CN107629379B - Reversible light-operated hydrophobic composite membrane of one kind and preparation method thereof - Google Patents
Reversible light-operated hydrophobic composite membrane of one kind and preparation method thereof Download PDFInfo
- Publication number
- CN107629379B CN107629379B CN201710953008.3A CN201710953008A CN107629379B CN 107629379 B CN107629379 B CN 107629379B CN 201710953008 A CN201710953008 A CN 201710953008A CN 107629379 B CN107629379 B CN 107629379B
- Authority
- CN
- China
- Prior art keywords
- composite membrane
- azobenzene
- preparation
- nano
- meter sio
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention discloses a kind of reversible light-operated hydrophobic azobenzene fluorinated copolymer/Nano-meter SiO_2s2Composite membrane and preparation method thereof, the preparation of the composite membrane is the following steps are included: trifluoroethyl methacrylate and acrylic ester monomer containing azobenzene group are added in solvent a by (1) according to molar ratio 10:1~1:10；Free radical solution polymerization is carried out by initiator of azodiisobutyronitrile；The polymer that reaction generates is dissolved repeatedly, is precipitated, then after drying, binary random copolymer is prepared；(2) binary random copolymer of step (1) is dissolved in solvent b, obtains copolymer solution；Nano-meter SiO_2 is added into copolymer solution2, make Nano-meter SiO_22Content be 0.1-10wt%, ultrasonic treatment is spun in substrate, forms the composite membrane after dry.Preparation method of the invention is simple, and the hydrophobicity reversible change range for the composite membrane being prepared is big, and boundary strength is high, the preparation especially suitable for light responsive material.
Description
Technical field
The present invention relates to the preparation technical fields of stimulating responsive material, and in particular to a kind of reversible light-operated hydrophobic multiple
Film and preparation method thereof is closed, more particularly to a kind of reversible light-operated hydrophobic azobenzene fluorinated copolymer/Nano-meter SiO_22It is multiple
Close film and preparation method thereof.
Background technique
Stimulating responsive material is a kind of material that one kind can generate " intelligence " response to outside stimulus.It can receive
The stimulus signal of the external environments such as pH value, light, temperature, reductant-oxidant and voltage makes itself molecular structure or state
It changes, to influence its physicochemical properties, and then shows corresponding intelligent response.Stimulus responsive polymers are being received
It has a wide range of applications in rice material science, life science and clinical medicine domain.
For other stimulating responsive materials, light responsive material is broken because of its clean and effective, to the structure of material
It goes bad the features such as small and there is wide development space.Azobenzene polymer is a kind of important polymerization for preparing light responsive material
Object, azobenzene compound contain conjugated π system, have very strong absorption in ultraviolet light to visible red wave band.Azobenzene chemical combination
Object shows one group of very strong π-π * transition in UV light region, and shows one group of weaker n- π * transition in visible light region.It is right
For most of azobenzene compounds, transisomer can efficiently be changed into syn-isomerism under the conditions of ultraviolet light
Body, and under the conditions of heating or radiation of visible light, cis-isomer can be changed into transisomer again with completely reversibility.Cause
This, for the wetability of material surface, the cis-trans isomerism process of azobenzene molecule can cause material surface surface can
Inversion, so that material surface be made to show reversible wetability variation under the irradiation of the alternating of ultraviolet light and visible light.
Method currently with the polymer preparation light responsive material containing azobenzene mainly includes electrostatic self-assembled, surface
Graft copolymerization and LB membrane technology etc., but variation of the wellability of the azobenzene film of above method preparation before and after ultraviolet light is not
Greatly, the variation of contact angle only has about 10 °, seriously restricts application of the azobenzene film as light responsive material；Moreover, because table
Face azo molecules content is lower, and isomerization process is influenced by polymer segment, leads to the photoresponse of the azobenzene film of preparation
Speed is slower.In addition, the above method generally will be by means of rough substrate prepared by other materials to obtain super-hydrophobicity, preparation
The process is more complicated, it is difficult to obtain that property is uniform, surface of high mechanical strength, after irradiation is repeated several times, film surface is easy
Existing breakage.
Summary of the invention
For the above-mentioned prior art, the object of the present invention is to provide a kind of reversible light-operated hydrophobic azobenzene is fluorine-containing total
Polymers/Nano-meter SiO_22Composite membrane and preparation method thereof.Preparation method of the invention is simple, by azobenzene fluorinated copolymer
Middle dopen Nano SiO2Asperity is constructed, it, can to prepare in conjunction with the light-operated performance of azobenzene fluorinated copolymer
Realize the hydrophobic composite membrane to hydrophilic reversible transformation.
To achieve the above object, the present invention adopts the following technical scheme:
The first aspect of the present invention provides a kind of reversible light-operated hydrophobic azobenzene fluorinated copolymer/nanometer
SiO2The preparation method of composite material, comprising the following steps:
(1) by trifluoroethyl methacrylate (TFEMA) and acrylic ester monomer containing azobenzene group according to mole
It is added in solvent a than 10:1~1:10；It is that initiator carries out free radical solution polymerization with azodiisobutyronitrile (AIBN)；Reaction
The polymer of generation is dissolved repeatedly, is precipitated, then after drying, and TFEMA and azobenzene acrylate monomer is prepared
Binary random copolymer；
(2) binary random copolymer of step (1) is dissolved in solvent b, obtains copolymer solution；To copolymer solution
Middle addition Nano-meter SiO_22, make Nano-meter SiO_22Content be 0.1-10wt%, ultrasonic treatment to get；
The solvent a is selected from N,N-dimethylformamide, DMAC N,N' dimethyl acetamide or tetrahydrofuran；
The solvent b is selected from N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, tetrahydrofuran, methylene chloride, trichlorine
Methane.
Preferably, in step (1), the temperature of free radical solution polymerization reaction is 60-80 DEG C, and the time of reaction is 12-
48h。
Preferably, in step (1), the polymer for reacting generation is dissolved using tetrahydrofuran, using distilled water, methanol, second
Alcohol or anhydrous ether precipitating, dissolve repeatedly, precipitate 2-4 times.
Preferably, in step (1), the acrylic ester monomer containing azobenzene group is 4- trifluoromethoxy azobenzene
Hexyloxypropene acid esters, 4- trifluoromethoxy azo bezene acrylic acid, azobenzene hexyloxypropene acid esters or azo cinnamic acid
Ester.
Preferably, in step (1), the molecular weight for the binary random copolymer being prepared is 3000-50000.
Preferably, in step (2), the concentration of binary random copolymer is 1-20wt% in copolymer solution.
Preferably, in step (2), the time of ultrasonic treatment is 20-40 minutes.
It is fluorine-containing to provide reversible light-operated hydrophobic azobenzene prepared by the above method for the second aspect of the present invention
Copolymer/Nano-meter SiO_22Composite material.
The third aspect of the present invention provides above-mentioned azobenzene fluorinated copolymer/Nano-meter SiO_22Composite material can in preparation
Application in the hydrophobic composite membrane of backlight control.
The fourth aspect of the present invention provides a kind of preparation method of reversible light-operated hydrophobic composite membrane, including walks as follows
It is rapid:
By above-mentioned azobenzene fluorinated copolymer/Nano-meter SiO_22Composite material is spun in substrate, forms institute after dry
State reversible light-operated hydrophobic composite membrane.
The preparation method of the reversible light-operated hydrophobic composite membrane provided according to the present invention, wherein the substrate can be
Any need forms the substrate of the composite membrane.In the present invention, the substrate is substrate of glass, however of the invention super-hydrophobic
Coating can also be applied to the substrates such as ceramics, metal, be not limited in being applied to substrate of glass.
The preparation method of the reversible light-operated hydrophobic composite membrane provided according to the present invention, it is preferred that the time of spin coating is
30~120 seconds, the speed of spin coating was 1000~4000 revs/min.
The fifth aspect of the present invention provides reversible light-operated hydrophobic composite membrane prepared by the above method.It is described
Composite film surface is the Nano-meter SiO_2 of azobenzene fluoropolymer cladding2Coarse structure, ultraviolet light and visible light alternately irradiate
When, the Static water contact angles on surface Reversible Cycle within the scope of 30~160 ° changes.
The sixth aspect of the present invention provides above-mentioned azobenzene fluorinated copolymer/Nano-meter SiO_22Composite material and/or multiple
Close application of the film in preparation light responsive material.
Beneficial effects of the present invention:
(1) present invention passes through the dopen Nano SiO in azobenzene fluorinated copolymer2Asperity is constructed, in conjunction with idol
The light-operated performance of pyridine class fluorinated copolymer can be realized the hydrophobic composite membrane to hydrophilic reversible transformation to prepare.This hair
Azobenzene fluorinated copolymer used in bright has good light sensitivity, under the irradiation of ultraviolet light and visible light, azo
Phenyl group can be realized complete isomerization transformation, light-operated efficiency with higher；Meanwhile trifluoroethyl methacrylate is deposited
Although making composite membrane can not reach the super-hydrophobic angle greater than 170 °, the presence of the fluorochemical monomer after ultraviolet light
The mechanical strength of composite membrane is enhanced, after irradiation is repeated several times, film surface is not in breakage.
(2) preparation method of the invention is simple, and the hydrophobicity for the reversible light-operated hydrophobic composite membrane being prepared is reversible
Variation range is big, and boundary strength is high, the preparation especially suitable for light responsive material.
Detailed description of the invention
The accompanying drawings constituting a part of this application is used to provide further understanding of the present application, and the application's shows
Meaning property embodiment and its explanation are not constituted an undue limitation on the present application for explaining the application.
Fig. 1: azobenzene fluorinated copolymer/Nano-meter SiO_2 prepared by the embodiment of the present invention 22Composite membrane rough surface is swept
Retouch electron microscope.
Specific embodiment
It is noted that following detailed description is all illustrative, it is intended to provide further instruction to the application.Unless another
It indicates, all technical and scientific terms used herein has usual with the application person of an ordinary skill in the technical field
The identical meanings of understanding.
It should be noted that term used herein above is merely to describe specific embodiment, and be not intended to restricted root
According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singular
Also it is intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet
Include " when, indicate existing characteristics, step, operation, device, component and/or their combination.
As background technique is introduced, the existing azobenzene film variation that there are wellabilities before and after ultraviolet light is not
Greatly, the problems such as speed of photoresponse is slowly, the mechanical strength of film is low.Based on this, the invention proposes a kind of reversible light-operated hydrophobic
Azobenzene fluorinated copolymer/Nano-meter SiO_22Composite membrane and preparation method thereof.
In one embodiment of the present invention, a kind of reversible light-operated hydrophobic fluorine-containing copolymerization of azobenzene is given
Object/Nano-meter SiO_22The preparation method of composite membrane, includes the following steps:
(1) by trifluoroethyl methacrylate (TFEMA) and acrylic ester monomer containing azobenzene group according to mole
It is added in reaction dissolvent than 10:1~1:10；It is that initiator carries out free radical solution polymerization with azodiisobutyronitrile (AIBN),
The temperature of free radical solution polymerization is between 60~80 DEG C；Reaction time is 12~48 hours；React the polymer generated repeatedly
Dissolution, precipitating are three times；24 hours binary to obtain TFEMA and azobenzene acrylate monomer are dried under 60 DEG C of vacuum environments
Random copolymer；
(2) dissolution of obtained binary random copolymer is made into polymer solution in a solvent, hydrophobic nano is added
SiO2, make Nano-meter SiO_22Content be 0.1-10wt%, then carry out ultrasonic treatment 20~40 minutes, the spin coating in substrate, spin coating
Good sample is placed 1 hour under 20 DEG C of vacuum environments, obtains having light-operated hydrophobic composite membrane after solvent volatilization.
The reactional equation of TFEMA and the acrylic ester monomer containing azobenzene group are as follows:
Polymethylacrylic acid trifluoro ethyl ester (PTFEMA) has the characteristics that water and oil repellant, weatherability, film forming are bright, but same
When there is also the glass transition temperature of polymethylacrylic acid trifluoro ethyl ester is higher, room temperature film-forming is difficult in water paint, as solvent
After film forming matter film forming in type coating the defects of embrittlement, the present invention passes through by trifluoroethyl methacrylate and containing azobenzene
The acrylic ester monomer copolymerization of group, and to trifluoroethyl methacrylate and the acrylic ester monomer containing azobenzene group
Investigation is optimized in additional proportion, as a result, it has been found that, when the two is added with molar ratio for 10:1~1:10, it both ensure that copolymer
Excellent water and oil repellant, and improve polymethylacrylic acid trifluoro ethyl ester glass transition temperature height and be not easy after forming a film and forming a film
The shortcomings that embrittlement；Simultaneously as the introducing of azobenzene group, also imparts the optical Response of copolymer.
Further, the present invention into the binary random copolymer of TFEMA and azobenzene acrylate monomer by mixing
Miscellaneous Nano-meter SiO_22Material constructs asperity, in conjunction with the characteristic and azobenzene of the fluorine atom drop low-surface-energy in copolymer
The excellent light sensitivity of group, to prepare the composite membrane that can be realized from hydrophobicity to hydrophily reversible transformation.Wherein,
The binary random copolymer and Nano-meter SiO_2 of TFEMA and azobenzene acrylate monomer2Between have well synergistic effect,
On the one hand, Nano-meter SiO_22The filling of material and effectively dispersion, can be improved the mechanical property of polymer matrices；On the other hand, altogether
Polymers improves Nano-meter SiO_2 by cladding, steric effect etc.2The dispersibility of material and compatibility in different media, pass through
Nano-meter SiO_22With the synergistic effect of TFEMA and the binary random copolymer of azobenzene acrylate monomer, make the compound of preparation
Film light-operated efficiency with higher, greatly, the variation of contact angle can be for the wellability variation of composite membrane before and after ultraviolet light
110 ° or more；And the high mechanical strength of composite membrane, after irradiation is repeated several times, the surface of composite membrane does not also occur breakage.
In order to enable those skilled in the art can clearly understand the technical solution of the application, below with reference to tool
The technical solution of the application is described in detail in the embodiment of body.
Test material used in the embodiment of the present invention is the test material of this field routine, can pass through commercial channel
It is commercially available.
Reaction monomers used in the embodiment of the present invention " 4- trifluoromethoxy azobenzene hexyloxypropene acid esters ", " idol
Pyridine hexyloxypropene acid esters ", " 4- trifluoromethoxy azo bezene acrylic acid " and " azo bezene acrylic acid ", in the prior art
In synthesis has been reported, for example, synthetic method can refer to " Photoreversibly Switchable
Superhydrophobic Surface with Erasable and Rewritable Pattern.Ho Sun Lim,
Joong Tark Han,Donghoon Kwak,Meihua Jin,and Kilwon Cho*.J.Am.Chem.Soc.2006,
128,14458-14459. " and " Photoswitching of glass transition temperatures of
azobenzene-containing polymers induces reversible solid-to-liquid
transitions.HongweiChangguoPhilippYasuhito Suzuki,Shilin
Huang,Kaloian Koynov,Günter K.Auernhammer,Rüdiger Berger,Hans-Jürgen Butt and
Si Wu*.Nature Chemistry.DOI:10.1038/nchem.2625”。
Embodiment 1:
By 3g TFEMA, 7g 4- trifluoromethoxy azobenzene hexyloxypropene acid esters, 60ml DMAC N,N' dimethyl acetamide
It is added in the single port bottle of 150ml with 0.1g AIBN.At room temperature using being started to warm up after magnetic agitation 15 minutes to 60 DEG C, N2
It is reacted under protection, stops reaction after 36 hours.Solution after reaction is added drop-wise in 500ml distilled water, stands 20 minutes
After filter out sediment, put it under 100 DEG C of environment and dry.Obtained crude product uses tetrahydrofuran and methanol repeatedly molten again
Solution, precipitating three times, 100 DEG C drying 48 hours after obtain TFEMA and 4- trifluoromethoxy azobenzene hexyloxypropene acid ester monomer
Binary random copolymer.
By 0.2g binary random copolymer and 0.02g Nano-meter SiO_22It is dissolved in 1ml n,N-Dimethylformamide, ultrasound
Processing 10 minutes takes 100 μ l spin coating liquid spin-coating film on the glass sheet, and spin speed is 2000 revs/min, and spin-coating time is
150 seconds.Finally the good sheet glass of spin coating is placed 2 hours in 30 DEG C of vacuum drying oven.
Take out the azobenzene fluorinated copolymer/Nano-meter SiO_2 prepared2Composite membrane is to test its wellability and photoresponse
Variation.First with after ultraviolet light composite membrane 5s, Static water contact angles are 55 °, and composite membrane is hydrophily；Then using can
After light-exposed irradiation 5s, Static water contact angles are 155 °, and composite membrane is restored to super-hydrophobic state.
It repeats repeatedly UV-visible light to irradiate 100 times, tests the situation of change of the Static water contact angles of composite membrane, and
Whether the surface of observation composite membrane there is breakage.
As a result, it has been found that composite membrane manufactured in the present embodiment, in the case where UV-visible light is alternately irradiated, contact angle variation has
Good invertibity, and contact angle is changed significantly；After retest 100 times, composite film surface does not occur breakage, illustrates to make
The high mechanical strength of standby composite membrane, long service life.
Embodiment 2:
3g TFEMA, 7g azobenzene hexyloxypropene acid esters, 60ml tetrahydrofuran and 0.1g AIBN are added to 150ml
Single port bottle in.At room temperature using being started to warm up after magnetic agitation 15 minutes to 80 DEG C, N2It is reacted under protection, after 36 hours
Stop reaction.Solution after reaction is added drop-wise in 500ml distilled water, standing filters out sediment after twenty minutes, puts it into
It is dried under 50 DEG C of environment.Obtained crude product is used tetrahydrofuran and methanol to dissolve repeatedly again, is precipitated three times, and 100 DEG C of drying 48 are small
When after obtain the binary random copolymer of TFEMA and azobenzene hexyloxypropene acid ester monomer.
By 0.1g binary random copolymer and 0.01g Nano-meter SiO_22It is dissolved in 2ml n,N-Dimethylformamide, ultrasound
Processing 15 minutes takes 50 μ l spin coating liquid spin-coating film on the glass sheet, and spin speed is 1000 revs/min, spin-coating time 100
Second.Finally the good sheet glass of spin coating is placed 2 hours in 30 DEG C of vacuum drying oven.
Take out the azobenzene fluorinated copolymer/Nano-meter SiO_2 prepared2Composite membrane is to test its wellability and photoresponse
Variation.First with after ultraviolet light composite membrane 5s, Static water contact angles are 45 °, and composite membrane is hydrophily；Then using can
After light-exposed irradiation 5s, Static water contact angles are 155 °, and composite membrane is restored to super-hydrophobic state.
It repeats repeatedly UV-visible light to irradiate 100 times, tests the situation of change of the Static water contact angles of composite membrane, and
Whether the surface of observation composite membrane there is breakage.
As a result, it has been found that composite membrane, in the case where UV-visible light is alternately irradiated, contact angle variation has good invertibity,
And contact angle is changed significantly；After retest 100 times, composite film surface does not occur breakage.
Embodiment 3:
By 3g TFEMA, 7g 4- trifluoromethoxy azo bezene acrylic acid, 60ml N,N-dimethylformamide and 0.1g
AIBN is added in the single port bottle of 150ml.At room temperature using being started to warm up after magnetic agitation 15 minutes to 75 DEG C, N2Under protection into
Row reaction, stops reaction after 24 hours.Solution after reaction is added drop-wise in 500ml distilled water, standing filters out after twenty minutes
Sediment puts it under 100 DEG C of environment and dries.Obtained crude product uses N,N-dimethylformamide and water to dissolve repeatedly again,
Precipitating three times, 100 DEG C drying 48 hours after obtain TFEMA and 4- trifluoromethoxy azobenzene acrylate monomer binary it is random
Copolymer.
By 0.06g binary random copolymer and 0.04g Nano-meter SiO_22It is dissolved in 5ml n,N-Dimethylformamide, ultrasound
Processing 30 minutes takes 75 μ l spin coating liquid spin-coating film on the glass sheet, and spin speed is 3000 revs/min, spin-coating time 200
Second.Finally the good sheet glass of spin coating is placed 2 hours in 30 DEG C of vacuum drying oven.
Take out the azobenzene fluorinated copolymer/Nano-meter SiO_2 prepared2Composite membrane is to test its wellability and photoresponse
Variation.First with after ultraviolet light composite membrane 5s, Static water contact angles are 45 °, and composite membrane is hydrophily；Then using can
After light-exposed irradiation 20s, Static water contact angles are 155 °, and composite membrane is restored to super-hydrophobic state.
It repeats repeatedly UV-visible light to irradiate 100 times, tests the situation of change of the Static water contact angles of composite membrane, and
Whether the surface of observation composite membrane there is breakage.
As a result, it has been found that composite membrane, in the case where UV-visible light is alternately irradiated, contact angle variation has good invertibity,
And contact angle is changed significantly；After retest 100 times, composite film surface does not occur breakage.
Embodiment 4:
3g TFEMA, 7g azo bezene acrylic acid, 60ml N,N-dimethylformamide and 0.1g AIBN are added to
In the single port bottle of 150ml.At room temperature using being started to warm up after magnetic agitation 15 minutes to 80 DEG C, N2It is reacted under protection, 14
Stop reaction after hour.Solution after reaction is added drop-wise in 500ml distilled water, standing filters out sediment after twenty minutes, will
It is put under 100 DEG C of environment and dries.Obtained crude product is used tetrahydrofuran and methanol to dissolve repeatedly again, is precipitated three times, 100 DEG C of bakings
The binary random copolymer of TFEMA and azobenzene acrylate monomer are obtained after 48 hours dry.
By 0.05g binary random copolymer and 0.02g Nano-meter SiO_22It is dissolved in 1ml n,N-Dimethylformamide, ultrasound
Processing 30 minutes takes 75 μ l spin coating liquid spin-coating film on the glass sheet, and spin speed is 4000 revs/min, spin-coating time 150
Second.Finally the good sheet glass of spin coating is placed 2 hours in 30 DEG C of vacuum drying oven.
Take out the azobenzene fluorinated copolymer/Nano-meter SiO_2 prepared2Composite membrane is to test its wellability and photoresponse
Variation.First with after ultraviolet light composite membrane 5s, Static water contact angles are 30 °, and composite membrane is hydrophily；Then using can
After light-exposed irradiation 20s, Static water contact angles are 135 °, and composite membrane is restored to super-hydrophobic state.
It repeats repeatedly UV-visible light to irradiate 100 times, tests the situation of change of the Static water contact angles of composite membrane, and
Whether the surface of observation composite membrane there is breakage.
As a result, it has been found that composite membrane, in the case where UV-visible light is alternately irradiated, contact angle variation has good invertibity,
And contact angle is changed significantly；After retest 100 times, composite film surface does not occur breakage.
Comparative example 1:
The Nano-meter SiO_2 that will be added in embodiment 12It omits, composite membrane is prepared with embodiment 1 in remaining.
The composite membrane for preparing is taken out to test the variation of its wellability and photoresponse.Ultraviolet light composite membrane is used first
After 10s, Static water contact angles are 65 °, and composite membrane is hydrophily；Then after using radiation of visible light 30s, Static water contact
Angle is 115 °, and composite membrane is restored to hydrophobic state.Compared with composite membrane prepared by embodiment 1, speed of photoresponse is slack-off.
It repeats repeatedly UV-visible light to irradiate, tests the situation of change of the Static water contact angles of composite membrane, and observe multiple
Whether the surface for closing film there is breakage.
As a result, it has been found that composite membrane, in the case where UV-visible light is alternately irradiated, the invertibity of contact angle variation is not good enough；And it is multiple
The boundary strength for closing film is insufficient, and after retest 54 times, composite film surface has started to occur damaged.
Comparative example 2:
By Nano-meter SiO_2 in embodiment 12Additive amount be adjusted to 12wt%, remaining is prepared and is answered with embodiment 1
Close film.
The composite membrane for preparing is taken out to test the variation of its wellability and photoresponse.Ultraviolet light composite membrane is used first
After 10s, Static water contact angles are 60 °, and composite membrane is hydrophily；Then after using radiation of visible light 35s, Static water contact
Angle is 145 °, and composite membrane is restored to hydrophobic state.Compared with composite membrane prepared by embodiment 1, speed of photoresponse is slack-off.
It repeats repeatedly UV-visible light to irradiate, tests the situation of change of the Static water contact angles of composite membrane, and observe multiple
Whether the surface for closing film there is breakage.
As a result, it has been found that composite membrane, in the case where UV-visible light is alternately irradiated, the invertibity of contact angle variation is not good enough；It repeats
After test 72 times, composite film surface has started to occur damaged.
It can be seen that Nano-meter SiO_22Addition whether and additive amount be affected to the performance of the composite membrane of preparation, no
Addition or Nano-meter SiO_22Additive amount it is too small when, will affect the speed of photoresponse of the composite membrane of preparation and the invertibity of contact angle
Variation；And the boundary strength that will lead to composite membrane is not high；But Nano-meter SiO_22Additive amount it is also not The more the better, it is excessive
SiO2The speed of photoresponse that will lead to composite membrane is slack-off, and excessive SiO2Nano particle can also reunite in composite membrane,
The boundary strength of composite membrane is reduced instead.
The foregoing is merely preferred embodiment of the present application, are not intended to limit this application, for the skill of this field
For art personnel, various changes and changes are possible in this application.Within the spirit and principles of this application, made any to repair
Change, equivalent replacement, improvement etc., should be included within the scope of protection of this application.
Claims (10)
1. a kind of reversible light-operated hydrophobic azobenzene fluorinated copolymer/Nano-meter SiO_22The preparation method of composite material, feature
It is, comprising the following steps:
(1) by trifluoroethyl methacrylate and acrylic ester monomer containing azobenzene group according to molar ratio 10:1~1:10
It is added in solvent a；Free radical solution polymerization is carried out by initiator of azodiisobutyronitrile；The polymer generated is reacted through repeatedly
Dissolution, precipitating, then after drying, binary random copolymer is prepared；
(2) binary random copolymer of step (1) is dissolved in solvent b, obtains copolymer solution；Add into copolymer solution
Enter Nano-meter SiO_22, make Nano-meter SiO_22Content be 0.1-10wt%, ultrasonic treatment to get；
The solvent a is selected from N,N-dimethylformamide, DMAC N,N' dimethyl acetamide or tetrahydrofuran；
The solvent b is selected from N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, tetrahydrofuran, methylene chloride, three chloromethanes
Alkane.
2. preparation method according to claim 1, which is characterized in that in step (1), the temperature of free radical solution polymerization reaction
Degree is 60-80 DEG C, and the time of reaction is 12-48h.
3. preparation method according to claim 1, which is characterized in that in step (1), react the polymer of generation using four
The dissolution of hydrogen furans, is precipitated using distilled water, methanol, ethyl alcohol or anhydrous ether, is dissolved, is precipitated 2-4 times repeatedly.
4. preparation method according to claim 1, which is characterized in that in step (1), the propylene containing azobenzene group
Esters of gallic acid monomer is 4- trifluoromethoxy azobenzene hexyloxypropene acid esters, 4- trifluoromethoxy azo bezene acrylic acid, azo
Benzene hexyloxypropene acid esters or azo bezene acrylic acid.
5. preparation method according to claim 1, which is characterized in that in step (2), binary is randomly total in copolymer solution
The concentration of polymers is 1-20wt%.
6. the reversible light-operated hydrophobic fluorine-containing copolymerization of azobenzene of the described in any item preparation method preparations of claim 1-5
Object/Nano-meter SiO_22Composite material.
7. azobenzene fluorinated copolymer/Nano-meter SiO_2 as claimed in claim 62Composite material prepare it is reversible light-operated hydrophobic
Application in composite membrane.
8. a kind of method for preparing reversible light-operated hydrophobic composite membrane, which comprises the steps of:
By azobenzene fluorinated copolymer/Nano-meter SiO_2 as claimed in claim 62Composite material is spun in substrate, shape after drying
At the reversible light-operated hydrophobic composite membrane.
9. the reversible light-operated hydrophobic composite membrane that method according to any one of claims 8 is prepared.
10. azobenzene fluorinated copolymer/Nano-meter SiO_2 as claimed in claim 62Composite material and/or as claimed in claim 9
Application of the composite membrane in preparation light responsive material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710953008.3A CN107629379B (en) | 2017-10-13 | 2017-10-13 | Reversible light-operated hydrophobic composite membrane of one kind and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710953008.3A CN107629379B (en) | 2017-10-13 | 2017-10-13 | Reversible light-operated hydrophobic composite membrane of one kind and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107629379A CN107629379A (en) | 2018-01-26 |
| CN107629379B true CN107629379B (en) | 2019-10-01 |
Family
ID=61104194
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710953008.3A Active CN107629379B (en) | 2017-10-13 | 2017-10-13 | Reversible light-operated hydrophobic composite membrane of one kind and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107629379B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108484825B (en) * | 2018-05-08 | 2020-05-26 | 济南大学 | Reversible light-operated hydrophobic azobenzene fluorine-containing copolymer and membrane preparation method thereof |
| CN109280165A (en) * | 2018-11-08 | 2019-01-29 | 济南大学 | A kind of reversible light-operated hydrophilic azobenzene PDO3Modified Membrane and preparation method thereof |
| CN109666438B (en) * | 2018-12-21 | 2020-09-01 | 广州市白云化工实业有限公司 | Photo-responsive adhesive and preparation method thereof |
| CN109786552B (en) * | 2019-01-22 | 2020-10-16 | 合肥京东方光电科技有限公司 | Organic thin film, manufacturing method thereof, display device and optical device |
| CN110499637B (en) * | 2019-08-30 | 2020-11-17 | 电子科技大学 | Material with adjustable surface hydrophilicity/hydrophobicity and preparation method thereof |
| CN114231113A (en) * | 2021-12-17 | 2022-03-25 | 武汉纺织大学 | Photo-thermal hydrophobic anti-icing anti-falling coating material, and preparation and application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101029112A (en) * | 2007-03-28 | 2007-09-05 | 天津工业大学 | Ultraviolet-pH response polymer hydrogel and its use |
| CN103408709B (en) * | 2013-08-08 | 2016-01-20 | 中科院广州化学有限公司 | Aqueous fluoropolymer and silicon dioxide hybrid materials and the transparent super two open coat be prepared from thereof |
| CN106007396A (en) * | 2016-05-25 | 2016-10-12 | 安徽中恩化工有限公司 | Superhydrophobic self-cleaning glass coating |
-
2017
- 2017-10-13 CN CN201710953008.3A patent/CN107629379B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN107629379A (en) | 2018-01-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107629379B (en) | Reversible light-operated hydrophobic composite membrane of one kind and preparation method thereof | |
| CN108484825B (en) | Reversible light-operated hydrophobic azobenzene fluorine-containing copolymer and membrane preparation method thereof | |
| CN102351983B (en) | Fluorine silicon acrylate copolymer, preparation process thereof and application thereof | |
| US11203523B2 (en) | Bionic SERS substrate with metal-based compound eye bowl structure and its construction method and application | |
| CN105368188A (en) | Water-tolerant long-acting anti-fog frost-resistant coating preparation method with controllable crosslinking degree | |
| CN106977905A (en) | A kind of photonic crystal composite with environment-responsive and preparation method thereof | |
| Tai et al. | A simple method for synthesis of thermal responsive silica nanoparticle/PNIPAAm hybrids | |
| CN104829771A (en) | Polymer containing cyclic azobenzene-dinaphthalene structure on side chain as well as preparation method and application of polymer | |
| He et al. | Fabrication of durable hierarchical superhydrophobic fabrics with Sichuan pepper-like structures via graft precipitation polymerization | |
| CN108314753B (en) | Transparent antistatic PMMA and preparation method thereof | |
| Luo et al. | Modifying glass fiber surface with grafting acrylamide by UV-grafting copolymerization for preparation of glass fiber reinforced PVDF composite membrane | |
| CN106496464B (en) | A kind of amphipathic network of UV light anti-fouling type and preparation method thereof | |
| Cai et al. | Weak acid–base interaction induced assembly for the formation of berry-like polystyrene/SiO2 composite particles | |
| CN114231160B (en) | Antifogging coating and preparation method and application thereof | |
| Chen et al. | Preparation and properties of antibacterial fluorinated acrylic emulsion | |
| Chang et al. | Roughness-enhanced thermal-responsive surfaces by surface-initiated polymerization of polymer on ordered ZnO pore-array films | |
| CN107286341A (en) | A kind of method on the auto polymerization reaction preparation temperature response type surface based on dopamine | |
| Cui et al. | Spiropyran-based photo-and thermal-responsive smart polymer with controllable wettability | |
| CN103242733A (en) | Simple method for preparing light-responsive super-hydrophobic surface | |
| CN110938940B (en) | Preparation method of super-hydrophobic nanofiber membrane | |
| CN103087608B (en) | Optical polymer film surface coating agent as well as preparation method and coating process thereof | |
| CN110551134B (en) | Preparation method of cross-linking agent, multiple-stimulus-response color-changing self-repairing coating and preparation method thereof | |
| CN103772630B (en) | A kind of preparation method of magnetic temperature sensing nano-particle | |
| CN107121844A (en) | The method that the golden nanometer particle modified by liquid crystal polymer regulates and controls liquid crystal aligning | |
| CN102897826B (en) | Method for preparing nanometer zinc oxide composite material from super concentrated emulsion |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |