CN101033304A - Method of preparing solvent response type intelligent surface - Google Patents
Method of preparing solvent response type intelligent surface Download PDFInfo
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- CN101033304A CN101033304A CN 200710067290 CN200710067290A CN101033304A CN 101033304 A CN101033304 A CN 101033304A CN 200710067290 CN200710067290 CN 200710067290 CN 200710067290 A CN200710067290 A CN 200710067290A CN 101033304 A CN101033304 A CN 101033304A
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Abstract
The invention discloses a method for preparing a solvent-type smart surface. In the invention, it modifies silane coupling agent on the glass surface or silicon surface of hydroxylation by using self-assembly of molecular, and then it grafts amphiphilic triblock copolymer, and then it handles the surface with different solvent to achieve reversible changes of the wetting characteristics on the surface.
Description
Technical field
The present invention relates to a kind of preparation method of intelligent surface, particularly a kind of method of utilizing silane coupling agent grafting amphipathic nature block polymer to prepare solvent response type intelligent surface.
Background technology
Solvent response type intelligent surface is meant, when extraneous SOLUTION PROPERTIES changes, be the variation or the stimulation of response external environment, the surface can optionally be moved by segment, the reorganization of generation surface tissue, thus make characteristics such as wettability of the surface, viscosity that reversible change surface take place.As everyone knows, the wettability of solid surface is closely-related with its chemical ingredients, and Solid Surface Free Energy is big more, and is just easy more wetted; Solid Surface Free Energy is more little, just is difficult for wetted.Therefore, seek and prepare to contain high surface free energy and low surface free energy component simultaneously, and the solid surface that can be selected by different solvents of two kinds of components, be the precondition of preparation solvent response type intelligent surface.The mixture molecular brush, terminal carboxyl(group) or amidized alkane polymer, segmented copolymer etc. are commonly used to prepare this class surface.
Method by " graft from " and " graft to " can be grafted to the component molecule various matrix surfaces.Use solvent treatment of different nature surface again, make different component molecules be exposed to outermost layer, just obtained the surface of different wetting.At present, relevant with this class surface preparation patent rarely has report; Comprehensive relevant paper, scholar both domestic and external adopts following method to prepare solvent response type intelligent surface usually: (1) is at solid surface grafting hydrophobic molecule and hydrophilic molecule mixture brush, as Yu Xi, Wang Zhiqian etc. are at " Advanced Materials " magazine 2005,17, reported gold surface grafting HS (CH on the 1289-1293
2)
9CH
3And HS (CH
2)
10The solvent response type intelligent surface that the COOH mixture prepares, this surface is in acid and neutral environment, and this surface is hydrophobicity; In alkaline environment, the surface then is wetting ability; (2) polymer surfaces is functionalized, as Stephen Randall Holmes-Farley etc. at " Langmuir " magazine 1987,3, the last reported first of 799-815 the PE-CO of carboxylated back, polyethylene (PE) surface gained
2Variation has the reversible respondent behavior to solvent pH value on the H surface; (3) solid surface in-situ polymerization segmented copolymer, as Zhao Bin etc. at " Macromolecules " magazine 2000,33, reported on the 8813-8820 and utilized atom transfer radical polymerization (ATRP), prepared solvent response type intelligent surface at silicon face in-situ polymerization polystyrene-poly methyl methacrylate (PS-b-PMMA) segmented copolymer.
Above listed preparation method, general complicated operation, surface composition controllability, reversibility and less stable, repeatability are not good, have limited the application on this class surface.
Summary of the invention
The objective of the invention is to solve the problem of solvent response type intelligent surface stability and respondent behavior reversibility difference, adopt the molecule self-assembly to make the silane coupling agent unimolecular film at substrate material surface, the grafting amphipathic nature block polymer makes solvent treatment rear surface wetting property the solvent response type intelligent surface that reversibility changes can take place then.
The preparation method of a kind of solvent response type intelligent surface of the present invention is as follows;
(1) preprocessing process:
With base material difference ultrasonic cleaning 5～15min in deionized water and dehydrated alcohol, immerse freshly prepared hot Piranha solution (98% vitriol oil: 30%H then
2O
2=7: 3, V/V) in, take out behind 20～60min, clean with a large amount of deionized water rinsings, nitrogen dries up, and obtains hydroxylated base material;
(2) self assembling process of silane coupling agent:
The base material of surface hydroxylation is immersed in the silane coupling agent ethanol solution of 1mM～10mM and soak 8～24h, take out the back with dehydrated alcohol rinsing number time, use a large amount of deionized water rinsings again, nitrogen dries up, at 100～130 ℃ of following thermal treatment 0.5h～2h, obtain having the substrate material surface of the fine and close crosslinked silane structure of individual layer;
(3) modification on solvent response surface:
Amphipathic nature block polymer is dissolved into makes the solution that concentration is 1～20g/L in the tetrahydrofuran (THF) (THF).This solution is spun to the substrate material surface that is assembled with the silane coupling agent film, and spin speed is 100rad/min～8000rad/min, and the spin coating time is 0.5min～5min, assembles 5～15h down for 100～160 ℃.Grafted PS-b-PAA segmented copolymer is not removed at apparatus,Soxhlet's extracting 5～15h with THF, obtains solvent response type intelligent surface;
(4) solvent triggers the change process of surface wettability:
Solvent response type intelligent surface is immersed in organic or inorganic triggers in the solvent, take out behind 0.5～3h, use deionized water rinsing, N rapidly
2Dry up, obtain having the surface of different wetting;
The used base material of the present invention is glass, silicon single crystal, quartz, mica, pottery or macromolecule polymer material.
The used silane coupling agent of the present invention is KH560 (γ-(2, the 3-glycidoxy) propyl trimethoxy silicane).
The used amphipathic nature block polymer of the present invention contains a hydrophobic segment, a hydrophilic segment and one or more carboxyl functional group, its hydrophobic segment is polystyrene (PS), and hydrophilic segment is polyacrylate(s), polyacrylic acid (PAA), polyethylene oxide (PEO) or polyvinylpyrrolidone (PS-PVP).
The used triggering solvent of the present invention is toluene, hexanaphthene, ethanol, methylene dichloride, acidic aqueous solution or alkaline aqueous solution.
The present invention is a kind of preparation method of solvent response type intelligent surface, has following advantage and purposes:
(1) adopt method of the present invention, simple to operate, raw material is easy to get, good reproducibility.
(2) for covalent linkage is connected, improved the stability of intelligent surface between the solvent response type intelligent surface by the inventive method preparation, silane coupling agent and base material and block polymer.
(3) by the solvent response type intelligent surface of the inventive method preparation, the grafted segmented copolymer contains hydrophobic segment and hydrophilic segment, by changing extraneous solvent property, the wetting property generation reversibility on surface is changed.
The solvent response type intelligent surface of the inventive method preparation, can be used for surperficial wetting regime is had the application scenario of particular requirement, particularly require surface wettability along with the occasion that reversibility is switched can take place in the stimulation of external solvent, flowing of pipeline inner fluid controlled in the modification that comprises function microfluid and chip lab duct wall, and adhesivity is controlled adhesive surface dynamically.
Description of drawings
Fig. 1 is PS-PVP grafting glass surface soaks the back contact angle with toluene state graph;
Fig. 2 is the acidic aqueous solution immersion back contact angle state graph of PS-PVP grafting glass surface with pH=1;
Fig. 3 is that PS-PAA grafting silicon face soaks back contact angle state graph with toluene;
Fig. 4 be PS-PAA grafting silicon face with alcohol immersion after the contact angle state graph;
Fig. 5 is that PS-PMA grafting quartz surfaces soaks back contact angle state graph with hexanaphthene;
Fig. 6 is that PS-PMA grafting quartz surfaces soaks back contact angle state graph with methylene dichloride;
Fig. 7 is the acidic aqueous solution immersion back contact angle state graph of PS-PAA grafting silicon face with pH=1;
Fig. 8 is the alkaline aqueous solution immersion back contact angle state graph of PS-PAA grafting silicon face with pH=13.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail.
The contact angle data are recorded by Dataphysics OCA20 contact angle instrument.
(1) preprocessing process:
With sheet glass difference ultrasonic cleaning 5min in deionized water and dehydrated alcohol, immerse freshly prepared hot Piranha solution (98% vitriol oil: 30%H then
2O
2=7: 3, V/V) in, take out behind the 20min, clean with a large amount of deionized water rinsings, nitrogen dries up, and obtains hydroxylated base material;
(2) self assembling process of silane coupling agent:
The base material of surface hydroxylation is immersed in the silane coupling agent KH560 ethanol solution of 1mM and soak 24h, take out the back with dehydrated alcohol rinsing number time, use a large amount of deionized water rinsings again, nitrogen dries up, at 110 ℃ of following thermal treatment 45min, obtain having the substrate material surface of the fine and close crosslinked silane structure of individual layer;
(3) modification on solvent response surface:
Segmented copolymer PS-PVP is dissolved into makes the solution that concentration is 10g/L in the tetrahydrofuran (THF) (THF).This solution is spun to the substrate material surface (600rad/min 5s, 5000rad/min 60s) that is assembled with the silane coupling agent film, assembles 7h down for 150 ℃.Grafted PS-PVP segmented copolymer is not removed with THF Soxhlet extraction 8h, obtains solvent response type intelligent surface.
(4) solvent triggers the change process of surface wettability:
Solvent response type intelligent surface is immersed in repeatedly in the aqueous solution of toluene or pH=1, takes out behind the 20min, use deionized water rinsing, N rapidly
2Dry up, obtain wettability the surface that reversibility changes can take place.
Shown in accompanying drawing 1, accompanying drawing 2, after the aqueous solution soaking of PS-PVP grafted glass surface with toluene or pH=1, the surface is respectively 81 ° and 48 ° to the contact angle of water.
Embodiment 2
(1) preprocessing process:
With monocrystalline silicon piece difference ultrasonic cleaning 5min in deionized water and dehydrated alcohol, immerse freshly prepared hot Piranha solution (98% vitriol oil: 30%H then
2O
2=7: 3, V/V) in, take out behind the 20min, clean with a large amount of deionized water rinsings, nitrogen dries up, and obtains hydroxylated base material;
(2) self assembling process of silane coupling agent:
The base material of surface hydroxylation is immersed in the silane coupling agent KH560 ethanol solution of 2mM and soak 12h, take out the back with dehydrated alcohol rinsing number time, use a large amount of deionized water rinsings again, nitrogen dries up, at 110 ℃ of following thermal treatment 45min, obtain having the substrate material surface of the fine and close crosslinked silane structure of individual layer;
(3) modification on solvent response surface:
Segmented copolymer PS-PAA is dissolved into makes the solution that concentration is 5g/L in the tetrahydrofuran (THF) (THF).This solution is spun to the substrate material surface (600rad/min 6s, 4000rad/min 30s) that is assembled with the silane coupling agent film, assembles 7h down for 150 ℃.Grafted PS-PAA segmented copolymer is not removed with THF Soxhlet extraction 8h, obtains solvent response type intelligent surface.
(4) solvent triggers the change process of surface wettability:
Solvent response type intelligent surface is immersed in toluene or the ethanol repeatedly, takes out behind the 20min, use deionized water rinsing, N rapidly
2Dry up, obtain wettability the surface that reversibility changes can take place.
As accompanying drawing 3, accompanying drawing 4 be PS-PAA grafted monocrystalline silicon surface with toluene or alcohol immersion after, the surface is respectively 79 ° and 56 ° to the contact angle of water.
Embodiment 3
(1) preprocessing process:
With quartz plate difference ultrasonic cleaning 5min in deionized water and dehydrated alcohol, immerse freshly prepared hot Piranha solution (98% vitriol oil: 30%H then
2O
2=7: 3, V/V) in, take out behind the 20min, clean with a large amount of deionized water rinsings, nitrogen dries up, and obtains hydroxylated base material;
(2) self assembling process of silane coupling agent:
The base material of surface hydroxylation is immersed in the silane coupling agent KH560 ethanol solution of 2mM and soak 24h, take out the back with dehydrated alcohol rinsing number time, use a large amount of deionized water rinsings again, nitrogen dries up, at 110 ℃ of following thermal treatment 45min, obtain having the substrate material surface of the fine and close crosslinked silane structure of individual layer;
(3) modification on solvent response surface:
Segmented copolymer PS-PMA is dissolved into makes the solution that concentration is 1g/L in the tetrahydrofuran (THF) (THF).This solution is spun to the substrate material surface that is assembled with the silane coupling agent film, and (600rad/min 10s 4000rad/min30s), assembles 7h down for 150 ℃.Grafted PS-PMA segmented copolymer is not removed with THF Soxhlet extraction 8h, obtains solvent response type intelligent surface.
(4) solvent triggers the change process of surface wettability:
Solvent response type intelligent surface is immersed in hexanaphthene or the methylene dichloride repeatedly, takes out behind the 30min, use deionized water rinsing, N rapidly
2Dry up, obtain wettability the surface that reversibility changes can take place.
As accompanying drawing 5, accompanying drawing 6 is that the surface was respectively 85 ° and 60 ° to the contact angle of water after PS-PMA grafted quartz surfaces soaked with hexanaphthene or methylene dichloride.
Embodiment 4
(1) preprocessing process:
With monocrystalline silicon piece difference ultrasonic cleaning 5min in deionized water and dehydrated alcohol, immerse freshly prepared hot Piranha solution (98% vitriol oil: 30%H then
2O
2=7: 3, V/V) in, take out behind the 20min, clean with a large amount of deionized water rinsings, nitrogen dries up, and obtains hydroxylated base material;
(2) self assembling process of silane coupling agent
The base material of surface hydroxylation is immersed in the silane coupling agent KH560 ethanol solution of 1mM and soak 24h, take out the back with dehydrated alcohol rinsing number time, use a large amount of deionized water rinsings again, nitrogen dries up, at 110 ℃ of following thermal treatment 45min, obtain having the substrate material surface of the fine and close crosslinked silane structure of individual layer;
(3) modification on solvent response surface:
Segmented copolymer PS-PAA is dissolved into makes the solution that concentration is 5g/L in the tetrahydrofuran (THF) (THF).This solution is spun to the substrate material surface (600r/min 6s, 4000r/min 30s) that is assembled with the silane coupling agent film, assembles 7h down for 150 ℃.Grafted PS-PAA segmented copolymer is not removed with THF Soxhlet extraction 8h, obtains solvent response type intelligent surface.
(4) solvent triggers the change process of surface wettability:
Solvent response type intelligent surface is immersed in repeatedly in the aqueous solution of pH=1 or pH=13, takes out behind the 45min, use deionized water rinsing, N rapidly
2Dry up, obtain wettability the surface that reversibility changes can take place.
After being the aqueous solution soaking of PS-PAA grafted monocrystalline silicon surface with pH=1 or pH=13 as accompanying drawing 7, accompanying drawing 8, the surface is respectively 74 ° and 47 ° to the contact angle of water.
Claims (5)
1, a kind of preparation method of solvent response type intelligent surface is characterized in that comprising the steps:
(1) preprocessing process:
With base material difference ultrasonic cleaning 5～15min in deionized water and dehydrated alcohol, immerse then in the freshly prepared hot Piranha solution, the component of described Piranha solution is: 98% vitriol oil: 30%H
2O
2=7: 3, V/V takes out behind 20～60min, cleans with a large amount of deionized water rinsings, and nitrogen dries up, and obtains hydroxylated base material;
(2) self assembling process of silane coupling agent:
The base material of surface hydroxylation is immersed in the silane coupling agent ethanol solution of 1mM～10mM and soak 8～24h, take out the back with dehydrated alcohol rinsing number time, use a large amount of deionized water rinsings again, nitrogen dries up, at 100～130 ℃ of following thermal treatment 0.5h～2h, obtain having the substrate material surface of the fine and close crosslinked silane structure of individual layer;
(3) modification on solvent response surface:
Amphipathic nature block polymer is dissolved into makes the solution that concentration is 1～20g/L in the tetrahydrofuran (THF), this solution is spun to the substrate material surface that is assembled with the silane coupling agent film, spin speed is 100rad/min～8000rad/min, the spin coating time is 0.5min～5min, assemble 5～15h down at 100～160 ℃, grafted PS-b-PAA segmented copolymer is not removed at apparatus,Soxhlet's extracting 5～15h with tetrahydrofuran (THF), obtains solvent response type intelligent surface;
(4) solvent triggers the change process of surface wettability:
Solvent response type intelligent surface is immersed in organic or inorganic triggers in the solvent, take out behind 0.5～3h, use deionized water rinsing, N rapidly
2Dry up, obtain having the surface of different wetting.
2, the preparation method of solvent response type intelligent surface according to claim 1 is characterized in that described base material is glass, silicon single crystal, quartz, mica, pottery or macromolecule polymer material.
3, the preparation method of solvent response type intelligent surface according to claim 1 is characterized in that described silane coupling agent is KH560, i.e. γ-(2, the 3-glycidoxy) propyl trimethoxy silicane.
4, the preparation method of solvent response type intelligent surface according to claim 1, it is characterized in that containing in the described amphipathic nature block polymer hydrophobic segment, a hydrophilic segment and one or more carboxyl functional group, its hydrophobic segment is a polystyrene, and hydrophilic segment is polyacrylate(s), polyacrylic acid, polyethylene oxide or polyvinylpyrrolidone.
5, the preparation method of solvent response type intelligent surface according to claim 1 is characterized in that described triggering solvent is toluene, hexanaphthene, ethanol, methylene dichloride, acidic aqueous solution or alkaline aqueous solution.
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| CN108671774B (en) * | 2018-06-05 | 2020-10-09 | 中国石油大学(华东) | Oil-water separation mesh membrane and preparation method and application thereof |
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| CN108744598A (en) * | 2018-06-13 | 2018-11-06 | 洛阳纳诺环保科技有限公司 | A kind of preparation method of the intelligent water-oil separationg film with antifouling property |
| CN109320640A (en) * | 2018-09-14 | 2019-02-12 | 西安理工大学 | A kind of preparation method of environment-responsive super-hydrophobic-hydrophilic material surface |
| CN109320640B (en) * | 2018-09-14 | 2021-01-15 | 西安理工大学 | Preparation method of environment-responsive super-hydrophobic-hydrophilic material surface |
| CN109989269A (en) * | 2019-03-14 | 2019-07-09 | 武汉纺织大学 | Dynamic solvent response type nano fiber base flexible and transparent composite membrane and preparation method thereof |
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| CN110183710A (en) * | 2019-06-06 | 2019-08-30 | 闽江学院 | A kind of preparation method on solvent response random copolymer brush surface |
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Assignee: Ningbo Dongdian Electric Equipment Manufacturing Co., Ltd. Assignor: Ningbo Inst of material technology and Engineering Chinese Academy of Sciences Contract fulfillment period: 2009.5.18 to 2014.5.17 contract change Contract record no.: 2009330001462 Denomination of invention: Method of preparing solvent response type intelligent surface Granted publication date: 20090422 License type: Exclusive license Record date: 2009.6.25 |
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