CN105671951B - A kind of method of substrate surface wellability regulation and control - Google Patents
A kind of method of substrate surface wellability regulation and control Download PDFInfo
- Publication number
- CN105671951B CN105671951B CN201610051564.7A CN201610051564A CN105671951B CN 105671951 B CN105671951 B CN 105671951B CN 201610051564 A CN201610051564 A CN 201610051564A CN 105671951 B CN105671951 B CN 105671951B
- Authority
- CN
- China
- Prior art keywords
- substrate
- reaction
- click
- coating
- solution
- 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
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
- D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
- D06M13/517—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond containing silicon-halogen bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/02—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using non-aqueous solutions
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/26—Anodisation of refractory metals or alloys based thereon
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
- D06M13/248—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing sulfur
- D06M13/252—Mercaptans, thiophenols, sulfides or polysulfides, e.g. mercapto acetic acid; Sulfonium compounds
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/20—Use of solutions containing silanes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/10—Repellency against liquids
- D06M2200/11—Oleophobic properties
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/10—Repellency against liquids
- D06M2200/12—Hydrophobic properties
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- Electrochemistry (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Laminated Bodies (AREA)
Abstract
The present invention provides a kind of methods of surface wettability regulation and control, substrate is impregnated in the organic solution of the silane containing alkenyl by it first, the substrate with hydrophobic coating is obtained after reaction, then obtained substrate is infiltrated in click-reaction solution, it is reacted under ultraviolet irradiation condition, obtains the matrix with hydrophilic coating.The application is coated with hydrophobic coating in substrate surface first, and click-reaction is recycled to connect hydrophilic radical on surface, realizes substrate surface by hydrophobicity to hydrophilic transformation.
Description
Technical field
The present invention relates to a kind of methods that process for modifying surface more particularly to substrate surface wellability regulate and control.
Background technology
The regulation and control of surface nature, such as substrate surface hydrophobicity and hydrophilic regulation and control are mostly being studied and had
Play the role of in terms of commercial Application existing for surface vital.The surface nature needed in order to obtain, chemical vapor deposition
The different surface modifying methods such as product, plasma treatment and photo-grafting are all widely used.It is exactly to keep material that surface, which is modified,
On the premise of material or product originality energy, assign its surface new performance, such as hydrophily, biocompatibility, antistatic property, dyeing
Performance etc..
Click chemistry purport is the splicing by junior unit, carrys out the chemistry conjunction of the fast and reliable varied molecule of completion
Into, it stress in particular open up by carbon-heteroatom bond synthesize based on primary chemical new method, it is and high by these chemical reactions
The acquisition molecular diversity of effect.Click chemistry becomes domestic and international life, medicine, chemistry once proposing just widely to be paid close attention to
With the hot spot of material multiple fields scientist research, it is using the reaction of a small number of almost Perfects, by effective and modular
Approach synthesizes diversified compound, has the characteristics that efficient, highly selective and has a wide range of application.Specifically, click-reaction
There is following feature：(1) raw material is easy to get, applied widely；(2) easy to operate, mild condition is insensitive to oxygen, water；(3) product
High income, region are good with stereoselectivity；(4) the easily separated purification of product, post processing are simple；(5) quick, high-throughput synthesis.
This application provides a kind of methods that substrate surface wellability regulation and control are carried out using click-reaction as a result,.
The content of the invention
Present invention solves the technical problem that it is to provide a kind of method of surface wettability regulation and control, the method that the application provides
Realization substrate surface hydrophobicity that can be controllable and hydrophilic transformation.
In view of this, this application provides a kind of method of surface wettability regulation and control, comprise the following steps：
A), substrate is impregnated in the organic solution of the silane containing alkenyl, the substrate with hydrophobic coating is obtained after reaction；
B), by step A) after obtained substrate infiltration click-reaction solution, react, had under the conditions of ultraviolet light
There is the matrix of hydrophilic coating；The click-reaction solution is organic molten for photoinitiator and the mercapto derivatives containing hydrophilic radical
Liquid.
Preferably, step B) it further includes afterwards：
Repeat step A),
Or it is repeated in step A) and step B).
Preferably, the silane containing alkenyl is selected from vinyl trichlorosilane, allyltrichlorosilane, 5- hexenyl trichlorines
One or more in silane and 7- octyltrichlorosilanes；The mercapto derivatives containing hydrophilic radical be selected from 3- mercaptopropionic acids,
One or more in 2 mercapto ethanol, 2-MEA and 2- mercaptonicotinic acids.
Preferably, it is specially in the process for preparation of the organic solution of the silane containing alkenyl：
It is ultrasonic after toluene is mixed with water, the silane containing alkenyl is added, is stood；
It is specially in the process for preparation of the click-reaction solution：
Surpass after tetrahydrofuran, 2,2- dimethoxy -2- phenyl acetophenones are mixed with the mercapto derivatives containing hydrophilic radical
Sound.
Preferably, the substrate is titanium sheet or pure cotton fabric.
Preferably, when the substrate is titanium sheet, the step A) it further includes before：
Titanium sheet is dry after the ultrasonic cleaning of acetone and ethyl alcohol successively, then in the electricity of anodic oxidation under 20V voltages
Oxidation processes in liquid are solved, it is dry after finally being cleaned successively using ethyl alcohol and deionized water；The electrolyte of the anodic oxidation is hydrogen
The mixed solution of fluoric acid and water.
Preferably, when the substrate is pure cotton fabric, the step A) it further includes before：
Pure cotton fabric is cleaned by ultrasonic successively by acetone, ethyl alcohol and deionized water.
Preferably, when the substrate is titanium sheet, step A) described in time for reacting for 8~for 24 hours, the temperature of the reaction
For 20~40 DEG C；
When the substrate is pure cotton fabric, step A) described in time for reacting be 3~4h, the temperature of the reaction is 20
~40 DEG C.
Preferably, step B) be specially：
By step A) obtained substrate is infiltrated in click-reaction solution, substrate is taken out towards ultraviolet source, after reaction
To the substrate with hydrophilic coating.
Preferably, the intensity of illumination of the ultraviolet light is 0.8W/m2~100W/m2, light application time is 10s~50min.
This application provides a kind of methods of surface wettability regulation and control, and substrate is impregnated in the silane containing alkenyl first
The substrate with hydrophobic coating is obtained in organic solution, after reaction, then obtained substrate is infiltrated in click-reaction solution,
It is reacted under ultraviolet irradiation condition, obtains the matrix with hydrophilic coating.The application is coated with hydrophobic painting in substrate surface first
Layer recycles click-reaction to connect hydrophilic radical on surface, realizes substrate surface by hydrophobicity to hydrophilic transformation.Into one
Step, the application can also continue to coat the organic solution of the silane containing alkenyl on hydrophilic surface, have substrate surface
Hydrophobicity is impregnated in click-reaction solution and is reacted under ultraviolet irradiation condition again, realizes again by hydrophobicity to hydrophily
Transformation.Therefore, the method that the application provides can realize controllable adjustment to the wellability of substrate surface.
Description of the drawings
Fig. 1 is the SEM photograph for the titanium sheet substrate that the present invention uses；
Fig. 2 is that hydrophobic coating part, the differential responses in electric heating constant temperature shaking water bath are constructed in method provided by the invention
The SEM photograph of the coating surface based on titanium sheet substrate prepared by time and surface static contact angle figure；
Fig. 3 is that hydrophobic coating part is constructed in method provided by the invention, uses the vinyl trichlorosilane of different volumes
The SEM photograph of the prepared coating surface based on titanium sheet substrate and coating surface static contact angle figure；
Fig. 4 is that hydrophobic coating part, the SEM photograph and table of the coating surface based on fabric substrate are constructed in the method provided
Face static contact angle figure；
Fig. 5 is the XPS spectrum figure of the hydrophobic coating based on titanium sheet substrate in the present invention；
Fig. 6 is the SEM photograph of the coating surface based on titanium sheet substrate prepared by embodiment 1；
Fig. 7 is the SEM photograph of the coating surface based on titanium sheet substrate prepared by embodiment 2；
Fig. 8 is the SEM photograph of the coating surface based on titanium sheet substrate prepared by embodiment 3；
Fig. 9 is the SEM photograph of the coating surface based on fabric substrate prepared by embodiment 4；
Figure 10 is the SEM photograph after the coating click-reaction based on titanium sheet substrate in method provided by the invention；
Figure 11 is quiet for the SEM photograph after the coating click-reaction based on fabric substrate in method provided by the invention and surface
State contact angle figure；
Figure 12 is that the EDS energy spectrum diagrams after reaction are respectively walked in method provided by the invention；
Figure 13 be method provided by the invention in different illumination intensity light source light according to the surface static after different time
Contact angle, Figure 13 a are in 0.8 ± 0.2W/m of light intensity2Surface static contact angle after lower different time, Figure 13 b are in light intensity 8.8
±1.2W/m2Surface static contact angle after lower different time, Figure 13 c are in 89.8 ± 0.4W/m of light intensity2After lower different time
Surface static contact angle；
Figure 14 is to construct hydrophobic coating part and the wellability transition step based on click-reaction in method provided by the invention
The surface static contact angle line chart of rapid repetition experiment.
Specific embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment, still
It should be appreciated that these descriptions are simply for the feature and advantage that further illustrate the present invention rather than to the claims in the present invention
Limitation.
The embodiment of the invention discloses a kind of methods of surface wettability regulation and control, comprise the following steps：
A), substrate is impregnated in the organic solution of the silane containing alkenyl, the substrate with hydrophobic coating is obtained after reaction；
B), by step A) after obtained substrate infiltration click-reaction solution, react, had under the conditions of ultraviolet light
There is the matrix of hydrophilic coating；The click-reaction solution is organic molten for photoinitiator and the mercapto derivatives containing hydrophilic radical
Liquid.
The present invention is using sulfydryl-alkene reaction of click-reaction, the hydrophobic coating of coated carbon-carbon double bond first in substrate,
Click-reaction is recycled to connect the transformation that hydrophilic radical realizes surface wettability on surface.
According to the present invention, substrate is impregnated in the organic solution of the silane containing alkenyl, is had after reaction first
The substrate of hydrophobic coating, during this process is structure hydrophobic coating.Herein described substrate can be rigid basement, also may be used
Think flexible substrate, this application is not particularly limited.Preferably, rigid basement described herein is preferably
Titanium sheet, flexible substrates are preferably fabric substrate, more preferably pure cotton fabric.The preparation of the organic solution of the silane containing alkenyl
It is specially in the process：
It is ultrasonic after toluene is mixed with water, the silane containing alkenyl is added, is stood.
The herein described silane containing alkenyl is preferably selected from vinyl trichlorosilane, allyltrichlorosilane, 5- hexenyls
One or more in trichlorosilane and 7- octyltrichlorosilanes, in embodiment, the silane containing alkenyl is preferably ethylene
Base trichlorosilane.During hydrophobic coating is built, the active group of substrate surface and the silane containing alkenyl are had an effect knot
It is combined, due to the relatively low surface energy of the silane containing alkenyl, makes its surface after coating that there is preferable hydrophobic effect.It is described
Reaction is preferably to be carried out in electric heating constant temperature shaking water bath.
According to the present invention, before the organic solution of silane of the substrate surface coating containing alkenyl, the application is preferably by substrate
Pre-treatment is carried out, the pre-treatment is processing mode well known to those skilled in the art, is no longer repeated herein.As preferred
Scheme, when the substrate is titanium sheet, the pre-treatment is specially：
Titanium sheet is dry after the ultrasonic cleaning of acetone and ethyl alcohol successively, then in the electricity of anodic oxidation under 20V voltages
Oxidation processes in liquid are solved, it is dry after finally being cleaned successively using ethyl alcohol and deionized water；The electrolyte of the anodic oxidation is hydrogen
The mixed solution of fluoric acid and water.
When the substrate is pure cotton fabric, the pre-treatment is specially：
Pure cotton fabric is cleaned by ultrasonic successively by acetone, ethyl alcohol and deionized water.
During above-mentioned structure hydrophobic coating, when the substrate is titanium sheet, time of the reaction is preferably 8~
For 24 hours, the temperature of the reaction is preferably 30 DEG C~40 DEG C；When the substrate is pure cotton fabric, the time of the reaction is preferably 3
~4h, the temperature of the reaction is preferably 30~40 DEG C.
The application is obtaining the substrate with hydrophobic coating, that is, then builds hydrophilic coating after building hydrophobic coating, soaked
The transformation of lubricant nature.Specially：It is anti-under ultraviolet irradiation condition after the solution of the substrate infiltration click-reaction with hydrophobic coating
Should, make the hydrophobic coating of substrate that the transformation of wellability occur, i.e., hydrophily is changed by hydrophobicity.In above process, it is described
The solution of click-reaction is the organic solution of photoinitiator and the mercapto derivatives containing hydrophilic radical.The photoinitiator is preferably
2,2- dimethoxy -2- phenyl acetophenones (DMPA), the mercapto derivatives containing hydrophilic radical be preferably selected from 3- mercaptopropionic acids,
One or more in 2 mercapto ethanol, 2-MEA and 2- mercaptonicotinic acids, in embodiment, the mercapto containing hydrophilic radical
Radical derivative is preferably 3- mercaptopropionic acids.The process for preparation of the solution of the click-reaction is specially：
Surpass after tetrahydrofuran, 2,2- dimethoxy -2- phenyl acetophenones are mixed with the mercapto derivatives containing hydrophilic radical
Sound.
The application is after obtaining having the substrate of hydrophobic coating, then carries out the transformation of wellability, makes substrate surface by dredging
Aqueous to be changed into hydrophily, the reaction that this process occurs is by taking vinyl trichlorosilane and 3- mercaptopropionic acids as an example, in particular to second
Alkenyl trichlorosilane provides double bond, and 3- mercaptopropionic acids provide hydrophilic radical, access hydrophilic radical in coating surface after click-reaction,
Change surface wettability, shown in above-mentioned reaction process following reaction formula：
In above-mentioned reaction process, the click-reaction can only carry out under ultraviolet irradiation condition, and the ultraviolet light
Intensity of illumination is preferably 0.8W/m2~100W/m2, more preferably 8~90W/m2, it is most preferably 25~60W/m2, the ultraviolet light
Light application time be preferably 10s~50min, more preferably 1min~40min, be most preferably 5min~30min.In order to make click
Reaction is more abundant, and the process of the click-reaction is specially：
There to be hydrophobic substrate to be infiltrated in click-reaction solution, and take out substrate towards ultraviolet source, obtained after reaction
To the substrate with hydrophilic coating.
The present invention to obtain having hydrophilic surface again, then may be used after obtaining having the substrate of hydrophilic surface
Above-mentioned silane organic solution of the dipping containing alkenyl is carried out so that obtained substrate to be repeated；If needing to make it have hydrophily again,
Above-mentioned click-reaction can be carried out again, i.e. the application can according to actual needs, carry out the transformation immediately of infiltrative type, as long as successively
Repeat above-mentioned two step.
The present invention provides a kind of methods of surface wettability regulation and control, can be summarized as following steps：(1) hydrophobic painting is constructed
Layer；(2) infiltration based on click-reaction sexually revises.
Specifically, comprise the following steps：
Step 1：Construct hydrophobic coating
The toluene solution of 40ml is measured, adds in the deionized water of 80 μ l, is uniformly mixed and is placed in centrifuge tube, at 70 DEG C
After when ultrasound 1 is small, the vinyl trichlorosilane solution of the μ l of 200 μ l~800 is added in, titanium sheet or fabric are put into after standing a period of time
Substrate, in electric heating constant temperature shaking water bath react 8~24 it is small when (titanium sheet substrate) or 4 it is small when (fabric substrate) after, in substrate table
Surface construction hydrophobic coating；
Step 2：Infiltration sex reversal based on click-reaction
The THF solution of 20ml is measured, adds 0.418g DMPA, the 3- mercaptopropionic acids of 136.83 μ l, ultrasound
20min is completely dissolved it, and obtained solution is click-reaction solution, has the substrate of hydrophobic coating in infiltration click-reaction
It is 0.8~100W/m in intensity of illumination after solution2Ultraviolet source illumination reaction 10s~50min, that is, complete surface infiltration
The transformation of property.
As shown in Figure 1, the SEM that Fig. 1 is titanium sheet substrate used in the present invention schemes, the titanium after hydrofluoric acid anodic oxidation
Piece substrate surface has nano tube structure, and with good reactivity, being more conducive to coating can uniformly coat.
This application provides a kind of methods of surface wettability regulation and control, and substrate is impregnated in the silane containing alkenyl first
The substrate with hydrophobic coating is obtained in organic solution, after reaction, then obtained substrate is infiltrated in click-reaction solution,
It is reacted under ultraviolet irradiation condition, obtains the matrix with hydrophilic coating.The application rigid material can be made with flexible material
For basal structure hydrophobic coating, applicability is wide；At low cost, small toxicity under the coating process that the present invention uses is compared relatively；Using point
Hitting reaction makes surface wettability transformation more efficient, and faster, operation is easier for reaction speed, while utilizes hydrophobic coating surface
Substance can access the substance of different functionalities functional group on surface.
For a further understanding of the present invention, substrate surface wellability provided by the invention is regulated and controled with reference to embodiment
Method is described in detail, and protection scope of the present invention is not limited by the following examples.
The letter said in the present invention is that this field is fixed referred to as, which part letter text is explained as follows referred to as：THF：
Tetrahydrofuran；DMPA：2,2- dimethoxy -2- phenyl acetophenones；SEM schemes：Scanning electron microscope diagram；XPS spectrum figure：X-ray
Photoelectron spectroscopy figure；EDS energy spectrum diagrams：X-ray energy spectrogram.
Embodiment 1
Step 1 constructs hydrophobic coating
The toluene solution of 40ml is measured, adds in the deionized water of 80 μ l, is uniformly mixed and is placed in centrifuge tube, at 70 DEG C
After when ultrasound 1 is small, the vinyl trichlorosilane solution of 200 μ l is added in, titanium sheet substrate is put into after standing a period of time, it is permanent in electric heating
After reacting 8h in warm shaking water bath just hydrophobic coating is constructed in substrate surface.
Infiltration sex reversal of the step 2 based on click-reaction
The THF solution of 20ml is measured, adds 0.418gDMPA, the 3- mercaptopropionic acids of 136.83 μ l, ultrasonic 20min
It is completely dissolved it, obtained solution is click-reaction solution, has the substrate of hydrophobic coating in infiltration click-reaction solution
Afterwards, it is 89W/m in intensity of illumination2Ultraviolet source under illumination reaction 5min, that is, complete the transformation of surface wettability.
The hydrophobic coating surface appearance structure based on titanium sheet substrate that the present embodiment is constructed is as shown in fig. 6, Fig. 6 is this reality
Apply the SEM photograph of the coating surface based on titanium sheet substrate prepared by example.
Embodiment 2
Step 1 constructs hydrophobic coating
The toluene solution of 40ml is measured, adds in the deionized water of 80 μ l, is uniformly mixed and is placed in centrifuge tube, at 70 DEG C
After when ultrasound 1 is small, the vinyl trichlorosilane solution of 200 μ l is added in, titanium sheet substrate is put into after standing a period of time, it is permanent in electric heating
After when reaction 12 is small in warm shaking water bath just hydrophobic coating is constructed in substrate surface.
Infiltration sex reversal of the step 2 based on click-reaction
The THF solution of 20ml is measured, adds 0.418g DMPA, the 3- mercaptopropionic acids of 136.83 μ l, ultrasound
20min is completely dissolved it, and obtained solution is click-reaction solution, has the substrate of hydrophobic coating in infiltration click-reaction
It is 89W/m in intensity of illumination after solution2Ultraviolet source under illumination reaction 30min, that is, complete the transformation of surface wettability.
The hydrophobic coating surface appearance structure based on titanium sheet substrate that the present embodiment is constructed is as shown in fig. 7, Fig. 7 is this reality
Apply the SEM photograph of the coating surface based on titanium sheet substrate prepared by example.
Embodiment 3
Step 1 constructs hydrophobic coating
The toluene solution of 40ml is measured, adds in the deionized water of 80 μ l, is uniformly mixed and is placed in centrifuge tube, at 70 DEG C
After when ultrasound 1 is small, the vinyl trichlorosilane solution of 800 μ l is added in, titanium sheet substrate is put into after standing a period of time, it is permanent in electric heating
After when reaction 12 is small in warm shaking water bath just hydrophobic coating is constructed in substrate surface.
Infiltration sex reversal of the step 2 based on click-reaction
The THF solution of 20ml is measured, adds 0.418g DMPA, the 3- mercaptopropionic acids of 136.83 μ l, ultrasound
20min is completely dissolved it, and obtained solution is click-reaction solution, has the substrate of hydrophobic coating in infiltration click-reaction
It is 8.8W/m in intensity of illumination after solution2Ultraviolet source under illumination reaction 5min, that is, complete the transformation of surface wettability.
The hydrophobic coating surface appearance structure based on titanium sheet substrate that the implementation case is constructed is as shown in figure 8, Fig. 8 is this
The SEM photograph of the coating surface based on titanium sheet substrate prepared by embodiment.
Embodiment 4
Step 1 constructs hydrophobic coating
The toluene solution of 40ml is measured, adds in the deionized water of 80 μ l, is uniformly mixed and is placed in centrifuge tube, at 70 DEG C
After when ultrasound 1 is small, the vinyl trichlorosilane solution of 200 μ l is added in, fabric substrate is put into after standing a period of time, it is permanent in electric heating
After when reaction 4 is small in warm shaking water bath just hydrophobic coating is constructed in substrate surface.
Infiltration sex reversal of the step 2 based on click-reaction
The THF solution of 20ml is measured, adds 0.418g DMPA, the 3- mercaptopropionic acids of 136.83 μ l, ultrasound
20min is completely dissolved it, and obtained solution is click-reaction solution, has the substrate of hydrophobic coating in infiltration click-reaction
It is 89W/m in intensity of illumination after solution2Ultraviolet source under illumination reaction 5min, that is, complete the transformation of surface wettability.
As described in Figure 9, Fig. 9 is this to the hydrophobic coating surface appearance structure based on fabric substrate that the implementation case is constructed
The SEM photograph of coating surface based on fabric substrate prepared by embodiment.
In order to observe the hydrophobic performance of the appearance structure of coating surface and coating, when having studied construction hydrophobic coating respectively,
The SEM figures of the coating surface based on titanium sheet substrate in electric heating constant temperature shaking water bath prepared by the differential responses time are quiet with surface
State contact angle figure, as shown in Fig. 2, as shown in Figure 2, with the extension (8h, 16h, for 24 hours) in reaction time, the bead of titanium plate surface
The density of shape substance gradually increases, i.e., the thicknesses of layers that coating surface is formed gradually increases；And from the table of surface static contact angle
Sign understands that the titanium sheet contact angle at three time points embodies excellent hydrophobic performance, while illustrate that 8h's is anti-at 150 ° or so
Substrate surface coating is complete between seasonable.
The reaction time is taken to be studied for 12h, coating part is added in prepared by the vinyl trichlorosilane of different volumes
Coating surface SEM figures and surface static contact angle figure based on titanium sheet substrate, as shown in figure 3, from the figure 3, it may be seen that as volume increases
Greatly, the diameter of the coccoid substance of titanium plate surface slightly increases, and contact angle the results show has no significant difference, illustrates vinyl
Saturated reaction when trichlorosilane volume takes 200 μ l.
As shown in figure 4, Fig. 4 is the SEM figures of the coating surface based on fabric substrate and surface static contact angle figure；By Fig. 4
It understands, the surface topography similar to titanium sheet coating, similary excellent hydrophobic performance is presented in fabric coating.As shown in figure 5, Fig. 5 is
The XPS spectrum figure of hydrophobic coating based on titanium sheet substrate in the present invention, as shown in Figure 5, the presence of C, O, Si element prove that coating is anti-
It should have occurred really.
Figure 10 is the SEM photograph after the coating click-reaction based on titanium sheet substrate, Tu11Wei in method provided by the invention
SEM photograph and surface static contact angle figure in method provided by the invention after the coating click-reaction based on fabric substrate；By
Figure 10 and Figure 11 understands that titanium sheet coating and the spherical substance on fabric coating surface are changed, from spherical state to cotton-shaped generation
Variation illustrates that in the case where illumination acts on the substance of coating surface is reacted.Figure 12 is that respectively step is anti-in method provided by the invention
EDS energy spectrum diagrams after answering, as shown in Figure 12, structure coating part has increased Si elements newly, and click-reaction part has increased S elements newly,
It can prove the generation of each step reaction.Figure 13 be method provided by the invention in different illumination intensity light source light according to it is different when
Between after surface static contact angle, Figure 13 a be in 0.8 ± 0.2W/m of light intensity2Surface static contact angle after lower different time, figure
13b is in 8.8 ± 1.2W/m of light intensity2Surface static contact angle after lower different time, Figure 13 c are in 89.8 ± 0.4W/m of light intensity2
Surface static contact angle after lower different time, it is seen from figure 13 that under different light intensity effects, different time titanium sheet coating is clicked on anti-
The contact angle variation answered embodies the advantages of click-reaction is efficient, quick.As shown in Figure 14, by the repeatability of five secondary responses
Experiment, the hydrophobic coating constructed every time all presents stable hydrophobic performance, and the transition effect of wellability is also fine, it was demonstrated that this
The good repeatability of wellability control technique of invention.
In conclusion the invention discloses a kind of control techniques of controllable special wellability, the present invention is in existing method base
Have found a kind of low cost, the method for hypotoxicity of construction hydrophobic coating on plinth, the hydrophobic coating of construction has excellent hydrophobic
Performance.Surface wettability is regulated and controled using click chemistry, reaction is mild, and easy to operate, raw material is easy to get, it is most important that anti-
It answers rapid and efficient, rigid basement and flexible substrates can be applied to simultaneously, be expected to widely promote.
The explanation of above example is only intended to help to understand method and its core concept of the invention.It should be pointed out that pair
For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out
Several improvement and modification, these improvement and modification are also fallen into the protection domain of the claims in the present invention.
The foregoing description of the disclosed embodiments enables professional and technical personnel in the field to realize or use the present invention.
A variety of modifications of these embodiments will be apparent for those skilled in the art, it is as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, it is of the invention
The embodiments shown herein is not intended to be limited to, and is to fit to and the principles and novel features disclosed herein phase one
The most wide scope caused.
Claims (6)
1. a kind of method of surface wettability regulation and control, comprises the following steps：
A), substrate is impregnated in the organic solution of the silane containing alkenyl, the substrate with hydrophobic coating is obtained after reaction；It is described
Substrate is pure cotton fabric；
B), by step A) after obtained substrate infiltration click-reaction solution, reacted under the conditions of ultraviolet light, obtain that there is parent
The matrix of water coating；The click-reaction solution is the organic solution of photoinitiator and the mercapto derivatives containing hydrophilic radical；
Repeat step A),
Or it is repeated in step A) and step B)；
When the substrate is pure cotton fabric, the step A) it further includes before：
Pure cotton fabric is cleaned by ultrasonic successively by acetone, ethyl alcohol and deionized water.
2. according to the method described in claim 1, it is characterized in that, the silane containing alkenyl be selected from vinyl trichlorosilane,
The one or more of allyltrichlorosilane and 5- hexenyltrichlorosilanes；The mercapto derivatives containing hydrophilic radical are selected from 3-
One or more in mercaptopropionic acid, 2 mercapto ethanol, 2-MEA and 2- mercaptonicotinic acids.
3. the according to the method described in claim 1, it is characterized in that, process for preparation of the organic solution of the silane containing alkenyl
In be specially：
It is ultrasonic after toluene is mixed with water, the silane containing alkenyl is added, is stood；
It is specially in the process for preparation of the click-reaction solution：
It is ultrasonic after tetrahydrofuran, 2,2- dimethoxy -2- phenyl acetophenones are mixed with the mercapto derivatives containing hydrophilic radical.
4. according to the method described in claim 1, it is characterized in that, step A) described in time for reacting be 3~4h, it is described anti-
The temperature answered is 20~40 DEG C.
5. according to the method described in claim 1, it is characterized in that, step B) be specially：
By step A) obtained substrate is infiltrated in click-reaction solution, takes out substrate towards ultraviolet source, had after reaction
There is the substrate of hydrophilic coating.
6. according to the method described in claim 1, it is characterized in that, the intensity of illumination of the ultraviolet light is 0.8W/m2~100W/
m2, light application time is 10s~50min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610051564.7A CN105671951B (en) | 2016-01-26 | 2016-01-26 | A kind of method of substrate surface wellability regulation and control |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610051564.7A CN105671951B (en) | 2016-01-26 | 2016-01-26 | A kind of method of substrate surface wellability regulation and control |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105671951A CN105671951A (en) | 2016-06-15 |
| CN105671951B true CN105671951B (en) | 2018-05-18 |
Family
ID=56303005
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610051564.7A Active CN105671951B (en) | 2016-01-26 | 2016-01-26 | A kind of method of substrate surface wellability regulation and control |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105671951B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109517736A (en) * | 2017-08-25 | 2019-03-26 | 中山大学 | A kind of controllable substrate of surface local infiltration and its application |
| CN108316050B (en) * | 2018-01-08 | 2020-10-16 | 东南大学 | Preparation method and application of functional paper |
| CN110038569B (en) * | 2019-05-22 | 2021-11-19 | 安徽理工大学 | Janus Cu (OH)2@Cu2O/Cu net and preparation method and application thereof |
| CN110364664A (en) * | 2019-07-18 | 2019-10-22 | 安徽新衡新材料科技有限公司 | A kind of Water based metal ion secondary battery diaphragm and its preparation method and application |
| CN113004728A (en) * | 2021-02-01 | 2021-06-22 | 中南林业科技大学 | Coating with hydrophilic self-cleaning capability and preparation method thereof |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1760113A (en) * | 2005-11-16 | 2006-04-19 | 厦门大学 | Method for preparing film of Nano tube array of titanium dioxide in both ultra hydrophilicity and lipophilicity, and ultra hydrophobicity |
| US20090096136A1 (en) * | 2007-10-12 | 2009-04-16 | The Regents Of The University Of California | Thiol-ene based poly(alkylsiloxane) materials |
| CN101603177A (en) * | 2009-07-06 | 2009-12-16 | 厦门大学 | A kind of method for micro-processing patterned surface based on super parent-superhydrophobic characteristic template |
| CN102021628A (en) * | 2009-09-11 | 2011-04-20 | 中国科学院兰州化学物理研究所 | Method for preparing metal titanium or titanium alloy super-oleophobic surface |
| WO2012129380A2 (en) * | 2011-03-23 | 2012-09-27 | The Regents Of The University Of California | Synthesis of thioether containing trialkoxysilanes |
| KR101260455B1 (en) * | 2011-07-21 | 2013-05-07 | 포항공과대학교 산학협력단 | Method for fabricating super-hydrophobic surface and evaporator having the super-hydrophobic surface |
| WO2014076682A1 (en) * | 2012-11-19 | 2014-05-22 | Institut Curie | Method for grafting polymers on metallic substrates |
| CN103966643B (en) * | 2014-04-24 | 2016-08-24 | 大连理工大学 | A kind of preparation method of the titanium alloy super-hydrophobic surface of low roughness |
| CN104404763B (en) * | 2014-12-04 | 2016-10-12 | 东华大学 | A kind of preparation method of the wool fabric of antistatic, felt proofing and good dyeability |
| CN105126772B (en) * | 2015-08-06 | 2017-05-17 | 中国林业科学研究院林产化学工业研究所 | Lignin-based heavy metal ion adsorbent containing thiol ether structure, and preparation method thereof |
-
2016
- 2016-01-26 CN CN201610051564.7A patent/CN105671951B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN105671951A (en) | 2016-06-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105671951B (en) | A kind of method of substrate surface wellability regulation and control | |
| CN101650981B (en) | Durable transparent conductors on polymeric substrates | |
| Wan et al. | Thermal stability of phosphonic acid self-assembled monolayers on alumina substrates | |
| WO2016079696A2 (en) | Conductive polymer coatings for three dimensional substrates | |
| CN113388293B (en) | Preparation method of durable photo-thermal real-time self-repairing super-amphiphobic coating | |
| CN106229426B (en) | A kind of method and quantum dot film of glue chain quantum dot film | |
| Zhang et al. | Humidity-and sunlight-driven motion of a chemically bonded polymer bilayer with programmable surface patterns | |
| CN108181363A (en) | A kind of flexible electrode based on dendritic nano-silver structure prepared using electrochemical deposition method | |
| WO2018040955A1 (en) | Preparation of chemical grafting-modified pet/nano silver wire transparent conductive film | |
| CN103456900A (en) | Flexible display device manufacturing method | |
| Hu et al. | SU-8-induced strong bonding of polymer ligands to flexible substrates via in situ cross-linked reaction for improved surface metallization and fast fabrication of high-quality flexible circuits | |
| CN109486207B (en) | High-cohesiveness flexible conductive electrode and preparation method thereof | |
| JP2019104169A (en) | Metal-coated resin substrate | |
| Oh et al. | Synthesis of a stretchable but superhydrophobic polymer thin film with conformal coverage and optical transparency | |
| Thiam et al. | Designing nanoporous membranes through templateless electropolymerization of thieno [3, 4-b] thiophene derivatives with high water content | |
| CN110534641A (en) | A kind of stretchable memristor and the preparation method and application thereof based on elastomeric polymer as active layer | |
| CN106245009A (en) | A kind of flexible substrate silver CNT composite coating and preparation method and application | |
| Li et al. | The enhanced corrosion resistance of UMAO coatings on Mg by silane treatment | |
| CN113161042B (en) | Preparation method of sodium carboxymethylcellulose flexible transparent conductive film based on silver nanowires | |
| CN110452406B (en) | Steam response intelligent thin film material, double-stimulation self-driven actuator and robot hand | |
| KR101990090B1 (en) | Glass coating Composition for preventing a fingerprint from becoming conspicuous, Method for Producing the Same and Glass coating layer | |
| CN107993972A (en) | A kind of flexible electronic functional material and preparation method thereof | |
| CN110735170A (en) | Preparation method of titanium dioxide nano thorn-shaped array fiber coatings | |
| KR20110071539A (en) | Transparent conductors and method of preparing same | |
| TW314546B (en) | Adhesive-free adhesion between polymeric surfaces |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220916 Address after: Room 410, Office Building, Hongxing Wodenka Quangang Petrochemical Technology Maker Park, No. 499, Yifeng West Road, Sanzhu Village, Qianhuang Town, Quangang District, Quanzhou City, Fujian Province, China Patentee after: Quanzhou Kunrun Nanotechnology Co.,Ltd. Address before: 215228 No. 1188 west two ring road, Shengze Town, Wujiang District, Suzhou, Jiangsu. Patentee before: SUZHOU RONGLYU NANO SCIENCE & TECHNLOGY Co.,Ltd. |
|
| TR01 | Transfer of patent right |