CN102008947B - Adsorbing material with microspheres as carriers - Google Patents
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- CN102008947B CN102008947B CN 201010253140 CN201010253140A CN102008947B CN 102008947 B CN102008947 B CN 102008947B CN 201010253140 CN201010253140 CN 201010253140 CN 201010253140 A CN201010253140 A CN 201010253140A CN 102008947 B CN102008947 B CN 102008947B
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Abstract
The invention discloses an adsorbing material with microspheres as carriers, relating to the field of trace analysis of volatile or semi-volatile organic matters in foods, environment and biological samples. The adsorbing material comprises carriers and coating sol coated on the carriers, the carriers are glass microspheres, and the coating sol is prepared from hydroxyl blocked polydimethylsiloxane, hydrogen-containing silicone oil, trifluoroacetic acid and a raw material X, wherein the raw material X is a mixture of epoxypropoxy propyl trimethoxy silane and silicane tetraethoxyl, or methyl trimethoxy silane. The adsorbing material has the advantages of larger specific area, appropriate surface structure, strong adsorbability to adsorbates, easy regeneration property and the like, and generates no chemical reaction with adsorbates and media, and compared with SPME (Solid Phase Micro Extraction) and SBSE (Stir Bar Sorptive Extraction) methods, the adsorbing material has larger coating quantity and is suitable for enriching samples of hydrocarbon, pesticides, seasonings, essences, spices and the like.
Description
Technical field
The invention belongs to the trace analysis field of volatility and semi-volatile organic matter, the trace analysis field that particularly relates to volatility and semi-volatile organic matter in food, environment, the biological sample, particularly, the present invention relates to a kind of sorbing material take microballoon as carrier.
Background technology
The content of VOC (VOC) in sample is lower, need to carry out example enrichment and detect required sensitivity to reach.Enrichment method commonly used is the adsorbent absorption method, has simple to operate, the advantages such as cost is lower, easy transportation storage.Usually in adsorption tube (sampling pipe), fill adsorbent, can capture volatility and the semi-volatile organic compounds of wide region.And adsorption tube can be by Fast Heating and is resolved fully, and adsorption tube can be reused.
Whether adsorbent is suitable, is directly connected to reliability and the accuracy of measurement result.Selected adsorbent should be considered: (1) in desired sampling volume, being gathered material should be above the adsorption capacity of sampling pipe; (2) kind of absorption VOC is many as far as possible; (3) VOC that is adsorbed the agent enrichment is easy to desorption; (4) adsorbent is little to the affinity of water; (5) background of adsorbent is low as far as possible.Adsorbent commonly used has the materials such as active carbon, carbon molecular sieve, Graphon and Tenax.Therefore, seek and study high performance adsorbent with set up simply, reliably the sampling and assay method be the important foundation of the Study of the Realization VOC.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of sorbing material take microballoon as carrier is provided.
A kind of sorbing material take microballoon as carrier, this sorbing material is comprised of carrier and the coating colloidal sol that is coated on the carrier, described carrier is glass microsphere, described coating colloidal sol is prepared by hydroxyl endblocked polydimethylsiloxane, containing hydrogen silicone oil, trifluoroacetic acid and raw material X, its Raw X is the mixture of epoxypropoxy trimethyl silane and tetraethoxysilane, or MTMS.
Preferably, the diameter of described glass microsphere is 5-5000 μ m.
Preferably, in the above-mentioned sorbing material, the usage ratio of used material is as follows:
Dimethyl silicone polymer 1mg
Containing hydrogen silicone oil 0.16-0.5mg
Trifluoroacetic acid 0.14-0.5 μ l
Raw material X 0.16-0.5 μ l
Described raw material X is the mixture of epoxypropoxy trimethyl silane and tetraethoxysilane, or MTMS.The volume ratio of epoxypropoxy trimethyl silane and tetraethoxysilane is 0.5-5 in the mixture of epoxypropoxy trimethyl silane and tetraethoxysilane: 1.
Described glass microsphere is by any substitutes in aerosil particles, ceramic particle, aluminum oxide micro-sphere, titania microsphere, oxidation original text microballoon or the styrene diethylene benzene copoly mer microballoon.
Any substitutes described dimethyl silicone polymer by polyacrylate, polydivinylbenezene, polyethylene glycol, polyacrylate, dimethyl silicone polymer/divinylbenzene, dimethyl silicone polymer/carboxyethyl, divinylbenzene/carboxyethyl, polyethylene glycol/divinylbenzene, polyethylene glycol/template resin or divinylbenzene/carboxyethyl/dimethyl silicone polymer.
Described glass microsphere is by any substitutes in aerosil particles, ceramic particle, aluminum oxide micro-sphere, titania microsphere, oxidation original text microballoon or the styrene diethylene benzene copoly mer microballoon; Any substitutes described dimethyl silicone polymer by polyacrylate, polydivinylbenezene, polyethylene glycol, polyacrylate, dimethyl silicone polymer/divinylbenzene, dimethyl silicone polymer/carboxyethyl, divinylbenzene/carboxyethyl, polyethylene glycol/divinylbenzene, polyethylene glycol/template resin or divinylbenzene/carboxyethyl/dimethyl silicone polymer.
The present invention also provides a kind of sorbing material, and this sorbing material is prepared by the method that comprises following steps:
(1) choosing and preliminary treatment of glass microsphere: the glass microsphere of choosing diameter and be 5-5000 μ m is some, uses successively CH
2Cl
2Process 0.5-2 hour, 1mol/L NaOH solution-treated 4-12 hour, 0.1mol/L HCl solution-treated 4-8 hour, again with washed with de-ionized water to neutral, in 120-150 ℃ at N
2The lower dry for standby of protection;
(2) making of coating: get hydroxyl endblocked polydimethylsiloxane, with carrene dilution dissolving, add containing hydrogen silicone oil, trifluoroacetic acid and raw material X, described raw material X is the mixture of epoxypropoxy trimethyl silane and tetraethoxysilane, or MTMS, fully stirs, make colloidal sol, with the glass microsphere of processing in the step (1), place colloidal sol 20-60min to take out, become glue 10-24 hour under the room temperature;
(3) coating is aging: under nitrogen protection, carry out aging 100-150 ℃ of temperature programming and keep 2-4h, 150-180 ℃ keeps 2-4h, and then 200-240 ℃ keeps 30～60min, namely finishes aging;
(4) removal of impurity: the sorbing material that will wear out places in the middle of the cable type extractor according, utilizes carrene 30-60 ℃ of backflow 1-4h.
Wherein the usage ratio of used material is as follows in the step (2):
Dimethyl silicone polymer 1mg
Containing hydrogen silicone oil 0.16-0.5mg
Trifluoroacetic acid 0.14-0.5 μ l
Raw material X 0.16-0.5 μ l
Described raw material X is the mixture of epoxypropoxy trimethyl silane and tetraethoxysilane, or MTMS, the volume ratio of epoxypropoxy trimethyl silane and tetraethoxysilane is 0.5-5 in the mixture of epoxypropoxy trimethyl silane and tetraethoxysilane: 1.
Described glass microsphere is by any substitutes in aerosil particles, ceramic particle, aluminum oxide micro-sphere, titania microsphere, oxidation original text microballoon or the styrene diethylene benzene copoly mer microballoon.
Any substitutes described dimethyl silicone polymer by polyacrylate, polydivinylbenezene, polyethylene glycol, polyacrylate, dimethyl silicone polymer/divinylbenzene, dimethyl silicone polymer/carboxyethyl, divinylbenzene/carboxyethyl, polyethylene glycol/divinylbenzene, polyethylene glycol/template resin or divinylbenzene/carboxyethyl/dimethyl silicone polymer.
Described glass microsphere is by any substitutes in aerosil particles, ceramic particle, aluminum oxide micro-sphere, titania microsphere, oxidation original text microballoon or the styrene diethylene benzene copoly mer microballoon; Any substitutes described dimethyl silicone polymer by polyacrylate, polydivinylbenezene, polyethylene glycol, polyacrylate, dimethyl silicone polymer/divinylbenzene, dimethyl silicone polymer/carboxyethyl, divinylbenzene/carboxyethyl, polyethylene glycol/divinylbenzene, polyethylene glycol/template resin or divinylbenzene/carboxyethyl/dimethyl silicone polymer.
The coating layer thickness scope of sorbing material of the present invention is 10-1000 μ m.
Beneficial effect of the present invention is:
(1), the present invention utilizes microballoon to be carrier surface bonding polymer, and the sorbing material that the makes adsorption tube of packing into is sampled, and compares with SPME, SBSE method, has larger coating amount; And the sample mode of adsorption tube belongs to dynamic head space, than the Static Headspace of SPME, more is conducive to detecting of trace materials.
(2), the present invention has larger specific surface, suitable surface texture, and adsorbate is had strong adsorption capacity, not with adsorbate and medium generation chemical reaction, the easy advantage such as regeneration.
(3), the present invention is applicable to the enrichment to samples such as hydro carbons, agricultural chemicals, flavouring, essence and flavoring agents.
Description of drawings:
Fig. 1 is not for using the gas-chromatography baseline chart of sorbing material;
Fig. 2 is for using the gas-chromatography baseline chart under the embodiment 1 desorbed of adsorbed materials temperature;
Fig. 3 is for utilizing the gas chromatogram of embodiment 1 sorbing material extraction (nitrogen blows-head space) n-alkane (C5-C10).
The specific embodiment
Embodiment 1
The glass microsphere of choosing diameter and be 50 μ m is some, uses successively CH
2Cl
2Process 0.5 hour, 1mol/LNaOH solution-treated 4 hours, 0.1mol/L HCl solution-treated 4 hours, again with washed with de-ionized water to neutral, in 150 ℃ at N
2The lower oven dry of protection; Get the 20g hydroxyl endblocked polydimethylsiloxane and dilute with the 30ml carrene, adding 5g containing hydrogen silicone oil, 5ml MTMS, 5ml trifluoroacetic acid fully stir; With the glass microsphere of processing, place colloidal sol 30min to take out, become glue 12 hours under the room temperature; Under nitrogen protection, carry out aging 120 ℃ of temperature programming and keep 3h, 180 ℃ keep 3h, and then 240 ℃ keep 30～60min, namely finish aging; The sorbing material that will wear out at last places in the middle of the cable type extractor according, utilizes 40 ℃ of backflow 2h of carrene, makes sorbing material.
Embodiment 2
With the glass microsphere in the silica gel microball alternate embodiment 1, all the other conditions are identical, make sorbing material.
Embodiment 3
The sorbing material of making is filled in the adsorption tube that a slice filter screen is housed, and the other end also adds a slice filter screen, and the mode of utilizing nitrogen to blow is carried out enrichment to the essence sample, utilizes the thermal desorption instrument to carry out desorb, and GC/MS detects.
Embodiment 4
The sorbing material of making is packed in the adsorption tube, aging, connect the constant current gas samping pump room air sample is carried out enrichment, utilize the thermal desorption instrument to carry out desorb, GC/MS detects.
Embodiment 5
The sorbing material of making is packed in the adsorption tube, aging, connect headspace sample bottle and nitrogen blowing apparatus, the cooking dish fragrance component is carried out enrichment, utilize the thermal desorption instrument to carry out desorb, GC/MS detects.
Embodiment 6
The sorbing material of making is packed in the adsorption tube, aging, connect headspace sample bottle and nitrogen blowing apparatus, wine flavor constituent is carried out enrichment, utilize the thermal desorption instrument to carry out desorb, GC/MS detects.
Embodiment 7
The sorbing material of making is packed in the adsorption tube, aging, connect headspace sample bottle and nitrogen blowing apparatus, meat flavor local flavor constituent is carried out enrichment, utilize the thermal desorption instrument to carry out desorb, GC/MS detects.
Sorbing material of the present invention is described by specific embodiment.Those skilled in the art can use for reference the links such as content appropriate change raw material of the present invention, process conditions and realize corresponding other purpose, its relevant change does not all break away from content of the present invention, all similar replacements and change will become apparent to those skilled in the art that and all be deemed to be included within the scope of the present invention.
Claims (1)
1. the preparation method of the sorbing material take microballoon as carrier is characterized in that: the glass microsphere that comprises the steps: to choose diameter and be 50 μ m is some, uses successively CH
2Cl
2Process 0.5 hour, 1 mol/L NaOH solution-treated 4 hours, 0.1 mol/L HCl solution-treated 4 hours, again with washed with de-ionized water to neutral, in 150 ℃ at N
2The lower oven dry of protection; Get the 20g hydroxyl endblocked polydimethylsiloxane and dilute with 30 ml carrene, adding 5g containing hydrogen silicone oil, 5ml MTMS, 5ml trifluoroacetic acid fully stir; With the glass microsphere of processing, place colloidal sol 30min to take out, become glue 12 hours under the room temperature; Under nitrogen protection, carry out aging 120 oC of temperature programming and keep 3 h, 180 oC keep 3 h, and then 240 oC keep 30～60min, namely finish aging; The sorbing material that will wear out at last places in the middle of the cable type extractor according, utilizes carrene 40 oC 2 h that reflux, and makes sorbing material.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 201010253140 CN102008947B (en) | 2010-08-12 | 2010-08-12 | Adsorbing material with microspheres as carriers |
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| CN 201010253140 CN102008947B (en) | 2010-08-12 | 2010-08-12 | Adsorbing material with microspheres as carriers |
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| CN102008947A CN102008947A (en) | 2011-04-13 |
| CN102008947B true CN102008947B (en) | 2013-04-24 |
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| CN105295611A (en) * | 2015-11-27 | 2016-02-03 | 常熟市江南电热元件厂 | U-shaped electric heating pipe |
| CN105907298B (en) * | 2016-05-25 | 2017-12-22 | 郑州翱翔医药科技股份有限公司 | A kind of graft type plug spray coating liquor and its processing method to plug surface |
| CN110280045B (en) * | 2019-06-19 | 2021-09-24 | 沈阳理工大学 | Catalytic digestion enrichment separation column, catalytic digestion enrichment separation cup and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5403898A (en) * | 1992-05-04 | 1995-04-04 | Brigham Young University | Single arm attached cyclodextrin polysiloxanes and use thereof as chiral stationary phases in chromatographic separation of enantiomers |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5403898A (en) * | 1992-05-04 | 1995-04-04 | Brigham Young University | Single arm attached cyclodextrin polysiloxanes and use thereof as chiral stationary phases in chromatographic separation of enantiomers |
Non-Patent Citations (1)
| Title |
|---|
| Wenmin Liu et al.."Preparation of stir bars for sorptive extraction using sol–gel technology".《Journal of Chromatography A》.2004,第1045卷第2部分. |
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