CN104150787B - A kind of Induced by Dopamine sol-gal process prepares the method for modifying of high hydrophiling coating - Google Patents
A kind of Induced by Dopamine sol-gal process prepares the method for modifying of high hydrophiling coating Download PDFInfo
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Abstract
A kind of Induced by Dopamine sol-gal process prepares the method for modifying of high hydrophiling coating, the present invention relates to the method for modifying of a kind of surface of solids height hydrophiling, it is in order to solve existing hydrophilic modification method and not have general applicability and process being loaded down with trivial details, the problem of hydrophilic modification DeGrain.Method of modifying: during one, dopamine is dissolved in alkaline aqueous solution, adds the ethanol solution containing tetraethyl orthosilicate, prepares dipping solution；Two, immersing in dipping solution by solid material to be modified, the solid material of taking-up with dehydrated alcohol and deionized water rinsing, completes the high hydrophilic modification of solid material successively.The Induced by Dopamine sol-gal process method of modifying of the present invention is the most effective, can disposably give body surface with high-hydrophilic, it is suitable for inorganic and high-molecular organic material, applied widely, the contact angle of modified glass surface is reduced to 12 °～20 °, the contact angle of polymeric membrane is 15 °～26 °, and modified effect is good.
Description
Technical field
The present invention relates to the method for modifying of a kind of surface of solids height hydrophiling.
Background technology
In modern material science and technology, surface modification is the most very important technology.Wherein body surface
Hydrophilic modification has application prospect widely, such as in fields such as glass automatically cleaning and polymeric membrane antipollutions.Glass
Surface hydrophilic processes and can give glass self-cleaning effect, so that glass is no longer by traditional artificial scrubbing method
It is issued to clean a new state in natural rainwash；The hydrophilicity-imparting treatment on polymeric membrane surface then can reduce film surface
Adsorption to pollutant such as albumen, improves film surface anti-pollution, reduces film washing time, and then reduces film operation maintenance
Cost also improves film service life.
The method of the most conventional glass surface hydrophiling mainly has chemical vapour deposition technique (CVD), sol-gel high temperature
Sintering process (sol-gel) and magnetron sputtering method.And polymeric membrane surface hydrophilic modification method mainly has surface grafting method, surface
The methods such as coating and hydrophilic material are blended.Although being below all hydrophilic modification, studies have found that the hydrophiling of glass changes
Property method is difficult to apply on polymeric membrane performing hydrophilic modification on surface because glass surface hydrophilic modification to generally require comparison severe
The condition such as condition such as high temperature, strong acid or strong basicity carved；And the hydrophilic modification on polymeric membrane surface also is difficult to be applied to
On the hydrophilic modification of glass, say, that above hydrophilic modification method is difficult to apply to different surfaces, and existing also
Do not have a kind of simple and effective hydrophilic modification method can be simultaneously suitable for the surface of inorganic matter and macromolecular material.
In ocean, mussel can stick to the various surface of solids, and Lee et al. is inspired by this, it was found that dopamine and derivative
Thing by the dioxygen oxidation in air under weakly alkaline environment, and (can include various inorganic matter, Organic substance and gold at body surface
Belong to and oxide) form one layer of firm poly-dopamine coating, and this coating is also used as new reaction platform, carries out
Secondary response or modification.Therefore, the research of dopamine becomes focus, and opens one and may be used for various material surface and change
The new method of property, carries out hydrophilic modification including utilizing dopamine to body surface.Although it is hydrophilic to utilize dopamine to carry out
Change modified method and be applicable to various material, including glass and macromolecular material, but by the hydrophilic limit of poly-dopamine itself
System, the hydrophilic effect of dopamine modifier surface is the most inconspicuous, and modified contact angle is general all at about 40 °, so
Hydrophilic be difficult to meet some high hydrophilic or super hydrophilic requirements (such as self-cleaning glass etc.).And in order to carry further
High-hydrophilic reaches super hydrophilic effect, often also needs to carry out twice-modified, and this can increase the most again the triviality of process.
Summary of the invention
The invention aims to solve the method for existing hydrophilic modification and not there is general applicability and process is loaded down with trivial details,
The problem of hydrophilic modification DeGrain, thus provide a kind of and simple and effective be applicable to inorganic or polymer surface is high
The method of hydrophilic modification.
Induced by Dopamine sol-gal process of the present invention is prepared the method for modifying of high hydrophiling coating and is followed these steps to realize:
One, dopamine is dissolved in the alkaline aqueous solution that pH is 8.5～11.5, obtains many after dopamine all dissolves
Bar amine aqueous solution, then by being injected in dopamine solution containing the ethanol solution of tetraethyl orthosilicate (TEOS), forms homogeneous leaching
Stain solution；
Two, solid material to be modified is immersed in the dipping solution that step one obtains, at room temperature stands impregnation process,
Then taking out solid material washes of absolute alcohol, finally use deionized water rinsing clean, the height completing solid material is hydrophilic
Change modification；
Wherein in the dipping solution described in step one, the weight/mass percentage composition of dopamine is 0.1%～1%, tetraethyl orthosilicate
Weight/mass percentage composition be 0.3%～1%, the weight/mass percentage composition of ethanol is 15%～30%.
The Induced by Dopamine sol-gel process method of modifying of the present invention is the most effective, it is possible to disposably give body surface
With high-hydrophilic, it is not necessary to twice-modified；Applied widely, it is suitable for inorganic and high-molecular organic material performing hydrophilic modification on surface；
Simultaneously because employing dipping method, do not affected by object appearance.
By the hydrophilic of modified solid material with contrast before modified, result shows, before simple glass is unmodified
Contact angle be about 69 °, be about 36 ° only with dopamine modification contact angle, and use the modified glass of method of the present invention
The contact angle on glass surface is reduced to 12 °～20 °；The contact angle of unmodified front Kynoar polymeric membrane is about 83 °, DOPA
The modified contact angle of amine is about 46 °, and uses the contact angle of the method modified Kynoar polymeric membrane of the present invention
It it is 15 °～26 °.
Substantially carry it follows that the effect that the most simple dopamine of hydrophilic modification effect of the method is modified has
Height, ratio existing additive method more versatility, it is suitable for the surface modification of the various material of various patterns, and does not the most change the original
The color and luster of body.Method of modifying of the present invention is simple, and cost is relatively low, has good industrial applications prospect.
Accompanying drawing explanation
Fig. 1 is the contact angle of the microscope slide of the high hydrophiling of embodiment one；
Fig. 2 is the contact angle of the pvdf membrane of the high hydrophiling of embodiment one；
Fig. 3 is the contact angle of the microscope slide of the high hydrophiling of embodiment two；
Fig. 4 is the contact angle of the pvdf membrane of the high hydrophiling of embodiment two；
Fig. 5 is the contact angle of the microscope slide of embodiment three-hypers hydrophiling；
Fig. 6 is the contact angle of the pvdf membrane of embodiment three-hypers hydrophiling；
Fig. 7 is the SEM figure of embodiment one hydrophiling pvdf membrane；
Fig. 8 is the SEM figure of embodiment two hydrophiling pvdf membrane；
Fig. 9 is the SEM figure of embodiment three hydrophiling pvdf membrane；
Figure 10 is the XPS figure of embodiment three hydrophiling pvdf membrane
Figure 11 is the AFM figure of embodiment three hydrophiling pvdf membrane；
Figure 12 is the AFM figure of embodiment three hydrophiling microscope slide.
Detailed description of the invention
Detailed description of the invention one: present embodiment Induced by Dopamine sol-gal process prepares the modification side of high hydrophiling coating
Method follows these steps to implement:
One, dopamine is dissolved in the alkaline aqueous solution that pH is 8.5～11.5, obtains many after dopamine all dissolves
Bar amine aqueous solution, then by being injected in dopamine solution containing the ethanol solution of tetraethyl orthosilicate (TEOS), forms homogeneous leaching
Stain solution；
Two, solid material to be modified is immersed in the dipping solution that step one obtains, at room temperature stands impregnation process,
Then taking out solid material washes of absolute alcohol, finally use deionized water rinsing clean, the height completing solid material is hydrophilic
Change modification；
Wherein in the dipping solution described in step one, the weight/mass percentage composition of dopamine is 0.1%～1%, tetraethyl orthosilicate
Weight/mass percentage composition be 0.3%～1%, the weight/mass percentage composition of ethanol is 15%～30%.
Detailed description of the invention two: present embodiment dipping solution described in step one unlike detailed description of the invention one
The weight/mass percentage composition of middle tetraethyl orthosilicate is 0.3%～0.8%.Other step and parameter are identical with detailed description of the invention one.
Detailed description of the invention three: the dipping described in present embodiment step one unlike detailed description of the invention one or two
In solution, the weight/mass percentage composition of dopamine is 0.15%～0.3%.Other step and parameter and detailed description of the invention one or two
Identical.
Detailed description of the invention four: described in present embodiment step one unlike one of detailed description of the invention one to three
In dipping solution, the weight/mass percentage composition of ethanol is 20%～30%.Other step and parameter and detailed description of the invention one to three it
One is identical.
Detailed description of the invention five: present embodiment dipping solution described in step one unlike detailed description of the invention one
The weight/mass percentage composition of neutral and alkali aqueous solution is 68%～84.6%.Other step and parameter are identical with detailed description of the invention one.
Detailed description of the invention six: present embodiment is unlike one of detailed description of the invention one to five described in step 2
Solid material to be modified be polymeric membrane or glass.Other step and parameter and one of detailed description of the invention one to five phase
With.
Detailed description of the invention seven: the macromolecule that present embodiment step 2 unlike detailed description of the invention six is to be modified
Film is polyvinylidene fluoride film, polyethylene film or polyacrylonitrile film.Other step and parameter are identical with detailed description of the invention six.
Detailed description of the invention eight: present embodiment step 2 unlike detailed description of the invention six glass to be modified is
Quartz glass.Other step and parameter are identical with detailed description of the invention six.
Detailed description of the invention nine: present embodiment unlike one of detailed description of the invention one to eight step 2 in room temperature
The lower time standing dipping will be 6h～24h.Other step and parameter are identical with one of detailed description of the invention one to eight.
Embodiment one: the present embodiment Induced by Dopamine sol-gal process prepares the method for modifying of high hydrophiling coating by following
Step is implemented:
In the Tris-HCl buffer solution of the pH=8.5 that, 0.2g dopamine is dissolved in 100mL, treat that dopamine is whole
Obtain dopamine solution after dissolving, then will be injected into DOPA containing the 20mL ethanol solution of 0.15g tetraethyl orthosilicate (TEOS)
In amine aqueous solution, form homogeneous dipping solution；
Two, pvdf membrane to be modified and microscope slide are immersed in the dipping solution that step one obtains, stand dipping in room temperature
Process 12h, then take out pvdf membrane and microscope slide washes of absolute alcohol, finally use deionized water rinsing clean, complete height
Molecular film and the high hydrophilic modification of glass.
Embodiment two: will be containing 0.3g tetraethyl orthosilicate (TEOS) in the present embodiment step one unlike embodiment one
20mL ethanol solution be injected in dopamine solution.
Embodiment three: will be containing 0.6g tetraethyl orthosilicate (TEOS) in the present embodiment step one unlike embodiment one
20mL ethanol solution be injected in dopamine solution.
From Fig. 1, Fig. 3 and Fig. 5 it can be seen that the contact angle that modified glass carries fragmentation has and significantly reduces, show it
Hydrophilic is obviously improved.And along with TEOS content increases, contact angle is gradually lowered to about 10 ° from about 70 °, shows
Hydrophilic raising is relevant with the content of TEOS.Equally, from Fig. 2, Fig. 4 and Fig. 6 it can be seen that pvdf membrane is carried out by the method
Modified, its contact angle also has and significantly reduces, and contact angle is gradually lowered to about 20 ° from about 80 °, and hydrophilic significantly carries
High.And only add TEOS and be added without dopamine, the contact angle of pvdf membrane does not the most change, and shows that dopamine and TEOS have
Having the effect reducing contact angle, a kind of composition is then difficult to increase substantially its hydrophilic.
Fig. 7～9 be pvdf membrane be modified SEM figure, it can be seen that add the modified pvdf membrane surface topography of TEOS
The film modified to only adding dopamine is similar, illustrates that the addition of TEOS has no effect on the coating effect of dopamine.Figure 10 is pvdf membrane
Modified XPS collection of illustrative plates, modified pvdf membrane surface occurs in that N element and O element, it was demonstrated that generate poly-dopamine, with
Time have also appeared obvious SiO2Si2s and 2p special type peak, show that body surface has successfully combined SiO2, this shows PVDF
Poly-dopamine and SiO are contained in film surface simultaneously2, the poly-dopamine of surface formation and SiO2It is evenly distributed.Figure 11 and Figure 12 is modified
After pvdf membrane and the AFM figure of sheet glass, it can be seen that through this method of modifying caudacoria surface and glass surface roughness by
Cumulative greatly, this is also one of reason of causing hydrophilic to improve.
Embodiment four: the present embodiment Induced by Dopamine sol-gal process prepares the method for modifying of high hydrophiling coating by following
Step is implemented:
In the Tris-HCl buffer solution of the pH=8.5 that, 0.4g dopamine is dissolved in 100mL, treat that dopamine is whole
Obtain dopamine solution after dissolving, then will be injected into dopamine containing the 20mL ethanol solution of 0.6g tetraethyl orthosilicate (TEOS)
In solution, form homogeneous dipping solution；
Two, pvdf membrane to be modified and microscope slide are immersed in the dipping solution that step one obtains, stand dipping in room temperature
Process 12h, then take out pvdf membrane and microscope slide washes of absolute alcohol, finally use deionized water rinsing clean, complete height
Molecular film and the high hydrophilic modification of glass.
Hydrophilic through the modified pvdf membrane of the present embodiment and sheet glass increases substantially, contact angle respectively from 80 ° and
70 ° are reduced to 20 ° and about 10 °.
Embodiment five: the present embodiment Induced by Dopamine sol-gal process prepares the method for modifying of high hydrophiling coating by following
Step is implemented:
In the Tris-HCl buffer solution of the pH=8.5 that, 0.8g dopamine is dissolved in 100mL, treat that dopamine is whole
Obtain dopamine solution after dissolving, then the 20mL ethanol solution containing 1g tetraethyl orthosilicate (TEOS) is injected into dopamine molten
In liquid, form homogeneous dipping solution；
Two, pvdf membrane to be modified and microscope slide are immersed in the dipping solution that step one obtains, stand dipping in room temperature
Process 12h, then take out pvdf membrane and microscope slide washes of absolute alcohol, finally use deionized water rinsing clean, complete height
Molecular film and the high hydrophilic modification of glass.
Hydrophilic through the modified pvdf membrane of the present embodiment and sheet glass increases substantially, contact angle respectively from 80 ° and
70 ° are reduced to 16 ° and about 8 °.
This method of modifying is applicable not only to inorganic material from the above results, applies also for the macromolecular material of hydrophobic,
Can increase substantially its hydrophilic, this method of modifying is simply effective simultaneously, can disposably increase substantially different materials (bag
Include inorganic material and high-molecular organic material) hydrophilic on surface so that it is there is high-hydrophilic.The method is expected to apply multiple
Field, including membrance separation field, biomedical materials field and functionalized surface field.
Claims (8)
1. an Induced by Dopamine sol-gal process prepares the method for modifying of high hydrophiling coating, it is characterised in that be by following step
Rapid realization:
One, dopamine is dissolved in the alkaline aqueous solution that pH is 8.5～11.5, after dopamine all dissolves, obtains dopamine
Solution, is then injected into the ethanol solution containing tetraethyl orthosilicate in dopamine solution, forms homogeneous dipping solution；
Two, solid material to be modified is immersed in the dipping solution that step one obtains, at room temperature stand impregnation process, then
Taking out solid material washes of absolute alcohol, finally use deionized water rinsing clean, the high hydrophiling completing solid material changes
Property；
Wherein in the dipping solution described in step one, the weight/mass percentage composition of dopamine is 0.1%～1%, the matter of tetraethyl orthosilicate
Amount percentage composition is 0.3%～1%, and the weight/mass percentage composition of ethanol is 15%～30%.
A kind of Induced by Dopamine sol-gal process the most according to claim 1 prepares the method for modifying of high hydrophiling coating,
It is characterized in that in the dipping solution described in step one, the weight/mass percentage composition of tetraethyl orthosilicate is 0.3%～0.8%.
A kind of Induced by Dopamine sol-gal process the most according to claim 1 prepares the method for modifying of high hydrophiling coating,
It is characterized in that in the dipping solution described in step one, the weight/mass percentage composition of dopamine is 0.15%～0.3%.
A kind of Induced by Dopamine sol-gal process the most according to claim 1 prepares the method for modifying of high hydrophiling coating,
It is characterized in that in the dipping solution described in step one, the weight/mass percentage composition of ethanol is 20%～30%.
A kind of Induced by Dopamine sol-gal process the most according to claim 1 prepares the method for modifying of high hydrophiling coating,
It is characterized in that the solid material to be modified described in step 2 is polymeric membrane or glass.
A kind of Induced by Dopamine sol-gal process the most according to claim 5 prepares the method for modifying of high hydrophiling coating,
It is characterized in that step 2 polymeric membrane to be modified is polyvinylidene fluoride film, polyethylene film or polyacrylonitrile film.
A kind of Induced by Dopamine sol-gal process the most according to claim 5 prepares the method for modifying of high hydrophiling coating,
It is characterized in that step 2 glass to be modified is quartz glass.
A kind of Induced by Dopamine sol-gal process the most according to claim 1 prepares the method for modifying of high hydrophiling coating,
It is characterized in that step 2 at room temperature stands the time of dipping is 6h～24h.
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| CN108395202B (en) * | 2018-03-30 | 2021-06-04 | 深圳市国日宏电子科技有限公司 | Preparation method of fiber modified aerogel material |
| CN110358435B (en) * | 2019-08-16 | 2021-09-14 | 苏州热工研究院有限公司 | Self-repairing super-hydrophobic coating and preparation method thereof |
| JPWO2021182100A1 (en) * | 2020-03-12 | 2021-09-16 | ||
| CN114293179B (en) * | 2021-12-08 | 2024-02-06 | 重庆材料研究院有限公司 | Preparation method of hafnium oxide coating for noble metal thermocouple |
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