissolved in 10g oxolane；By 0.5g TiO2Nanoparticle (grain
Footpath 50-60nm) add above-mentioned solution, obtain benzimidazole dihydrochloride/nanoparticle after ultrasonic mixing dispersion 2h and be blended
Thing；
(3), under room temperature, clean polypropylene fiber non-woven fabrics is immersed benzimidazole dihydrochloride/nanoparticle blend 90s
After, pull it with the pull rate of 80mm/min, with binder clip, it is vertically picked up, the most immediately
Put in 150 DEG C of solidification casees and solidify 1h.
Its operating procedure and implementation are all with embodiment 1.
Embodiment 8
(1) by the Kynoar filter membrane (Shanghai Tian Lve new textile material company limited) of 4 × 5cm through water,
Ethanol, acetone ultrasonic cleaning 15min, dry standby at normal temperatures；
(2) by 1g benzoxazine monomer (double (3-(trimethoxy silane) n-pro-pyl-3,4-dihydro-2H-1,3-
Benzimidazole dihydrochloride base) disulfone, BS-aptms, such as Formulas I-8) be dissolved in 20g chloroform；By 2g TiO2Nanometer
Particle (particle diameter 25-70nm) adds above-mentioned solution, obtains benzimidazole dihydrochloride/nanometer after ultrasonic mixing dispersion 2h
Particle blend；
(3), under room temperature, clean Kynoar filter membrane is immersed benzimidazole dihydrochloride/nanoparticle blend 120
After s, pull it with the pull rate of 100mm/min, with binder clip, it is vertically picked up, stand after drying
I.e. put in 170 DEG C of solidification casees and solidify 2h.
Oil water mixture all with embodiment 1, is only changed to the mixing of toluene and water by its operating procedure and implementation
Thing.
Embodiment 9
(1) by the ferrum net (Shanghai sapphire blue experimental apparatus Manufacturing Co., Ltd) of 4 × 5cm, through water, ethanol,
Acetone ultrasonic cleaning 15min, dries standby at normal temperatures；
(2) by 1g benzoxazine monomer (double (3-methyl-3,4-dihydro-2H-1,3-benzimidazole dihydrochloride base) disulfone,
BS-m, such as Formulas I-9) it is dissolved in 25g pyridine；By 1g TiO2Nanoparticle (particle diameter 25-70nm) adds
Enter above-mentioned solution, after ultrasonic mixing dispersion 2h, obtain benzimidazole dihydrochloride/nanoparticle blend；
(3) under room temperature, after clean ferrum net is immersed benzimidazole dihydrochloride/nanoparticle blend 90s, with 80
The pull rate of mm/min pulls it, and it is vertically picked up with binder clip, is immediately placed in 170 DEG C after drying
Solidification case solidifies 2h.
Its operating procedure and implementation are all with embodiment 1.
Embodiment 10
(1) by the polyster fibre non-woven fabrics (Shanghai Tian Lve new textile material company limited) of 4 × 5cm, through water,
Ethanol, acetone ultrasonic cleaning 15min, dry standby at normal temperatures；
(2) 1g benzoxazine monomer (such as Formulas I-1) is dissolved in 15g oxolane；By 0.8g TiO2
Nanoparticle (particle diameter 25-70nm) and 0.2g SiO2Nanoparticle (particle diameter 100-500nm) adds above-mentioned
Solution, obtains benzimidazole dihydrochloride/nanoparticle blend after ultrasonic mixing dispersion 2h；
(3), under room temperature, clean polyster fibre non-woven fabrics is immersed benzimidazole dihydrochloride/nanoparticle blend 60s
After, pull it with the pull rate of 80mm/min, with binder clip, it is vertically picked up, the most immediately
Put in 180 DEG C of solidification casees and solidify 1h.
Oil water mixture, all with embodiment 1, is only changed to the mixed of isobutyltrimethylmethane. and water by its operating procedure and implementation
Compound.
Comparison example 1
(1) by the fabrics of polyester (Shanghai Tian Lve new textile material company limited) of 4 × 5cm through water,
Ethanol, acetone ultrasonic cleaning 15min, dry standby at normal temperatures；
(2) by 1g benzoxazine monomer (3-(3-trimethoxy silane) n-pro-pyl-6-methyl-3,4-dihydro
-2H-1,3-benzimidazole dihydrochloride, MP-aptms, such as Formulas I-1) be dissolved in 25g chloroform；Obtain after ultrasonic 1h
Benzimidazole dihydrochloride homogeneous solution；
Its operating procedure and implementation are all with embodiment 1.
Comparison example 2
By the fabrics of polyester (Shanghai Tian Lve new textile material company limited) of 4 × 5cm through water, ethanol,
Acetone ultrasonic cleaning 15min, dries standby at normal temperatures；Only by clean fabrics of polyester the most immediately
Put in 160 DEG C of solidification casees and solidify 2h.
Its operating procedure and implementation are all with embodiment 1.
Comparison example 3
(1) by the stainless steel metal filter screen of 200 mesh, 4 × 5cm, (the sapphire blue experimental apparatus in Shanghai manufactures limited public affairs
Department), through water, ethanol, acetone ultrasonic cleaning 15min, dry standby at normal temperatures；
(2) by 1g benzoxazine monomer (6-methyl-3-phenyl-3,4-dihydro-2H-1,3-benzimidazole dihydrochloride, MP-a,
Such as Formulas I-2) it is dissolved in 10g oxolane；Benzimidazole dihydrochloride homogeneous solution is obtained after ultrasonic disperse 2h；
Its operating procedure and implementation are all with embodiment 2.
Comparison example 4
By 200 mesh, the stainless steel metal filter screen (Shanghai sapphire blue experimental apparatus Manufacturing Co., Ltd) of 4 × 5cm,
Through water, ethanol, acetone ultrasonic cleaning 15min, dry standby at normal temperatures；Only by clean stainless steel metal
Filter screen is immediately placed in after drying in 210 DEG C of solidification casees and solidifies 1h.
Its operating procedure and implementation are all with embodiment 2.
Retinal surface water contact angle and the automatically cleaning characteristic prepared by each embodiment are as shown in table 1.
Retinal surface water contact angle prepared by table 1 embodiment and photic automatically cleaning characteristic
As shown in Table 1, after adding polybenzoxazine material, the water contact angle of retinal surface increases, all
More than 150 °, illustrate that polybenzoxazine is conducive to preparing hydrophobic surface；Add TiO2Or and alloy after,
Can effectively obtain super-hydrophobic super-oleophylic nethike embrane, and make it possess photic automatically cleaning characteristic and light degradation characteristic,
Illustrating that being formed with of micro-nano two-stage structure is beneficial to prepare super hydrophobic surface, the addition of photocatalytic nanometer particle is favourable
In preparing photic self-cleaning material, improve the service life of oil-water separation mesh film.
The above is only the preferred embodiment of the present invention, it is noted that common for the art
Technical staff, without departing from the inventive concept of the premise, it is also possible to make some improvements and modifications, these
Improvements and modifications also should be regarded as in protection scope of the present invention.
Claims (10)
1. an automatically cleaning polybenzoxazine super-hydrophobic super-oleophylic fiber web material, it is characterised in that described automatically cleaning
Polybenzoxazine super-hydrophobic super-oleophylic fiber web material is formed blend by weight percentage by following raw material:
Benzoxazine monomer 1
Nanoparticle 0.001～60
Solvent 1～100；
The chemical structural formula of described benzoxazine monomer is shown in formula I:
In Formulas I, X, Y can be identical or different, and X is selected from H, C1～C4Alkyl, C1～C4Hydroxyl, C6～C10
One in aromatic ring yl or substituted aromatic ring yl；Y is selected from H, C1～C18Alkyl, C1～C4Hydroxyl, C6～C10
One in aromatic ring yl or siloxy group；
Described nanoparticle, for titanium dioxide, titanium dioxide and alloy thereof, nanoparticle mean diameter
It is 5～500nm.
A kind of automatically cleaning polybenzoxazine super-hydrophobic super-oleophylic fiber web material the most according to claim 1, it is special
Levying and be, described benzoxazine monomer, when X is selected from substituted aromatic ring yl, its chemical structural formula is selected from
Arbitrary:
Automatically cleaning polybenzoxazine super-hydrophobic super-oleophylic fiber web material the most according to claim 1, its feature exists
In, when described nanoparticle is titanium dioxide and alloy thereof, described alloy selected from silicon dioxide,
One or both in zinc oxide, ferroso-ferric oxide, silver phosphate, CNT, nanoclay, Graphene
Above.
Automatically cleaning polybenzoxazine super-hydrophobic super-oleophylic fiber web material the most according to claim 1, its feature exists
In, it is characterised in that: described solvent selected from chloroform, toluene, dichloromethane, ethanol, dimethylbenzene, four
One or more in hydrogen furan, dioxane, pyridine, ethyl acetate.
5. an automatically cleaning polybenzoxazine super-hydrophobic super-oleophylic nethike embrane, it is characterised in that described automatically cleaning polyphenyl
And piperazine super-hydrophobic super-oleophylic nethike embrane is to be dipped in polymer fiber filter cloth or metal screen such as Claims 1-4
In benzimidazole dihydrochloride nanoparticle blend shown in arbitrary, by lifting coating method and further heat cure system
For obtaining.
A kind of automatically cleaning polybenzoxazine super-hydrophobic super-oleophylic nethike embrane the most according to claim 5, its feature exists
In, described polymer filter cloth is terylene, chinlon, polyvinyl, polypropylene, polyvinylidene fluoride non-woven fabrics,
Or be the one in 100-8000 mesh terylene, chinlon, polyvinyl, polypropylene, polyvinylidene fluoride filter cloth；Institute
The metal screen stated is the one in 10～1000 mesh stainless steel filtering nets, copper mesh, ferrum net.
7. the preparation side of the automatically cleaning polybenzoxazine super-hydrophobic super-oleophylic nethike embrane as described in claim 5 or 6
Method, it is characterised in that described preparation method comprises the following steps:
A, benzoxazine monomer is dissolved in solvent；Nanoparticle adds above-mentioned solution, and ultrasonic mixing divides
Benzimidazole dihydrochloride and nanoparticle blend is obtained after dissipating uniformly；
B, the benzimidazole dihydrochloride that clean polymer fiber filter cloth or metal screen immersion step A are obtained and nanometer
In particle blend 5～300s, the speed with 40～120mm/min is dried after lifting, then is placed in
Cross-linking reaction 0.1～24h at 120～300 DEG C.
The preparation method of automatically cleaning polybenzoxazine super-hydrophobic super-oleophylic nethike embrane the most according to claim 7, its
Being characterised by, described preparation method comprises the following steps:
In step B, clean polymer fiber filter cloth or metal screen, be by polymer fiber filter cloth/film
Or metal screen dries through water, ethanol, washing with acetone room temperature；
Clean polymer fiber filter cloth or metal screen are immersed benzimidazole dihydrochloride and the nanoparticle that step A obtains
In sub-blend 5～300s, it is dried after lifting with the speed of 60mm/min, then is placed at 160 DEG C friendship
Connection reaction 0.1～24h.
9. the automatically cleaning polybenzoxazine super-hydrophobic super-oleophylic nethike embrane as described in claim 5 or 6 divides at profit
Application in from, it is characterised in that: in oil-water separation, oil water mixture be vegetable oil and the mixture of water,
Industry oil and the mixture of water, or organic solvent and the mixture of water.
Automatically cleaning polybenzoxazine super-hydrophobic super-oleophylic nethike embrane the most according to claim 9 is in oil-water separation
In application, it is characterised in that: described vegetable oil selected from Semen Maydis oil, soybean oil, Oleum Arachidis hypogaeae semen, olive oil,
One in Oleum sesami；Described industry oil one in diesel oil, kerosene, gasoline；Described organic solvent
Selected from C6～C16Alkane, the C of halogen substiuted6～C16Alkane, C6～C10One in aromatic hydrocarbon.
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