CN102600816B - Preparation method of solid-phase microextraction fibers by bonding metal wire with polyion liquid - Google Patents
Preparation method of solid-phase microextraction fibers by bonding metal wire with polyion liquid Download PDFInfo
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Abstract
The invention discloses a method for preparing solid-phase microextraction fibers with a polyion liquid bonding coating on a metal wire carrier, particularly relates to a preparation method by utilizing a surface-initiated atom transfer radical polymerization reaction to graft an ionic liquid on the metal wire in a situ polymerizing manner. The novel method is characterized in that the method comprises the steps of adopting the metal wire as the carrier, performing chemical silvering on the surface of the metal wire firstly, then performing hydroxylation on the silvered layer, bonding an atom transfer radical polymerization initiation site, and preparing the polyion liquid bonding coating on the surface of the metal wire with the ionic liquid containing alkenyl as a monomer by utilizing the surface-initiated atom transfer radical polymerization technology. The solid-phase microextraction fibers prepared by the preparation method disclosed by the invention have the advantages of high mechanical strength, good coating stability, good extraction property and the like, can be used for enrichment analysis of trace components of samples of food, environment, drugs and biochemistry and the like, and are very good in application potential.
Description
Technical field
The present invention relates to a kind of technology of preparing the solid-phase micro-extraction fibre of poly ion liquid bonding coating in wire carrier.
Background technology
SPME (SPME) is centralized procurement sample, enrichment, purifying that last century, the nineties grew up, resolves the novel Sample Pretreatment Technique in one, have easy, quick, sensitive, be convenient to the advantages such as automation and Instrument crosslinking, in fields such as environment, food, medicine and bioanalysis, be applied widely.Conventionally the SPME of indication refers to fiber solid phase micro-extraction, and core is the preparation of extracting fiber.The stability of extracting fiber and extraction ability depend on carrier and extraction coating.Quartz is the common carrier of preparing solid-phase micro-extraction fibre, and quartzy mechanical performance is poor, very easily occurs fracture in operating process, has had a strong impact on the service life of extracting fiber.In order to improve the mechanical strength of solid-phase micro-extraction fibre, people begin one's study wire as carrier, prepare the solid-phase micro-extraction fibre of the carriers such as some titanium silks, nickel wire, stainless steel wire, although can improve mechanical strength, but metal surface is difficult for carrying out modification, has limited applied metal silk carrier and prepared solid-phase micro-extraction fibre.
The nano material of metal can form stable firmly decorative layer by metallic bond and the metal surface with advantages such as mechanical strength are high and cheap.The chemical stability of noble metal (gold, silver, copper etc.) is good, and can form stable covalent bond (as Au-S, Ag-S) with sulfydryl, organic molecule with sulfydryl can form self assembly molecule layer at precious metal surface, mercapto-functionalized material also can be bonded to precious metal surface, reaction easily occurs, and under normal temperature, just can carry out.By the nanometer-material-modified wire surface of noble metal, then by the method for chemical bonding, the functional coating bonding with sulfydryl is got on, can obtain wire carrier bonding coating solid phase micro-extraction fiber.Electroless plating technology is by controlled redox reaction, metal ion is reduced into metal simple-substance and is deposited on the method that various material surfaces form close coatings, has coating densification, the feature such as even, easy to control.This technology can form the coat of metal of nanometer or micrometer structure in metal surface, not only can increase surface area, and the metallic bond between coating and substrate makes coating very firm.By means of electroless plating technology, in wire surface, can form firmly precious metal plating, and micron or the nanostructured of coating increase surface area greatly, prepare the wire that coating is firm and surface area is large, be beneficial to chemical modification preparation extraction coating.
Ionic liquid has unique physicochemical properties, as low in fusing point, liquid temperature wide ranges, steam force down, Heat stability is good, dissolving and extraction ability excellence etc., have been applied to the various aspects of the analytical chemistry such as gas-chromatography, liquid chromatogram, Capillary Electrophoresis, micro-extraction.There are some researches show that ionic liquid is a kind of SPME coating of extraction ability excellence, can efficiently extract condensed ring class, phenols, amine, dimethylbenzene, long chain alkane, fatty acid methyl ester, phthalic acid ester, ethers etc.Initial research is to utilize the ionic liquid of free state as applying coating, because the loss of ionic liquid causes that sensitivity is low, poor reproducibility etc.Reported afterwards that polymeric ionic liquid physics applied quartzy carrier and prepares solid-phase micro-extraction fibre, heat endurance, reappearance etc. have been improved to a certain extent, but owing to there is no chemical bonding between coating and carrier, can not fundamentally eliminate the loss of ionic liquid coating.There is subsequently ionic liquid bonding quartz fibre, can overcome coating runs off, but quartzy carrier is easily broken, had a strong impact on the service life of extracting fiber, and the low loading capacity that makes of the monomolecular bonded amount of ionic liquid is little, and the bonded amount of poly ion liquid is difficult to effective control, make to prepare poor reproducibility.Want to obtain high performance ionic liquid coating SPME fiber, must study a kind of novel preparation method, make polymeric ionic liquid controllably be bonded to stainless steel wire surface.ATRP (ATRP) is a kind of novel polymeric technology that development in recent years is got up, and can realize the effective control to polymerisation, can obtain the extremely narrow polymer of molecular weight distribution, can also easily obtain surface of solids graft copolymer.By means of ATRP method, can prepare even thickness, the controlled polymeric ionic liquid extraction coating of bonded amount at carrier surface.
Summary of the invention
The object of the present invention is to provide a kind of technology of preparing poly ion liquid bonding coating solid phase micro-extraction fiber in wire carrier.The present invention is based on surperficial Atom Transfer Radical Polymerization reaction ionic liquid in-situ polymerization is grafted to wire surface, obtain bonding type poly ion liquid extract layer, preparation process is specific as follows:
A. the chemical silvering of wire surface
Wire is rinsed and removes surperficial oxide layer with sulfuric acid, and increase surperficial roughness.Wire after processing is put into chemical silvering solution and soak certain hour, on its surface, form silvering.
B. the bonding of ATRP priming site
First the silvering of wire surface is carried out to hydroxylating, then atom transition free radical polymerization reaction is caused to reagent and be bonded on hydroxylated wire.
C. the preparation of poly ion liquid bonding coating
Utilization is polymerization single polymerization monomer with the ionic liquid functional molecular of thiazolinyl, by surperficial Atom Transfer Radical Polymerization, reacts, and in wire surface, prepares poly ion liquid bonding coating.
It is stainless steel wire, iron wire, titanium silk, nickel wire etc. that the present invention adopts wire in the chemical silvering of wire surface.
The present invention's chemical silvering solution in the chemical silvering of wire surface is the mixed solution of silver ammino solution and glucose solution, the mol ratio of silver ammonium ion and glucose is 1: 0.5-3, the mass concentration of glucose is 5-30%, the time that wire is immersed in chemical silvering solution is 0.2-2 hour, and reaction temperature is room temperature.
The present invention adopts mercapto propyl silane reagent, at the molecular self-assembling on silvering surface, it is carried out to silanization in the bonding of ATRP priming site, hydrolysis makes silvering surface hydroxylation again, mercapto propyl silane reagent is mercapto propyl group front three (second) TMOS, volumetric concentration is 1-10%, under room temperature, the silane reagent self assembly time is 1-24 hour, and under room temperature, hydrolysis time is 1-6 hour.
The present invention adopts in the bonding of ATRP priming site that to cause reagent be the amide product that aminopropyl front three (second) TMOS and 2-bromine isobutyryl bromine reaction make, and the ratio of both amounts is 1: 1, reacts 2-12 hour at 0 ℃.
It is 5-10% that the present invention adopts the mass concentration that causes reagent in the bonding of ATRP priming site, and the reaction time is 6-12 hour at 110 ℃.
It is polymerization single polymerization monomer that the present invention adopts the ionic liquid with thiazolinyl in the preparation of poly ion liquid bonding coating.
The present invention adopts CuBr and CuBr in the preparation of poly ion liquid bonding coating
2for catalyst, 2,2 '-bipyridyl is part, CuBr, CuBr
2, 2, the ratio of the amount of 2 '-bipyridyl, ionic liquid monomer is 1: 1: 2-4: 20-50, with high pure nitrogen or argon gas, carry out noble gas protection, reaction temperature is 30-140 ℃, the reaction time is 6-48h.
The present invention adopts wire surface bonding poly ion liquid coating solid phase micro-extraction fiber prepared by surperficial Atom Transfer Radical Polymerization technology to have the following advantages:
(1) wire can improve the frangible shortcoming of quartz fibre effectively as fiber carrier, has improved the mechanical strength of micro-extraction fabric, has extended its service life.
(2) ionic liquid bonding type coating has effectively improved the stability of extraction coating, has expanded its range of application.
(3) adopt surperficial Atom Transfer Radical Polymerization technology, effectively controlled polymeric ionic liquid coating layer thickness and preparation repeatability.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of preparing that atom transition free radical polymerization reaction causes reagent.
Fig. 2 is the reaction schematic diagram of stainless steel wire surface bond atom transition free radical polymerization reaction priming site.
Fig. 3 is the schematic diagram that poly ion liquid bonding coating is prepared on stainless steel wire surface.
The specific embodiment
In order to understand better the present invention, by example, describe:
Embodiment 1: the preparation of poly ion liquid bonding stainless steel wire solid-phase micro-extraction fibre
Comprise successively following A, B, tri-steps of C:
A. the chemical silvering on stainless steel wire surface
By stainless steel wire surface, with after fine sandpaper polishing, water, ethanol clean successively, remove surperficial impurity and increase surface area.The mixed solution of stainless steel wire after processing being put into silver ammino solution and glucose solution, the mol ratio of silver-colored ammonium ion and glucose is 1: 0.5, the mass concentration of glucose is 30%, reacts 2 hours under room temperature.
B. the bonding of ATRP priming site
The aminopropyl trimethoxysilane that the ratio of amount is 1: 1 is reacted 2 hours with 2-bromine isobutyl acylbromide at 0 ℃, makes ATRP and causes reagent (seeing Fig. 1).Silver-plated stainless steel wire is placed in to the ethanolic solution that volumetric concentration is 1% mercaptopropyl trimethoxysilane, under room temperature, soaks 24 hours, take out with after alcohol flushing, be placed in and under water room temperature, be hydrolyzed 6 hours and make its hydroxylating.Hydroxylated stainless steel wire is placed in to the toluene solution that mass concentration is 5% initiation reagent, reacts 12 hours (seeing Fig. 2) at 110 ℃.
C. the preparation of poly ion liquid bonding coating
1-vinyl-3-propyl imidazole two (trifluoro sulphonyl) imines ion liquid of take is polymerization single polymerization monomer, with CuBr and CuBr
2for catalyst, 2,2 '-bipyridyl is part, CuBr, CuBr
2, 2, the ratio of the amount of 2 '-bipyridyl, ionic liquid monomer is 1: 1: 2: 20, with high pure nitrogen or argon gas, carry out noble gas protection, reaction temperature is 140 ℃, the reaction time is 48 hours (seeing Fig. 3).
Embodiment 2: the preparation of poly ion liquid bonding titanium silk solid-phase micro-extraction fibre
Comprise successively following A, B, tri-steps of C:
A. the chemical silvering on titanium silk surface
By titanium silk surface, with after fine sandpaper polishing, water, ethanol clean successively, remove surperficial impurity and increase surface area.The mixed solution of titanium silk after processing being put into silver ammino solution and glucose solution, the mol ratio of silver-colored ammonium ion and glucose is 1: 3, the mass concentration of glucose is 5%, reacts 1 hour under room temperature.
B. the bonding of ATRP priming site
The aminopropyl trimethoxysilane that the ratio of amount is 1: 1 is reacted 12 hours with 2-bromine isobutyl acylbromide at 0 ℃, makes ATRP and causes reagent.Silver-plated stainless steel wire is placed in to the ethanolic solution that volumetric concentration is 10% mercaptopropyl trimethoxysilane, under room temperature, soaks 1 hour, take out with after alcohol flushing, be placed in and under water room temperature, be hydrolyzed 1 hour and make its hydroxylating.Hydroxylated stainless steel wire is placed in to the toluene solution that mass concentration is 10% initiation reagent, reacts 6 hours at 110 ℃.
C. the preparation of poly ion liquid bonding coating
1-vinyl-3-ethyl imidazol(e) hexafluorophosphoricacid acid ions liquid of take is polymerization single polymerization monomer, with CuBr and CuBr
2for catalyst, 2,2 '-bipyridyl is part, CuBr, CuBr
2, 2, the ratio of the amount of 2 '-bipyridyl, ionic liquid monomer is 1: 1: 4: 50, with high pure nitrogen or argon gas, carry out noble gas protection, reaction temperature is 80 ℃, the reaction time is 6 hours.
Embodiment 3: the preparation of poly ion liquid bonding nickel wire solid-phase micro-extraction fibre
Comprise successively following A, B, tri-steps of C:
A. the chemical silvering on nickel wire surface
By nickel wire surface, with after fine sandpaper polishing, water, ethanol clean successively, remove surperficial impurity and increase surface area.The mixed solution of nickel wire after processing being put into silver ammino solution and glucose solution, the mol ratio of silver-colored ammonium ion and glucose is 1: 2, the mass concentration of glucose is 15%, reacts 0.5 hour under room temperature.
B. the bonding of ATRP priming site
The aminopropyl trimethoxysilane that the ratio of amount is 1: 1 is reacted 6 hours with 2-bromine isobutyl acylbromide at 0 ℃, makes ATRP and causes reagent.Silver-plated stainless steel wire is placed in to the ethanolic solution that volumetric concentration is 5% mercaptopropyl trimethoxysilane, under room temperature, soaks 6 hours, take out with after alcohol flushing, be placed in and under water room temperature, be hydrolyzed 3 hours and make its hydroxylating.Hydroxylated stainless steel wire is placed in to the toluene solution that mass concentration is 8% initiation reagent, reacts 9 hours at 110 ℃.
C. the preparation of poly ion liquid bonding coating
1-vinyl-3-propyl imidazole two (trifluoro sulphonyl) imines ion liquid of take is polymerization single polymerization monomer, with CuBr and CuBr
2for catalyst, 2,2 '-bipyridyl is part, CuBr, CuBr
2, 2, the ratio of the amount of 2 '-bipyridyl, ionic liquid monomer is 1: 1: 3: 30, with high pure nitrogen or argon gas, carry out noble gas protection, reaction temperature is 120 ℃, the reaction time is 24 hours.
Claims (8)
1. the preparation method of poly ion liquid bonding wire solid-phase micro-extraction fibre, is characterized in that method comprises following A, B, tri-steps of C successively:
A. the chemical silvering of wire surface
Wire is rinsed and removes surperficial oxide layer with sulfuric acid, and increase surperficial roughness, the wire after processing is put into chemical silvering solution and soak certain hour, on its surface, form silvering;
B. the bonding of ATRP priming site
First the silvering of wire surface is carried out to hydroxylating, then atom transition free radical polymerization reaction is caused to reagent and be bonded on hydroxylated wire;
C. the preparation of poly ion liquid bonding coating
Utilization is polymerization single polymerization monomer with the ionic liquid functional molecular of thiazolinyl, by surperficial Atom Transfer Radical Polymerization, reacts, and in wire surface, prepares poly ion liquid bonding coating.
2. the method for claim 1, is characterized in that in the chemical silvering step of wire surface, adopting wire is stainless steel wire, iron wire, titanium silk, nickel wire.
3. the method for claim 1, it is characterized in that in the chemical silvering step of wire surface, chemical silvering solution is the mixed solution of silver ammino solution and glucose solution, the mol ratio of silver ammonium ion and glucose is 1:0.5-3, the mass concentration of glucose is 5-30%, the time that wire is immersed in chemical silvering solution is 0.2-2 hour, and reaction temperature is room temperature.
4. the method for claim 1, it is characterized in that adopting mercapto propyl silane reagent, at the molecular self-assembling on silvering surface, it is carried out to silanization in the bonding step of ATRP priming site, hydrolysis makes silvering surface hydroxylation again, mercapto propyl silane reagent is mercapto propyl group front three (second) TMOS, volumetric concentration is 1-10%, under room temperature, the silane reagent self assembly time is 1-24 hour, and under room temperature, hydrolysis time is 1-6 hour.
5. the method for claim 1, it is characterized in that adopting in the bonding step of ATRP priming site that to cause reagent be the amide product that aminopropyl front three (second) TMOS and 2-bromine isobutyryl bromine reaction make, the ratio of both amounts is 1:1, reacts 2-12 hour at 0 ℃.
6. the method for claim 1, it is characterized in that adopting in the bonding step of ATRP priming site the mass concentration that causes reagent is 5-10%, the reaction time is 6-12 hour at 110 ℃.
7. the method for claim 1, is characterized in that in the preparation process of poly ion liquid bonding coating, adopting the ionic liquid with thiazolinyl is polymerization single polymerization monomer.
8. the method for claim 1, is characterized in that adopting CuBr and CuBr in the preparation process of poly ion liquid bonding coating
2for catalyst, 2,2 '-bipyridyl is part, CuBr, CuBr
2, 2, the ratio of the amount of 2 '-bipyridyl, ionic liquid monomer is 1:1:2-4:20-50, with high pure nitrogen or argon gas, carries out noble gas protection, reaction temperature is 30-140 ℃, the reaction time is 6-48h.
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| CN104437441B (en) * | 2014-11-03 | 2016-10-19 | 济南大学 | A kind of preparation method of Graphene coating solid phase micro-extraction fiber |
| CN106390948B (en) * | 2016-03-23 | 2019-04-26 | 深圳市北测检测技术有限公司 | A kind of grafting has silicon wafer of poly ion liquid and its preparation method and application |
| CN106215907B (en) * | 2016-08-22 | 2018-09-18 | 鲁东大学 | A kind of magnetic cellulose base poly ion liquid type adsorbent and preparation method thereof |
| CN109173983B (en) * | 2018-08-07 | 2021-07-27 | 济南大学 | Method for in-situ preparation of ionic liquid hybrid silica aerogel coating solid-phase micro-extraction fiber |
| CN109364901A (en) * | 2018-12-06 | 2019-02-22 | 福州大学 | The solid-phase micro-extraction coating fiber and application of a kind of carboxylated porous oxidation carbon-nitrogen nano-material and its preparation |
| CN109589937B (en) * | 2019-01-25 | 2021-09-14 | 河南科技学院 | Preparation method and application of solid-phase micro-extraction fiber of self-assembled multilayer porphyrin organic framework compound |
| CN116212832B (en) * | 2023-04-04 | 2024-07-26 | 湖南大学 | Polyion liquid-cellulose composite double-absorption purifying material and preparation thereof |
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