CN102634279B - Method for preparing stationary phase coating material for trace substance identification and application of material - Google Patents
Method for preparing stationary phase coating material for trace substance identification and application of material Download PDFInfo
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Abstract
The invention relates to a method for preparing a stationary phase coating material for trace substance identification and application of the material. The method comprises the following steps of: adding carbosilane hyperbranched macromolecules with allyl terminals and MeHSiCl2 into a solvent, adding a Kastedt catalyst, and performing hydrosilylation reaction in the presence of nitrogen; adding triethylamine, fully dried cyclodextrin and fully dried tetrahydrofuran (THF) for bonding reaction; and finally cooling and separating, thus obtaining the material. The material is coated on capillary inner columns; and the material has the advantages of uniform film formation, high column efficiency and high adsorption quantity, and has analysis and identification capability for trace substances.
Description
Technical field
The present invention relates to a kind of chromatogram detection stationary phase material, particularly a kind of stationary phase coated material of differentiating for trace substance and its preparation method and application.
Background technology
Trace analysis because tested element content in sample is very low, distribute very inhomogeneous, particularly environmental sample, often in time, spatial variations fluctuation is very large, for accuracy and the reliability of trace analysis have caused certain difficulty.In order to strengthen the Detection capability of trace constituent and to remove basic interference, separation and the enrichment of trace components are usually absolutely necessary.
Solid-phase microextraction is the novel sample making technology developing in the last few years.Owing to having abandoned a large amount of uses for solvent in traditional sample making technology, then become zero solvent sample preparation, there is very important environment protection significance.Its equipment is small and exquisite, and shape is like a chromatographic injector, by handle (Holder) and extracting head or fiber head (Fiber) two portions formation.Extracting head is the fused quartz fiber head that the 1cm of an outer casing stainless steel tubule is long, scribble different chromatographic stationary phases or sorbent material, and fiber head is retractable in stainless steel tube, for extraction, adsorption sample; Handle, for installing or fixed extractor head, can forever use.
Conventional coated material mostly is linear macromolecule, and as polydimethylsiloxane, its viscosity is relatively large, and functional group is few, is unfavorable for mass transfer and trace enrichment, and trace analysis ability is low.The viscosity of hyperbranched macromolecular greatly reduces on the basis of polysiloxane, and there is abundant end group, can utilize a large amount of end groups to carry out purposive chemically modified, to realize the micro-selective absorption of coating and the also object of enriched with trace material of a large amount of absorption of getting of solid phase.
There is external scientific effort that dendritic macromole (phenyl is terminal group) is bonded on quartz capillary column wall and is separated to realize high resolution capillary gas chromatography by sol-gel method.But the synthetic of dendritic macromole wasted time and energy, consume a large amount of organic solvents, be unfavorable for that industrialization is used, and is unfavorable for environment protection.And hyperbranched macromolecular is on the advantage basis of low sticky, a large amount of end group that has kept dendritic macromole; also have synthetic relatively simple advantage, can adopt the method for the treatment of different things alike synthetic, the synthetic middle organic solvent using will reduce a lot relatively; be conducive to a large amount of synthesizing, be conducive to environment protection.
Gas chromatographic technique is efficient, sensitive, quick and accurate and be widely used in medicine, environment and the various fields such as biological is carried out compartment analysis with it.In the research of GC chiral separation, cyclodextrin stationary phase is because its special structure and good fractionation performance are one of chiral stationary phases being most widely used at present.But high without derivative cyclodextrin fusing point, film-forming properties is poor, need to carry out suitable modification to reduce fusing point, and then reach the object that improves film-forming properties.
Summary of the invention
The object of the invention is to overcome above-mentioned deficiency, a kind of stationary phase coated material of differentiating for trace substance and its preparation method and application is provided, use as capillary gas chromatographic column coating and solid-phase micro-extraction coating passing through cyclodextrin modified silicon-carbon alkane hyperbranched macromolecular, reach the object of ppm level and the trace analysis of nanogram level.
The technical scheme that the present invention takes is:
The preparation method of the stationary phase coated material of differentiating for trace substance, comprises that step is as follows:
(1) in the solvent of appropriate complete drying, add methyl diallylsilane [MeHSi (CH
2-CH=CH
2)
2], Karstedt catalyzer, addition reaction of silicon with hydrogen 8-10 hour in 80-90 DEG C of enclosed system, prepares allyl group end silicon-carbon alkane hyperbranched macromolecular;
(2) by silicon-carbon alkane hyperbranched macromolecular HBP-allyl, MeHSiCl with allyl group end
2(dimethyl dichlorosilane (DMCS)) adds in solvent, adds Karstedt catalyzer, under air tight condition at 80-90 DEG C of addition reaction of silicon with hydrogen 6-10 hour; Steaming desolventizes and unreacted dimethyl dichlorosilane (DMCS);
(3) under nitrogen protection, in silicon hydrogen adduct, add fully dry cyclodextrin, appropriate triethylamine, abundant dry solvent, sealed reaction vessel, fully stirs, and continues reaction 8-10 hour at 80-90 DEG C;
(4) cooling, release of pressure, after system pressure is down to normal atmosphere, add wherein the THF of undried processing, fully stir 20-30min, more under agitation add suitable quantity of water to carry out abundant hydrolysis condensation reaction, fully cooling, decompress filter, separates upper strata suspended solids cross-linking agent, gets supernatant liquid in filtrate in the reagent bottle of the narrow footpath of cleaning, fully dry with anhydrous magnesium sulfate, solids removed by filtration siccative, filtrate steaming is removed THF, obtains cyclodextrin modified carbon silane hyperbranched macromolecular.
The described silicon-carbon alkane hyperbranched macromolecular HBP-allyl with allyl group end, the following example of its molecular formula:
Its synthetic method is referring to document [C.Kim, H.Kim, Journal of Polymer Science Part A:Polymer Chemistry, 39 (2001) 3287-3293].
In above-mentioned steps (1): solvent is tetrahydrofuran (THF) (THF) or normal hexane.Solvent refluxes and is fully dried by sodium.MeHSi (CH
2-CH=CH
2)
2and the volume ratio of solvent is value between 1: 3～1: 5.Karstedt catalyst volume used and system (methyl diallylsilane+solvent) cumulative volume ratio is 1～2: 100.
In above-mentioned steps (2): MeHSiCl
2methyl diallylsilane N in molar ratio in consumption and step (1)
meHSiCl2: N
meHSi (CH2-CH=CH2) 2=2～4: 1 value.Karstedt catalyzer add-on is 0.1～0.5% of hyperbranched macromolecular HBP-allyl and solvent system cumulative volume.The synthetic method of Karstedt catalyzer is referring to document [Karstedt, B. (1973) .Platinum complexes of unsaturated siloxanes and platinum containing organopolysiloxanes GEN ELECTRIC.US3775452].Taking fully dry THF or normal hexane as reaction solvent, THF or the hexane solution of the hyperbranched macromolecular HBP-allyl that dose volume concentration is 10～20%.
In step (3), the molar weight of fully dry cyclodextrin is 4/21～5/21 of the middle methyl diallylsilane of step (1).Triethylamine consumption mole number is the MeHSiCl in step (2)
23～4 times of mole number.Abundant dry solvent load is 2～4 times of silicon hydrogen adduct liquid volume.Described abundant dry cyclodextrin process for purification is: distilled water is heated to micro-boiling, adds beta-cyclodextrin, be heated with stirring to dissolving, and filtered while hot, filtrate crystallization, obtains beta-cyclodextrin crystallization, will after the beta-cyclodextrin vacuum-drying of separating out, store.
Described abundant dry THF preparation method is: sodium Metal 99.5 refluxes, and the benzophenone indicator to THF becomes blue.The consumption of THF, water is (3～5) with the volume ratio of reactant during this reacts in step (4): (3～5): 1.
Above-mentioned preparation method's products therefrom is differentiated for trace substance as stationary phase coated material.
Shown in silicon-carbon alkane hyperbranched macromolecular bonding beta-cyclodextrin structural representation Fig. 8.
The application method of described material on capillary column is: by capillary column inwall CH
2cl
2washing also dries up with nitrogen, and above-mentioned stationary phase coated material is pressed in capillary column, stops 20-30 minute, evicts remaining liquid from cylinder with nitrogen, capillary column under nitrogen protection 220-240 DEG C dry ageing 2-3h, use CH
2cl
2washing nitrogen dry up.
Capillary column after coating can directly carry out chromatographic separation.
Hyperbranched macromolecular is owing to having three-dimensional structure, and body is low sticky, and good fluidity, carries a large amount of functional end-groups.By its functional end-group is reacted with cyclodextrin, make cyclodextrin bondedly in over-expense shape macromole end, can, by means of the low sticky and good mobility of hyperbranched macromolecular, give cyclodextrin with good mobility, and then reach good film forming object.
Material preparation process of the present invention is simple, and coating is immobilized firmly, and column bleeding rate is low, good stability; With traditional material comparison, there is film forming more even, post effect is higher, the advantage that adsorptive capacity is larger; With quartz capillary column after the coating of 0.25 micron of 15 meters of column length, diameter, trace level material there is the ability of analysis and identification.Paratartaric acid class chiral material, haloalkane hydro carbons mixture, benzene class mixture, esters of acrylic acid mixture, ketone mixture etc. have been realized the trace analysis of ppm and nanogram level, have excellent trace distinguishing ability.Can be applicable to comprise the fields such as environmental protection and water conditioning, clinical pharmacology, public security case analysis, pharmacy, chemical industry, national defence.
Brief description of the drawings
Fig. 1 is the infrared spectra of beta-cyclodextrin;
The infrared spectra of the cyclodextrin modified carbon silane hyperbranched macromolecular obtaining after Fig. 2 embodiment 1 reaction;
Fig. 3 is the collection of illustrative plates that esters of acrylic acid homologue is separated, a. methyl acrylate, b. methyl methacrylate, c. butyl acrylate
Fig. 4 is the collection of illustrative plates that benzene class homologue is separated, a. benzene, b. toluene, c.c '. dimethylbenzene, d naphthalene;
Fig. 5 is the trace detection collection of illustrative plates to ppm level toluene/hexane solution, a. normal hexane color atlas, b. toluene color atlas, c.ppm toluene/normal hexane;
Fig. 6 is the trace detection collection of illustrative plates to nanogram level butyl acrylate/hexane solution, 20 times of a. dilutions, 1000 times of b. dilutions.
Fig. 7 is the color atlas that paratartaric acid carries out chiral separation, a. pure acetone solvent, b. tartrate/acetone dilute solution.
Fig. 8 is silicon-carbon alkane hyperbranched macromolecular bonding beta-cyclodextrin structural representation.
Embodiment
Further illustrate the present invention below in conjunction with specific embodiment.
Embodiment 1
The preparation of fully dry cyclodextrin: add 100ml distilled water in 300ml beaker, be heated to micro-boiling.Take 5g beta-cyclodextrin, be heated with stirring to dissolving, filtered while hot, filtrate crystallization, obtains beta-cyclodextrin crystallization.Filter water, β mono-cyclodextrin is put into 50ml small beaker, be placed in 110 DEG C of-120 DEG C of vacuum drying ovens and process 1 hour, in moisture eliminator, store.
Fully dry THF preparation method is: sodium Metal 99.5 refluxes, and becomes blue to benzophenone indicator.
The preparation method of the stationary phase coated material of differentiating for trace substance: get one of Contes pipe, fully dry, under nitrogen protection, add MeHSi (CH
2-CH=CH
2)
25ml, THF 10ml, 3 Karstedt catalyzer, 80 DEG C are reacted 8 hours.Steaming desolventizes, and obtains HBP-allyl.
Get HBP-allyl 2ml, MeHSiCl
24ml, THF 10ml, 3 Karstedt catalyzer, 80 DEG C are reacted 8 hours, infrared monitoring allyl group disappears, and under nitrogen protection, steams and removes solvent and unreacted MeHSiCl
2, obtain chlorine end group silicon-carbon alkane hyperbranched macromolecular HBP
-Cl, the THF that fully dry beta-cyclodextrin 0.2g, 2ml triethylamine and 10ml are fully dried adds in Kontes pipe under nitrogen protection, and the lower magneton of sealing stirs, and 80 DEG C of reactions are spent the night, cooling, slowly open stopper, reaction system die-offs and is boiling shape because of pressure, wait to reach and normal atmosphere balance, after liquid level stabilizing, to the THF 5ml that adds undried processing in system, opening stirs 20min, then add 15ml water, stir 10min, system heats up violent, fully cooling, decompress filter, remove the floating crosslinked impurity (oyster white) in upper strata, supernatant liquid in dropper absorption filtrate is in the reagent bottle of the narrow footpath of cleaning, the fully dry 5h of 5g anhydrous magnesium sulfate, filter, filtrate steaming is removed THF, obtain the cyclodextrin modified silicon-carbon alkane hyperbranched macromolecular of faint yellow transparent oily matter.
The sign of product is the judging means as bonding with infrared spectra.Variation using spectrum peak, bonding front and back judges the formation of new key and the minimizing of original absorption peak or disappears as basis for estimation.The infrared spectra of product as shown in Figure 2.As can be seen from the figure, remove at the original 3500cm of cyclodextrin
-1outside a large amount of minimizings in the large steamed bun of Si-OH peak, place, key compound is also at 1086.06cm
-1there is new peak---the strong vibration absorption peak of Si-O-C in place.This is the basis for estimation that forms chemical bonding between cyclodextrin and hyperbranched macromolecular.In addition, 1457.25cm
-1, 800.16cm
-1, 1267.25cm
-1all there is the vibration peak of Si-C key to occur.
The preparation of fully dry cyclodextrin: add 100ml distilled water in 300ml beaker, be heated to micro-boiling.Take 20g beta-cyclodextrin, be heated with stirring to dissolving, filtered while hot, filtrate crystallization, obtains beta-cyclodextrin crystallization.Filter water, beta-cyclodextrin is put into 50ml small beaker, be placed in 110 DEG C of-120 DEG C of vacuum drying ovens and process 1 hour, in moisture eliminator, store.
Embodiment 2
The preparation of fully dry cyclodextrin: add 100ml distilled water in 300ml beaker, be heated to micro-boiling.Take 5g beta-cyclodextrin, be heated with stirring to dissolving, filtered while hot, filtrate crystallization, obtains beta-cyclodextrin crystallization.Filter water, β mono-cyclodextrin is put into 50ml small beaker, be placed in 110 DEG C of-120 DEG C of vacuum drying ovens and process 1 hour, in moisture eliminator, store.
Fully dry normal hexane preparation method is: sodium Metal 99.5 refluxes, and becomes blue to benzophenone indicator.
The preparation method of the stationary phase coated material of differentiating for trace substance: get one of Contes pipe, fully dry, under nitrogen protection, add MeHSi (CH
2-CH=CH
2)
25ml, normal hexane 10ml, 3 Karstedt catalyzer, 80 DEG C are reacted 8 hours.Steaming desolventizes, and obtains HBP-allyl.HBP-allyl 2ml, MeHSiCl
24ml, normal hexane 10ml, 3 chloroplatinic acid catalysts, 90 DEG C are reacted 6 hours; Infrared monitoring allyl group disappears, and under nitrogen protection, steams and removes solvent and unreacted MeHSiCl
2, obtain chlorine end group silicon-carbon alkane hyperbranched macromolecular HBP
-Cl; The normal hexane that fully dry beta-cyclodextrin 0.2g, 4ml triethylamine and 10ml are fully dried adds in Kontes pipe under nitrogen protection, and the lower magneton of sealing stirs, and 80 DEG C of reactions are spent the night; Cooling, slowly open stopper, reaction system die-offs and is boiling shape because of pressure, wait reach with normal atmosphere balance, liquid level stabilizing after, to the THF 20ml that adds undried processing in system, opening stirs, system heats up violent, after fully cooling, and decompress filter, remove the floating crosslinked impurity (oyster white) in upper strata, supernatant liquid in dropper absorption filtrate is in the reagent bottle of the narrow footpath of cleaning, and the fully dry 5h of 5g anhydrous magnesium sulfate, filters, filtrate steaming is removed THF, obtains the cyclodextrin modified carbon silane hyperbranched macromolecular of faint yellow transparent oily matter.
The application of the stationary phase coated material of differentiating for trace substance:
Drive CH with high pressure nitrogen
2cl
2after cleaning capillary tube inner wall 20min, dry up with nitrogen.Get the faint yellow transparent oily matter 200 μ l that embodiment 1 makes and mix in disposable plastic tube mesoscale eddies, impurity is removed in centrifugation, gets supernatant liquid in small test tube and puts into self-control device for filling.Be pressed into nitrogen, control the liquid cylinder of slowly at the uniform velocity flowing through.Leave standstill after 20min, evict remaining liquid from cylinder with nitrogen.Nitrogen protection, ageing 3h at 220 DEG C.Use 20ml CH
2cl
2clean cylinder 20-30min, nitrogen dries up.Post is installed on to gas chromatograph inside, and end openings is (without detector) outside post case, connects high pressure nitrogen, and 250 DEG C of ageings of column temperature are stand-by.
Respectively esters of acrylic acid homologue, benzene class homologue, ppm level toluene/hexane solution, nanogram level butyl acrylate/hexane solution are carried out to gas-chromatography discrete testing, result is as follows:
(1) esters of acrylic acid homologue is carried out to discrete testing
Sample introduction temperature: 200 DEG C, detected temperatures: 200 DEG C, post case temperature: 100 DEG C, press before post: 0.08Mpa, splitting ratio: 600; Separating resulting is shown in Fig. 3;
(2) benzene class homologue is carried out to discrete testing
Sample introduction temperature: 200 DEG C, detected temperatures: 200 DEG C, temperature programmed control: 80 DEG C～220 DEG C, 40 DEG C/min, insulation 1min.Before post, press: 0.08Mpa, splitting ratio: 600; Separating resulting is shown in Fig. 4;
(3) the examination experiment to ppm level toluene/hexane solution
1. the preparation of ppm level toluene/hexane solution
Get 0.04 μ l toluene and add in 50ml volumetric flask, be settled to scale with normal hexane.Be mixed with trace monochloro-benzene/hexane solution of 1.051ppm.
2. the above-mentioned solution of microsyringe sampling 1ul, is injected into gas chromatographic sample introduction device, post case temperature: 130 DEG C, and sample introduction temperature: 200 DEG C, detected temperatures: 200 DEG C, press before post: 0.08Mpa, splitting ratio: 600; Gained spectrogram as shown in Figure 5.
(4) the examination experiment to nanogram level butyl acrylate/hexane solution
[1] preparation of ppm level butyl acrylate/hexane solution
1. get 0.04 μ l butyl acrylate and add in 50ml volumetric flask, be settled to scale with normal hexane.Be mixed with trace phenyl-monobromide/hexane solution of 1.09ppm.
2. measure above-mentioned solution 1ml with 20ml syringe, and draw again normal hexane to 20ml scale.Now strength of solution is 1.09/20ppm.
3. from 1.09/20ppm solution, get 1ml and add in 50ml volumetric flask, hexane is settled to scale.Now strength of solution is 1.09/1000ppm, the solution of Da Nake trace level.
[2] get 1ul solution 1., 3. with microsyringe, be injected into successively in gas chromatographic sample introduction device, post case temperature: 130 DEG C, sample introduction temperature: 200 DEG C, detected temperatures: 200 DEG C, press before post: 0.08Mpa, splitting ratio: 600; Gained spectrogram as shown in Figure 6.As we can see from the figure, in b, although the peak type at 2-3min place is very little, can distinguish.Therefore effective for the trace detection of Ng level butyl acrylate.
(5) paratartaric acid chiral material splits experiment
Use acetone is solvent, preparation tartrate/acetone 0.01M/L dilute solution.2ul micro-sampling.Sample introduction temperature: 250 DEG C, detected temperatures: 250 DEG C, column temperature: 200 DEG C.Before post, press: 0.08Mpa, splitting ratio: 600.Gained spectrogram as shown in Figure 7.Can see, enantiomorph has obtained good fractionation through capillary chromatographic column and has separated.
Claims (4)
1. the preparation method of the stationary phase coated material of differentiating for trace substance, is characterized in that, comprises that step is as follows:
(1) in the solvent of appropriate complete drying, add methyl diallylsilane, Karstedt catalyzer, addition reaction of silicon with hydrogen 8-10 hour in 80-90 DEG C of enclosed system, preparation is with the silicon-carbon alkane hyperbranched macromolecular of allyl group end; The described silicon-carbon alkane hyperbranched macromolecular general structure with allyl group end:
The volume ratio of methyl diallylsilane and solvent is between 1:3～1:5, and Karstedt catalyst volume used is 1～2:100 with methyl diallylsilane and solvent cumulative volume ratio, and solvent is tetrahydrofuran (THF) or normal hexane;
(2) by silicon-carbon alkane hyperbranched macromolecular HBP-allyl, MeHSiCl with allyl group end
2add in solvent, add Karstedt catalyzer, under air tight condition at 80-90 DEG C of addition reaction of silicon with hydrogen 6-10 hour; Steaming desolventizes and unreacted dimethyl dichlorosilane (DMCS); MeHSiCl
2methyl diallylsilane N in molar ratio in consumption and step (1)
meHSiCl2: N
meHSi (CH2-CH=CH2) 2=2～4:1 value, Karstedt catalyzer add-on is 0.1～0.5% of hyperbranched macromolecular HBP-allyl and solvent system cumulative volume; Taking fully dry THF or normal hexane as reaction solvent, THF or the hexane solution of the hyperbranched macromolecular HBP-allyl that dose volume concentration is 10～20%;
(3) under nitrogen protection, in silicon hydrogen adduct, add fully dry cyclodextrin, appropriate triethylamine, abundant dry solvent, sealed reaction vessel, fully stirs, and continues reaction 8-10 hour at 80-90 DEG C; The molar weight of fully dry cyclodextrin is 4/21～5/21 of the middle methyl diallylsilane of step (1), and triethylamine consumption mole number is the MeHSiCl in step (2)
23～4 times of mole number, fully dry solvent load is 2～4 times of silicon hydrogen adduct liquid volume;
(4) cooling, release of pressure, after system pressure is down to normal atmosphere, add wherein the THF of undried processing, fully stir 20-30min, more under agitation add suitable quantity of water to carry out abundant hydrolysis condensation reaction, fully cooling, decompress filter, separates upper strata suspended solids cross-linking agent, gets supernatant liquid in filtrate in the reagent bottle of the narrow footpath of cleaning, fully dry with anhydrous magnesium sulfate, solids removed by filtration siccative, filtrate steaming is removed THF, obtains cyclodextrin modified carbon silane hyperbranched macromolecular; The consumption of THF, water is 3～5:3～5:1 with the volume ratio of reactant during this reacts.
2. the material that prepared by method claimed in claim 1.
3. the application of material claimed in claim 2 on capillary column.
4. application according to claim 3, is characterized in that, method is for using CH in capillary column
2cl
2washing also dries up with nitrogen, and above-mentioned stationary phase coated material is pressed in capillary column, stops 20-30 minute, evicts remaining liquid from cylinder with nitrogen, capillary column under nitrogen protection 220-240 DEG C dry ageing 2-3h, use CH
2cl
2washing nitrogen dry up.
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Non-Patent Citations (4)
| Title |
|---|
| "End-Capped AB3-Type Hyperbranched Carbosilane Macromolecules";CHUNGKYUN KIM et al;《Journal of Polymer Science》;20011231;第39卷;3287–3293 * |
| "改性超支化聚硅碳烷物理吸附涂层毛细管柱的分离性能研究";徐文超等;《分析化学》;20100831;第38卷(第8期);1167-1171 * |
| CHUNGKYUN KIM et al."End-Capped AB3-Type Hyperbranched Carbosilane Macromolecules".《Journal of Polymer Science》.2001,第39卷3287–3293. |
| 徐文超等."改性超支化聚硅碳烷物理吸附涂层毛细管柱的分离性能研究".《分析化学》.2010,第38卷(第8期),1167-1171. |
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