CN106178599B - A kind of automatically cleaning polybenzoxazine super-hydrophobic super-oleophylic fiber web material and its preparation and the application in water-oil separating - Google Patents
A kind of automatically cleaning polybenzoxazine super-hydrophobic super-oleophylic fiber web material and its preparation and the application in water-oil separating 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 its preparations and the application in water-oil separating.The composition of super-hydrophobic super-oleophylic fiber web material of the invention are as follows: 1 parts by weight of benzoxazine, 0.001~60 parts by weight of nanoparticle, 1~100 parts by weight of solvent；Its preparation process: nanoparticle is added in benzoxazine solution, mixing is uniformly dispersed；Polymer fiber filter cloth or metal screen are placed in blends described above, automatically cleaning polybenzoxazine super-hydrophobic super-oleophylic fiber web material is prepared by lifting coating method and further thermal curing method.The present invention provide a kind of raw material it is inexpensive, without fluorochemical additive, simple process, the super-hydrophobic super-oleophylic fiber web material suitable for continuous industrial production with excellent water-oil separating characteristic and preparation, the water-oil separating material acid and alkali-resistance, resistance to ultraviolet irradiation, high temperature resistant, it can be recycled for multiple times, and there is good automatically cleaning characteristic under the collective effect of illumination and heat treatment.
Description
Technical field
The invention belongs to chemicals, material surface modifying technology field, and in particular to a kind of automatically cleaning polybenzoxazine
Super-hydrophobic super-oleophylic fiber web material and preparation method thereof, and the application in water-oil separating.
Background technique
Water-oil separating all has a very important significance in daily life and field of industrial production, and membrane separation technique is processing
A kind of effective ways of oily water.However, fouling membrane is the matter of utmost importance for nowadays needing to solve, it is logical that it can reduce water-oil separationg film
Amount reduces separative efficiency, reduces the oil finally generated or water quality.Therefore, it is necessary to prepare a kind of with automatically cleaning characteristic
Water-oil separating membrane material improves or solves the pollution problem of water-oil separating material, effectively to carry out water-oil separating.
A kind of Publication No. CN102925877A (entitled " hollowed-out vessel and its preparation with special wellability
Method and application ", application No. is CN201210454486.7), a kind of CN102961893A (entitled " super-hydrophobic super parent
The oil-water separation mesh film and preparation method thereof of oil ", application No. is CN201210440282.8), CN103157392A (denomination of invention
For " a kind of with super-hydrophobic super-oleophylic property and degradable oil-water separation mesh film and preparation method thereof ", application No. is
CN201310093434.6), CN104117287A (entitled " a kind of responsiveness water-oil separating with superhydrophobic property
Nethike embrane and preparation method thereof ", application No. is CN201410315799.3) Chinese patent (application) individually disclose have it is super thin
The oil-water separation mesh film or water-oil separating hollowed-out vessel of the super oil-wet behavior of water.Publication No. CN104193999A is (entitled
" a kind of preparation method of fluorine silicon benzoxazine copolymer ", application No. is CN201410454287.5) Chinese patent application
The preparation method for disclosing a kind of fluorine silicon polybenzoxazine copolymer and its application in water-oil separating.Although this five kinds of skills
Art all has the effect of water-oil separating, but in the treatment process of oily wastewater, and nethike embrane or container have suffered from a degree of
Oily pollution, this makes membrane flux reduction, separative efficiency reduction, grease quality decline, materials'use service life shorten.Moreover, open
Number platinum class catalysis is used in the preparation process of fluorine silicon polybenzoxazine copolymer for the Chinese patent of CN104193999A
Agent contains fluorine atom in molecule, increases production cost.
In addition, Publication No. CN1387932A (it is entitled " nano-interface separating net with self-cleaning function and its
Preparation method and purposes ", application No. is CN01118387.X) Chinese patent two be doped with photocatalytic self-cleaning property are disclosed
Titanium oxide (TiO2) monolayer net, although oil-water separating net prepared by the technology has photic automatic cleaning action, it was manufactured
Journey is complicated, raw material composition is many and diverse, fluorochemical usage amount is big.In addition, Publication No. CN102764536A is (entitled
" a kind of oily wastewater purification nethike embrane and the preparation method and application thereof ", application No. is CN201210241886.X) Chinese patent
Disclose photic automatically cleaning oil-water separating net, but time-consuming for its manufacturing process, need to impregnate if in silicic acid anhydride 48h with
On.Its manufacturing process is cumbersome, needs to prepare two layers of strainer, and one layer is to be deposited with TiO2Photic automatically cleaning strainer, another layer be
Hydrophobic screen.
The research and development focus that water-oil separating is always this field is carried out based on the special wettability of material, how to guarantee grease point
Off-network membrane material not only has super-hydrophobic super-oleophylic characteristic but also has automatically cleaning characteristic, can lack again with or without fluorine compounds,
Cost and manufacturing process difficulty are reduced, is always this field technical problem to be solved.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of super-hydrophobic super parents of automatically cleaning polybenzoxazine
Oil network membrane material；Another object of the present invention is to provide a kind of automatically cleaning polybenzoxazine super-hydrophobic super-oleophylic fiber web materials
Preparation method；The third object of the present invention is to provide a kind of automatically cleaning polybenzoxazine super-hydrophobic super-oleophylic fiber web material in oil
Application in water separation.
Main technical schemes of the invention are as follows: a kind of preparation of automatically cleaning polybenzoxazine super-hydrophobic super-oleophylic membrane material
Technology, raw material composition are as follows: 1 parts by weight of benzoxazine, 0.001~20 parts by weight of nanoparticle, 1~100 parts by weight of solvent.Tool
Preparation process: benzoxazine solution is added in nanoparticle, mixing is uniformly dispersed；By clean polymer fiber filter cloth or gold
Belong to strainer to be placed in blends described above, it is super thin to prepare automatically cleaning polybenzoxazine by lifting coating method and further heat cure
The super oleophylic nethike embrane of water.There are H, C in the main substituent groups group in amine source and phenol source in the benzoxazine monomer and polybenzoxazine1~
C18Alkyl, C1~C4Hydroxyl, C6~C10Aromatic ring yl, substituted aromatic ring yl, siloxy group.
The first aspect of the present invention provides a kind of automatically cleaning polybenzoxazine super-hydrophobic super-oleophylic fiber web material, described
Automatically cleaning polybenzoxazine super-hydrophobic super-oleophylic fiber web material blend is formed by following raw material by weight percentage:
Benzoxazine monomer 1
Nanoparticle 0.001~60
Solvent 1~100；
The chemical structural formula of the 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~C10Aromatic ring yl takes
One of the aromatic ring yl in generation；Y is selected from H, C1~C18Alkyl, C1~C4Hydroxyl, C6~C10One in aromatic ring yl or siloxy group
Kind；
The benzoxazine monomer, when X is selected from the aromatic ring yl replaced, it is any that chemical structural formula is selected from following abc:
The chemical structural formula of polybenzoxazine of the invention is as follows, wherein n >=2:
Preferably, the benzoxazine monomer, compound I-1, I-2, I-3, I-4, I-5, I- in embodiment
6, I-7, I-8, I-9 etc..
The nanoparticle is titanium dioxide (TiO2) or TiO2And its when dopant, the dopant is selected from two
One or more of silica, zinc oxide, ferroso-ferric oxide, silver orthophosphate, carbon nanotube, nanoclay, graphene.
Preferably, the nanoparticle is TiO2Or the nanoparticle is TiO2And SiO2Mixture.
When the nanoparticle is TiO2And its when dopant, wherein TiO2The ratio of nanoparticle should be in weight ratio
50% or more.
The solvent is selected from chloroform, toluene, methylene chloride, ethyl alcohol, dimethylbenzene, tetrahydrofuran, dioxanes, pyridine, second
One or more of acetoacetic ester.
Preferably, benzoxazine monomer, nanoparticle, solvent weight ratio be 1:0.1~5:5~50；More preferably, benzo
Oxazines monomer, nanoparticle, solvent weight ratio be 1:1:25.
The second aspect of the present invention, provides a kind of automatically cleaning polybenzoxazine super-hydrophobic super-oleophylic nethike embrane, it is described from
Cleaning polybenzoxazine super-hydrophobic super-oleophylic nethike embrane is that polymer fiber filter cloth or metal screen are dipped in such as above-mentioned automatically cleaning
In polybenzoxazine super-hydrophobic super-oleophylic fiber web material, it is prepared by lifting coating method and further heat cure.
This field routine techniques, such as bibliography: Tang X, Si Y, Ge J can be used in the lifting coating method,
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.
Benzoxazine polymerization routine techniques can be used, such as bibliography in the heat cure: 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, the lifting coating method and further heat cure condition are as follows: soaking time is 5~300s；Lifting
Speed is 40~120mm/min；Heat curing temperature is 120~300 DEG C；Thermal curing time be 0.1~for 24 hours.
Invention further provides the preparation method of above-mentioned automatically cleaning polybenzoxazine super-hydrophobic super-oleophylic nethike embrane, institutes
The preparation method stated the following steps are included:
A, benzoxazine monomer is dissolved in solvent；Above-mentioned solution is added in nanoparticle, ultrasonic mixing is uniformly dispersed
After obtain benzoxazine and nanoparticle blend；
B, the obtained benzoxazine of clean polymer fiber filter cloth or metal screen immersion step A and nanoparticle are total to
5~300s in mixed object to be dried after the speed lifting of 40~120mm/min, then is placed in cross-linking reaction at 120~300 DEG C
0.1~for 24 hours.
The preparation method the following steps are included:
In step B, clean polymer fiber filter cloth or metal screen are to filter polymer fiber filter cloth/film or metal
Net is dried through water, ethyl alcohol, acetone washing and room temperature；
In step B, preferably, the pull rate 60mm/min, 160 DEG C carry out cross-linking reaction in solidification case.
The third aspect of the present invention provides above-mentioned automatically cleaning polybenzoxazine super-hydrophobic super-oleophylic fiber web material, net
Application of the film in water-oil separating.
In water-oil separating of the invention, oil water mixture is the mixture of the mixture of vegetable oil and water, industry oil and water,
Or the mixture of organic solvent and water.
The oil water mixture is vegetable oil and the mixture of water, the mixture of industry oil and water, organic solvent and water
Mixture；The vegetable oil is selected from one of corn oil, soybean oil, peanut oil, olive oil, sesame oil；The industry oil
Selected from one of diesel oil, kerosene, gasoline；The organic solvent is selected from C6~C16The C that alkane, halogen replace6~C16Alkane, C6
~C10One of aromatic hydrocarbon.
Beneficial effects of the present invention:
The surface of the super-hydrophobic super-oleophylic polybenzoxazine fiber web material is twin-stage composite construction, specially micron meter
The fiber or mesh of degree and the photocatalytic nanometer particle of nanoscale or and its dopant.
The surface water contact angle of the super-hydrophobic super-oleophylic polybenzoxazine fiber web material be greater than 150 °, oily contact angle it is small
In 5 °.
After the super-hydrophobic super-oleophylic fiber web material impregnates in strong acid, highly basic, still have super-hydrophobic super-oleophylic characteristic,
The soak pH range is 1~13, and soaking time is greater than 1h；The super-hydrophobic super-oleophylic fiber web material is under ultraviolet light
After exposure, still has super-hydrophobic super-oleophylic characteristic, the exposure duration is greater than 10h；The super-hydrophobic super-oleophylic nethike embrane material
Material still has super-hydrophobic super-oleophylic characteristic after high-temperature process, and the temperature is 250~300 DEG C, and the processing time is greater than 1h.
Of the invention being technically characterized in that is fluorine-containing hydrophobic using novel polyphenyl and oxazines hydrophobic material substitution cheap and easy to get
Reagent reduces costs.Secondly, technical matters of the invention is simple, can be prepared by lifting film and subsequent direct solidification
Functional oil-water separation mesh film, this substantially reduces process time, reduces cost, is more suitable for industrial continuous production.
Again, super-hydrophobic super-oleophylic nethike embrane of the invention has automatically cleaning characteristic, and the automatically cleaning of oil-water separation mesh film not only may be implemented,
The service life of oil-water separation mesh film, and solvable organic pollutant in the water that can degrade are improved, water body will not be generated secondary
Pollution.Finally, super-hydrophobic super-oleophylic nethike embrane of the invention has excellent acid and alkali-resistance, resistance to ultraviolet irradiation, high-temperature stability, it can also
Water-oil separating for extreme environments such as strong acid and strong base, high temperature.
Detailed description of the invention
Fig. 1 is the surface shape of automatically cleaning polybenzoxazine super-hydrophobic super-oleophylic fiber web material prepared by the embodiment of the present invention 1
Looks scanning electron microscopic picture.
Fig. 2 is automatically cleaning polybenzoxazine super-hydrophobic super-oleophylic fiber web material water-oil separating prepared by the embodiment of the present invention 1
The experimental provision picture of application.
Fig. 3 is the automatically cleaning polybenzoxazine super-hydrophobic super-oleophylic fiber web material of the preparation of the embodiment of the present invention 1 in simulation oil
(a) before polluting, after (b) pollution and after (c) illumination heating, the aerial contact angle picture of surface water droplet.
Specific embodiment
Now in conjunction with embodiment and attached drawing, the present invention is described in detail, but implementation of the invention is not limited only to this.
In the following examples, the experimental methods for specific conditions are not specified, usually according to normal condition, or according to manufacturer
Proposed condition.
Embodiment 1
(1) by the polyester fiber non-woven fabrics of 4 × 5cm (Shanghai Tian Lve new textile material Co., Ltd) through water, ethyl alcohol, acetone
It is cleaned by ultrasonic 15min, dries at room temperature spare；
(2) by 1g benzoxazine monomer (3- (3- trimethoxy silane) n-propyl -6- methyl -3,4- dihydro -2H-1,3-
Benzoxazine, MP-aptms, such as Formulas I -1) it is dissolved in 25g chloroform；By 1g TiO2Nanoparticle (partial size 25-70nm) is added
Above-mentioned solution, ultrasonic mixing obtain benzoxazine/nanoparticle blend after dispersing 2h；
(3) at room temperature, after clean fabrics of polyester being immersed benzoxazine/nanoparticle blend 30s, with
The pull rate of 60mm/min pulls it, and is picked up it vertically with binder clip, is immediately placed in after dry solid in 160 DEG C of solidification cases
Change 2h.
Its surface topography scanning electron microscopic picture is as shown in Figure 1, it is known that the surface has the fiber and nanometer by micro-meter scale
The molecular twin-stage composite construction of the photocatalytic nanometer grain of scale；It is tested through contact angle measurement, the grease of above method preparation
Separating nethike embrane is 156 ° to the contact angle of water, and the contact angle to oil is 0 °.It prepares acid-base solution and impregnates prepared material
The contact angle of its surface water and oil is dried and tested to room temperature after wherein 1h；Prepared material is placed in 250~450 DEG C of high temperature
The contact angle of its surface water and oil is tested after lower 1h.Prepared super-hydrophobic super-oleophylic water-oil separating material is resistant to 300 DEG C or more
High temperature impregnates rear surface wettability in strong acid (such as pH=1), highly basic (such as pH=13) and stablizes.
Water-oil separating application experiment is carried out using device shown in Fig. 2, polybenzoxazine obtained above is super-hydrophobic super
Oleophylic nethike embrane is clipped between the bottle,suction for being lined with annular gasket and feed glass container, by the mixture (body of methylene chloride and water
Product is than being 1:1) it is directly poured by the feed containers of top.Water-oil separating is realized under the effect of gravity, is separated in 25s
The oil water mixture of 100ml.Above-mentioned nethike embrane is placed in the aqueous solution of 1-100ppm methylene blue, is irradiated under 100W Hg lamp,
Photochemical catalyst TiO2Soluble dye in catalytic degradation water, the colourless pure water after being purified.Finally, being simulated using oleic acid
The photic automatically cleaning characteristic for polluting the above-mentioned nethike embrane of experimental study, above-mentioned nethike embrane is soaked in oleic acid solutions and takes out room after 15min
Temperature is dried.Heat 30min at 100 DEG C again after irradiating under 100W Hg lamp.From the figure 3, it may be seen that after oily pollution, net
Film no longer has super-hydrophobic super-oleophylic characteristic；After illumination and heat treatment, nethike embrane restores its super-hydrophobic super-oleophylic characteristic again, can
Water-oil separating is carried out again, shows photic automatically cleaning characteristic.
Embodiment 2
(1) by 200 mesh, 4 × 5cm stainless steel metal strainer (the sapphire blue laboratory apparatus Manufacturing Co., Ltd in Shanghai) through water,
Ethyl alcohol, acetone are cleaned by ultrasonic 15min, dry at normal temperature spare；
(2) by 1g benzoxazine monomer (6- methyl -3- phenyl -3,4- dihydro -2H-1,3- benzoxazine, MP-a, such as formula
I-2 it) is dissolved in 10g tetrahydrofuran；By 0.5g TiO2Above-mentioned solution, ultrasonic mixing is added in nanoparticle (partial size 25-70nm)
Benzoxazine/nanoparticle blend is obtained after dispersion 2h；
(3) at room temperature, after clean stainless steel filtering net being immersed benzoxazine/nanoparticle blend 30s, with 100mm/
The pull rate of min pulls it, and is picked up it vertically with binder clip, is immediately placed in 210 DEG C of solidification cases after dry and solidifies 1h.
Oil water mixture is only changed to the mixture of diesel oil and water with embodiment 1 by its operating procedure and implementation method.
Embodiment 3
(1) the nylon fibre filter cloth of 4 × 5cm (Shanghai Tian Lve new textile material Co., Ltd) is super through water, ethyl alcohol, acetone
Sound cleans 15min, dries at normal temperature spare；
(2) by 1g benzoxazine monomer (3- ethoxy -6- methyl -3,4- dihydro -2H-1,3- benzoxazine, MP-eta,
Such as Formulas I -3) it is dissolved in 15g ethyl alcohol；By 0.7g TiO2Above-mentioned solution, ultrasonic mixing is added in nanoparticle (partial size 50-60nm)
Benzoxazine/nanoparticle blend is obtained after dispersion 2h；
(3) at room temperature, after clean nylon fibre filter cloth being immersed benzoxazine/nanoparticle blend 60s, with
The pull rate of 120mm/min pulls it, and is picked up it vertically with binder clip, is immediately placed in 150 DEG C of solidification cases after dry
Solidify 1h.
Oil water mixture is only changed to the mixture of toluene and water with embodiment 1 by its operating procedure and implementation method.
Embodiment 4
(1) the vinylon fibre filter cloth of 4 × 5cm (Shanghai Tian Lve new textile material Co., Ltd) is super through water, ethyl alcohol, acetone
Sound cleans 15min, dries at normal temperature spare；
(2) by 1g benzoxazine monomer (2,2- bis- (3- trimethoxy silane -3,4- dihydro -2H-1,3- benzoxazinyl-s)
Isopropyl alkane, BA-aptms, such as Formulas I -4) it is dissolved in 5g toluene；By 0.2g TiO2In nanoparticle (partial size 25-70nm) addition
Solution is stated, obtains benzoxazine/nanoparticle blend after ultrasonic mixing dispersion 2h；
(3) at room temperature, after clean vinylon fibre filter cloth being immersed benzoxazine/nanoparticle blend 60s, with
The pull rate of 120mm/min pulls it, and is picked up it vertically with binder clip, is immediately placed in 160 DEG C of solidification cases after dry
Solidify 2h.
Oil water mixture is only changed to the mixture of n-hexane and water with embodiment 1 by its operating procedure and implementation method.
Embodiment 5
(1) the polypropylene fiber filter cloth of 4 × 5cm (Shanghai Tian Lve new textile material Co., Ltd) is super through water, ethyl alcohol, acetone
Sound cleans 15min, dries at normal temperature spare；
(2) by 1g benzoxazine monomer (2,2- bis- (3- phenyl -3,4- dihydro -2H-1,3- benzoxazinyl-) isopropyl alkanes,
BA-a, such as Formulas I -5) it is dissolved in 20g dioxanes；By 1g TiO2Above-mentioned solution is added in nanoparticle (partial size 25-70nm), surpasses
Benzoxazine/nanoparticle blend is obtained after sound mixing dispersion 2h；
(3) at room temperature, after clean polypropylene fiber filter cloth being immersed benzoxazine/nanoparticle blend 210s, with
The pull rate of 120mm/min pulls it, and is picked up it vertically with binder clip, is immediately placed in 150 DEG C of solidification cases after dry
Solidify 1.5h.
Oil water mixture is only changed to the mixture of hexadecane and water with embodiment 1 by its operating procedure and implementation method.
Embodiment 6
(1) by 600 mesh, the copper mesh (the sapphire blue laboratory apparatus Manufacturing Co., Ltd in Shanghai) of 4 × 5cm, through water, ethyl alcohol, acetone
It is cleaned by ultrasonic 15min, dries at normal temperature spare；
(2) by 1g benzoxazine monomer, (bis- (3- (trimethoxy silane) n-propyl -3,4- dihydro -2H-1,3- benzo is disliked
Piperazine base) Ketene dimethyl, BN-aptms, such as Formulas I -6) it is dissolved in 50g ethyl acetate；By 5g TiO2Nanoparticle (partial size 25-
Above-mentioned solution 70nm) is added, obtains benzoxazine/nanoparticle blend after ultrasonic mixing dispersion 2h；
(3) at room temperature, after clean copper mesh being immersed benzoxazine/nanoparticle blend 90s, with 100mm/min's
Pull rate pulls it, and is picked up it vertically with binder clip, is immediately placed in 180 DEG C of solidification cases after dry and solidifies 1h.
Oil water mixture is only changed to the mixture of corn oil and water with embodiment 1 by its operating procedure and implementation method.
Embodiment 7
(1) the polypropylene fiber filter cloth of 4 × 5cm (Shanghai Tian Lve new textile material Co., Ltd) is super through water, ethyl alcohol, acetone
Sound cleans 15min, dries at normal temperature spare；
(2) by 1g benzoxazine monomer (bis- (3- ethoxy -3,4- dihydro -2H-1,3- benzoxazinyl-) Ketene dimethyls, BN-
Eta, such as Formulas I -7) it is dissolved in 10g tetrahydrofuran；By 0.5g TiO2Above-mentioned solution is added in nanoparticle (partial size 50-60nm),
Benzoxazine/nanoparticle blend is obtained after ultrasonic mixing dispersion 2h；
(3) at room temperature, after clean polypropylene fiber non-woven fabrics being immersed benzoxazine/nanoparticle blend 90s, with
The pull rate of 80mm/min pulls it, and is picked up it vertically with binder clip, is immediately placed in after dry solid in 150 DEG C of solidification cases
Change 1h.
Its operating procedure and implementation method are the same as embodiment 1.
Embodiment 8
(1) by the Kynoar filter membrane of 4 × 5cm (Shanghai Tian Lve new textile material Co., Ltd) through water, ethyl alcohol, acetone
It is cleaned by ultrasonic 15min, dries at normal temperature spare；
(2) by 1g benzoxazine monomer, (bis- (3- (trimethoxy silane) n-propyl -3,4- dihydro -2H-1,3- benzo is disliked
Piperazine base) two sulfones, BS-aptms, such as Formulas I -8) it is dissolved in 20g chloroform；By 2g TiO2Nanoparticle (partial size 25-70nm) is added
Above-mentioned solution, ultrasonic mixing obtain benzoxazine/nanoparticle blend after dispersing 2h；
(3) at room temperature, after clean Kynoar filter membrane being immersed benzoxazine/nanoparticle blend 120s, with
The pull rate of 100mm/min pulls it, and is picked up it vertically with binder clip, is immediately placed in 170 DEG C of solidification cases after dry
Solidify 2h.
Oil water mixture is only changed to the mixture of toluene and water with embodiment 1 by its operating procedure and implementation method.
Embodiment 9
(1) clear through water, ethyl alcohol, acetone ultrasound by the iron net of 4 × 5cm (the sapphire blue laboratory apparatus Manufacturing Co., Ltd in Shanghai)
15min is washed, is dried at normal temperature spare；
(2) by 1g benzoxazine monomer (bis- (3- methyl -3,4- dihydro -2H-1,3- benzoxazinyl-s) two sulfones, BS-m, such as
Formulas I -9) it is dissolved in 25g pyridine；By 1g TiO2Above-mentioned solution, ultrasonic mixing dispersion is added in nanoparticle (partial size 25-70nm)
Benzoxazine/nanoparticle blend is obtained after 2h；
(3) at room temperature, after clean iron net being immersed benzoxazine/nanoparticle blend 90s, with mentioning for 80mm/min
Pulling rate degree pulls it, and is picked up it vertically with binder clip, is immediately placed in 170 DEG C of solidification cases after dry and solidifies 2h.
Its operating procedure and implementation method are the same as embodiment 1.
Embodiment 10
(1) by the polyester fiber non-woven fabrics of 4 × 5cm (Shanghai Tian Lve new textile material Co., Ltd), through water, ethyl alcohol, third
Ketone is cleaned by ultrasonic 15min, dries at normal temperature spare；
(2) 1g benzoxazine monomer (such as Formulas I -1) is dissolved in 15g tetrahydrofuran；By 0.8g TiO2Nanoparticle
(partial size 25-70nm) and 0.2g SiO2Above-mentioned solution is added in nanoparticle (partial size 100-500nm), after ultrasonic mixing disperses 2h
Obtain benzoxazine/nanoparticle blend；
(3) at room temperature, after clean polyester fiber non-woven fabrics being immersed benzoxazine/nanoparticle blend 60s, with
The pull rate of 80mm/min pulls it, and is picked up it vertically with binder clip, is immediately placed in after dry solid in 180 DEG C of solidification cases
Change 1h.
Oil water mixture is only changed to the mixture of isooctane and water with embodiment 1 by its operating procedure and implementation method.
Comparison example 1
(1) fabrics of polyester of 4 × 5cm (Shanghai Tian Lve new textile material Co., Ltd) is super through water, ethyl alcohol, acetone
Sound cleans 15min, dries at normal temperature spare；
(2) by 1g benzoxazine monomer (3- (3- trimethoxy silane) n-propyl -6- methyl -3,4- dihydro -2H-1,3-
Benzoxazine, MP-aptms, such as Formulas I -1) it is dissolved in 25g chloroform；Benzoxazine homogeneous solution is obtained after ultrasonic 1h；
Its operating procedure and implementation method are the same as embodiment 1.
Comparison example 2
By the fabrics of polyester (Shanghai Tian Lve new textile material Co., Ltd) of 4 × 5cm through water, ethyl alcohol, acetone ultrasound
15min is cleaned, is dried at normal temperature spare；It will be only immediately placed in 160 DEG C of solidification cases after the drying of clean fabrics of polyester solid
Change 2h.
Its operating procedure and implementation method are the same as embodiment 1.
Comparison example 3
(1) by 200 mesh, the stainless steel metal strainer (the sapphire blue laboratory apparatus Manufacturing Co., Ltd in Shanghai) of 4 × 5cm, through water,
Ethyl alcohol, acetone are cleaned by ultrasonic 15min, dry at normal temperature spare；
(2) by 1g benzoxazine monomer (6- methyl -3- phenyl -3,4- dihydro -2H-1,3- benzoxazine, MP-a, such as formula
I-2 it) is dissolved in 10g tetrahydrofuran；Benzoxazine homogeneous solution is obtained after ultrasonic disperse 2h；
Its operating procedure and implementation method are the same as embodiment 2.
Comparison example 4
By 200 mesh, the stainless steel metal strainer (the sapphire blue laboratory apparatus Manufacturing Co., Ltd in Shanghai) of 4 × 5cm, through water, second
Alcohol, acetone are cleaned by ultrasonic 15min, dry at normal temperature spare；Only 210 will be immediately placed in after the drying of clean stainless steel metal strainer
Solidify 1h in DEG C solidification case.
Its operating procedure and implementation method are the same as embodiment 2.
The retinal surface water contact angle and automatically cleaning characteristic prepared by each embodiment is as shown in table 1.
The retinal surface water contact angle of 1 embodiment of table preparation and photic automatically cleaning characteristic
As shown in Table 1, after polybenzoxazine material being added, the water contact angle of retinal surface increases, and is all larger than 150 °,
Illustrate that polybenzoxazine is conducive to prepare hydrophobic surface；TiO is added2Or and its dopant after, can effectively obtain super-hydrophobic super
Oleophylic nethike embrane, and it is made to have photic automatically cleaning characteristic and light degradation characteristic, illustrate that the formation of micro-nano two-stage structure has and is conducive to system
Standby super hydrophobic surface, the addition of photocatalytic nanometer particle are conducive to prepare photic self-cleaning material, improve oil-water separation mesh film
Service life.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
Member, without departing from the inventive concept of the premise, can also make several improvements and modifications, these improvements and modifications also should be regarded as
In protection scope of the present invention.
Claims (10)
1. a kind of automatically cleaning polybenzoxazine super-hydrophobic super-oleophylic fiber web material, which is characterized in that the automatically cleaning polyphenyl is simultaneously
Oxazines super-hydrophobic super-oleophylic fiber web material forms blend by following raw material by weight percentage:
Benzoxazine monomer 1
Nanoparticle 0.001~60
Solvent 1~100；
The chemical structural formula of the 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~C10Aromatic ring yl or substituted virtue
One of ring group；Y is selected from H, C1~C18Alkyl, C1~C4Hydroxyl, C6~C10One of aromatic ring yl or siloxy group；
The nanoparticle, is titanium dioxide, titanium dioxide and its dopant, and nanoparticle average grain diameter is 5~500nm.
2. a kind of automatically cleaning polybenzoxazine super-hydrophobic super-oleophylic fiber web material according to claim 1, which is characterized in that
The benzoxazine monomer, when X is selected from the aromatic ring yl replaced, chemical structural formula is selected from following any:
3. automatically cleaning polybenzoxazine super-hydrophobic super-oleophylic fiber web material according to claim 1, which is characterized in that described
Nanoparticle be titanium dioxide and its dopant when, the dopant be selected from silica, zinc oxide, ferroso-ferric oxide,
One or more of silver orthophosphate, carbon nanotube, nanoclay, graphene.
4. automatically cleaning polybenzoxazine super-hydrophobic super-oleophylic fiber web material according to claim 1, which is characterized in that it is special
Sign is: the solvent is selected from chloroform, toluene, methylene chloride, ethyl alcohol, dimethylbenzene, tetrahydrofuran, dioxanes, pyridine, acetic acid
One or more of ethyl ester.
5. a kind of automatically cleaning polybenzoxazine super-hydrophobic super-oleophylic nethike embrane, which is characterized in that the automatically cleaning polybenzoxazine
Super-hydrophobic super-oleophylic nethike embrane be polymer fiber filter cloth or metal screen are dipped in as Claims 1-4 it is any shown in benzo
In oxazines nanoparticle blend, it is prepared by lifting coating method and further heat cure；
Wherein, the polymer fiber filter cloth is the non-woven fabrics of terylene, polyamide fibre, polyvinyl, polypropylene fibre or polyvinylidene fluoride, institute
Stating metal screen is stainless steel filtering net, copper mesh or iron net.
6. a kind of automatically cleaning polybenzoxazine super-hydrophobic super-oleophylic nethike embrane according to claim 5, which is characterized in that wherein
The polymer fiber filter cloth is the nonwoven of the terylene of 100-8000 mesh, polyamide fibre, polyvinyl, polypropylene fibre or polyvinylidene fluoride
Cloth, the metal screen are stainless steel filtering net, copper mesh or the iron net of 10~1000 mesh.
7. a kind of preparation method of such as automatically cleaning polybenzoxazine super-hydrophobic super-oleophylic nethike embrane described in claim 5 or 6, special
Sign is, the preparation method the following steps are included:
A, benzoxazine monomer is dissolved in solvent；Above-mentioned solution is added in nanoparticle, ultrasonic mixing obtains after being uniformly dispersed
To benzoxazine and nanoparticle blend；
B, clean polymer fiber filter cloth or metal screen are immersed into the benzoxazine and nanoparticle blend that step A is obtained
In 5~300s, to be dried after the lifting of the speed of 40~120mm/min, then be placed in cross-linking reaction 0.1 at 120~300 DEG C~
24h。
8. the preparation method of automatically cleaning polybenzoxazine super-hydrophobic super-oleophylic nethike embrane according to claim 7, feature exist
In, the preparation method the following steps are included:
In step B, clean polymer fiber filter cloth or metal screen, be by polymer fiber filter cloth or metal screen through water,
Simultaneously room temperature is dried for ethyl alcohol, acetone washing；
Clean polymer fiber filter cloth or metal screen are immersed in the benzoxazine and nanoparticle blend that step A is obtained
5~300s to be dried after the lifting of the speed of 60mm/min, then is placed in cross-linking reaction 0.1 at 160 DEG C~for 24 hours.
9. a kind of if automatically cleaning polybenzoxazine super-hydrophobic super-oleophylic nethike embrane described in claim 5 or 6 is in water-oil separating
Using, it is characterised in that: in water-oil separating, oil water mixture is the mixture of the mixture of vegetable oil and water, industry oil and water,
Or the mixture of organic solvent and water.
10. application of the automatically cleaning polybenzoxazine super-hydrophobic super-oleophylic nethike embrane according to claim 9 in water-oil separating,
It is characterized by: the vegetable oil is selected from one of corn oil, soybean oil, peanut oil, olive oil, sesame oil；The industry
Oil is selected from one of diesel oil, kerosene, gasoline；The organic solvent is selected from C6~C16The C that alkane, halogen replace6~C16Alkane,
C6~C10One of aromatic hydrocarbon.
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| CN110204776A (en) * | 2019-06-05 | 2019-09-06 | 东华大学 | A kind of polyvinylidene fluoride nanometer fiber aerogel material and preparation method thereof |
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| CN112933984B (en) * | 2021-01-29 | 2022-05-10 | 三明学院 | GYSNs (gysan) -filled polyurethane hybrid film and preparation method thereof |
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| CN113235303B (en) * | 2021-06-08 | 2023-08-18 | 青岛大学 | Polybenzoxazine modified polyphenylene sulfide material and preparation method thereof |
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