CN1951577A - Preparation method of solid phase micro-extraction coat layer - Google Patents
Preparation method of solid phase micro-extraction coat layer Download PDFInfo
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- CN1951577A CN1951577A CN 200510047444 CN200510047444A CN1951577A CN 1951577 A CN1951577 A CN 1951577A CN 200510047444 CN200510047444 CN 200510047444 CN 200510047444 A CN200510047444 A CN 200510047444A CN 1951577 A CN1951577 A CN 1951577A
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Abstract
The invention relates to a method for using gel sol package method to produce solid micro extractive coat. Wherein, on the surface of glass fiber, it uses sol-gel package technique to bond one layer of polysiloxane organic film, to extract the micro volatile and semi-volatile materials in condition or food sample. Compared with traditional method, the invention uses the polysiloxane without hydroxyl end, whose molecule weight is thousands; said fixed phase is completely packed in the gel network, via high-temperature aging, to remove the component with low boiling point; and in the aging process at 250-340Deg. C, the polysiloxane with ethane group will be bonded in thermal induction, to combine the gel network, to form the extractive, which is resistant to 290Deg. C thermal adsorption, with high mechanical strength and long service life.
Description
Technical field
The present invention relates to the technology of preparing of coating, be specially a kind of sol-gel embedding fabrication techniques preparation method of solid phase micro-extraction coat layer.
Background technology
SPME (Solid Phase Microextraction, SPME) be that the centralized procurement sample concentrates, sample introduction is in one, simply, the abstraction technique of the green organic solvent-free of convenience, the organic pollution that can be used for samples such as analysis environments, food, this technology 1993 is by the commercialization of Supelco company.Difference according to the extraction phase kind can be divided into polar form, middle polarity and nonpolar extraction phase, the selectivity and the sensitivity of the selection decision extraction of coating, and need suitable molecular structure, guarantee that analyte has diffusion velocity faster therein, can reach partition equilibrium at short notice, and when thermal desorption, can hightail fixedly phase coating, and can not cause the peak broadening, because analyte is at high temperature resolved, therefore selected coating also must have good heat endurance.At present, most commercialization coating is to be adhered to the extracting head surface by physical action, so theirs is stable poor.Adopt sol-gel technique that extraction phase is bonded to and to obtain high temperature resistant on the fiber head and effect that increase the service life, can extract and analyze the higher compound of boiling point, can be described as the breakthrough on the SPME coat preparing technology.This technology adopts and contains hydroxy-end capped extraction phase and react with sol solutions, has formed a bonding type network structure by gel process, and has formed the bonding type coating with the hydroxyl effect on glass or quartz fibre surface, thereby has resistant to elevated temperatures characteristic.And that the extraction phase that this technology adopts is necessary for is hydroxy-end capped, this fixing also rarely found on the market at present mutually, so it is used the certain restriction of generation.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of solid phase micro-extraction coat layer, adopt fixedly phase of sol-gel technique preparation extraction, and fixedly the phase coating is a fixedly phase (not needing to contain hydroxyl) of common gas-chromatography, and the coating of this technology preparation has the characteristics of high temperature resistant, anti-solvent and long service life.
The technical solution adopted in the present invention is as follows:
Earlier with glass fibre CH
2Cl
2Clean, use the NaOH solution-treated 1 hour of 1mol/L then, handled 0.5 hour with the hydrochloric acid solution of 0.1mol/L again, clean to neutral with deionized water at last, under 100 ℃ of conditions, dry.
Preparation method of solid phase micro-extraction coat layer is: get a certain amount of polysiloxanes series raw material (molecular weight 40000～500000) with carrene dilution dissolving, add the containing hydrogen silicone oil of polysiloxanes series raw material 1/3～1/5 quality and the MTMS of 20～50% quality.Add moisture percent by volume at last and be 3～7% trifluoroacetic acid, addition is identical with the volume of MTMS, the vibration mixing, centrifugal 5～10 minutes, the fiber needle of handling well is put into the colloidal sol clear liquid to be taken out after 5～40 minutes, became glue under the room temperature 2～18 hours, the adjusting of fiber coat thickness can realize by the stain number of times that is coated with of new preparation sol solutions; Aging is at N
2220～240 ℃ of constant temperature is 3～10 hours under the condition of protection, is raised to 250～340 ℃ of constant temperature 3～20 hours at last.
Can obtain the solid phase coating of following similar structures according to technical scheme of the present invention.
SPME coating by this method preparation has higher heat endurance and mechanical strength.
The invention has the beneficial effects as follows:
The present invention is the method for sol-gel embedding fabrication techniques solid-phase micro-extraction coating.On glass or quartz fibre surface, utilize colloidal sol-gel embedding technical key unification strata siloxanes (contain vinyl or do not contain vinyl) organic film of polymerization, to realize extracting and enriching to trace and the trace volatilization class and the class material that partly volatilizees in environmental sample or the food.Different with traditional sol-gel technique making solid-phase micro-extraction coating method, organic coating adopts the not polysiloxanes of hydroxyl end-blocking in this method, but adopt molecular weight is several ten thousand polysiloxanes to hundreds of thousands, this type of fixing being embedded in fully in the gel network is removed the low-boiling composition of low-molecular-weight by the high temperature ageing process.For the polysiloxanes that contains vinyl, in 250 ℃ to 340 ℃ ageing process, the vinyl that polysiloxanes itself contains bonding each other under the condition that heat causes, with the gel network mat, form organic solvent-resistant flushing, 290 ℃ of thermal desorptions of tolerance and not have the extraction phase of loss, mechanical strength height and long service life.
Description of drawings
Fig. 1 is the gas-chromatography baseline chart; Wherein, Figure 1A is the Chromatogram Baseline of SPME under 290 ℃ of conditions of desorption temperature; Figure 1B is depicted as the Chromatogram Baseline figure under the condition that does not have SPME, and relatively two figure can cause the loss of coating as can be seen hardly 290 ℃ high temperature desorb.
Fig. 2 is the gas-chromatography spectrogram of headspace extraction benzene homologue.
Fig. 3 is the gas-chromatography spectrogram of water sample kind organophosphorus pesticide.
The specific embodiment
Below in conjunction with specific embodiment technical scheme of the present invention is described further:
The sol gel process of preparation glass fibre coating: get the 200mg dimethyl silicone polymer and (contain vinyl 3%, about molecular weight 500,000) fully dissolve with 300 μ L carrene, add the 50mg containing hydrogen silicone oil, 90 μ L MTMSs and 90 μ L trifluoroacetic acids (moisture percent by volume is 3～7%) vibration make it abundant mixing, take out the colloidal sol clear liquid after centrifugal 5 minutes, the fiber immersion was taken out after 20 minutes, under the condition of room temperature, become glue 12 hours, then at N
2The following 230 ℃ of constant temperature of condition of protection 4 hours are raised to 300 ℃ of constant temperature 5 hours at last, and adopting the coating layer thickness of the absorption rod/stirring and adsorbing rod of this method preparation is 45 μ m.
The sol gel process of preparation glass fibre coating: get 200mg dimethyl silicone polymer (about molecular weight 500,000) and fully dissolve with 300 μ L carrene, add the 50mg containing hydrogen silicone oil, 90 μ L MTMSs and 90 μ L trifluoroacetic acids (moisture percent by volume is 3～7%) vibration make it abundant mixing, take out the colloidal sol clear liquid after centrifugal 5 minutes, the fiber immersion was taken out after 20 minutes, under the condition of room temperature, become glue 12 hours, then at N
2The following 240 ℃ of constant temperature of condition of protection 4 hours are raised to 300 ℃ of constant temperature 5 hours at last.
The method of the collosol and gel of preparation glass fibre coating: get 250mg 5% diphenyl-95% dimethyl polysiloxane (about molecular weight 45000) and fully dissolve with 300 μ L carrene, add the 50mg containing hydrogen silicone oil, 100 μ L MTMSs and 100 μ L trifluoroacetic acids (moisture percent by volume is 3～7%) vibration make it abundant mixing, take out the colloidal sol clear liquid after centrifugal 5 minutes, the glass immersion was taken out after 10 minutes, handle adsorbing rod/stirring rod according to the processing method of embodiment 1 then.
Embodiment 4
The method of the collosol and gel of preparation glass fibre coating: get hydroxy-end capped 5% diphenyl-95% dimethyl polysiloxane (about molecular weight 45000) of 200mg and fully dissolve with 300 μ L carrene, add the 50mg containing hydrogen silicone oil, 50 μ L MTMSs and the vibration of 50 μ L trifluoroacetic acids make it abundant mixing, take out the colloidal sol clear liquid after centrifugal 5 minutes, the glass fibre immersion was taken out after 10 minutes, handle adsorbing rod/stirring rod according to the processing method of embodiment 1 then.
As shown in Figure 2, adopt the SPME of embodiment 1 gained to adopt the head space mode to extract the gas-chromatography spectrogram of gained to benzene homologue in the water.Benzene homologue (benzene, toluene, meta-xylene, paraxylene, ortho-xylene) concentration: 10ng/mL; Sample volume: 10mL; Extraction temperature: 30 ℃; The extraction time: 30min; Mixing speed: 1250rpm.
As shown in Figure 3, adopt the gas-chromatography spectrogram of the SPME of embodiment 1 gained to organophosphorus pesticide extraction analysis gained in the water.Sample concentration: 1ng/mL; Sample volume: 20mL; Extraction temperature: 30 ℃; The extraction time: 30min; Salinity: 15%; Mixing speed: 1250rpm.
Fig. 1: gas-chromatography baseline chart.SPME is in the Chromatogram Baseline (A) under 290 ℃ of conditions of desorption temperature and do not have Chromatogram Baseline figure (B) under the condition of SPME.
Fig. 2: the gas-chromatography spectrogram of headspace extraction benzene homologue.1. benzene, 2. toluene, 3. meta-xylene, 4. paraxylene, 5. ortho-xylene.
Fig. 3: the gas-chromatography spectrogram of water sample kind organophosphorus pesticide.1. Azodrin; 2. thimet; 3. Rogor; 4. parathion-methyl; 5. malathion; 6. fenifrothion; 7. Entex; 8. chlopyrifos; 9. parathion; 10. methidathion; 11. Hostathion; 12. Ethodan.
Claims (3)
1, preparation method of solid phase micro-extraction coat layer is characterized in that glass surface, utilizes colloidal sol-organic film of gel embedding technical key unification strata siloxane polymerization, and concrete steps are as follows:
(1) gets polysiloxanes series raw material and dissolve, add the containing hydrogen silicone oil of polysiloxanes series raw material 1/3-1/5 quality, as the sealing reagent of organic facies coating with the dichloromethane solvent dilution;
(2) add methyl three TMOSs of above-mentioned polysiloxanes series raw material quality 20～50% as colloidal sol-gel reaction predecessor;
(3) add the catalyst of trifluoroacetic acid as the colloidal sol-gel reaction described in the step (2), addition is identical with the volume of MTMS;
(4) said mixture is vibrated mixing gets solgel reaction liquid, and centrifugal 5～10 minutes, fiber needle is put into the colloidal sol clear liquid take out after 5～40 minutes, became glue under the room temperature 2～18 hours; The adjusting of fiber coat thickness realizes by being coated with the stain number of times; Aging method is: at N
2220～240 ℃ of constant temperature is 3～10 hours under the condition of protection, is raised to 250～340 ℃ of constant temperature 3～20 hours at last.
2, according to the described preparation method of solid phase micro-extraction coat layer of claim 1, it is characterized in that: adopting molecular weight is that 4000～500000 polysiloxanes is as coating material.
3, according to the described preparation method of solid phase micro-extraction coat layer of claim 1, it is characterized in that: in the described step (3), the moisture percent by volume of trifluoroacetic acid is 3～7%.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101149359B (en) * | 2007-11-09 | 2010-12-08 | 西华师范大学 | Solid phase micro-extraction probe and its analysis method for polycyclic aromatic hydrocarbon of environmental sample |
| CN102068963A (en) * | 2010-10-19 | 2011-05-25 | 天津春发食品配料有限公司 | Stainless steel solid phase micro extraction fiber |
| CN105424459A (en) * | 2015-12-31 | 2016-03-23 | 力合科技（湖南）股份有限公司 | Adsorption element and solid phase micro-extraction device |
| CN109173981A (en) * | 2018-08-07 | 2019-01-11 | 济南大学 | A kind of preparation method of polyethyleneimine functionalized SiO 2 aeroge coating solid phase micro-extraction fiber |
| CN110749484A (en) * | 2019-11-14 | 2020-02-04 | 深圳至秦仪器有限公司 | Malachite green detection method, malachite green detection device and probe manufacturing method |
| CN110857914A (en) * | 2018-08-23 | 2020-03-03 | 南京理工大学 | Poly (trifluoropropylmethylsiloxane)/silver composite surface enhanced Raman substrate and preparation method thereof |
| CN113385154A (en) * | 2021-07-15 | 2021-09-14 | 吉林化工学院 | Molecular imprinting sol-gel coating fiber tube internal solid phase micro-extraction device and preparation method thereof |
| CN114259887A (en) * | 2021-12-29 | 2022-04-01 | 西南大学 | Preparation method of efficient durable solid phase extraction membrane |
-
2005
- 2005-10-19 CN CN 200510047444 patent/CN1951577A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101149359B (en) * | 2007-11-09 | 2010-12-08 | 西华师范大学 | Solid phase micro-extraction probe and its analysis method for polycyclic aromatic hydrocarbon of environmental sample |
| CN102068963A (en) * | 2010-10-19 | 2011-05-25 | 天津春发食品配料有限公司 | Stainless steel solid phase micro extraction fiber |
| CN102068963B (en) * | 2010-10-19 | 2013-07-10 | 天津春发生物科技集团有限公司 | Stainless steel solid phase micro extraction fiber |
| CN105424459A (en) * | 2015-12-31 | 2016-03-23 | 力合科技（湖南）股份有限公司 | Adsorption element and solid phase micro-extraction device |
| CN105424459B (en) * | 2015-12-31 | 2019-07-09 | 力合科技（湖南）股份有限公司 | A kind of absorptive element and solid-phase micro-extracting device |
| CN109173981A (en) * | 2018-08-07 | 2019-01-11 | 济南大学 | A kind of preparation method of polyethyleneimine functionalized SiO 2 aeroge coating solid phase micro-extraction fiber |
| CN110857914A (en) * | 2018-08-23 | 2020-03-03 | 南京理工大学 | Poly (trifluoropropylmethylsiloxane)/silver composite surface enhanced Raman substrate and preparation method thereof |
| CN110749484A (en) * | 2019-11-14 | 2020-02-04 | 深圳至秦仪器有限公司 | Malachite green detection method, malachite green detection device and probe manufacturing method |
| CN113385154A (en) * | 2021-07-15 | 2021-09-14 | 吉林化工学院 | Molecular imprinting sol-gel coating fiber tube internal solid phase micro-extraction device and preparation method thereof |
| CN113385154B (en) * | 2021-07-15 | 2022-09-27 | 吉林化工学院 | Molecular imprinting sol-gel coating fiber tube internal solid phase micro-extraction device and preparation method thereof |
| CN114259887A (en) * | 2021-12-29 | 2022-04-01 | 西南大学 | Preparation method of efficient durable solid phase extraction membrane |
| CN114259887B (en) * | 2021-12-29 | 2022-12-27 | 西南大学 | Preparation method of efficient durable solid-phase extraction membrane |
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