CN116626224B - Coulomb method Karl Fischer reagent and preparation method and application thereof - Google Patents
Coulomb method Karl Fischer reagent and preparation method and application thereof Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 59
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 84
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 81
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 72
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 37
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910000043 hydrogen iodide Inorganic materials 0.000 claims abstract description 37
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims abstract description 27
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000001514 detection method Methods 0.000 claims abstract description 18
- 239000012046 mixed solvent Substances 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 23
- 239000007789 gas Substances 0.000 claims description 16
- 238000011049 filling Methods 0.000 claims description 9
- 239000005457 ice water Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 abstract description 10
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052740 iodine Inorganic materials 0.000 abstract description 5
- 239000011630 iodine Substances 0.000 abstract description 5
- 230000004913 activation Effects 0.000 abstract description 4
- 230000002708 enhancing effect Effects 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- -1 lithium hexafluorophosphate Chemical compound 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000018044 dehydration Effects 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- 150000007530 organic bases Chemical class 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical group [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/16—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using titration
- G01N31/168—Determining water content by using Karl Fischer reagent
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
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- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Molecular Biology (AREA)
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention relates to the technical field of moisture detection, and provides a coulombic method karl fischer reagent, a preparation method and application thereof. The coulombic method karl fischer reagent provided by the invention comprises the components of hydrogen iodide, sulfur dioxide, imidazole, diethanolamine, dimethyl imidazole, methanol, methylene dichloride and methyl iodide. According to the invention, hydrogen iodide is adopted to replace elemental iodine in the traditional Coulomb Fakarl Fischer reagent, so that water activation before use can be avoided, the equilibrium time of an instrument is shortened, the stability of a product can be improved, and the shelf life is prolonged; according to the invention, the methyl iodide is added, so that the methyl iodide can release elemental iodine, and trace moisture introduced in the product split charging process can be reacted, thereby further improving the stability of the product and enhancing the solubility of the product. The results of the examples show that the coulombic method karl fischer reagent is used for detecting the moisture content of the sample, the equilibrium time of the instrument is short, the accuracy of the detection result is good, and the quality guarantee period is long.
Description
Technical Field
The invention relates to the technical field of moisture detection, in particular to a Coulomb Fabricius Karl Fischer reagent and a preparation method and application thereof.
Background
With the continuous development of science and technology, products with special requirements on moisture, such as ultra-clean solvents in electronic chemicals, are more and more increased, and the products are mainly applied to cleaning of chips, and if the moisture of the products is high, the moisture can remain on the surfaces of the chips, so that the chips are corroded. For example, lithium hexafluorophosphate electrolyte, high water content can lead to lithium hexafluorophosphate hydrolysis to release highly corrosive hydrofluoric acid, corroding equipment; in addition, ultra-dry reagents and the like used in organic synthesis are also required to have strict moisture content. The water content of the above products is generally required to be within 50ppm, and a coulombic method karl fischer reagent must be used for a sample having a water content of 100ppm depending on the detection range of the karl fischer reagent.
The principle of detecting the moisture content by using the Coulomb Fakarl Fischer reagent is as follows: quantitative water is needed to participate in the reaction when the sulfur dioxide is oxidized by iodine, the detection of the moisture content is realized according to the chemical reaction, and the specific reaction mechanism is as follows:
I 2 +SO 2 +2H 2 O＝2HI+H 2 SO 4 ；
the reaction is reversible and requires the addition of an organic base, such as: pyridine, imidazole, ethanolamine, etc., the reaction mechanism is as follows:
(HOCH 3 CH 2 ) 2 NH·I 2 +(HOCH 3 CH 2 ) 2 NH·SO 2 +(HOCH 3 CH 2 ) 2 NH+H 2 O→
(HOCH 3 CH 2 ) 2 NH·SO 3 +(HOCH 3 CH 2 ) 2 NH·HI。
at the same time, it is necessary to add alcohols, such as: ethanol, methanol, etc., to prevent formation of (HOCH 3 CH 2 ) 2 NH·SO 3 React with water by the following reaction mechanism:
(HOCH 3 CH 2 ) 2 NH·SO 3 +CH 3 CH 2 OH→(HOCH 3 CH 2 ) 2 NH 2 ·SO 2 OCH 2 CH 3
at present, the coulombic method karl fischer reagent has poorer anti-interference performance and stability, and is mainly characterized in that: (1) Before use, a trace amount of water is needed to be manually added to activate the reagent, and the water addition amount directly affects the equilibrium time of the instrument; (2) the shelf life is shorter.
Disclosure of Invention
In view of this, the invention provides a coulombic method karl fischer reagent and its preparation method and application. The coulombic method karl fischer reagent provided by the invention does not need to be activated by adding water before use, the instrument balance time is short, the stability of the reagent is good, and the shelf life is long.
In order to achieve the above object, the present invention provides the following technical solutions:
a coulombic method karl fischer reagent comprising the following components in mass fraction: 1 to 8 percent of hydrogen iodide, 5 to 15 percent of sulfur dioxide, 5 to 20 percent of imidazole, 5 to 15 percent of diethanolamine, 0.05 to 2 percent of dimethylimidazole, 50 to 70 percent of methanol, 10 to 15 percent of methylene dichloride and 1 to 8 percent of methyl iodide.
Preferably, the Coulomb Fabricius Fischer reagent comprises the following components in parts by mass: 2 to 5 percent of hydrogen iodide, 6 to 12 percent of sulfur dioxide, 6 to 18 percent of imidazole, 6 to 13 percent of diethanolamine, 0.05 to 1.5 percent of dimethylimidazole, 52 to 63 percent of methanol, 11 to 14 percent of methylene dichloride and 2 to 7 percent of methyl iodide.
Preferably, the Coulomb Fabricius Fischer reagent comprises the following components in parts by mass: hydrogen iodide 2%, sulfur dioxide 12%, imidazole 15%, diethanolamine 5%, dimethyl imidazole 0.05%, methanol 53%, methylene chloride 10% and methyl iodide 2.95%.
Preferably, the Coulomb Fabricius Fischer reagent comprises the following components in parts by mass: 3% of hydrogen iodide, 8% of sulfur dioxide, 8% of imidazole, 10% of diethanolamine, 1% of dimethylimidazole, 56% of methanol, 12% of dichloromethane and 2% of methyl iodide.
Preferably, the Coulomb Fabricius Fischer reagent comprises the following components in parts by mass: hydrogen iodide 2.5%, sulfur dioxide 7%, imidazole 6%, diethanolamine 8%, dimethylimidazole 2%, methanol 57%, methylene chloride 15% and methyl iodide 2.5%.
The invention also provides a preparation method of the Coulomb Fabricius Karl Fischer reagent, which comprises the following steps:
mixing methanol, dichloromethane, imidazole, dimethyl imidazole and diethanolamine to obtain a mixed solvent;
and (3) filling sulfur dioxide gas into the mixed solvent, then carrying out first standing, filling hydrogen iodide gas, carrying out second standing, and then adding methyl iodide to obtain the Coulomb Fabricius Fischer reagent.
Preferably, the water content of the mixed solvent is 200ppm or less.
Preferably, the charging of sulfur dioxide gas and charging of hydrogen iodide gas is performed under cooling of an ice-water mixture.
Preferably, after adding methyl iodide, filtering the obtained mixed system; the pore size of the filter membrane for filtration was 0.22. Mu.m.
The invention also provides the application of the coulombic method karl fischer reagent in the above scheme or the coulombic method karl fischer reagent prepared by the preparation method in the above scheme in moisture detection.
The invention provides a Coulomb Fabricius Fischer reagent, which comprises the following components in parts by mass: 1 to 8 percent of hydrogen iodide, 5 to 15 percent of sulfur dioxide, 5 to 20 percent of imidazole, 5 to 15 percent of diethanolamine, 0.05 to 2 percent of dimethylimidazole, 50 to 70 percent of methanol, 10 to 15 percent of methylene dichloride and 1 to 8 percent of methyl iodide. According to the invention, hydrogen iodide is adopted to replace elemental iodine in the traditional Coulomb method Karl Fischer reagent, so that water activation before use can be avoided, and the equilibrium time of an instrument is shortened; meanwhile, the invention adopts hydrogen iodide to replace elemental iodine, so that the stability of the product can be improved, and the shelf life can be prolonged; according to the invention, the methyl iodide is added, so that the methyl iodide can release elemental iodine, and trace moisture introduced in the product split charging process can be reacted, thereby further improving the stability of the product and enhancing the solubility of the product. The results of the examples show that the coulombic method karl fischer reagent provided by the invention is used for detecting the moisture content of a sample, the equilibrium time of the instrument is only 13-21 min, the standard deviation is small, the accuracy of the detection result is good, and the coulombic method karl fischer reagent still has higher detection accuracy after being stored for 365 days, which indicates that the shelf life of the coulombic method karl fischer reagent is longer.
Detailed Description
The invention provides a Coulomb Fabricius Fischer reagent, which comprises the following components in parts by mass: 1 to 8 percent of hydrogen iodide, 5 to 15 percent of sulfur dioxide, 5 to 20 percent of imidazole, 5 to 15 percent of diethanolamine, 0.05 to 2 percent of dimethylimidazole, 50 to 70 percent of methanol, 10 to 15 percent of methylene dichloride and 1 to 8 percent of methyl iodide.
In the present invention, the coulombic method karl fischer reagent preferably comprises the following components in mass fraction: 2 to 5 percent of hydrogen iodide, 6 to 12 percent of sulfur dioxide, 6 to 18 percent of imidazole, 6 to 13 percent of diethanolamine, 0.05 to 1.5 percent of dimethylimidazole, 52 to 63 percent of methanol, 11 to 14 percent of methylene dichloride and 2 to 7 percent of methyl iodide.
In the present invention, the coulombic method karl fischer reagent preferably comprises the following components in mass fraction: hydrogen iodide 2%, sulfur dioxide 12%, imidazole 15%, diethanolamine 5%, dimethyl imidazole 0.05%, methanol 53%, methylene chloride 10% and methyl iodide 2.95%.
In the present invention, the coulombic method karl fischer reagent preferably comprises the following components in mass fraction: 3% of hydrogen iodide, 8% of sulfur dioxide, 8% of imidazole, 10% of diethanolamine, 1% of dimethylimidazole, 56% of methanol, 12% of dichloromethane and 2% of methyl iodide.
In the present invention, the coulombic method karl fischer reagent preferably comprises the following components in mass fraction: hydrogen iodide 2.5%, sulfur dioxide 7%, imidazole 6%, diethanolamine 8%, dimethylimidazole 2%, methanol 57%, methylene chloride 15% and methyl iodide 2.5%.
In the invention, the imidazole, the diethanolamine and the dimethylimidazole are organic bases, and the three organic bases are combined for use, so that the stability of the product can be further enhanced, and the formation of crystals in the analysis process is reduced; the dichloromethane is used as a solvent, so that the solubility of a product to be tested can be increased; the methyl iodide can release elemental iodine, so that trace moisture introduced in the product split charging process is reacted, the stability of the product is further improved, and the solubility of the product can be enhanced.
When the coulomb method Karl Fischer reagent is adopted for detection, the detection principle of the instrument is that the iodide ions are removed from an electron at the anode to generate elemental iodine, and when the iodide ions and the monoiodine in the cathode and anode pools of the instrument obtain a certain quantity, the instrument reaches balance to perform detection analysis. At present, simple substance iodine is added into the traditional Coulomb Fakarl Fischer reagent, and trace water is needed to be added to convert the simple substance iodine into iodide ions, and the addition amount of the water of an analysis person of a sample in the daily operation process cannot be accurately controlled, so that the instrument balance time is long or the instrument balance is not balanced. The invention adopts hydrogen iodide to replace elemental iodine, and can omit the step of water adding activation, thereby reducing the balance time of the instrument.
In addition, the traditional coulombic method karl fischer reagent is added with elemental iodine, the elemental iodine can slowly react in the presence of water, sulfur dioxide and organic alkali, and under the condition that the water or poor sealing exists in the reagent, the effective components of sulfur dioxide and organic alkali in the reagent can be completely consumed, so that the product is invalid and the shelf life is not long. Hydrogen iodide and sulfur dioxide do not react; in the presence of moisture, hydrogen iodide and organic base can undergo acid-base neutralization reaction, but the addition of organic base is in a far excessive amount, even if a small amount of hydrogen iodide reacts with organic base, the influence on the quality and stability of the reagent is small, because the product of the acid-base neutralization reaction is organic iodized salt, the iodized salt still ionizes to form iodide ions in solution, and the iodide ions still exist in the form of iodide ions, so that the product still has high stability. Therefore, the invention adopts hydrogen iodide to replace elemental iodine, which is beneficial to increasing the stability of the product and prolonging the shelf life.
The invention also provides a preparation method of the Coulomb Fabricius Karl Fischer reagent, which comprises the following steps:
mixing methanol, dichloromethane, imidazole, dimethyl imidazole and diethanolamine to obtain a mixed solvent;
and (3) filling sulfur dioxide gas into the mixed solvent, then carrying out first standing, filling hydrogen iodide gas, carrying out second standing, and then adding methyl iodide to obtain the Coulomb Fabricius Fischer reagent.
The invention mixes methanol, methylene dichloride, imidazole, dimethyl imidazole and diethanolamine to obtain a mixed solvent. The method has no special requirement on the mixing method, and the components are stirred and mixed to obtain clear and transparent solution. In the present invention, the water content of the mixed solvent is 200ppm or less, and in a specific embodiment of the present invention, after the mixed solvent is obtained, the water content of the mixed solvent is preferably detected, and when the water content of the mixed solvent is more than 200ppm, the mixed solvent is preferably dehydrated; the dehydration is preferably carried out using a 3A molecular sieve; the dehydration is preferably performed by removing the water content of the mixed solvent to 200ppm or less; after the dehydration is completed, the dehydrated mixed solvent is preferably filtered to remove molecular sieve fragments in the mixed solvent; the filtration is preferably carried out using a 0.22 μm PTFE filter.
After the mixed solvent is obtained, the invention fills sulfur dioxide gas into the mixed solvent, then carries out first standing, then fills hydrogen iodide gas, carries out second standing, and then adds methyl iodide to obtain the Coulomb Fabricius Fischer reagent. In the invention, the process of filling sulfur dioxide gas and hydrogen iodide gas is preferably carried out under the cooling of an ice-water mixture, specifically, a container filled with a mixed solvent is placed in the ice-water mixture, and then sulfur dioxide or hydrogen iodide is introduced into the container; the time of the first standing and the second standing is independently preferably 12-24 hours; after the addition of methyl iodide, stirring is preferably performed to dissolve methyl iodide.
In the present invention, it is preferable that the method further comprises filtering the resultant mixed system after adding methyl iodide; the pore size of the filtration membrane is preferably 0.22. Mu.m. After filtration, the resulting Coulomb Fabricius Fisher reagent is preferably dispensed into packaging bottles, which are preferably replaced with nitrogen prior to use.
The invention also provides the application of the Coulomb Fabricius Fisher reagent in the above scheme or the Coulomb Fabricius Fisher reagent prepared by the preparation method in the above scheme in moisture detection; the method of the invention has no special requirements for the application, and the method is well known to the person skilled in the art; in the specific embodiment of the invention, a Switzerland Wanton 831 coulomb method card type moisture tester is preferably adopted for moisture test, when the moisture test is carried out, 100mL of the coulomb method Karl Fischer reagent of the invention is added into an anode pool, 5mL of the coulomb method Karl Fischer reagent of the invention is added into a cathode, and after the instrument is stable, the moisture of a sample is sampled and measured, and the sample feeding amount is preferably 1-2 mL.
The following description of the embodiments of the present invention will clearly and fully describe the technical solutions of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
150g of imidazole, 0.5g of dimethylimidazole, 530g of methanol, 100g of dichloromethane and 50g of diethanolamine are weighed into a glass bottle, and the mixture is stirred until the mixture is completely dissolved, and the water content of the mixture is 489ppm. The mixture was dehydrated by adding a 3A molecular sieve, the water content was found to be 120ppm after dehydration, and the molecular sieve fragments in the mixture were filtered off by a 0.22 μm PTFE filter. The dehydrated mixed solvent is put into a container of ice-water mixture, 120g of sulfur dioxide is introduced, and the container is left overnight. Introducing 20g of hydrogen iodide, standing overnight, adding 29.5g of methyl iodide, stirring uniformly, covering a bottle cap, and standing overnight to obtain the Coulomb Fakarl Fischer reagent.
Example 2
80g of imidazole, 10g of dimethylimidazole, 560g of methanol, 120g of dichloromethane and 100g of diethanolamine are weighed into a glass bottle, and the mixture is stirred continuously until the mixture is completely dissolved, and the water content of the mixture is measured to be 422ppm. The mixture was dehydrated by adding a 3A molecular sieve, and after dehydration, the water content was found to be 105ppm, and then the molecular sieve fragments in the mixture were filtered off by using a PTFE filter of 0.22. Mu.m. The dehydrated mixed solvent is put into a container of ice-water mixture, 80g of sulfur dioxide is introduced, and the container is left overnight. Introducing 30g of hydrogen iodide, standing overnight, adding 20g of methyl iodide, stirring uniformly, covering a bottle cap, and standing overnight to obtain the Coulomb Fakarl Fischer reagent.
Example 3
60g of imidazole, 20g of dimethylimidazole, 570g of methanol, 150g of methylene chloride and 80g of diethanolamine are weighed into a glass bottle, and the mixture is stirred continuously until the mixture is completely dissolved, and the water content of the mixture is 353ppm. The mixture was dehydrated by adding a 3A molecular sieve, and after dehydration, the water content was found to be 96ppm, and then the molecular sieve fragments in the mixture were filtered off by using a PTFE filter of 0.22. Mu.m. The dehydrated mixed solvent is put into a container of ice-water mixture, 70g of sulfur dioxide is introduced, and the container is left overnight. Introducing 25g of hydrogen iodide, standing overnight, adding 25g of methyl iodide, stirring uniformly, covering a bottle cap, and standing overnight to obtain the Coulomb Fakarl Fischer reagent.
Comparative example 1
Weighing 150g of imidazole, 530g of methanol, 100g of dichloromethane and 50g of diethanolamine into a glass bottle, continuously stirring until the solution is completely dissolved, putting the solvent into a container of ice-water mixture, introducing 120g of sulfur dioxide, adding 50g of elemental iodine, uniformly stirring, covering a bottle cap, and standing overnight to obtain the traditional Coulomb Fakarl Fischer reagent, and adding water for activation before use.
Test example 1
Respectively adopting 100ppm of standard water, toluene, tetrahydrofuran and N, N-dimethylformamide as samples to be detected, and carrying out moisture content detection by utilizing the coulombic method karl fischer reagent prepared in examples 1-3 and comparative example 1; all are tested by using a Switzerland Wanton 831 coulomb method card type moisture tester, during the test, about 100mL of coulomb method Karl Fischer reagent is added into an anode pool, about 5mL of coulomb method Karl Fischer reagent is added into a cathode, after the initial recording time is recorded, and after the instrument is stabilized, the moisture of a sample is measured, and the sample feeding amount is 1mL.
The test results are shown in Table 1.
Table 1 moisture content test results
According to the data in Table 1, it can be seen that the coulombic method Karl Fischer reagent prepared in examples 1-3 of the invention is used for detecting the moisture of the sample, the equilibrium time of the instrument is only 13-21 min, while the coulombic method Karl Fischer reagent prepared in comparative example 1 is used for detecting the moisture of the sample, the equilibrium time of the instrument is 45-52 min, and the coulombic method Karl Fischer reagent of the invention can greatly shorten the equilibrium time of the instrument; in addition, the coulombic Fakarl Fischer reagent is adopted to detect the sample, and the standard deviation of three times of detection is small, so that the accuracy of the method is better.
The coulomb method fischer reagent in example 1 was stored for different times using 100ppm standard water as the sample to be tested, and 100ppm standard water was tested (three times of parallel tests, respectively 1.00, 2.00 and 3.00) using coulomb method fischer reagent stored for different times, and the test conditions were the same as the above-mentioned schemes to verify the stability of the coulomb method fischer reagent of the present invention. The detection results are shown in Table 2.
TABLE 2 detection results of Coulomb Fakarl Fischer reagent on 100ppm Standard Water after various time periods
As can be seen from the data in Table 2, after the coulombic method Karl Fischer reagent is stored for 30-365 days, the coulombic method Karl Fischer reagent is used for detecting 100ppm of standard water, and still can obtain more accurate detection results, which indicates that the coulombic method Karl Fischer reagent has higher stability and long quality guarantee period.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. A coulombic method karl fischer reagent, characterized by comprising the following components in mass fraction: 1 to 8 percent of hydrogen iodide, 5 to 15 percent of sulfur dioxide, 5 to 20 percent of imidazole, 5 to 15 percent of diethanolamine, 0.05 to 2 percent of dimethylimidazole, 50 to 70 percent of methanol, 10 to 15 percent of methylene dichloride and 1 to 8 percent of methyl iodide; the preparation method of the Coulomb Fabricius Karl Fischer reagent comprises the following steps: mixing methanol, dichloromethane, imidazole, dimethyl imidazole and diethanolamine to obtain a mixed solvent; and (3) filling sulfur dioxide gas into the mixed solvent, then carrying out first standing, filling hydrogen iodide gas, carrying out second standing, and then adding methyl iodide to obtain the Coulomb Fabricius Fischer reagent.
2. Coulombic method karl fischer-tropsch reagent according to claim 1, characterized by consisting of the following components in mass fraction: 2 to 5 percent of hydrogen iodide, 6 to 12 percent of sulfur dioxide, 6 to 18 percent of imidazole, 6 to 13 percent of diethanolamine, 0.05 to 1.5 percent of dimethylimidazole, 52 to 63 percent of methanol, 11 to 14 percent of methylene dichloride and 2 to 7 percent of methyl iodide.
3. Coulombic method karl fischer-tropsch reagent according to claim 1, characterized by consisting of the following components in mass fraction: hydrogen iodide 2%, sulfur dioxide 12%, imidazole 15%, diethanolamine 5%, dimethyl imidazole 0.05%, methanol 53%, methylene chloride 10% and methyl iodide 2.95%.
4. Coulombic method karl fischer-tropsch reagent according to claim 1, characterized by consisting of the following components in mass fraction: 3% of hydrogen iodide, 8% of sulfur dioxide, 8% of imidazole, 10% of diethanolamine, 1% of dimethylimidazole, 56% of methanol, 12% of dichloromethane and 2% of methyl iodide.
5. Coulombic method karl fischer-tropsch reagent according to claim 1, characterized by consisting of the following components in mass fraction: hydrogen iodide 2.5%, sulfur dioxide 7%, imidazole 6%, diethanolamine 8%, dimethylimidazole 2%, methanol 57%, methylene chloride 15% and methyl iodide 2.5%.
6. A process for the preparation of coulombic karl fischer-tropsch reagent according to any one of claims 1 to 5, characterised in that it comprises the steps of:
mixing methanol, dichloromethane, imidazole, dimethyl imidazole and diethanolamine to obtain a mixed solvent;
and (3) filling sulfur dioxide gas into the mixed solvent, then carrying out first standing, filling hydrogen iodide gas, carrying out second standing, and then adding methyl iodide to obtain the Coulomb Fabricius Fischer reagent.
7. The method according to claim 6, wherein the water content of the mixed solvent is 200ppm or less.
8. The method according to claim 6, wherein the charging of sulfur dioxide gas and charging of hydrogen iodide gas is performed under cooling of an ice-water mixture.
9. The method according to claim 6, wherein after adding methyl iodide, the obtained mixed system is filtered; the pore size of the filter membrane for filtration was 0.22. Mu.m.
10. Use of a coulombic karl fischer reagent according to any one of claims 1 to 5 or prepared by a preparation method according to any one of claims 6 to 9 in moisture detection.
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