CN1453583A - Analysis of minute amount of impurities in high-purity phenol - Google Patents
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Abstract
The analysis of minute amount of impurities in high-purity phenol includes heating phenol to melt, adding organic solvent suitable for phenol to recrystallize while stirring to mutually dissolve, cooling to separate phenol crystal, collecting the residual liquid after phenol crystallization, analysis of the residual liquid with GCMS and quantitative analysis of the residual liquid with gas chromatograph. The said method can analyze qualitatively and quantitatively minute amount of organic phenol impurities and/or organic non-phenol impurities in phenol sample. The present invention makes it possible for the downstream user to research the influence of the minute amount of impurities on phenol and to further eliminate harmful impurities.
Description
Technical field
The present invention relates to Determination of Micro Quantity Impurities method in the high-purity phenol.
Background technology
Phenol is widely used in aspects such as bisphenol-A, phenolics, medicine, agricultural chemicals and dyestuff as a kind of important basic Organic Chemicals, and its demand is still in continuous growth.Phenol is separation and Extraction from coal tar the earliest, begins to be mainly used in disinfecting of wound, synthetic along with a large amount of phenol derivativess afterwards, and the phenol derived product of high-quality, high added value has been opened up wide application for today.Extract phenol from coal tar, purity can reach 99.6% through great efforts; Earlier 1900s begins to use the chemical method synthesizing phenol, and existing several technologies have realized suitability for industrialized production, and at present based on cumene method technology, the phenol purity of production is not less than 99.9%.Although industrial phenol purity is higher, but phenol is when being used for the downstream application exploitation, wherein potential harmfulness impurity still can exert an influence to its follow-up further reaction, therefore, downstream user is urgently wanted to determine it is further reacted influential major impurity, remove harmful impurity with selective, this just need analyze the trace impurity in the high-purity phenol, and the method that main organic impurities is analyzed in pair high-purity phenol is only arranged at present.A kind of gas chromatography analysis method by main organic impurities in the phenol of isopropyl benzene explained hereafter is disclosed as U.S.'s ASTMD4961-93 method, wherein method A is used for Mesityl oxide, isopropyl benzene, α-Jia Jibenyixi, 2-methyl coumarone, acetophenone, six kinds of impurity of dimethyl benzyl alcohol of analysis of Phenol, be suitable for every kind of impurity content 10 to the scope of 100mg/kg; Method B is used for the hydroxypropanone-of analysis of Phenol, and the scope of application is 5 to 500mg/kg.Obviously, purity being not less than the trace impurity that impurity content in 99.9% phenol is lower than above-mentioned scope can not detect with this method.
Summary of the invention
The object of the present invention is to provide Determination of Micro Quantity Impurities method in a kind of high-purity phenol, this method can determine that purity is not less than the trace impurity in 99.9% phenol.
To achieve the above object of the invention, the invention provides Determination of Micro Quantity Impurities method in a kind of high-purity phenol, comprise the phenol heating and melting, add the organic solvent that is suitable for the phenol recrystallization then, after dissolving each other under stirring, phenol crystal is separated out in cooling, the residual liquid after the crystallization of collection phenol, and adopt gas chromatograph-mass spectrometer (GCMS) that residual liquid is carried out qualitative analysis, adopts gas chromatography that residual liquid is carried out quantitative test.Thereby definite wherein composition of trace impurity and the content in high-purity phenol.
Phenol is still key component in the residual liquid that obtains with method of the present invention, but wherein impurity composition comprises the corresponding raising of phenol impurity component relative content, promptly obtains enrichment.In order to improve concentration effect, recrystallization process can be carried out repeatedly: the phenol (separating with residual liquid) of recrystallization curing soon is heating and melting again, add the organic solvent that is suitable for the phenol recrystallization then, after dissolving each other under stirring, phenol crystal is separated out in cooling, residual liquid after the crystallization of collection phenol, can repeat repeatedly, again residual liquid is brought together, after concentrating again crystallisation by cooling separate out phenol, impurity in the residual liquid obtains further enrichment, adopt gas chromatograph-mass spectrometer (GCMS) that the residual liquid after concentrating is carried out qualitative analysis again, adopt gas chromatography that the residual liquid after concentrating is carried out quantitative test, can determine content impurity still less in the high-purity phenol.
Chilling temperature of the present invention can change in very wide scope, and temperature is low more, and crystallization effect is good more, but special low temperature then needs with specific process or equipment.Therefore the present invention preferred-18-25 ℃ cooling.Can change in very wide scope cool time of the present invention, and the time is long more, and crystallization effect is good more, but the time is oversize, and consuming time too many as a kind of analytical approach, therefore, the present invention preferably cooled off 0.5-24 hour.
Organic solvent of the present invention is preferably and the immiscible organic solvent of water, more preferably C
1-C
4Halogenated hydrocarbons, consider from gained sample aftertreatment difficulty or ease angle, be best with volatile methylene chloride, methenyl choloride.The addition of organic solvent is: the weight ratio of phenol and organic solvent is at 1/0.03-1/0.17.For accelerating the dissolving of phenol in organic solvent, can stir it.
The high-purity phenol sample is after recrystallization is handled, though its organic impurities component obtains effective enrichment, but phenol remains the component that accounts for absolute majority in the sample, when carrying out qualitative analysis with gas chromatograph-mass spectrometer (GCMS), impurity composition below detectability can not carry out qualitative detection, and some impurity peaks have been covered at the phenol peak.Because phenol is being used for downstream application when exploitation, wherein potential harmfulness impurity master is if it were not for phenol impurity, and is therefore particularly important to the qualitative and quantitative analysis of the organic impurities of other type.Can carry out reaction, extraction with the aqueous solution and the residual liquid of highly basic for this reason, phenolic compound and highly basic reaction enter water, other organic impurities that reacts with highly basic is not then stayed in the organic phase, after the static layering, the organic phase that obtains is carried out gas chromatographic analysis, gas chromatography-mass spectrometry analysis, also can wash and concentrate laggard promoting the circulation of qi analysis of hplc, gas chromatography-mass spectrometry analysis organic phase.
As long as can all can be used for the present invention, preferred potassium hydroxide, NaOH with the highly basic of phenols reaction generation phenates.The concentration of strong alkali aqueous solution of the present invention is 10%-50% (weight).The consumption of described strong alkali aqueous solution (in highly basic) is advisable with excessive for phenol, can more effectively remove phenol and phenol impurity like this, highly basic is excessive many more, phenol and phenol impurity are few more in the residual quantity of organic phase, also can cause unnecessary waste too much but highly basic is excessive, therefore, the consumption of described strong alkali aqueous solution (in highly basic) is advisable with excessive 1-200% (weight) for phenol.The aqueous solution of described highly basic and the reaction time of residual liquid are 1 minute-1 hour; Temperature of reaction is a room temperature-50 ℃.
Because phenol is when being used for the downstream application exploitation, wherein potential harmfulness impurity master is if it were not for phenol impurity.If do not need the phenol impurity in definite high-purity phenol, available following short-cut method is analyzed the micro-non-phenol impurity in the high-purity phenol:
Determination of Micro Quantity Impurities method in a kind of high-purity phenol, comprise with the aqueous solution of immiscible organic solvent of water and highly basic successively or add simultaneously in the phenol, fully behind the stirring reaction, standing demix is collected organic phase; Perhaps the aqueous solution with highly basic adds in the phenol, fully behind the stirring reaction, adds and the immiscible organic solvent of water again, fully mixes the back standing demix, collects organic phase; Adopt gas chromatograph-mass spectrometer (GCMS) that organic phase is carried out qualitative analysis, adopted gas chromatography that organic phase is carried out quantitative test.Thereby definite wherein composition of trace impurity and the content in high-purity phenol.
Of the present invention and the immiscible organic solvent of water is preferably C
1-C
4Halogenated hydrocarbons, consider from gained sample aftertreatment difficulty or ease angle, be best with volatile methylene chloride, methenyl choloride.The addition of organic solvent is: the weight ratio of phenol and organic solvent is at 1/0.03-1/2.
As long as can all can be used for the present invention, preferred potassium hydroxide, NaOH with the highly basic of phenols reaction generation phenates.The concentration of strong alkali aqueous solution of the present invention is 10%-50% (weight).The consumption of described strong alkali aqueous solution (in highly basic) is advisable with excessive for phenol, can more effectively remove phenol and phenol impurity like this, highly basic is excessive many more, phenol and phenol impurity are few more in the residual quantity of organic phase, also can cause unnecessary waste too much but highly basic is excessive, therefore, the consumption of described strong alkali aqueous solution (in highly basic) is advisable with excessive 1-200% (weight) for phenol.The aqueous solution of described highly basic and the reaction time of residual liquid are 1 minute-1 hour; Temperature of reaction is a room temperature-50 ℃.
Accompanying drawing 1 is the gas chromatogram of high-purity phenol sample A
Accompanying drawing 2 is the gas chromatogram of residual liquid behind the sample A room temperature recrystallization
Accompanying drawing 3 is the gas chromatogram of the residual liquid of sample A frozen recrystallization
Accompanying drawing 4 is the gas chromatogram of residual liquid behind the sample A room temperature recrystallization
Accompanying drawing 5 is the gas chromatogram of organic phase after the sample A alkali cleaning
Accompanying drawing 6 is the gas chromatogram of high-purity phenol sample B
Accompanying drawing 7 is the gas chromatogram of organic phase after the sample B alkali cleaning
Embodiment
The following examples will help to illustrate the present invention, but not limit to its scope.
The used chromatograph of following embodiment is U.S. Agilent company 6890 type gas chromatographs (join the HP3398 chem workstation, Hewlett-Packard produces); Used chromatograph-mas spectrometer is a Britain VG company's T S-250 type gas chromatograph-mass spectrometer (GCMS), adopts HP-FFAP quartz capillary chromatographic column (Hewlett-Packard's production): 30m * 0.32mm internal diameter * 0.5 μ m thickness of liquid film.
Phenol sample A, B are from phenol production producer-chemicals division department of yanshan petrochemical joint-stock company, and reagent such as methylene chloride, NaOH are analytical reagent, and water is redistilled water.
Chromatogram ration analysis condition and gas chromatography-mass spectrum qualitative analysis condition are as follows: the high-purity phenol sample is analyzed with the HP-FFAP quartz capillary chromatographic column, employing is regardless of and flows to sample loading mode, sample size 1 μ L, the column temperature program is: 100 ℃-5 ℃/min → 220 ℃/constant temperature; The residual liquid sample of enrichment impurity or the organic phase sample that is rich in impurity adopt above-mentioned analysis condition or adopt following analysis condition: split sampling mode (split ratio 10: 1), the column temperature program is: 60 ℃-5 ℃/min → 120 ℃-10 ℃/min → 220 ℃/constant temperature.Embodiment 12 adopts second kind of analysis condition, promptly adopts split sampling mode and corresponding conditions; All the other embodiment and Comparative Examples all adopt first kind of analysis condition, promptly adopt to be regardless of to flow to sample loading mode and corresponding conditions.Comparative Examples 1
High-purity phenol sample A (former state) is carried out gas chromatographic analysis.Gas chromatographic analysis figure sees accompanying drawing 1, and the content that obtains phenol among the sample A with the peak area normalization method is 99.95% (weight).Pyrogentisinic Acid's sample A does not carry out the gas chromatography-mass spectrum qualitative analysis, and its qualitative results is to determine according to the retention time of impurity, and the qualitative and quantitative analysis result of impurity is as table 1-4.
Embodiment 1
Take by weighing 100g phenol sample A and place Erlenmeyer flask, heating and melting under infrared lamp, adding the 5mL methylene chloride then stirs, natural cooling at room temperature, phenol is acicular crystal and separates out, the about 1mL of residual liquid after the crystallization of collection phenol carries out gas chromatographic analysis, gas chromatography-mass spectrometry analysis with the residual liquid that obtains.Gas chromatographic analysis figure sees accompanying drawing 2.Qualitative and quantitative analysis result such as table 1.
Table 1
* impurity content is a mass ratio, for removing the relative content that solvent peak is outer, all the other chromatographic peaks carry out the area normalization gained (down together).
| Phenol impurity contains phenol impurity in the residual liquid/min amount in the component retention time component title former state *，10 -6Content *，10 -6 |
| 15.319 10 19 24.833 cyclohexylphenol 21 39 of paracresol 5 10 16.491 cumic aldehyde 12 22.349 o cyclohexyl phenols, 39 74 23.356 p-cyclohexylphenols |
Embodiment 2
Take by weighing 100g phenol sample A, heating and melting under infrared lamp, adding the 5mL methylene chloride then stirs, elder generation is natural cooling at room temperature, phenol is acicular crystal separates out, and in order to obtain the more crystalline effect, the phenol mixture of cooling is at room temperature placed freezing 12 hours of the refrigerating chamber (temperature is-18 ℃) of refrigerator, take out the back and collect the about 1mL of residual liquid in the phenol crystal rapidly, the liquid that obtains is carried out gas chromatographic analysis, gas chromatography-mass spectrometry analysis.Gas chromatogram is seen Fig. 3.Qualitative and quantitative analysis result such as table 2.
Table 2
Embodiment 3
| Phenol impurity/min content in the residual liquid of phenol impurity in the component retention time component title former state, 10 -6Content, 10 -6 |
| 15.319 10 54 24.833 cyclohexylphenol 21 109 of paracresol 5 28 16.491 australol 16 22.349 o cyclohexyl phenols, 39 219 23.356 p-cyclohexylphenols |
Except that the addition of methylene chloride is the 10mL, other condition is with embodiment 1, and gas chromatographic analysis figure sees accompanying drawing 4.Qualitative and quantitative analysis result such as table 3.
Table 3
Embodiment 4
| The content of phenol impurity/min in the residual liquid of phenol impurity in the component retention time component title former state, 10 -6Content, 10 -6 |
| 15.319 10 18 24.833 cyclohexylphenol 21 36 of paracresol 59 16.491 australol 12 22.349 o cyclohexyl phenols, 39 72 23.356 p-cyclohexylphenols |
Except that replace methylene chloride, its addition with chloroform is the 5mL, and other condition is with implementing 1.Qualitative and quantitative analysis result such as table 4.
Table 4
Embodiment 5
| Content in the component retention time component title former state, 10 -6Content in the residual liquid, 10 -6??/min |
| 15.319 10 22 24.833 cyclohexylphenol 21 43 of paracresol 5 11 16.491 australol 12 22.349 o cyclohexyl phenols, 39 77 23.356 p-cyclohexylphenols |
Get 1mL50% (weight, sodium hydroxide solution down together), among the residual liquid 1mL of phenol recrystallization that adding obtains by the method for embodiment 2, at room temperature (25 ℃) abundant stirring reaction is 0.1 hour, left standstill after the reaction 50 minutes, obtaining lower floor is impure organic phase, and the upper strata is the water that contains phenol, takes out lower floor's organic phase and carries out gas chromatographic analysis, gas chromatography-mass spectrometry analysis.Gas chromatogram is seen Fig. 5.Qualitative and quantitative analysis result such as table 5.
Table 5
| Component retention time component title relative content *????/min |
| 1.269 chloromethanes-----5.427 the unknowns (from blank) 3.33 9.557-11.1 33 C 10The 1.58 13.927-14.033 the unknowns of alkyl benzene isomeride 17.59 11.342 phenol **1.10 unknown 2.76 18.688 diphenoxyl methanes of 14.716 alkylbenzenes, 1.41 15.298 alkylbenzenes, 2.38 16.557-18.346 (reaction generates) 5.40 19.289-19.998 unknown 0.95 20.873 adjacent benzyl dimethyl phenol 4.00 21.715 unknown 0.89 22.432 o cyclohexyl phenol, 18.00 23.134 neighbour (α; Alpha-alpha-dimethyl) unknown 9.05 34.615 phthalates (solvent contamination thing), 3.99 38.676 2-tertiary butyl-4-(α, the alpha-alpha-dimethyl) benzylphenol 17.34 of benzylphenol 6.71 23.262 phthalates (solvent contamination thing) 3.52 23.449-34.219 |
* relative content is to remove the content that solvent peak is outer, all the other chromatographic peaks carry out the area normalization gained, is mass ratio (down together).* the unknown is meant the component (down together) that content less (below mass spectral detectability) or mass spectrum do not parse.
Embodiment 6
Get the sodium hydroxide solution of 1mL50%, among the residual liquid 1mL of phenol recrystallization that adding obtains by the method for embodiment 2, at room temperature (25 ℃) abundant stirring reaction is 0.1 hour, left standstill after the reaction 30 minutes, obtaining lower floor is impure organic phase, and the upper strata is the water that contains phenol, taking out lower floor's organic phase washes with water three times, the organic phase that obtains (was placed 5 hours, so that the methylene chloride volatilization) after enrichment and is carried out gas chromatographic analysis, gas chromatography-mass spectrometry analysis.Qualitative and quantitative analysis result such as table 6.
Table 6
Embodiment 7
| Component retention time component title relative content/min |
| 1.269 methylene chloride----5.427 the unknowns (from blank) 1.71 9.557-11.133 C 10Unknown 2.28 18.688 diphenoxyl methanes of unknown 0.94 14.716 alkylbenzene, 1.38 15.298 alkylbenzenes of alkylbenzene isomer 16.52 11.342 phenol 6.12 13.927-14.003 2.15 16.557-18.346 (reaction generates) 4.79 19.289-19.998 unknown 0.97 20.873 adjacent benzyl dimethyl phenol 3.88 21.715 unknown 1.08 22.432 o cyclohexyl phenols, 16.10 23.134 neighbour (α; Alpha-alpha-dimethyl) unknown 9.95 34.615 phthalates (solvent contamination thing), 6.11 38.676 2-tertiary butyl-4-(α, the alpha-alpha-dimethyl) benzylphenol 16.17 of benzylphenol 6.15 23.262 phthalates (solvent contamination thing) 3.70 23.449-34.219 |
Except that the consumption of sodium hydroxide solution is the 0.8mL, all the other conditions are with embodiment 5, qualitative and quantitative analysis result such as table 7.
Table 7
Embodiment 8
| Component retention time/min | The component title | Relative content |
| ????1.269 ????5.427 ????9.557-11.133 ????11.342 ????13.927-14.003 ????14.716 ????15.298 ????16.557-18.346 ????18.688 ????19.289-19.998 | Methylene chloride the unknown (from blank) C 10The unknown diphenoxyl methane of the unknown alkylbenzene alkylbenzene of alkylbenzene isomer phenol (reaction generates) the unknown | ????---- ????1.52 ????14.87 ????15.21 ????0.83 ????1.26 ????1.91 ????2.02 ????4.27 ????0.90 |
| 20.873 adjacent benzyl dimethyl phenol 3.34 21.715 unknown 0.92 22.432 o cyclohexyl phenol, 14.55 23.134 neighbour (α; Alpha-alpha-dimethyl) unknown 9.10 34.615 phthalates (solvent contamination thing), 5.66 38.676 2-tertiary butyl-4-(α, the alpha-alpha-dimethyl) benzylphenol 14.87 of benzylphenol 5.45 23.262 phthalates (solvent contamination thing) 3.32 23.449-34.219 |
Except that the consumption of sodium hydroxide solution is the 0.7mL, all the other conditions are with embodiment 5, qualitative and quantitative analysis result such as table 8.
Table 8
Embodiment 9
| Component retention time component title relative content/min |
| 1.269 methylene chloride----5.427 the unknowns (from blank) 1.52 9.557-11.1 33 C 10The unknown 1.92 18.688 phenoxy group methane of unknown 0.71 14.716 alkylbenzene, 1.38 15.298 alkylbenzenes of alkylbenzene isomer 12.39 11.342 phenol 26.33 13.927-14.003 1.84 16.557-18.346 (reaction generates) 3.83 19.289-19.998 unknown 0.76 20.873 adjacent benzyl dimethyl phenol 3.04 21.715 unknown 0.90 22.432 o cyclohexyl phenol, 12.18 23.134 neighbour (α; Alpha-alpha-dimethyl) unknown 7.90 34.615 phthalates (solvent contamination thing), 4.85 38.676 2-tertiary butyl-4-(α, the alpha-alpha-dimethyl) benzylphenol 12.23 of benzylphenol 5.43 23.262 phthalates (solvent contamination thing) 2.79 23.449-34.219 |
Except that the concentration of sodium hydroxide solution is 15%, consumption is that 3.0mL, temperature of reaction are that 30 ℃, reaction time are 20 minutes, all the other conditions are with embodiment 5, qualitative and quantitative analysis result such as table 9.
Table 9
Embodiment 10
| Component retention time component title relative content/min |
| 1.269 methylene chloride----5.427 the unknowns (from blank) 1.58 9.557-11.133 C 10Unknown 2.15 18.688 diphenoxyl methanes of unknown 0.90 14.716 alkylbenzene, 1.27 15.298 alkylbenzenes of alkylbenzene isomer 15.94 11.342 phenol 10.34 13.927-14.003 2.04 16.557-18.346 (reaction generates) 4.26 19.289-19.998 unknown 0.92 20.873 adjacent benzyl dimethyl phenol 3.58 21.715 unknown 1.01 22.432 o cyclohexyl phenols, 15.87 23.134 neighbour (α; Alpha-alpha-dimethyl) unknown 9.53 34.615 phthalates (solvent contamination thing), 5.92 38.676 2-tertiary butyl-4-(α, the alpha-alpha-dimethyl) benzylphenol 14.93 of benzylphenol 5.88 23.262 phthalates (solvent contamination thing) 3.88 23.449-34.219 |
Except that the concentration of sodium hydroxide solution is 30%, consumption is that 2.0mL, temperature of reaction are that 40 ℃, reaction time are 40 minutes, all the other conditions are with embodiment 5, qualitative and quantitative analysis result such as table 10.
Table 10
Embodiment 11
| Component retention time component title relative content/min |
| 1.269 methylene chloride----5.427 the unknowns (from blank) 1.84 9.557-11.133 C 10The unknown 1.03 20.873 adjacent benzyl dimethyl phenol 4.07 of unknown 2.40 18.688 diphenoxyl methanes of unknown 0.99 14.716 alkylbenzene, 1.51 15.298 alkylbenzenes of alkylbenzene isomer 17.57 11.342 phenol 1.43 13.927-14.003 2.25 16.557-18.346 (reaction generates) 4.98 19.289-19.998 |
| 21.715 unknown 1.12 22.432 o cyclohexyl phenols, 16.91 23.134 neighbour (α; Alpha-alpha-dimethyl) unknown 10.34 34.615 phthalates (solvent contamination thing), 6.40 38.676 2-tertiary butyl-4-(α, the alpha-alpha-dimethyl) benzylphenol 16.84 of benzylphenol 6.47 23.262 phthalates (solvent contamination thing) 3.85 23.449-34.219 |
Except that replacing with potassium hydroxide solution the sodium hydroxide solution, all the other conditions are with embodiment 5, qualitative and quantitative analysis result such as table 11.
Table 11
Comparative Examples 2
| Component retention time component title relative content/min |
| 1.269 methylene chloride----5.427 the unknowns (from blank) 1.65 9.557-11.133 C 10Unknown 2.19 18.688 diphenoxyl methanes of unknown 0.89 14.716 alkylbenzene, 1.30 15.298 alkylbenzenes of alkylbenzene isomer 15.90 11.342 phenol 10.56 13.927-14.003 2.07 16.557-18.346 (reaction generates) 4.59 19.289-19.998 unknown 0.92 20.873 adjacent benzyl dimethyl phenol 3.73 21.715 unknown 1.03 22.432 o cyclohexyl phenols, 15.54 23.134 neighbour (α; Alpha-alpha-dimethyl) unknown 9.56 34.615 phthalates (solvent contamination thing), 5.85 38.676 2-tertiary butyl-4-(α, the alpha-alpha-dimethyl) benzylphenol 14.74 of benzylphenol 5.91 23.262 phthalates (solvent contamination thing) 3.57 23.449-34.219 |
B carries out gas chromatographic analysis with the high-purity phenol sample.Gas chromatographic analysis figure sees accompanying drawing 6.The content that obtains phenol among the sample A with the peak area normalization method is 99.85% (weight).Impurity among the phenol sample B can't separate effectively with gas chromatography, gas chromatography-mass spectrum, therefore can't obtain qualitative, the quantitative result of impurity.Embodiment 12
Take by weighing 100g phenol sample B and place Erlenmeyer flask, heating and melting under infrared lamp, adding the 5mL methylene chloride then stirs, natural cooling at room temperature, phenol is acicular crystal and separates out, collect the about 1mL of residual liquid in the phenol crystal, the sodium hydroxide solution that adds 1mL50% again, at room temperature (25 ℃) abundant stirring reaction is 0.1 hour, left standstill after the reaction 50 minutes, obtaining lower floor is impure organic phase, and the upper strata is the water that contains phenol, takes out lower floor's organic phase and carries out gas chromatographic analysis, gas chromatography-mass spectrometry analysis.Gas chromatographic analysis figure sees accompanying drawing 7.Qualitative and quantitative analysis result such as table 12.
Table 12
Embodiment 13
| Retention time | The component title | Relative content |
| ????1.267 ????3.847 ????4.193 ????4.394 ????4.831 ????5.256-5.729 ????6.166 ????7.837 ????8.479 ????8.825 ????9.027 ????9.241 ????9.774 ????9.981-10.123 ????10.726 ????11.259 ????13.523 ????14.425 ????17.115 ????17.967 ????21.556 ????24.286 | Carrene, (solvent) Mesityl oxide cyclohexanone methyl-cyclopentanone AMS ether or ketone compounds cyclohexanol hexenyl benzene isomer benzaldehyde hexenyl benzene isomer hexenyl benzene isomer isopropyl cyclohexanol hexenyl benzene isomer methyl benzo hexofuranos alkenyl benzene isomer acetophenone dimethyl benzyl alcohol xylyl alcohol phenol decyl alcohol-5 diphenoxyl methane, (reaction produces) diisobutyl phthalate, (pollutant) | ????----- ????5.22 ????9.41 ????2.10 ????0.70 ????1.57 ????29.52 ????1.53 ????1.76 ????6.31 ????0.15 ????0.30 ????0.89 ????4.56 ????1.35 ????5.12 ????1.00 ????0.27 ????9.67 ????1.00 ????9.62 ????1.30 |
Take by weighing 1g phenol sample B and place Erlenmeyer flask, add the 5mL methylene chloride, the sodium hydroxide solution that adds 1mL50% again, at room temperature (25 ℃) abundant stirring reaction is 1 hour, left standstill after the reaction 30 minutes, obtaining lower floor is impure organic phase, and the upper strata is the water that contains phenol, takes out lower floor's organic phase and carries out gas chromatographic analysis, gas chromatography-mass spectrometry analysis.Qualitative and quantitative analysis result such as table 13.
Table 13
Embodiment 14
| Retention time | The component title | Relative content |
| ????1.267 ????3.847 ????4.193 ????4.394 ????4.831 ????5.256-5.729 ????6.166 ????7.837 ????8.479 ????8.825 ????9.027 ????9.241 ????9.774 ????9.981-10.123 ????10.726 ????11.259 ????13.523 ????14.425 ????17.115 ????17.967 ????21.556 ????24.286 | Carrene, (solvent) Mesityl oxide cyclohexanone methyl-cyclopentanone AMS ether or ketone compounds cyclohexanol hexenyl benzene isomer benzaldehyde hexenyl benzene isomer hexenyl benzene isomer isopropyl cyclohexanol hexenyl benzene isomer methyl benzo hexofuranos alkenyl benzene isomer acetophenone dimethyl benzyl alcohol xylyl alcohol phenol decyl alcohol-5 diphenoxyl methane, (reaction produces) diisobutyl phthalate, (pollutant) | ????----- ????4.70 ????8.47 ????1.87 ????0.61 ????1.42 ????26.54 ????1.37 ????1.59 ????5.67 ????0.13 ????0.27 ????0.80 ????4.06 ????1.22 ????4.66 ????0.88 ????0.24 ????19.21 ????0.89 ????8.71 ????1.17 |
Take by weighing 1g phenol sample A and place Erlenmeyer flask, the sodium hydroxide solution and the 5mL methylene chloride that add 1mL50%, again at room temperature (25 ℃) abundant stirring reaction is 0.1 hour, left standstill after the reaction 40 minutes, obtaining lower floor is impure organic phase, the upper strata is the water that contains phenol, takes out lower floor's organic phase and carries out gas chromatographic analysis, gas chromatography-mass spectrometry analysis.Qualitative and quantitative analysis result such as table 14.
Table 14
Embodiment 15
| Component retention time component title relative content/min |
| 1.269 methylene chloride-----5.427 the unknowns (from blank) 1.59 |
| ??9.557-11.133????C 10Unknown 2.11 18.688 diphenoxyl methanes of unknown 0.86 14.716 alkylbenzene, 1.25 15.298 alkylbenzenes of alkylbenzene isomer 15.36 11.342 phenol 14.32 13.927-14.003 2.01 16.557-18.346 (reaction generates) 4.41 19.289-19.998 unknown 0.88 20.873 adjacent benzyl dimethyl phenol 3.58 21.715 unknown 1.00 22.432 o cyclohexyl phenols, 15.01 23.134 neighbour (α; Alpha-alpha-dimethyl) unknown 9.18 34.615 phthalates (solvent contamination thing), 5.65 38.676 2-tertiary butyl-4-(α, the alpha-alpha-dimethyl) benzylphenol 13.65 of benzylphenol 5.69 23.262 phthalates (solvent contamination thing) 3.45 23.449-34.219 |
Take by weighing 1g phenol sample B and place Erlenmeyer flask, add 1mL50% (weight, sodium hydroxide solution down together), at room temperature (25 ℃) abundant stirring reaction is 0.1 hour, adds the 5mL methylene chloride, after fully mixing, left standstill 1 hour, obtaining lower floor is impure organic phase, and the upper strata is the water that contains phenol, takes out lower floor's organic phase and carries out gas chromatographic analysis, gas chromatography-mass spectrometry analysis.Qualitative and quantitative analysis result such as table 15.
Table 15
| Retention time | The component title | Relative content |
| ????1.267 ????3.847 ????4.193 ????4.394 ????4.831 ????5.256-5.729 ????6.166 ????7.837 ????8.479 ????8.825 ????9.027 ????9.241 ????9.774 ????9.981-10.123 ????10.726 | Carrene (solvent) Mesityl oxide cyclohexanone methyl-cyclopentanone AMS ether or ketone compounds cyclohexanol hexenyl benzene isomer benzaldehyde hexenyl benzene isomer hexenyl benzene isomer isopropyl cyclohexanol hexenyl benzene isomer methyl benzo hexofuranos alkenyl benzene isomer | ????----- ????4.32 ????7.57 ????1.74 ????0.60 ????1.29 ????24.09 ????1.25 ????1.43 ????5.21 ????0.12 ????0.23 ????0.73 ????3.68 ????1.09 |
| ????11.259 ????13.523 ????14.425 ????17.115 ????17.967 ????21.556 ????24.286 | Acetophenone dimethyl benzyl alcohol xylyl alcohol phenol decyl alcohol-5 hexichol oxygen methylmethane, (reaction produces) diisobutyl phthalate, (pollutant) | ??4.25 ??0.81 ??0.20 ??27.87 ??0.83 ??7.78 ??1.09 |
Can carry out qualitative and quantitative analysis to micro-phenols organic impurities in the high-purity phenol sample and/or micro-non-phenols organic impurities with method of the present invention.Thereby make downstream user can study the further influence of reaction of trace impurity Pyrogentisinic Acid in the phenol, and then can remove the further harmful impurity of reaction of Pyrogentisinic Acid selectively.
Claims (20)
1. Determination of Micro Quantity Impurities method in the high-purity phenol, comprise the phenol heating and melting, add the organic solvent that is suitable for the phenol recrystallization then, after dissolving each other under stirring, phenol crystal is separated out in cooling, residual liquid after the crystallization of collection phenol, and adopt gas chromatograph-mass spectrometer (GCMS) that residual liquid is carried out qualitative analysis, adopts gas chromatography that residual liquid is carried out quantitative test.
2. analytical approach according to claim 1, it is characterized in that residual liquid is carried out adding the aqueous solution of highly basic in residual liquid before qualitative, the quantitative test, fully behind the stirring reaction, standing demix, collect organic phase, adopt gas chromatograph-mass spectrometer (GCMS) that organic phase is carried out qualitative analysis, adopted gas chromatography that organic phase is carried out quantitative test again.
3. analytical approach according to claim 1 and 2 is carried out qualitative and quantitative analysis to organic phase after it is characterized in that organic phase washed, concentrates again.
4. according to each described analytical approach of claim 1-3, the organic solvent solution that it is characterized in that described phenol was-18-25 ℃ cooling 0.5-24 hour.
5. according to each described analytical approach of claim 1-4, it is characterized in that described organic solvent is with the immiscible organic solvent of water, is preferably C
1-C
4Halogenated hydrocarbons, more preferably methylene chloride, methenyl choloride.
6. according to each described analytical approach of claim 1-5, it is characterized in that the addition of organic solvent is: the weight ratio of phenol and organic solvent is at 1/0.03-1/0.17.
7. according to each described analytical approach of claim 2-6, it is characterized in that described highly basic is potassium hydroxide, NaOH.
8. according to each described analytical approach of claim 2-7, the concentration that it is characterized in that described strong alkali aqueous solution is 10%-50% (weight).
9. according to each described analytical approach of claim 2-8, it is characterized in that the consumption (in highly basic) of described strong alkali aqueous solution is advisable with excessive for the phenol in the residual liquid.
10. analytical approach according to claim 9 is characterized in that the consumption (in highly basic) of described strong alkali aqueous solution is advisable with excessive 1-200% (weight) for the phenol in the residual liquid.
11., it is characterized in that the aqueous solution of highly basic and the reaction time of residual liquid are 1 minute-1 hour according to each described analytical approach of claim 2-10; Temperature of reaction is a room temperature-50 ℃.
12. Determination of Micro Quantity Impurities method in the high-purity phenol, comprise with the aqueous solution of immiscible organic solvent of water and highly basic successively or add simultaneously in the phenol, fully behind the stirring reaction, standing demix is collected organic phase; Perhaps the aqueous solution with highly basic adds in the phenol, fully behind the stirring reaction, adds and the immiscible organic solvent of water again, fully mixes the back standing demix, collects organic phase; Adopt gas chromatograph-mass spectrometer (GCMS) that organic phase is carried out qualitative analysis, adopted gas chromatography that organic phase is carried out quantitative test.
13. analytical approach according to claim 12 is carried out qualitative and quantitative analysis to organic phase after it is characterized in that organic phase washed, concentrates again.
14., it is characterized in that described organic solvent is C according to claim 12 or 13 each described analytical approachs
1-C
4Halogenated hydrocarbons, more preferably methylene chloride, methenyl choloride.
15. according to each described analytical approach of claim 12-14, it is characterized in that the addition of organic solvent is: the weight ratio of phenol and organic solvent is at 1/0.03-1/2.
16., it is characterized in that described highly basic is potassium hydroxide, NaOH according to each described analytical approach of claim 12-15.
17. according to each described analytical approach of claim 12-16, the concentration that it is characterized in that described strong alkali aqueous solution is 10%-50% (weight).
18., it is characterized in that the consumption (in highly basic) of described strong alkali aqueous solution is advisable with excessive for phenol according to each described analytical approach of claim 12-17.
19. analytical approach according to claim 18 is characterized in that the consumption (in highly basic) of described strong alkali aqueous solution is advisable with excessive 1-200% (weight) for phenol.
20., it is characterized in that the aqueous solution of highly basic and the reaction time of phenol are 1 minute-1 hour according to each described analytical approach of claim 12-19; Temperature of reaction is a room temperature-50 ℃.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1320355C (en) * | 2003-04-22 | 2007-06-06 | 江南大学 | Method for analyzing fragrancer matter in apple wine |
| CN101470106B (en) * | 2007-12-27 | 2012-01-25 | 深圳市华测检测技术股份有限公司 | Chlorcosane detection method |
| CN101871916B (en) * | 2009-04-24 | 2012-11-07 | 淄博蓝帆化工有限公司 | Method for measuring purity of trioctyl trimellitate |
| CN106770720A (en) * | 2016-11-29 | 2017-05-31 | 深圳职业技术学院 | The analysis method of organic solvent sample composition |
| CN107167529A (en) * | 2017-05-03 | 2017-09-15 | 浙江省计量科学研究院 | The assay method of the Reinheitszahl and uncertainty of phenol and hydroquinones standard substance |
-
2002
- 2002-04-28 CN CNB021169640A patent/CN1177221C/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1320355C (en) * | 2003-04-22 | 2007-06-06 | 江南大学 | Method for analyzing fragrancer matter in apple wine |
| CN101470106B (en) * | 2007-12-27 | 2012-01-25 | 深圳市华测检测技术股份有限公司 | Chlorcosane detection method |
| CN101871916B (en) * | 2009-04-24 | 2012-11-07 | 淄博蓝帆化工有限公司 | Method for measuring purity of trioctyl trimellitate |
| CN106770720A (en) * | 2016-11-29 | 2017-05-31 | 深圳职业技术学院 | The analysis method of organic solvent sample composition |
| CN106770720B (en) * | 2016-11-29 | 2019-07-02 | 深圳职业技术学院 | The analysis method of organic solvent sample composition |
| CN107167529A (en) * | 2017-05-03 | 2017-09-15 | 浙江省计量科学研究院 | The assay method of the Reinheitszahl and uncertainty of phenol and hydroquinones standard substance |
| CN107167529B (en) * | 2017-05-03 | 2019-09-13 | 浙江省计量科学研究院 | The measuring method of the Reinheitszahl and uncertainty of phenol and hydroquinone standard substance |
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| Publication number | Publication date |
|---|---|
| CN1177221C (en) | 2004-11-24 |
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