CN102643397B - Preparation method of underwater pH-responsive super-oleophobic reversible adhesion interface switch - Google Patents
Preparation method of underwater pH-responsive super-oleophobic reversible adhesion interface switch Download PDFInfo
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Abstract
The invention relates to a preparation method of an underwater pH-responsive super-oleophobic reversible adhesion interface switch. The reversible oleophobic adhesion interface switch is obtained by constructing a polyacrylic acid (PAA) thin film on a plane substrate. When the pH value of the ambient solution is lower than the dissociation constant (pKa=4.7) of PAA, the interface presents high adhesion property to oil drops; and when the pH value of the ambient solution is higher than the dissociation constant of PAA, the interface presents super-oleophobic and low adhesion properties to oil drops. The interface adhesion switch with responsivity to pH of ambient solution has potential application value in the biological medical treatment field.
Description
Technical field
The present invention relates to the preparation method of the super oleophobic reversible adhesion of a kind of responsiveness of pH under water interface switch (abbreviation interface switch), belong to intelligent boundary material preparation field.
Background technology
Be subjected to the inspiration of occurring in nature fish scale (Adv.Mater.2009,21,665.) and lotus leaf lower surface (Soft Matter 2011,7,5948.), applicant's develop super oleophobic boundary material under water.Traditional super oleophobic material is to fall low surface energy by introduce fluorine and compound thereof on the surface, thereby realize super oleophobic in air (contact angle that refers to oil droplet greater than 150 ° less than 180 °), this super oleophobic boundary material under water need not to introduce fluorine and compound thereof, only can realize at the super oleophobic of aqueous phase by constructing micron and nanometer composite structure.Therefore, this super oleophobic boundary material has under water shown the using value that it is excellent, as novel oil-water separation system (Adv.Mater.2011,23,2861.).Particularly super oleophobic boundary material is controlled at a lot of fields to the adhesive power of oil droplet important application is arranged under water, as bioadhesion (J.Am.Chem.Soc.2009,131,10467.), micropatterning (Angew.Chem., Int.Ed.2011,50,8424.), (Science 2001 for intelligent microfluid switch, 291,1023.).Be scarcely out of swaddling-clothes about the controlled adhesive power research of super oleophobic boundary material under water at present, the work of report recently, as the epidermal structure (Adv.Mater.2009 by animal in imitation soil, 21,1840.), the silicon nanowires (J.Am.Chem.Soc.2009 of surface grafting poly N-isopropyl acrylamide, 131,10467.), self-assembling photonic crystal film (Adv.Funct.Mater.2011,21,4436.) and thermo-responsive interface (Soft Matter 2010,6,2708.).But development has environment-responsive super oleophobic adhesion under water switch and remains a huge challenge.
Not yet relevant super oleophobic under water adheres to the relevant open source literature report of switch at present.
Summary of the invention
Technology of the present invention is dealt with problems: overcome the deficiencies in the prior art, the super oleophobic reversible adhesion of a kind of responsiveness of pH under water interface switch is provided, the polymkeric substance using plasma that will have the pH responsiveness is grafted in substrate, realization realizes that by changing change pH values the method is simple to operate to the reversible regulation and control of oil droplet adhesion in the aqueous solution.
The present invention is achieved through the following technical solutions: the preparation method of the super oleophobic reversible adhesion of a kind of responsiveness of pH under water interface switch, and performing step is as follows:
(1) stopper is removed in vinylformic acid (acrylic acid, AA) distillation;
(2) plasm reaction cavity is put in substrate;
(3) pass into rare gas element in plasm reaction cavity, the pressure of controlling rare gas element is 20-100Pa, and pressure hold time is 10-30 minute, fully removes air;
(4) open plasma power supply, and the plasma electric source power is controlled at 30-100W, pass into Acrylic Acid Monomer, adjust the vacuum tightness 100-200Pa of plasm reaction cavity, carry out plasma induced polymerization, grafting 10-45 minute, then air is passed into plasm reaction cavity, namely obtain polyacrylic acid (PAA) interface switch, also namely have the super oleophobic reversible adhesion of pH responsiveness interface switch.The contact angle that described super oleophobic refers to oil droplet greater than 150 ° less than 180 °; Described reversible adhesion refers to that the adhesive power between oil droplet and described interface switch passes through the regulation and control pH value control of solution on every side, and the adhesive power size is from 0 to the highest 43.4 μ N (little ox); Prepared has the super oleophobic reversible adhesion of pH responsiveness interface switch in the aqueous solution of pH value lower than the dissociation constant (pKa=4.7) of PAA, oil droplet had oleophobic, high adhesion characteristics, in the aqueous solution of pH value higher than the dissociation constant (pKa=4.7) of PAA, oil droplet had super oleophobic, low adhesion characteristics; Described oleophobic property refers to the oil droplet contact angle lower than 150 °, and described high adhesion characteristics refers to that adhesive power reaches as high as 43.4 μ N; Described low adhesion characteristics refers to that the adhesive power minimum is 0 μ N.
Described substrate comprises sheet glass, quartz plate, silicon chip or sheet mica.
Described rare gas element is argon gas or nitrogen.
Described substrate adopts the vitriol oil or nitric acid to clean up before putting into plasm reaction cavity.
The polyacrylic acid of described preparation (PAA) interface switch is completed in changing in 1-2 two seconds to the adhesivity of oil droplet in the process that the pH value changes.
Described polyacrylic acid interface switch has reversible adhesive power to the oil droplet of different surfaces tension force, and the surface tension scope of oil droplet is 18.0-36.7mNm
-1
Described oil droplet is normal hexane, 1,2-ethylene dichloride, chloroform, tetrachloroethane or dichlorobenzene.
Principle of the present invention: at first the present invention removes stopper with the vinylformic acid underpressure distillation, and plasm reaction cavity is put in substrate, passes into rare gas element, gets rid of the air in the gas ions reaction cavity.Then the open plasma power supply, pass into Acrylic Acid Monomer, graft reaction; Pass at last air, can obtain having the super oleophobic reversible adhesion of pH responsiveness interface switch, it all has the reversible feature of adhesive power to different surfaces tension force oil droplet, has realized by changing the change pH values regulation and control to the regulation and control of oil droplet adhesive power.
The present invention's advantage compared with prior art is:
(1) by carrying out the plasma grafting polyacrylic acid at substrate surface, can control acrylic acid chain length like this, thereby realize high-sensitive pH response, realized first constructing of pH responsiveness super oleophobic reversible adhesion interface switch under water, realized the reversible regulation and control of the adhesive power of various surface tension oil droplets, this pH responsiveness reversible adhesion power interface switch is with a wide range of applications at biological field.
(2) using plasma grafted polyacrylic acid of the present invention, simple to operate, and polyacrylic thickness is controlled simultaneously.
(3) the super oleophobic reversible adhesion of the responsiveness of pH under water of the present invention switch Reusability, stable performance.
Description of drawings
Fig. 1 is a) matrix plasma induced polymerization vinylformic acid schematic diagram, polyacrylic acid grafted to substrate surface, when the pH value during lower than polyacrylic electrolysis constant, the polyacrylic acid segment forms intramolecular hydrogen bond, the polyacrylic acid segment is curling shape, during higher than polyacrylic electrolysis constant, polyacrylic acid and ambient water molecule form intermolecular hydrogen bonding when the pH value, and the polyacrylic acid segment is stretch-like; Fig. 1 b) for being grafted on suprabasil polyacrylic acid in pH is 2.4 the aqueous solution, it is very coarse that its surface becomes, and roughness is 5nm; Fig. 1 c) be that in 8.0 the aqueous solution, identical surface, position shows as more smooth pattern for same sample being immersed pH, its roughness is only 1nm.
Fig. 2 is adhesive power-displacement measurement curve in 1.0 the aqueous solution for super oleophobic reversible adhesion interface switch under water in the pH value, process 1: sample contacts the oil droplet that is suspended in water gradually, process 2: sample leaves after touching oil droplet, process 3: sample separates with oil droplet, and in its each process, the pattern state of oil droplet is seen illustration.
Fig. 3 is that the present invention proposes interface switch in polyacrylic electrolysis constant upper and lower surface roughness and mechanism that the oil droplet adhesive power is undergone mutation thereof, when the pH value during lower than polyacrylic electrolysis constant, form hydrogen bond in the polyacrylic acid segment, cause surface irregularity, oil droplet is produced high adhesive power, when pH value during higher than polyacrylic electrolysis constant, polyacrylic acid segment and on every side water molecules formation intermolecular hydrogen bonding, cause smooth surface, oil droplet is produced lower adhesive power.
Fig. 4 is the adhesive power to 1,2-ethylene dichloride oil droplet of pH responsiveness reversible adhesion interface switch in different pH solution under water, and when pH＜4.7, adhesive power increases gradually along with the reduction of pH value; When pH＞4.7, adhesive power acutely reduces, and when the pH value was 12, adhesive power was zero.
Fig. 5 is a) that the dynamic adhesive power of pH responsiveness reversible adhesion interface switch changes, the pH value from 12.0 to 1.0 of the aqueous solution; Fig. 5 b) be the adhesive power switch circulation of interface switch between pH solution 2.4 and 8.0, prove repeatability and the wearing quality of interface switch;
Fig. 6 is a) that in 4.0 the aqueous solution, surfaceness is 4.5nm for atomic power photo display interface switch under water in the pH value; Fig. 6 b) for interface switch in the pH value is 5.0 the aqueous solution, the surfaceness of same position is reduced to 1.5nm.
Embodiment
Introduce in detail the present invention below in conjunction with drawings and the specific embodiments.But following embodiment only limits to explain the present invention, and protection scope of the present invention should comprise the full content of claim, and the narration by following examples, and those skilled in the art is the full content that can realize claim of the present invention fully.
Stopper is removed in the vinylformic acid underpressure distillation, and substrate of glass is put into plasm reaction cavity after cleaning with the vitriol oil, passes into argon gas, and the pressure of controlling plasm reaction cavity is 20Pa, keeps 10 minutes, gets rid of the air in cavity.Then open plasma power supply, the adjustment plasma power is 30W, passes into Acrylic Acid Monomer, the vacuum tightness of adjusting reaction chamber is 100Pa, 10 minutes grafting time; Pass at last air, can obtain having the super oleophobic reversible adhesion of pH responsiveness interface switch, as shown in Figure 1.Oil droplet is chosen 1,2-ethylene dichloride, and measuring respectively interface switch is 1.0,2.4 at pH, 4.6,5.0,8.0,12.0 the time adhesive power, the adhesive power of the different pH value aqueous solution is as shown in table 1, when pH is 1.0, adhesive power is 21.6 μ N, and the pH value is elevated at 4.6 o'clock, is reduced to 15 μ N, when the pH value surpassed the electrolysis constant of PAA, adhesive power sharply descended, and is 5.0 o'clock as pH, adhesive power is reduced to 2.0 μ N, and the pH value is raised at 12.0 o'clock, and adhesive power is zero.Fig. 2 is that interface switch is 1.0 o'clock at pH, is example with 1,2-ethylene dichloride oil droplet, the curve of test adhesive power.Fig. 3 is interface switch at polyacrylic electrolysis constant upper and lower surface roughness and mechanism schematic diagram that the oil droplet adhesive power is undergone mutation thereof.Fig. 4 is the variation of pH responsiveness interface switch adhesive power in the different pH value aqueous solution, around changing interface switch during the pH value of solution, the adhesive power size variation of oil droplet to interface switch, and can circulation change, as shown in Figure 5, with 1,2-ethylene dichloride oil droplet is example, as rapid change pH, corresponding change and under two pH solution, the reversible cycle of interface switch adhesive power size also occur in adhesive power.Fig. 6 is the mechanism of the interface switch for preparing of the present invention, be that the pH value is during lower than polyacrylic electrolysis constant, thereby the interface becomes coarse oil droplet is produced high the adhesion, and when the pH value during higher than polyacrylic electrolysis constant, the interface smooth adhesive power to oil droplet that becomes reduces rapidly.
Stopper is removed in the vinylformic acid underpressure distillation, and the quartz plate substrate is put into plasm reaction cavity after cleaning with the vitriol oil, passes into argon gas, and the pressure of controlling reaction chamber is 50Pa, keeps 15 minutes, gets rid of the air in cavity.Then open plasma power supply, the adjustment plasma power is 50W, passes into Acrylic Acid Monomer, the vacuum tightness of adjusting reaction chamber is 120Pa, 20 minutes grafting time.Pass at last air, can obtain having the super oleophobic reversible adhesion of pH responsiveness interface switch.Oil droplet is chosen hexane, and measuring respectively interface switch is 1.0,2.4 at pH, 4.6,5.0,8.0,12.0 the time adhesive power, as shown in table 1, when pH is 1.0, adhesive power is 43.4 μ N, and the pH value is elevated at 4.6 o'clock, is reduced to 20.4 μ N, when the pH value surpassed the electrolysis constant of PAA, adhesive power sharply descended, and is 5.0 o'clock as pH, adhesive power is reduced to 5.1 μ N, and the pH value is raised at 12.0 o'clock, and adhesive power is zero.
Stopper is removed in the vinylformic acid underpressure distillation, put into plasm reaction cavity after cleaning with concentrated nitric acid at the bottom of silicon wafer-based, pass into argon gas, the pressure of controlling reaction chamber is 80Pa, keeps 20 minutes, gets rid of the air in cavity.Then open plasma power supply, the adjustment plasma power is 70W, passes into Acrylic Acid Monomer, the vacuum tightness of adjusting reaction chamber is 150Pa, 30 minutes grafting time.Pass at last air, can obtain having the super oleophobic reversible adhesion of pH responsiveness interface switch.Oil droplet is chosen chloroform, and measuring respectively interface switch is 1.0,2.4 at pH, 4.6,5.0,8.0,12.0 the time adhesive power, as shown in table 1, when pH is 1.0, adhesive power is 27.8 μ N, and the pH value is elevated at 4.6 o'clock, is reduced to 19.3 μ N, when the pH value surpassed the electrolysis constant of PAA, adhesive power sharply descended, and is 5.0 o'clock as pH, adhesive power is reduced to 5.0 μ N, and the pH value is raised at 12.0 o'clock, and adhesive power is zero.。
Stopper is removed in the vinylformic acid underpressure distillation, and the sheet mica substrate is put into plasm reaction cavity after cleaning with concentrated nitric acid, passes into argon gas, and the pressure of controlling reaction chamber is 80Pa, keeps 25 minutes, gets rid of the air in cavity.Then open plasma power supply, the adjustment plasma power is 80W, passes into Acrylic Acid Monomer, the vacuum tightness of adjusting reaction chamber is 160Pa, 40 minutes grafting time.Pass at last air, can obtain having the super oleophobic reversible adhesion of pH responsiveness interface switch.Oil droplet is chosen tetracol phenixin, and measuring respectively interface switch is 1.0,2.4 at pH, 4.6,5.0,8.0,12.0 the time adhesive power, as shown in table 1, when pH is 1.0, adhesive power is 22.3 μ N, and the pH value is elevated at 4.6 o'clock, is reduced to 18.4 μ N, when the pH value surpassed the electrolysis constant of PAA, adhesive power sharply descended, and is 5.0 o'clock as pH, adhesive power is reduced to 1.8 μ N, and the pH value is raised at 12.0 o'clock, and adhesive power is zero.
Stopper is removed in the vinylformic acid underpressure distillation, put into plasm reaction cavity after cleaning with the vitriol oil at the bottom of silicon wafer-based, pass into argon gas, the pressure of controlling reaction chamber is 100Pa, keeps 30 minutes, gets rid of the air in cavity.Then open plasma power supply, the adjustment plasma power is 100W, passes into Acrylic Acid Monomer, the vacuum tightness of adjusting reaction chamber is 200Pa, 45 minutes grafting time.Pass at last air, can obtain having the super oleophobic reversible adhesion of pH responsiveness interface switch.Oil droplet is chosen dichlorobenzene, and measuring respectively interface switch is 1.0,2.4 at pH, 4.6,5.0,8.0,12.0 the time adhesive power, as shown in table 1, when pH is 1.0, adhesive power is 25.1 μ N, and the pH value is elevated at 4.6 o'clock, is reduced to 20.8 μ N, when the pH value surpassed the electrolysis constant of PAA, adhesive power sharply descended, and is 5.0 o'clock as pH, adhesive power is reduced to 3.0 μ N, and the pH value is raised at 12.0 o'clock, and adhesive power is zero.
Table 1, interface switch is at the adhesive power of the different oil droplets of different pH solution squadron
The non-elaborated part of the present invention belongs to those skilled in the art's known technology.
Although the above is described the illustrative embodiment of the present invention; so that the technician of present technique neck understands the present invention; but should be clear; the invention is not restricted to the scope of embodiment; to those skilled in the art; as long as various variations appended claim limit and the spirit and scope of the present invention determined in, these variations are apparent, all utilize innovation and creation that the present invention conceives all at the row of protection.
Claims (6)
1. preparation method of the super oleophobic reversible adhesion of pH responsiveness interface switch under water is characterized in that performing step is as follows:
(1) stopper is removed in vinylformic acid (acrylic acid, AA) distillation;
(2) plasm reaction cavity is put in the substrate that cleans up;
(3) pass into rare gas element in plasm reaction cavity, the pressure of controlling rare gas element is 20-100Pa, and pressure hold time is 10-30 minute, fully removes air;
(4) open plasma power supply, and the plasma electric source power is controlled at 30-100W, pass into Acrylic Acid Monomer, adjust the vacuum tightness 100-200Pa of plasm reaction cavity, carry out plasma induced polymerization, grafting 10-45 minute, then air is passed into plasm reaction cavity, namely obtain polyacrylic acid (PAA) interface switch, also namely have the super oleophobic reversible adhesion of pH responsiveness interface switch; The contact angle that described super oleophobic refers to oil droplet greater than 150 ° less than 180 °; Described reversible adhesion refers to that the adhesive power between oil droplet and described interface switch passes through the regulation and control pH value control of solution on every side, and the adhesive power size is from 0 to the highest 43.4 μ N; Prepared has the super oleophobic reversible adhesion of pH responsiveness interface switch in the aqueous solution of pH value lower than the dissociation constant pKa=4.7 of PAA, oil droplet had oleophobic, high adhesion characteristics, in the aqueous solution of pH value higher than the dissociation constant pKa=4.7 of PAA, oil droplet had super oleophobic, low adhesion characteristics; Described oleophobic property refers to the oil droplet contact angle lower than 150 °, and described high adhesion characteristics refers to that adhesive power reaches as high as 43.4 μ N; Described low adhesion characteristics refers to that the adhesive power minimum is 0 μ N; Substrate comprises sheet glass, quartz plate, silicon chip or sheet mica.
2. the preparation method of the super oleophobic reversible adhesion of the responsiveness of pH under water according to claim 1 interface switch, it is characterized in that: described rare gas element is argon gas or nitrogen.
3. the preparation method of the super oleophobic reversible adhesion of the responsiveness of pH under water according to claim 1 interface switch is characterized in that: described substrate adopts the vitriol oil or nitric acid to clean up before putting into plasm reaction cavity.
4. the preparation method of the super oleophobic reversible adhesion of the responsiveness of pH under water according to claim 1 interface switch, it is characterized in that: the polyacrylic acid of described preparation (PAA) interface switch is completed in 1-2 is in second the adhesivity transformation of oil droplet in the process that the pH value changes.
5. the preparation method of the super oleophobic reversible adhesion of the responsiveness of pH under water according to claim 1 interface switch, it is characterized in that: described polyacrylic acid interface switch has reversible adhesive power to the oil droplet of different surfaces tension force, and the surface tension scope of oil droplet is 18.0-36.7mNm
-1
6. the preparation method of the super oleophobic reversible adhesion of pH responsiveness interface switch under water according to claim 1 or 5, it is characterized in that: described oil droplet is normal hexane, 1,2-ethylene dichloride, chloroform, tetrachloroethane or dichlorobenzene.
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| CN101220165A (en) * | 2007-12-21 | 2008-07-16 | 中国科学院化学研究所 | Underwater ultra-oleophobic polyalcohol membrane of bionic structure and method for producing the same |
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