CN106475075A - A kind of preparation method of Nano tube array of titanium dioxide base solid-phase micro-extraction fibre - Google Patents
A kind of preparation method of Nano tube array of titanium dioxide base solid-phase micro-extraction fibre Download PDFInfo
- Publication number
- CN106475075A CN106475075A CN201510547979.9A CN201510547979A CN106475075A CN 106475075 A CN106475075 A CN 106475075A CN 201510547979 A CN201510547979 A CN 201510547979A CN 106475075 A CN106475075 A CN 106475075A
- Authority
- CN
- China
- Prior art keywords
- titanium silk
- titanium
- silk
- ionic liquid
- extraction
- 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.)
- Pending
Links
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention provides a kind of preparation method of Nano tube array of titanium dioxide base solid-phase micro-extraction fibre, belongs to solid-phase micro-extraction fibre preparation field.The method is carried out as follows：（a）. surface cleaning is processed, and the surface of titanium silk is cleaned processing；（b）. will pass through（a）The titanium silk of step process is electrochemically reacted, and first titanium silk is carried out anodized, then again the titanium silk after oxidation processes is carried out crystallization, obtains the titanium silk that titanium oxide nanotube array structure is covered on surface；（c）.（b）The surface that step is obtained is covered and is modified polymeric ionic liquid on the titanium silk of titanium oxide nanotube array structure, so that reaching efficient selective extraction to multiple compounds of different nature.
Description
Technical field：
The present invention relates to solid-phase micro-extraction fibre preparation field, particularly to a kind of preparation method of Nano tube array of titanium dioxide base solid-phase micro-extraction fibre.
Background technology：
Nanotube-shaped TiO2 structure, it is that there is high-specific surface area, thermally-stabilised, high mechanical properties monodimension nanometer material, and surface has the Ti-OH of abundant activity, these features enable the titanium of titanium oxide nanotube array structure load very easily to pass through active surface and inorganic or organic material effect, realize more modifications；The feature of high-specific surface area makes it can be used as a kind of excellent fiber material.The titanium silk of titanium oxide nanotube array structure is prepared using the method for electrochemical anodic oxidation.
At present, conventional solid-phase micro-extraction fibre matrix is quartzy carrier, stainless steel silk carrier etc..
During realizing the present invention, inventor finds that prior art at least has problems with：
Vitreous silica fiber is brittle easily broken, and the maximum limiting factor that metal is used as SPME substrate is the modification activation that the metal surface inertia that metal chemical inertness inherently leads to is unfavorable for metal surface.Limited by above-mentioned material itself and technology, fiber manufacturing process is complicated, fiber lifetime is not high.
Content of the invention：
The purpose of the present invention aims to solve the problem that prior art is difficult to prepare the problem of the solid-phase micro-extraction fibre with tinsel as matrix, a kind of preparation method of Nano tube array of titanium dioxide base solid-phase micro-extraction fibre is provided, it is bonded upper polymeric ionic liquid on this basis, realize the high efficiency extraction to multiclass compound.
The purpose of the present invention can be achieved by the following technical measures：
The method is carried out as follows：
(a). surface cleaning is processed, and the surface of titanium silk is cleaned processing；
(b). the titanium silk through (a) step process is electrochemically reacted, first titanium silk is carried out anodized, then again the titanium silk after oxidation processes is carried out crystallization, obtain the titanium silk that titanium oxide nanotube array structure is covered on surface；
(c). cover on the surface that (b) step is obtained and modify polymeric ionic liquid on the titanium silk of titanium oxide nanotube array structure, so that efficient selective extraction is reached to multiple compounds of different nature.
The purpose of the present invention also can be achieved by the following technical measures：
Further, the cleaning treatment described in (a) step is that titanium silk carries out in acetone, ethanol, water supersound process (voltage 220V, operating frequency 40kHz, ultrasonic electrical power 300W) successively.
Further, the anodized described in (b) step is that the titanium silk of cleaned for (a) step process is fixed to DC source anode, and lower end 2～3cm is partially soaked in fluorine-containing electrolyte, in the oxidation at voltages 1～4 hour of 10～20V.
Further, described fluorine-containing electrolyte is 0.5wt%NH4F/2vol%H2O/ ethylene glycol.
Further, the crystallization temperature described in (b) step is 450～550 DEG C, and crystallization time is 1～4 hour；Titanium silk after crystallization is cooled to room temperature, is then drawn off again and uses distilled water flushing.
Further, the synthetic method of the polymeric ionic liquid described in (c) step is as follows：
The synthesis of monomer 1- vinyl -3- nonyl alcohol imidazoles bromide：Take 1- vinyl imidazole：Bromo- 1 nonyl alcohol=1 of 9-:0.8～1:1.2 molar part proportioning is dissolved in acetonitrile solvent, reacts 12～30h at 50～80 DEG C, then remove reaction dissolvent, solid content will be remained in absolute ether, repeat crystallization purifying, be dried under vacuum condition, obtain monomer 1- vinyl -3- nonyl alcohol imidazoles bromide；
The synthesis of double (3- vinyl imidazole) the butane dibromo salt of dication liquid cross-linker 1,4-：Take 1- vinyl imidazole：1,4- dibromobutane=1:1～1:2 molar part proportionings are dissolved in acetone, and at 40～50 DEG C, lucifuge is reacted 18～40 hours, then leaches precipitation, three recrystallization purifyings, obtains dication liquid cross-linker Isosorbide-5-Nitrae-bis- (3- vinyl imidazole) butane dibromo salt, 4 DEG C store for future use.
Double (3- vinyl imidazole) butane dibromo salt of monomer 1- vinyl -3- nonyl alcohol imidazoles bromide after synthesis and dication liquid cross-linker 1,4- in molar ratio 1:1 is mixed into polymeric ionic liquid.
Further, the modification described in (c) step：
The titanium silk of (b) step process is first dipped in 3- (methacryloxypropyl) propyl trimethoxy silicane solution soaking 12～24 hours, makes titanium silk surface introduce the double bond with reactivity；Then in the titanium silk immersion polymeric ionic liquid after processing, subsequently add the 1～2% of polymeric ionic liquid quality azodiisobutyronitrile, solution deoxygenation lucifuge at 50～70 DEG C is reacted 3～6 hours.
The present invention carries out anodized to high purity titanium silk first, form nano-tube array structure, and realize the hydroxylating on surface, easy modified, the activearm recycling the Ti-OH on surface loads onto the polymeric ionic liquid with certain absorption specificity, realize high efficiency, the high selectivity extraction of fiber, investigate successively and obtain the titania nanotube array solid-phase micro-extraction fibre with good adsorbent performance.
By first titanium silk being prepared titania nanotube array base SPME fibrous matrix using the method for anodized, realize activation and the high-specific surface area of fiber, increase its absorption property, have modification polymeric ionic liquid on the carrier of high-specific surface area by here, expand the extraction to multiple compounds for the fiber, reach higher extraction efficiency, realize the multiformity of target analytes, thus obtaining the solid-phase micro-extraction fibre with excellent extraction ability.
Using the preparation method of the present invention, obtained fiber has advantages below：
1) titania nanotube array due to obtaining through anodized has high-specific surface area, and adsorption area is big, therefore has stronger extraction ability to compound.
2) surface of titania nanotube array base solid-phase micro-extraction fibre has Ti-OH, and the presence of hydroxyl makes fibrous matrix be conducive to the modification to fiber for other compounds, realizes the high-performance extraction to polytype compound.
3) titanium silk has stability height, the strong feature of mechanical performance, is conducive to the enhancing of fiber lifetime.
Brief description：
For the technical scheme being illustrated more clearly that in the embodiment of the present invention, below the accompanying drawing of required use in embodiment description is briefly described, obviously, drawings in the following description are only some embodiments of the present invention, for those of ordinary skill in the art, on the premise of not paying creative work, can also obtain other accompanying drawings according to these accompanying drawings.
Fig. 1 is poly provided in an embodiment of the present invention [C9OHVIm] Br/ (VIM) 2C4] 2 [Br] modify NAAT preparation process schematic diagram；Wherein, the composite diagram of (a)-ionic liquid monomer, the preparation figure of (b)=Ionic Liquid Modified NAAT-SPME；
Fig. 2 is anodized titanium silk scanning electron microscope surface topography map provided in an embodiment of the present invention；Wherein (a) × 500, (b) × 5000, (c) × 30000, (d) × 500；
Fig. 3 is poly provided in an embodiment of the present invention [C9OHVIm] Br/ (VIM) 2C4] 2 [Br] modify NAAT fiber scanning electron microscope phenogram；The surface topography of wherein (a-b) PILs/NAAT-SPME fiber, the NAAT fiber surface morphology of (c) no PILs, (d) only has titanium silk surface topography of PILs；
The study on the stability of Fig. 4 fiber.
The present invention carries out parameter characterization to the titania nanotube array base solid-phase micro-extraction fibre sampling of preparation.
The method characterizing and result are as follows.
The sign of scanning electron microscope：The JSM-6701F type scanning electron microscope that is formed by of titania nanotube array covers the titanium silk of titanium oxide nanotube array structure and carries out morphology characterization (Fig. 2) to the surface of anodising.The nano-tube array structure of titanium oxide as we can see from the figure.Fig. 3 is the SEM phenogram of PILs/NAAT SPME fiber.Homogeneous coating is formed in fiber surface by the visible PILs of a.B, c, d are respectively the surface topography of tri- kinds of fibers of PILs/NAAT, NAAT, PILs under identical amplification, NAAT (c) rough surface has higher specific surface area, and titanium silk after the presence of visible NAAT makes in-situ polymerization ILs compared with d for the b still has coarse surface.A is pattern under more high-amplification-factor for the b it can be seen that PILs is aggregated in fiber surface with nanometer agglomerate.The coating layer thickness of PILs/NAAT fiber is about 3 μm.
Nuclear magnetic resonance, NMR characterizes：The synthesis of ionic liquid monomer and coupling agent is characterized using the UNITY INOVA-400MHz nuclear magnetic resonance analyser of U.S. Varian.1- vinyl -3- nonyl alcohol imidazoles bromide：1H NMR(DMSO-d6,400MHz):δ 9.674 (s, 1H), 8.262 (s, 1H), 7.985 (s, 1H), 7.294 7.355 (q, 1H), 5.972 6.011 (d, 1H), 5.390 5.412 (d, 1H), 4.183 4.219 (t, 2H), 3.323 3.355 (t, 2H), 1.806 1.822 (t, 2H), 1.353 1.367 (t, 2H), 1.225 (m, 11H). (IT-MS) m/z [VHIM+]=237.3amu.Double (3- vinyl imidazole) the butane dibromo salt of dication ionic liquid cross-linking agent -1,4-：1H NMR(DMSO-d6,400MHz):δ 9.694 (t, 1H), 8.1261 (t, 1H), 7.997 (t, 1H), 7.239 7.439 (q, 1H), 5.922 6.050 (q, 1H), 5.351 5.475 (q, 1H), 4.175 4.352 (t, 2H), 1.748 1.924 (t, 2H). (IT-MS) m/z [C2 (VIM)+]=122.3amu, m/z [C4 (VIM) 22+]=243.1amu, m/z [C4 (VIM) 2Br+]=323.1amu.
The present invention carries out extraction ability investigation to the titania nanotube array solid-phase micro-extraction fibre sampling of preparation.
The method investigated and result are as follows.
The solid-phase micro-extraction fibre of preparation is combined with gas chromatogram, realizes the investigation to its performance, and the analysis to actual sample.
Before the use need in gas chromatographic sample introduction device and at a suitable temperature aging 6h by the titania nanotube array solid-phase micro-extraction fibre of preparation.All of extraction experiments are carried out all in the tool plug glass container of 25mL by the way of direct extraction or headspace extraction.Aromatic hydrocarbon, n-alkane, phenols, aminated compoundss storing solution are prepared by ethanol, and aromatic hydrocarbon concentration is 0.2mg mL-1, and remaining stock sample solution concentration is 1mg mL-1.Working solution adopts distilled water diluting storing solution to prepare, and the volume of working solution is 20mL.Accelerate to extract by the way of electromagnetic agitation, after stir speed (S.S.) is optimized, be fixed on a suitable value.During extraction, fiber is released 2cm in protection pipe immersion solution, after the completion of extraction, fiber is received to protection pipe, removes extraction flask, be then placed in carrying out at gas chromatographic sample introduction mouth being desorbed and follow-up analysis.
The investigation of stability：The titania nanotube array solid-phase micro-extraction fibre of preparation is separately immersed in each 12h in ethanol (polar solvent), normal hexane (non-polar solven), 0.1M NaOH and 0.1M HCl solution, then the extraction ability before and after it being soaked carries out test and comparison, investigates its stability in organic solvent and soda acid.The fiber of Fig. 4 display preparation no obvious effect of extracting difference before and after soaking, illustrates that the fiber of this preparation not only has fine resistance to acids and bases, and also has preferable stability in organic solvent.
After having investigated the stability of fiber, various analytes are carried out with the investigation (extraction conditionss and desorption conditions are optimized) of system, extraction time, extraction temperature, the ionic strength of working solution and desorption temperature and time etc. are all impact extraction efficiencies, needs are optimized experiment, at optimum conditions various compounds are extracted, realize the investigation to titania nanotube array fibre abstraction.
The explanation that the investigation of the parameter characterization of above solid-phase micro-extraction fibre and extraction ability is carried out with the titania nanotube array fiber sampling prepared, only illustrates as example, is not intended to limit invention.
It is as shown in table 1 that fiber parameters of the present invention characterize, extraction ability investigates article used.
Table 1
Specific embodiment：
Embodiment 1：
The preparation method of this Nano tube array of titanium dioxide base solid-phase micro-extraction fibre is carried out as follows：
Step 100, carries out pre-treatment to titanium silk, titanium silk is carried out successively in acetone, ethanol, water supersound process (voltage 220V, operating frequency 40kHz, ultrasonic electrical power 300W), cleans its surface；
Step 101, titanium silk through (a) step process is electrochemically reacted, anodic oxidation is carried out to the titanium silk of cleaning, after drying at room temperature, the titanium silk of cleaning is fixed to DC source anode, lower end about 2cm part is dipped in fluorine-containing electrolyte (0.5wt%NH4F/2vol%H2O/ ethylene glycol), in the oxidation at voltages 1h of 20V；
Step 102, carries out Crystallizing treatment, after oxidation terminates, by titanium silk in 450 DEG C of Crystallizing treatment 4h, after being cooled to room temperature, is drawn off and uses distilled water flushing, obtain the titanium silk that titanium oxide nanotube array structure is covered on surface to titanium silk；
Step 200, covers in the surface that step 102 is obtained and modifies polymeric ionic liquid on the titanium silk of titanium oxide nanotube array structure；
Step 201, the synthetic method of polymeric ionic liquid is as follows：
The synthesis of monomer 1- vinyl -3- nonyl alcohol imidazoles bromide ([C9OHVIm] Br)：Take 1- vinyl imidazole：Bromo- 1 nonyl alcohol=1 of 9-:0.8 molar part proportioning is dissolved in acetonitrile solvent, reacts 12h, then remove reaction dissolvent, will remain solid content and repeat crystallization purifying in absolute ether at 80 DEG C, is dried, obtains monomer 1- vinyl -3- nonyl alcohol imidazoles bromide under vacuum condition；
The synthesis of double (3- vinyl imidazole) the butane dibromo salt ([(VIM) 2C4] 2 [Br]) of dication liquid cross-linker 1,4-：Take 1- vinyl imidazole：1,4- dibromobutane=1:1 molar part proportioning is dissolved in acetone, and at 50 DEG C, lucifuge is reacted 18 hours, then leaches precipitation, three recrystallization purifyings, obtains dication liquid cross-linker Isosorbide-5-Nitrae-bis- (3- vinyl imidazole) butane dibromo salt；
Double (3- vinyl imidazole) butane dibromo salt of monomer 1- vinyl -3- nonyl alcohol imidazoles bromide after synthesis and dication liquid cross-linker 1,4- in molar ratio 1:1 is mixed into polymeric ionic liquid.
Step 300, the titanium silk of (b) step process is first dipped into 3- (methacryloxypropyl) propyl trimethoxy silicane solution (by 80% first alcohol and water by volume 95:5 preparations) in soak 12 hours, so that titanium silk surface is introduced and there is the double bond of reactivity；Then in the titanium silk immersion polymeric ionic liquid after processing, subsequently add the 1～2% of polymeric ionic liquid quality azodiisobutyronitrile, solution deoxygenation lucifuge at 70 DEG C is reacted 3 hours.
Embodiment 2：
The preparation method of this Nano tube array of titanium dioxide base solid-phase micro-extraction fibre is carried out as follows：
Step 100, carries out pre-treatment to titanium silk, titanium silk is carried out successively in acetone, ethanol, water supersound process (voltage 220V, operating frequency 40kHz, ultrasonic electrical power 300W), cleans its surface；
Step 101, titanium silk through (a) step process is electrochemically reacted, anodic oxidation is carried out to the titanium silk of cleaning, after drying at room temperature, the titanium silk of cleaning is fixed to DC source anode, lower end about 3cm part is dipped in fluorine-containing electrolyte (0.5wt%NH4F/2vol%H2O/ ethylene glycol), in the oxidation at voltages 4h of 10V；
Step 102, carries out Crystallizing treatment, after oxidation terminates, by titanium silk in 550 DEG C of Crystallizing treatment 1h, after being cooled to room temperature, is drawn off and uses distilled water flushing, obtain the titanium silk that titanium oxide nanotube array structure is covered on surface to titanium silk；
Step 200, covers in the surface that step 102 is obtained and modifies polymeric ionic liquid on the titanium silk of titanium oxide nanotube array structure；
Step 201, the synthetic method of polymeric ionic liquid is as follows：
The synthesis of monomer 1- vinyl -3- nonyl alcohol imidazoles bromide ([C9OHVIm] Br)：Take 1- vinyl imidazole：Bromo- 1 nonyl alcohol=1 of 9-:1.2 molar part proportionings are dissolved in acetonitrile solvent, react 30h, then remove reaction dissolvent, will remain solid content and repeat crystallization purifying in absolute ether at 50 DEG C, be dried, obtain monomer 1- vinyl -3- nonyl alcohol imidazoles bromide under vacuum condition；
The synthesis of double (3- vinyl imidazole) the butane dibromo salt ([(VIM) 2C4] 2 [Br]) of dication liquid cross-linker 1,4-：Take 1- vinyl imidazole：1,4- dibromobutane=1:2 molar part proportionings are dissolved in acetone, and at 40 DEG C, lucifuge is reacted 40 hours, then leaches precipitation, three recrystallization purifyings, obtains dication liquid cross-linker Isosorbide-5-Nitrae-bis- (3- vinyl imidazole) butane dibromo salt；
Double (3- vinyl imidazole) butane dibromo salt of monomer 1- vinyl -3- nonyl alcohol imidazoles bromide after synthesis and dication liquid cross-linker 1,4- in molar ratio 1:1 is mixed into polymeric ionic liquid.
Step 300, the titanium silk of (b) step process is first dipped into 3- (methacryloxypropyl) propyl trimethoxy silicane solution (by 80% first alcohol and water by volume 95:5 preparations) in soak 24 hours, so that titanium silk surface is introduced and there is the double bond of reactivity；Then in the titanium silk immersion polymeric ionic liquid after processing, subsequently add the 1～2% of polymeric ionic liquid quality azodiisobutyronitrile, solution deoxygenation lucifuge at 50 DEG C is reacted 6 hours.
Embodiment 3：
The preparation method of this Nano tube array of titanium dioxide base solid-phase micro-extraction fibre is carried out as follows：
Step 100, carries out pre-treatment to titanium silk, titanium silk is carried out successively in acetone, ethanol, water supersound process (voltage 220V, operating frequency 40kHz, ultrasonic electrical power 300W), cleans its surface；
Step 101, titanium silk through (a) step process is electrochemically reacted, anodic oxidation is carried out to the titanium silk of cleaning, after drying at room temperature, the titanium silk of cleaning is fixed to DC source anode, lower end about 2.5cm part is dipped in fluorine-containing electrolyte (0.5wt%NH4F/2vol%H2O/ ethylene glycol), in the oxidation at voltages 2h of 15V；
Step 102, carries out Crystallizing treatment, after oxidation terminates, by titanium silk in 500 DEG C of Crystallizing treatment 2h, after being cooled to room temperature, is drawn off and uses distilled water flushing, obtain the titanium silk that titanium oxide nanotube array structure is covered on surface to titanium silk；
Step 200, covers in the surface that step 102 is obtained and modifies polymeric ionic liquid on the titanium silk of titanium oxide nanotube array structure；
Step 201, the synthetic method of polymeric ionic liquid is as follows：
The synthesis of monomer 1- vinyl -3- nonyl alcohol imidazoles bromide ([C9OHVIm] Br)：Take 1- vinyl imidazole：Bromo- 1 nonyl alcohol=1 of 9-:1 molar part proportioning is dissolved in acetonitrile solvent, reacts 20h, then remove reaction dissolvent, will remain solid content and repeat crystallization purifying in absolute ether at 65 DEG C, is dried, obtains monomer 1- vinyl -3- nonyl alcohol imidazoles bromide under vacuum condition；
The synthesis of double (3- vinyl imidazole) the butane dibromo salt ([(VIM) 2C4] 2 [Br]) of dication liquid cross-linker 1,4-：Take 1- vinyl imidazole：1,4- dibromobutane=1:1.5 molar part proportionings are dissolved in acetone, and at 45 DEG C, lucifuge is reacted 30 hours, then leaches precipitation, three recrystallization purifyings, obtains dication liquid cross-linker Isosorbide-5-Nitrae-bis- (3- vinyl imidazole) butane dibromo salt；
Double (3- vinyl imidazole) butane dibromo salt of monomer 1- vinyl -3- nonyl alcohol imidazoles bromide after synthesis and dication liquid cross-linker 1,4- in molar ratio 1:1 is mixed into polymeric ionic liquid.
Step 300, the titanium silk of (b) step process is first dipped into 3- (methacryloxypropyl) propyl trimethoxy silicane solution (by 80% first alcohol and water by volume 95:5 preparations) in soak 18 hours, so that titanium silk surface is introduced and there is the double bond of reactivity；Then in the titanium silk immersion polymeric ionic liquid after processing, subsequently add the 1.5% of polymeric ionic liquid quality azodiisobutyronitrile, solution deoxygenation lucifuge at 60 DEG C is reacted 4 hours.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all within the spirit and principles in the present invention, any modification, equivalent substitution and improvement made etc., should be included within the scope of the present invention.
Claims (7)
1. a kind of preparation method of Nano tube array of titanium dioxide base solid-phase micro-extraction fibre is it is characterised in that the method presses following walking
Suddenly carry out：
(a). surface cleaning is processed, and the surface of titanium silk is cleaned processing；
(b). the titanium silk through (a) step process is electrochemically reacted, first titanium silk is carried out anodized, so
Again the titanium silk after oxidation processes is carried out crystallization afterwards, obtain the titanium silk that titanium oxide nanotube array structure is covered on surface；
(c). cover on the surface that (b) step is obtained and polymeric ionic liquid is modified on the titanium silk of titanium oxide nanotube array structure, with
Reach efficient selective extraction as multiple compounds of different nature.
2. method according to claim 1 is it is characterised in that the cleaning treatment described in (a) step is successively in third by titanium silk
Carry out supersound process in ketone, ethanol, water.
3. method according to claim 1 is it is characterised in that the anodized described in (b) step is by (a) step
The titanium silk of cleaned process is fixed to DC source anode, and lower end 2～3cm is partially soaked in fluorine-containing electrolyte, 10～
The oxidation at voltages of 20V 1～4 hour.
4. method according to claim 3 is it is characterised in that described fluorine-containing electrolyte is 0.5wt%NH4F/2vol%H2O/
Ethylene glycol.
5. method according to claim 1 is it is characterised in that crystallization temperature described in (b) step is 450～550 DEG C,
Crystallization time is 1～4 hour；Titanium silk after crystallization is cooled to room temperature, is then drawn off again and uses distilled water flushing.
6. method according to claim 1 is it is characterised in that the synthetic method of polymeric ionic liquid described in (c) step
As follows：
The synthesis of monomer 1- vinyl -3- nonyl alcohol imidazoles bromide：Take 1- vinyl imidazole：Bromo- 1 nonyl alcohol=1 of 9-:0.8～1:1.2
Molar part proportioning is dissolved in acetonitrile solvent, reacts 12～30h, then remove reaction dissolvent at 50～80 DEG C, will be residual
Stay solid content to repeat crystallization purifying in absolute ether, be dried under vacuum condition, obtain monomer 1- vinyl -3- nonyl alcohol imidazoles bromine
Salt；
The synthesis of double (3- vinyl imidazole) the butane dibromo salt of dication liquid cross-linker 1,4-：Take 1- vinyl imidazole：1,4-
Dibromobutane=1:1～1:2 molar part proportionings are dissolved in acetone, lucifuge reaction 18～40 hours at 40～50 DEG C, so
Afterwards precipitation is leached, three recrystallization purifyings, obtain dication liquid cross-linker Isosorbide-5-Nitrae-bis- (3- vinyl imidazole) butane two
Bromide.
Monomer 1- vinyl -3- nonyl alcohol imidazoles bromide after synthesis and dication liquid cross-linker 1,4- are double (3- vinyl imidazole)
Butane dibromo salt in molar ratio 1:1 is mixed into polymeric ionic liquid.
7. method according to claim 1 is it is characterised in that modification described in (c) step：
By the titanium silk of (b) step process be first dipped in 3- (methacryloxypropyl) propyl trimethoxy silicane solution soak 12～
24 hours, titanium silk surface is made to introduce the double bond with reactivity；Then the titanium silk immersion polymeric ionic liquid after processing
In, subsequently add the 1～2% of polymeric ionic liquid quality azodiisobutyronitrile, solution deoxygenation keeps away at 50～70 DEG C
Photoreaction 3～6 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510547979.9A CN106475075A (en) | 2015-08-31 | 2015-08-31 | A kind of preparation method of Nano tube array of titanium dioxide base solid-phase micro-extraction fibre |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510547979.9A CN106475075A (en) | 2015-08-31 | 2015-08-31 | A kind of preparation method of Nano tube array of titanium dioxide base solid-phase micro-extraction fibre |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106475075A true CN106475075A (en) | 2017-03-08 |
Family
ID=58236033
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510547979.9A Pending CN106475075A (en) | 2015-08-31 | 2015-08-31 | A kind of preparation method of Nano tube array of titanium dioxide base solid-phase micro-extraction fibre |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106475075A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109173983A (en) * | 2018-08-07 | 2019-01-11 | 济南大学 | A method of hybridization of ionic liquid aerosil coating solid phase micro-extraction fiber is prepared in situ |
| CN110327897A (en) * | 2019-06-28 | 2019-10-15 | 桂林理工大学 | A kind of titanate radical nanopipe SPME coating and the preparation method and application thereof |
| CN110735170A (en) * | 2019-10-23 | 2020-01-31 | 西北师范大学 | Preparation method of titanium dioxide nano thorn-shaped array fiber coatings |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103028382A (en) * | 2011-10-09 | 2013-04-10 | 中国科学院生态环境研究中心 | Method for preparing solid-phase microextraction fiber from chemical bonded stationary aggregate ion liquid coating |
-
2015
- 2015-08-31 CN CN201510547979.9A patent/CN106475075A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103028382A (en) * | 2011-10-09 | 2013-04-10 | 中国科学院生态环境研究中心 | Method for preparing solid-phase microextraction fiber from chemical bonded stationary aggregate ion liquid coating |
Non-Patent Citations (1)
| Title |
|---|
| JING JIA等: "Nanoporous array anodic titanium-supported co-polymeric ionicliquids as high performance solid-phase microextraction sorbents for hydrogen bonding compounds", 《JOURNAL OF CHROMATOGRAPHY A》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109173983A (en) * | 2018-08-07 | 2019-01-11 | 济南大学 | A method of hybridization of ionic liquid aerosil coating solid phase micro-extraction fiber is prepared in situ |
| CN110327897A (en) * | 2019-06-28 | 2019-10-15 | 桂林理工大学 | A kind of titanate radical nanopipe SPME coating and the preparation method and application thereof |
| CN110735170A (en) * | 2019-10-23 | 2020-01-31 | 西北师范大学 | Preparation method of titanium dioxide nano thorn-shaped array fiber coatings |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Mondal et al. | Novel quaternized aromatic amine based hybrid PVA membranes for acid recovery | |
| WO2022041852A1 (en) | Ni-mof thin-film photocatalyst grown in-situ on foamed nickel surface, preparation method therefor, and use thereof | |
| CN106693444A (en) | Preparing method of reproducible super-hydrophobic graphite alkenyl oil absorption sponge | |
| CN105013340A (en) | Preparation method for novel carbon-nanotube-doped composite membrane with double selective layers | |
| CN104868079B (en) | Method for preparing high invasive lithium ion battery diaphragm | |
| CN106475075A (en) | A kind of preparation method of Nano tube array of titanium dioxide base solid-phase micro-extraction fibre | |
| CN107551999A (en) | The preparation method of activated carbon fiber-loaded ordered mesoporous silicon dioxide composite material | |
| Bakangura et al. | Hierarchically structured porous anion exchange membranes containing zwetterionic pores for ion separation | |
| CN101538034B (en) | Preparation method of one-step synthesis carbon ball | |
| CN108997599A (en) | High-intensitive binary is crosslinked alkaline negative ion exchange composite film, preparation method and application | |
| CN109289531A (en) | A kind of preparation method of the dimethyl silicone polymer for organic solvent nanofiltration/meso-porous nano silicon composite membrane | |
| Du et al. | Template-directed fabrication of zeolitic imidazolate framework-67-derived coating materials on nickel/titanium alloy fiber substrate for selective solid-phase microextraction | |
| CN103726233B (en) | A kind of preparation method of poly(isophthaloyl metaphenylene diamine)-polyacrylonitrile composite nanofiber membrane and application thereof | |
| CN108649257B (en) | High-temperature proton exchange membrane and preparation method thereof | |
| CN107658478B (en) | All-vanadium redox flow battery diaphragm and preparation method thereof | |
| CN106283894A (en) | A kind of graphene oxide modification filter paper and preparation method and application | |
| Wang et al. | Egg yolk/ZIF-8/CLPAA composite aerogel: Preparation, characterization and adsorption properties for organic dyes | |
| CN109818024B (en) | Composite proton exchange membrane and preparation method thereof | |
| CN109161927B (en) | It is a kind of using porous anode membrane as Bipolar Membrane of substrate and preparation method thereof | |
| CN113402725B (en) | Preparation method and application of heteropoly acid modified metal organic framework compound | |
| CN103203187A (en) | A preparation method for solid film dip-coated with a novel chiral recognition agent | |
| CN104091936B (en) | A kind of MoS2nanometer watt/graphene composite nano material and preparation method thereof | |
| CN103833943B (en) | A kind of preparation method of proton conductor based on grafting titania nanotube polyelectrolyte brush | |
| CN104950034B (en) | Open tubular capillary column with nano-crystalline cellulose derivative modified surface and application of open tubular capillary column with nano-crystalline cellulose derivative modified surface | |
| CN110694599A (en) | Preparation method of polypropylene imine modified magnetic nanocrystalline cellulose molecularly imprinted polymer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170308 |
|
| RJ01 | Rejection of invention patent application after publication |