CN101241111A - Dibutyl tin oxide detection method - Google Patents
Dibutyl tin oxide detection method Download PDFInfo
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- CN101241111A CN101241111A CNA2007100197965A CN200710019796A CN101241111A CN 101241111 A CN101241111 A CN 101241111A CN A2007100197965 A CNA2007100197965 A CN A2007100197965A CN 200710019796 A CN200710019796 A CN 200710019796A CN 101241111 A CN101241111 A CN 101241111A
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- CN
- China
- Prior art keywords
- grignard reagent
- dibutyltin
- detection method
- dibutyltin oxide
- alkyl
- 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.)
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- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000001514 detection method Methods 0.000 title claims abstract description 20
- 239000007818 Grignard reagent Substances 0.000 claims abstract description 29
- -1 alkyl derivatives grignard reagent Chemical class 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 150000004795 grignard reagents Chemical class 0.000 claims abstract description 14
- 239000012454 non-polar solvent Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000009835 boiling Methods 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 6
- 239000012074 organic phase Substances 0.000 claims abstract description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 238000001212 derivatisation Methods 0.000 claims description 10
- 230000000694 effects Effects 0.000 claims description 10
- 238000002604 ultrasonography Methods 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000000638 solvent extraction Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 9
- 238000004587 chromatography analysis Methods 0.000 abstract 3
- 238000006467 substitution reaction Methods 0.000 abstract 3
- 238000004458 analytical method Methods 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- RJGHQTVXGKYATR-UHFFFAOYSA-L dibutyl(dichloro)stannane Chemical compound CCCC[Sn](Cl)(Cl)CCCC RJGHQTVXGKYATR-UHFFFAOYSA-L 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- APQHKWPGGHMYKJ-UHFFFAOYSA-N Tributyltin oxide Chemical compound CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC APQHKWPGGHMYKJ-UHFFFAOYSA-N 0.000 description 1
- 230000000680 avirulence Effects 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- BVFSYZFXJYAPQJ-UHFFFAOYSA-N butyl(oxo)tin Chemical compound CCCC[Sn]=O BVFSYZFXJYAPQJ-UHFFFAOYSA-N 0.000 description 1
- LUZSPGQEISANPO-UHFFFAOYSA-N butyltin Chemical compound CCCC[Sn] LUZSPGQEISANPO-UHFFFAOYSA-N 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 1
- 229910001623 magnesium bromide Inorganic materials 0.000 description 1
- 239000006199 nebulizer Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000013094 purity test Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- AFCAKJKUYFLYFK-UHFFFAOYSA-N tetrabutyltin Chemical compound CCCC[Sn](CCCC)(CCCC)CCCC AFCAKJKUYFLYFK-UHFFFAOYSA-N 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000003809 water extraction Methods 0.000 description 1
Landscapes
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The present invention relates to a method for detecting content of dibutyltin oxide (DBTO) by chromatography exactly. Wherein, the dibutytin oxide and excessive 1-8 C alkyl derivatives grignard reagent are reacted under ultrasonic action, residual grignard reagent is destroyed by excessive acid, organic non-polar solvent is added to extract to obtain dibutyltin alkyl substitution which is insoluble in water and has lower boiling point, content of dibutyltin alkyl substitution is detected by organic phase chromatography. The dibutyltin oxide precision detection can be realized by equivalent conversion of dibutyltin alkyl substitution which can be analyzed by chromatography. The present invention is simple, feasible and the detection precision is high, the problem that no method in present can detect exactly the dibutyltin oxide content is solved.
Description
Technical field
The present invention relates to a kind ofly can use look general accurate mensuration Dibutyltin oxide (DBTO) content detecting method.
Background technology
The organic compound Dibutyltin oxide (DBTO) of metallic tin, its content detection are used DBTO very important influence.DBTO is a kind of white powder, because the singularity of its structure, be insoluble to most of organic solvents, be only soluble in strong acid, add that it is higher-boiling compound again, its boiling point is much higher than the chromatogram maximum operation (service) temperature limit, thus can not direct injected carry out stratographic analysis, thereby its content detection difficulty is very big.To the DBTO assay, can only then carry out calculation by measuring the content of tin among the DBTO usually at present by molecular formula.But contain other tin compound impurity toward contact among the DBTO, as monobutyl tin oxide and bigger, the poisonous tributyltin oxide of impact on environmental and human body, and the ionic compound of other tin, therefore only measure tin content among the DBTO, the real content that can not reflect Dibutyltin oxide fully, testing result inaccurate also can influence use.
Report (not seeing detailed document) is abroad arranged, generate dibutyl tin dichloride, derive with Grignard reagent again, then the air inlet analysis of hplc with hydrochloric acid and DBTO reaction.This method when detecting because of there being a spot of acid to exist, deriving of dibutyl tin dichloride influenced very big, measure three butyl tin still can, but still can not accurately measure Dibutyltin oxide content.
Therefore, at present both at home and abroad to the BDTO purity testing, all only can only measuring wherein, the content of tin carries out calculation, carry out look general public affairs and analyse and be difficult to direct injected, accurately measure Dibutyltin oxide content, become this compound and accurately measured content one big technical barrier, unresolved for a long time.
Summary of the invention
The objective of the invention is to overcome the deficiency of above-mentioned prior art, a kind of detection method that can accurately measure the Dibutyltin oxide of Dibutyltin oxide content is provided.
The object of the invention realizes, the technical measures of taking are: make solid Dibutyltin oxide and 1-8 excessive C alkyl derivative Grignard reagent, under the ultrasound wave effect, carry out derivatization reaction, generate liquid, low boiling, the dibutyl alkyl that can carry out look general detection replaces tin, replace tin content with look general assay determination dibutyl alkyl, by chemical equation, it is consistent with Dibutyltin oxide content before the reaction that reaction gained dibutyl alkyl replaces tin, therefore the fixed dibutyl alkyl of look general survey replaces tin content, promptly be exactly Dibutyltin oxide content, can not be with the deficiency of look general detection thereby solved Dibutyltin oxide, reach accurately detection level, realize the object of the invention.Specifically, the detection method of Dibutyltin oxide of the present invention, it is characterized in that making Dibutyltin oxide and 1-8 excessive C alkyl derivative Grignard reagent, under the ultrasound wave effect, carry out derivatization reaction, destroy the residue Grignard reagent with excess acid again, add organic non-polar solvent extraction, obtain water insoluble, lower boiling dibutyl alkyl and replace tin, get the organic phase chromatogram and detect dibutyl alkyl replacement tin content.
Described in the present invention:
1-8 C alkyl derivative Grignard reagent lattice low reaction, its effect is the Dibutyltin oxide that can not carry out look general detection, equivalent converts the dibutyl alkyl that can carry out look general analysis to and replaces tin, thereby reaches with look general accurate quantification analysis.Through a kind of propyl group Grignard reagent that more preferably adopts, for example N-Propyl Bromide magnesium (CH are compared in described Grignard reagent test
3CH
2CH
2MgBr), gained dibutyl propyl group replaces tin, than methyl Grignard reagent, ethyl Grignard reagent, butyl Grignard reagent and other Grignard reagent, has better separating effect relatively, and the products therefrom avirulence, is therefore preferentially selected for use in the present invention.The methyl Grignard reagent, because boiling point is lower, separating effect is low relatively, has increased follow-up public affairs from difficulty and operation; The ethyl Grignard reagent, toxic with the dibutyl tin diethyl that the Dibutyltin oxide derivatization reaction obtains, unfavorable to the testing staff, increase gas precautions separately, can increase the detection cost again; The butyl Grignard reagent generates the dibutyl dibutyl tin with the Dibutyltin oxide derivatization reaction, separates difficulty with finished product, can cause the Dibutyltin oxide derivatization reaction thing test duration oversize, and practical application is restricted.
Said ultrasonic, mainly be the Dibutyltin oxide that promotes to be insoluble to organic solvent, reaction easily, thereby can shorten the complete reaction time, and ultrasonic frequency is not particularly limited, can adopt commercially available ultrasound wave.In addition, the derivatization reaction of the present invention under the ultrasound wave effect, a kind of better is that (for example 60 ℃) carry out heating down, heats can more help derivatization reaction and carry out fast.
Add excess acid and destroy the residue Grignard reagent, main effect is to destroy excessive, unreacted Grignard reagent in the reaction product.
Organic non-polar solvent extraction, its effect is to remove inorganics and water in the derivatization reaction product, the damage of the general instrument of avoiding checking colors, and preferably those are water insoluble, can play organic non-polar solvent of bed separation again, for example toluene, benzene, hexane, cyclohexane, dimethylbenzene, ether, butyl ether etc.
In addition, the inventive method is a kind of to be more preferably, and after the extraction of organic non-polar solvent, adds alcohol and the water extraction of 1-6 C again, gets organic phase and advances the chromatogram detection, the layering difficulty (breakdown of emulsion layering) that causes with the emulsification of avoiding organic phase.
The inventive method, because the Dibutyltin oxide of taking directly to carry out look general detection, with the alkyl derivative lattice low reaction of 1-8 C, equivalent converts the dibutyl alkyl that can carry out look general analysis to and replaces tin, thereby realizes the accurate mensuration to Dibutyltin oxide under the ultrasound wave effect.The inventive method, method is simple, feasible, detects the degree of accuracy height, has solved the technical barrier that does not have method can accurately measure Dibutyltin oxide content at present.
Below in conjunction with four specific embodiments, further specify the present invention, but embodiment should not be construed as the restriction to invention.
Embodiment
Embodiment 1: gets 0.1g DBTO and places the 25ml volumetric flask, add 2ml 4mol/l N-Propyl Bromide magnesium, be heated to about 60 ℃, and ultrasonic 15 minutes, treat white powder dissolving back (themopositive reaction not occurring), take out cooling; Add 1mol/l sulfuric acid 5ml, cooling destroys unnecessary Grignard reagent while dripping, and adds 3.5ml methyl alcohol, adds water to 25ml, and jolting 10 minutes staticly makes its layering, and the machine layer of getting carries out look general analysis.
Chromatographic condition: carrier gas: N
2, nebulizer gas pressure: 0.1MPa, combustion-supporting gas: air, combustion-supporting atmospheric pressure: 0.05MPa, combustion gas: hydrogen, gaseous-pressure: 0.1MPa, capillary column: Se-30, temperature of vaporization chamber: 250 ℃, sensing chamber's temperature: 250 ℃, column temperature: 180 ℃.
Embodiment 2: get 0.1g DBTO and place the 25ml volumetric flask, add the propyl magnesium chloride Grignard reagent 2ml of 4mol/l, be heated to about 60 ℃, ultrasonic 15 minutes, treat white powder dissolving after, take out cooling, add the 5ml cyclohexane, use 1N H
2SO
45ml destroys unnecessary Grignard reagent, adds methyl alcohol 3.5ml, H
2O 5ml, jolting 10min, static layering is got organic layer analysis.Look general condition is the same.
Embodiment 3: get 0.1g DBTO and place the 25ml volumetric flask, add the ethyl group magnesium bromide (CH of 4mol/l
3CH
2MgCl
2) Grignard reagent 2ml, be heated to about 60 ℃, ultrasonic 15 minutes, treat white powder dissolving after, take out cooling, add the 5ml butyl ether, use 1N H
2SO
45ml destroys unnecessary Grignard reagent, adds ethanol 3.5ml, H
2O5ml, jolting 10min, static layering is got organic layer analysis.
Embodiment 4: get DBTO0.1g, place the 25ml volumetric flask, add the cyclohexyl bromination magnesium (MgCl of 4mol/l
2) Grignard reagent 2ml, be heated to about 60 ℃, ultrasonic 15 minutes, treat white powder dissolving after, take out cooling, add 5ml toluene, use 1N H
2SO
45ml destroys unnecessary Grignard reagent, adds methyl alcohol 3.5ml, H
2O5ml, jolting 10min, static layering is got organic layer analysis.
Claims (5)
1. the detection method of Dibutyltin oxide, it is characterized in that making Dibutyltin oxide and 1-8 excessive C alkyl derivative Grignard reagent, under the ultrasound wave effect, carry out derivatization reaction, destroy the residue Grignard reagent with excess acid again, add organic non-polar solvent extraction, obtain water insoluble, lower boiling dibutyl alkyl and replace tin, get the organic phase chromatogram and detect dibutyl alkyl replacement tin content.
2. according to the desirable detection method that requires 1 described Dibutyltin oxide, it is characterized in that the alkyl derivative Grignard reagent is the propyl group Grignard reagent.
3. according to the desirable detection method that requires 1 or 2 described Dibutyltin oxides, it is characterized in that derivatization reaction carries out under heating.
4. according to the desirable detection method that requires 3 described Dibutyltin oxides, it is characterized in that organic non-polar solvent extraction after, the alcohol and the water that add 1-6 C again extract.
5. according to the desirable detection method that requires 1 or 2 described Dibutyltin oxides, it is characterized in that organic non-polar solvent extraction after, the alcohol and the water that add 1-6 C again extract.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100197965A CN101241111A (en) | 2007-02-11 | 2007-02-11 | Dibutyl tin oxide detection method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100197965A CN101241111A (en) | 2007-02-11 | 2007-02-11 | Dibutyl tin oxide detection method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101241111A true CN101241111A (en) | 2008-08-13 |
Family
ID=39932802
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007100197965A Pending CN101241111A (en) | 2007-02-11 | 2007-02-11 | Dibutyl tin oxide detection method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101241111A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109142554A (en) * | 2017-06-27 | 2019-01-04 | 河北百灵威超精细材料有限公司 | The detection method of activity component concentration in a kind of grignard reagent solution |
-
2007
- 2007-02-11 CN CNA2007100197965A patent/CN101241111A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109142554A (en) * | 2017-06-27 | 2019-01-04 | 河北百灵威超精细材料有限公司 | The detection method of activity component concentration in a kind of grignard reagent solution |
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Open date: 20080813 |