CN106323891B - Azo dyes synthesis process rapid analysis method - Google Patents
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Abstract
A kind of azo dyes synthesis process rapid analysis method is related to a kind of dyestuff rapid analysis method, the coupled processes analysis detection of the diazo process analysis detection and step S2, azo dyes synthesis that synthesize including step S1, azo dyes；Step S1 is first to establish para-ester diazonium salt analysis model, prepares series para-ester diazo liquid sample to be measured in real time, and acquire spectroscopic data with light spectrometer immediately, measures the content of the para-ester diazonium salt under the differential responses time of para-ester diazo-reaction process；Step S2 is first to establish coupled processes reaction product analysis model, prepares series coupling reaction liquid sample to be measured in real time, and acquire spectroscopic data with light spectrometer immediately, measures the content of the azo dyes under the differential responses time of coupling reaction process, realize process control.The present invention is suitable for the real-time control of Dyestuff synthesis process, easy to operate, round of visits is short, and accuracy is high, inspection cost is low, has great importance in dye product quality monitoring.
Description
Technical field
The present invention relates to a kind of dyestuff rapid analysis method, the quick side of analysis of especially a kind of azo dyes synthesis process
Method.
Background technique
Azo dyes is fabric clothing most widely used one kind synthetic dyestuffs in dyeing and printing process, for a variety of natural
Dyeing and stamp with synthetic fibers, are also used for the coloring of paint, plastics, rubber etc..Azo is must examining for International Environmental Protection requirement
One of project, standard provides must not be containing the azo dyes intermediate of disabling in examined product.Dyestuff point currently used for inspection
Analysis method has high performance liquid chromatography, thin-layered chromatography, standard spectrophotometric method, chemical titration analysis etc..Wherein chromatography is quasi-
Exactness is high, but haves the shortcomings that complicated for operation, round of visits is long, inspection cost is high；Standard spectrophotometric method is based on Single wavelength more
Or dual wavelength analysis, quantitative analysis measurement result accuracy be not high.Present inventor is calculated it is proposed that crossing based on oblique projection
The dye content analysis method of method, i.e. Authorization Notice No. are a kind of " quick detection side of dye content of CN103954713B
Method ", this method is a kind of simple and easy, rapidly and accurately measurement dye content method for dyestuff finished product, but due to it
Not in view of background component disturbed condition complicated during Dyestuff synthesis, it is not suitable for the real-time control of Dyestuff synthesis process.
Summary of the invention
The technical problem to be solved by the present invention is a kind of azo dyes synthesis process rapid analysis method is provided, to solve
It is of the existing technology it is complicated for operation, round of visits is long, inspection cost is high, accuracy is not high, is not suitable for Dyestuff synthesis process
The shortcoming of real-time control.
The technical solution for solving above-mentioned technical problem is: a kind of azo dyes synthesis process rapid analysis method, this method
The coupled processes point of the diazo process analysis detection and step S2, azo dyes synthesis that are synthesized including step S1, azo dyes
Analysis detection；The step S1 is first to establish para-ester diazonium salt analysis model, and real during para-ester diazo-reaction
When prepare series para-ester diazo liquid sample to be measured, adopted immediately with spectrometer after obtaining each para-ester diazo liquid sample to be measured
Collect spectroscopic data, measures the content of the para-ester diazonium salt under the differential responses time of para-ester diazo-reaction process；It is described
Step S2 be first establish coupled processes reaction product analysis model during diazonium salt coupling reaction, and in real time prepare system
Coupling reaction liquid sample to be measured is arranged, uses spectrometer collection spectroscopic data immediately after obtaining each coupling reaction liquid sample to be measured,
The content of the azo dyes under the differential responses time of coupling reaction process is measured, realizes process control.
A further technical solution of the present invention is: the step S1 is comprised the following steps:
S11, para-ester diazonium salt analysis model is established,
S12, series para-ester diazo liquid sample to be measured is prepared in real time,
S13, spectrometer collection multi-wavelength ultraviolet-visible light is used immediately after obtaining each para-ester diazo liquid sample to be measured
Modal data,
The content of para-ester diazonium salt in S14, measurement para-ester diazo liquid to be measured；
S15, step S14 is repeated, measures the para-ester diazonium under the differential responses time of para-ester diazo-reaction process
The content of salt realizes process control；
The step S2 is comprised the following steps:
S21, coupled processes reaction product analysis model is established,
S22, series coupling reaction liquid sample to be measured is prepared in real time,
S23, spectrometer collection multi-wavelength ultraviolet-visible spectrum is used immediately after obtaining each coupling reaction liquid sample to be measured
Data,
The content of azo dyes in S24, measurement coupling reaction liquid to be measured,
S25, step S24 is repeated, measures the content of the azo dyes under the differential responses time of coupling reaction process, realized
Process control.
The further technical solution of the present invention is: in step s 11, described establishes para-ester diazonium salt analysis model
Including following process:
The acquisition of S111, reference para-ester diazonium salt ultraviolet-visible light modal data:
It pipettes the solution of different volumes respectively from the para-ester diazo liquid of para-ester diazo-reaction process and holds to 100mL
In measuring bottle, constant volume is shaken up, and obtains the reference para-ester diazo liquid of series of concentrations；It is acquired using ultraviolet-visible fiber spectrometer and is
The spectroscopic data of the reference para-ester diazo liquid of column concentration, obtains spectrum data matrix A；
Active principle and other components in S112, liquid chromatogram-spectrum combination separation reference para-ester diazo liquid:
A kind of reference para-ester diazo liquid is arbitrarily chosen from the reference para-ester diazo liquid of series of concentrations, in selected liquid
Liquid-phase chromatographic analysis is carried out under phase chromatographic condition, while acquiring multi-wavelength ultraviolet-visible luminous intensity formatted data M；By luminous intensity
Formatted data is converted to the absorbance matrix M under different time under multi-wavelength1；Some wavelength therein is chosen to absorbance square
Battle array M1Mapping, judges the peak position of active principle, by absorbance matrix M1Middle active principle spectroscopic data Z1With other component spectras
Data B1It separates；
The content of para-ester diazonium salt in S113, measurement reference para-ester diazo liquid:
Respectively to absorbance matrix M1With active principle spectroscopic data Z1Summation integral is carried out, the ratio integrated by the two
Calculate the content x of active principle para-ester diazonium salt in reference para-ester diazo liquid1；
The Signal separator of S114, the active principle of reference para-ester diazo liquid and other components:
With singular value decomposition to active principle spectroscopic data Z1With other component spectra data B1Dimensionality reduction is carried out, using judgement
System independent variable method method determines active principle spectroscopic data Z1Number of principal components m1With other component spectra data B1It is main at
Score n1, from other component spectra data B after dimensionality reduction1N before middle selection1Column are used as background spectrum data H, from having after dimensionality reduction
Imitate component spectra data Z1M before middle selection1Column are used as effective spectroscopic data S；
The reference para-ester diazo liquid in various concentration is calculated separately out from spectrum data matrix A using oblique projection algorithm
The signal of middle active principle and other components, is denoted as ZF respectivelyaAnd BJb, while the basis of active principle when obtaining zero-dose is rung
Induction signal zjWith the base response signal b of other componentsj。
The further technical solution of the present invention is: in step S112, the selected liquid phase chromatogram condition are as follows:
Chromatographic column: C18 chromatographic column (4.6mm*150mm)；
Mobile phase: the aqueous solution prepared using 1g four butyl bromation amine and 3g sodium dihydrogen phosphate as buffer solution, wash by gradient
It is de-；
0-30min；Acetonitrile: water=40:60(V/V)；
30-55min；Acetonitrile: water=5:95(V/V)；
55-80min；Acetonitrile: water=95:5 (V/V)；
Flow velocity: 1.0mL/min；
Sample volume: 20 μ L；
Column temperature: 20 DEG C；
Detection wavelength: 270nm.
The further technical solution of the present invention is: in step s 12, the real-time preparation series para-ester weight to be measured
Nitrogen liquid sample includes following content:
During diazo-reaction, para-ester was taken with pipette every 2~5 minutes since being added dropwise sodium nitrite solution
Diazo liquid is diluted to beaker 100mL scale in beaker, with distilled water, obtains series para-ester diazo liquid sample to be measured.
The further technical solution of the present invention is: in step S14, it is right in measurement para-ester diazo liquid to be measured
The content of position ester diazonium salt includes following content:
Using Matlab computing platform, the multi-wavelength ultraviolet-visible light modal data of para-ester diazo liquid sample to be measured is imported,
In conjunction with oblique projection algorithm, the active principle para-ester diazonium salt signal value D of para-ester diazo liquid to be measured is calculatedaWith other components
Signal value Db, the content y for acquiring tested para-ester diazonium salt is calculated by formula I1:
In formula I；
DaAnd DbThe active principle of para-ester diazo liquid respectively to be measured and the signal of other components；
ZFaAnd BJbThe respectively signal of the active principle of reference para-ester diazo liquid and other components；
zj And bjFor the base response signal of active principle under zero-dose and other components；
x1For the content of reference para-ester diazonium salt.
The further technical solution of the present invention is: in the step s 21, described establishes the analysis of coupled processes reaction product
Model comprises the following steps:
S211, from the solution of different volumes is pipetted in coupling reaction liquid respectively into 100mL volumetric flask, constant volume shakes up, and obtains
To the reference coupling reaction liquid of series of concentrations；The reference coupling for acquiring the series of concentrations using ultraviolet-visible fiber spectrometer is anti-
The spectroscopic data for answering liquid obtains spectrum data matrix O；
S212, appoint from the reference coupling reaction liquid of series of concentrations and take portion, carried out under selected liquid phase chromatogram condition
Liquid-phase chromatographic analysis calculates the content x of its azo dyes with peak area normalization method2；It is acquired simultaneously in efficient liquid phase chromatographic analysis
Its multi-wavelength ultraviolet-visible luminous intensity formatted data M2, and luminous intensity formatted data is converted under different time multi-wavelength
Absorbance matrix M3；
S213, a certain wavelength of selection are to absorbance matrix M3It maps, behind the peak position for judging azo dyes, from absorbance square
Battle array M3In isolated azo dyes spectroscopic data Z2With other component spectra data B2；
S214, using judging that system independent variable counting method determines azo dyes spectroscopic data Z2With other component spectra numbers
According to B2Number of principal components m2；Using singular value decomposition [u, s, v]=SVD [B2] to other component spectra data B2Carry out dimensionality reduction；It will
Preceding m in data u2Column selection, which goes out, is used as background spectrum data BJ；Same azo dyes spectroscopic data Z2Dimensionality reduction chooses azo dyes
Spectroscopic data Z2Intermediate m2Column data is as active principle spectroscopic data ZF；
S215, computation platform import effective component spectra data ZF, background spectrum data BJ and reference coupling reaction
Liquid series of concentrations spectrum data matrix O calculates the letter of active principle and other components in coupling reaction liquid in conjunction with oblique projection algorithm
Number, it is denoted as ZaAnd Bb, it is fitted to obtain linear equation y21And y22, record the intercept z of equationj1And bj1, the zj1And bj1It is dense to respectively indicate zero
Spend the base response signal of lower active principle and other components.
The further technical solution of the present invention is: in step S22, the real-time preparation series coupling reaction to be measured
Liquid sample includes following content:
During diazonium salt coupling reaction, a certain amount of coupling was taken with pipette every 1~2 minute from being added after H acid
Reaction solution is diluted to beaker 100mL scale in beaker, with distilled water, obtains series coupling reaction liquid sample to be measured.
The further technical solution of the present invention is: in step s 24, azo in measurement coupling reaction liquid to be measured
The content of dyestuff includes following content:
Using Matlab computing platform, the multi-wavelength ultraviolet-visible light modal data of coupling reaction liquid sample to be measured is imported, is tied
Oblique projection algorithm is closed, the active principle azo dyes signal value O of coupling reaction liquid to be measured is calculatedaWith the signal value of background component
Ob, the content y for acquiring azo dyes in coupling reaction liquid to be measured is calculated by formula II2:
In formula II,
OaAnd ObThe active principle of coupling reaction liquid respectively to be measured and other constituent signals；
ZaAnd BbThe respectively active principle of reference coupling reaction liquid and other constituent signals；
zj1And bj1For the base response signal of active principle under zero-dose and other components；
x2For the content of the azo dyes of reference coupling reaction liquid.
Due to using the above structure, the azo dyes synthesis process rapid analysis method of the present invention compared with prior art,
It has the advantages that
1. being applicable to the real-time control of Dyestuff synthesis process
Since the present invention includes step S1, the diazo process analysis detection of azo dyes synthesis and step S2, azo dye
Expect the coupled processes analysis detection of synthesis；Wherein, step S1 is first to establish para-ester weight during para-ester diazo-reaction
Nitrogen salt analysis model, and series para-ester diazo liquid sample to be measured is prepared in real time, obtaining each para-ester diazo liquid sample to be measured
Spectrometer collection spectroscopic data is used after product immediately, measures the para-ester under the differential responses time of para-ester diazo-reaction process
The content of diazonium salt；Step S2 be first establish coupled processes reaction product analysis model during diazonium salt coupling reaction, and
Series coupling reaction liquid sample to be measured is prepared in real time, uses spectrometer collection immediately after obtaining each coupling reaction liquid sample to be measured
Spectroscopic data measures the content of the azo dyes under the differential responses time of coupling reaction process, realizes process control.Therefore,
The present invention is analysis object with azo dyes diazotising and the reaction system of coupled processes, is adopted by spectrum-liquid chromatogram combination
The multi-wavelength ultraviolet-visible light intensity formatted data for collecting dyestuff reaction process system obtains tested component data by data processing
Library and background component database without tested component eliminate complicated background component interference during Dyestuff synthesis in real time,
It is then based on oblique projection algorithm, azo dyes diazotising is established and coupled processes is tested the analysis model of component, realize to azo
Dyestuff diazotising and coupled processes are tested the analysis of component, are highly suitable for the real-time control of Dyestuff synthesis process.
2. easy to operate, round of visits is short:
The rapid analysis method that the present invention establishes can quickly analyze prepare liquid without accurately carrying out solution preparation to be measured
In be tested constituent content, easy to operate, round of visits is short, hence it is evident that improves analysis efficiency.
3. accuracy is high, inspection cost is low:
The present invention is obtained by data processing is tested component database and the background component database without tested component, real
When eliminate background component interference complicated during Dyestuff synthesis, be then based on oblique projection algorithm, establish azo dyes diazonium
Change the analysis model for being tested component with coupled processes, realize that azo dyes diazotising and coupled processes are tested the analysis of component,
Its accuracy is higher, can meet accuracy of quantitative analysis, can also reduce reagent loss, inspection cost is reduced, in dye product quality
Monitoring has great importance.
In the following, in conjunction with the accompanying drawings and embodiments to the technical characteristic of the azo dyes synthesis process rapid analysis method of the present invention
It is further described.
Detailed description of the invention
Fig. 1: in the step S112 of embodiment one, absorbance value schematic diagram under different time under multi-wavelength,
Fig. 2: in the step S112 of embodiment one, the time of integration of para-ester diazo liquid and response in the case where wavelength is 270nm
The relational graph of value,
Fig. 3: in the step S114 of embodiment one, serial reference para-ester diazo liquid different volumes ratio and principal component (contraposition
Ester diazonium salt) signal relational graph,
Fig. 4: in the step S114 of embodiment one, serial reference para-ester diazo liquid different volumes ratio and background component signal
Relational graph,
Fig. 5: in the step S15 of embodiment one, para-ester diazonium salt content with the differential responses time variation schematic diagram,
Fig. 6: in the step S212 of embodiment one, absorbance value schematic diagram under different time under multi-wavelength,
Fig. 7: in the step S213 of embodiment one, the time of integration of reference coupling reaction liquid and the relational graph of response,
Fig. 8: in the step S215 of embodiment one, reference coupling reaction liquid difference sample volume and principal component (reactive dye
KN-B) signal relation figure,
Fig. 9: in the step S215 of embodiment one, reference coupling reaction liquid difference sample volume and background component signal relation
Figure,
Figure 10: in the step S25 of embodiment one, coupling reaction product (Reactive dye red M-3BE) content is with the differential responses time
Change schematic diagram.
Specific embodiment
A kind of azo dyes synthesis process rapid analysis method, the method comprising the steps of S1, azo dyes synthesis diazonium
Change the coupled processes analysis detection of process analysis procedure analysis detection and step S2, azo dyes synthesis；The step S1 is in para-ester
During diazo-reaction, para-ester diazonium salt analysis model is first established, and prepares series para-ester diazo liquid sample to be measured in real time
Product use spectrometer collection spectroscopic data immediately after obtaining each para-ester diazo liquid sample to be measured, measure para-ester diazotising
The content of para-ester diazonium salt under the differential responses time of reaction process；The step S2 is in diazonium salt coupling reaction mistake
Cheng Zhong first establishes coupled processes reaction product analysis model, and prepares series coupling reaction liquid sample to be measured in real time, every obtaining
Spectrometer collection spectroscopic data is used after a coupling reaction liquid sample to be measured immediately, measures the differential responses time of coupling reaction process
Under azo dyes content, realize process control.
Above-mentioned step S1 is comprised the following steps:
S11, para-ester diazonium salt analysis model is established:
The acquisition of S111, reference para-ester diazonium salt ultraviolet-visible light modal data:
It pipettes the solution of different volumes respectively from the para-ester diazo liquid of para-ester diazo-reaction process and holds to 100ml
In measuring bottle, constant volume is shaken up, and obtains the reference para-ester diazo liquid of series of concentrations；It is acquired using ultraviolet-visible fiber spectrometer and is
The spectroscopic data of the reference para-ester diazo liquid of column concentration, obtains spectrum data matrix A；
Active principle and other components in S112, liquid chromatogram-spectrum combination separation reference para-ester diazo liquid:
A kind of reference para-ester diazo liquid is arbitrarily chosen from the reference para-ester diazo liquid of series of concentrations, in selected liquid
Liquid-phase chromatographic analysis is carried out under phase chromatographic condition, while acquiring multi-wavelength ultraviolet-visible luminous intensity formatted data M；By luminous intensity
Formatted data is converted to the absorbance matrix M under different time under multi-wavelength1；Some wavelength therein is chosen to absorbance square
Battle array M1Mapping, judges the peak position of active principle, by absorbance matrix M1Middle active principle spectroscopic data Z1With other component spectras
Data B1It separates；The selected liquid phase chromatogram condition are as follows:
Chromatographic column: C18 chromatographic column (4.6mm*150mm)；
Mobile phase: the aqueous solution prepared using 1g four butyl bromation amine and 3g sodium dihydrogen phosphate as buffer solution, wash by gradient
It is de-；
0-30min；Acetonitrile: water=40:60(V/V)；
30-55min；Acetonitrile: water=5:95(V/V)；
55-80min；Acetonitrile: water=95:5 (V/V)；
Flow velocity: 1.0mL/min；
Sample volume: 20 μ L；
Column temperature: 20 DEG C；
Detection wavelength: 270nm；
The content of para-ester diazonium salt in S113, measurement reference para-ester diazo liquid:
Respectively to absorbance matrix M1With active principle spectroscopic data Z1Summation integral is carried out, the ratio integrated by the two
Calculate the content x of active principle para-ester diazonium salt in reference para-ester diazo liquid1；
The Signal separator of S114, the active principle of reference para-ester diazo liquid and other components:
With singular value decomposition to active principle spectroscopic data Z1With other component spectra data B1Dimensionality reduction is carried out, using judgement
System independent variable method method determines active principle spectroscopic data Z1Number of principal components m1With other component spectra data B1It is main at
Score n1, from other component spectra data B after dimensionality reduction1N before middle selection1Column are used as background spectrum data H, from having after dimensionality reduction
Imitate component spectra data Z1M before middle selection1Column are used as effective spectroscopic data S；
The reference para-ester diazo liquid in various concentration is calculated separately out from spectrum data matrix A using oblique projection algorithm
The signal of middle active principle and other components, is denoted as ZF respectivelyaAnd BJb, while the basis of active principle when obtaining zero-dose is rung
Induction signal zjWith the base response signal b of other componentsj；
S12, series para-ester diazo liquid sample to be measured is prepared in real time:
During diazo-reaction, taken with pipette since being added dropwise sodium nitrite solution every 2~5 minutes a certain amount of
The para-ester diazo liquid of (about 0.1-0.2mL) is diluted to beaker 100mL scale in 100mL beaker, with distilled water, obtains series
Para-ester diazo liquid sample to be measured；
S13, spectrometer collection multi-wavelength ultraviolet-visible light is used immediately after obtaining each para-ester diazo liquid sample to be measured
Modal data；
The content of para-ester diazonium salt in S14, measurement para-ester diazo liquid to be measured；
Using Matlab computing platform, the multi-wavelength ultraviolet-visible light modal data of para-ester diazo liquid sample to be measured is imported,
In conjunction with oblique projection algorithm, the active principle para-ester diazonium salt signal value D of para-ester diazo liquid to be measured is calculatedaWith other components
Signal value Db, the content y for acquiring tested para-ester diazonium salt is calculated by formula I1:
In formula I；
DaAnd DbThe active principle of para-ester diazo liquid respectively to be measured and the signal of other components；
ZFaAnd BJbThe respectively signal of the active principle of reference para-ester diazo liquid and other components；
zj And bjFor the base response signal of active principle under zero-dose and other components；
x1For the content of reference para-ester diazonium salt；
S15, step S14 is repeated, measures the para-ester diazonium under the differential responses time of para-ester diazo-reaction process
The content of salt realizes process control；
Above-mentioned step S2 is comprised the following steps:
S21, coupled processes reaction product analysis model is established:
S211, from the solution of different volumes is pipetted in coupling reaction liquid respectively into 100mL volumetric flask, constant volume shakes up, and obtains
To the reference coupling reaction liquid of series of concentrations；The reference coupling for acquiring the series of concentrations using ultraviolet-visible fiber spectrometer is anti-
The spectroscopic data for answering liquid obtains spectrum data matrix O；
S212, appoint from the reference coupling reaction liquid of series of concentrations and take portion, carried out under selected liquid phase chromatogram condition
Liquid-phase chromatographic analysis calculates the content x of its azo dyes with peak area normalization method2；It is acquired simultaneously in efficient liquid phase chromatographic analysis
Its multi-wavelength ultraviolet-visible luminous intensity formatted data M2, and luminous intensity formatted data is converted under different time multi-wavelength
Absorbance matrix M3；Wherein liquid phase chromatogram condition:
Chromatographic column: C18 chromatographic column (4.6mm*150mm)；
Mobile phase: using the aqueous solution that 1g four butyl bromation amine and 3g sodium dihydrogen phosphate are prepared as buffer solution；Gradient is washed
It is de-；
0-30min；Acetonitrile: water=40:60(V/V)；
30-55min；Acetonitrile: water=5:95(V/V)
55-80min；Acetonitrile: water=95:5 (V/V)
Flow velocity: 1.0mL/min；
Sample volume: 20 μ L；
Column temperature: 20 DEG C；
Detection wavelength: 270nm；
S213, a certain wavelength of selection are to absorbance matrix M3It maps, behind the peak position for judging azo dyes, from absorbance square
Battle array M3In isolated azo dyes spectroscopic data Z2With other component spectra data B2；
S214, using judging that system independent variable counting method determines azo dyes spectroscopic data Z2With other component spectra numbers
According to B2Number of principal components m2；Using singular value decomposition [u, s, v]=SVD [B2] to other component spectra data B2Carry out dimensionality reduction；It will
Preceding m in data u2Column selection, which goes out, is used as background spectrum data BJ；Same azo dyes spectroscopic data Z2Dimensionality reduction chooses azo dyes
Spectroscopic data Z2Intermediate m2Column data is as active principle spectroscopic data ZF；
S215, computation platform import effective component spectra data ZF, background spectrum data BJ and reference coupling reaction
Liquid series of concentrations spectrum data matrix O calculates the letter of active principle and other components in coupling reaction liquid in conjunction with oblique projection algorithm
Number, it is denoted as ZaAnd Bb, it is fitted to obtain linear equation y21And y22, record the intercept z of equationj1And bj1, the zj1And bj1It is dense to respectively indicate zero
Spend the base response signal of lower active principle and other components；
S22, series coupling reaction liquid sample to be measured is prepared in real time:
During diazonium salt coupling reaction, a certain amount of (about 0.1- was taken with pipette every 1~2 minute from being added after H acid
Coupling reaction liquid 0.2mL) is diluted to beaker 100mL scale in beaker, with distilled water, obtains series coupling reaction liquid to be measured
Sample；
S23, spectrometer collection multi-wavelength ultraviolet-visible spectrum is used immediately after obtaining each coupling reaction liquid sample to be measured
Data；
The content of azo dyes in S24, measurement coupling reaction liquid to be measured,
Using Matlab computing platform, the multi-wavelength ultraviolet-visible light modal data of coupling reaction liquid sample to be measured is imported, is tied
Oblique projection algorithm is closed, the active principle azo dyes signal value O of coupling reaction liquid to be measured is calculatedaWith the signal value of background component
Ob, the content y for acquiring azo dyes in coupling reaction liquid to be measured is calculated by formula II2:
In formula II,
OaAnd ObThe active principle of coupling reaction liquid respectively to be measured and other constituent signals；
ZaAnd BbThe respectively active principle of reference coupling reaction liquid and other constituent signals；
zjAnd bjFor the base response signal of active principle under zero-dose and other components；
x2For the content of the azo dyes of reference coupling reaction liquid；
S25, step S24 is repeated, measures the content of the azo dyes under the differential responses time of coupling reaction process, realized
Process control.
It is the example that the present invention is embodied below:
Embodiment one
The present invention is using Reactive dye red M-3BE dyestuff as research object, to illustrate diazotising and coupled processes in azo dyes synthesis
Rapid analysis method.
A kind of azo dyes --- Reactive dye red M-3BE Dyestuff synthesis process rapid analysis method, the method comprising the steps of S1,
Diazo process analysis detection and step S2, the coupled processes analysis detection of azo dyes synthesis of azo dyes synthesis；Wherein:
The diazo process analysis detection that S1, azo dyes synthesize
Firstly, steps are as follows for para-ester diazo-reaction:
200mL distilled water, control is added in 1000mL three-necked flask in precise para-ester 5.860g (0.02mol)
For reaction temperature at 5-6 DEG C, electric stirring is beaten 10min；
36% HCl of HCl 0.06mol(6.083g is added dropwise in 10min), then stir 10min；
Weigh sodium nitrite 0.021mol(1.509g) and water 3.521g be configured to 30% solution, dropping liquid is used in 10min
30% sodium nitrite solution is added dropwise in funnel；
5-6 DEG C of reaction temperature of control is reacted 30 minutes to 1 hour.
Step S1, the diazo process analysis detection of azo dyes synthesis comprises the following steps:
S11, para-ester diazonium salt analysis model is established:
The acquisition of S111, reference para-ester diazonium salt ultraviolet-visible light modal data:
Pipetted respectively from the para-ester diazo liquid of para-ester diazo-reaction process 25 μ L, 50 μ L, 100 μ L, 150 μ L,
Into 100mL volumetric flask, constant volume shakes up 200 μ L solution, obtains reference para-ester diazo liquid D1-D5；Using ultraviolet-visible optical fiber
Spectrometer collection reference para-ester diazo liquid D1-D5Spectroscopic data, obtain spectrum data matrix A；
Active principle and other components in S112, liquid chromatogram-spectrum combination separation reference para-ester diazo liquid:
Choose reference para-ester diazo liquid D4, liquid-phase chromatographic analysis is carried out under selected chromatographic condition, while acquiring more
Length ultraviolet-visual intensity formatted data M；Light intensity formatted data is converted to the absorbance square under different time under multi-wavelength
Battle array M1, such as Fig. 1；
Selecting wavelength is 270nm to absorbance matrix M1Mapping, as shown in Fig. 2, judging the peak position of active principle from Fig. 2
It sets, and then from absorbance matrix M1In isolate active principle spectroscopic data Z1With other component spectra data B1；Selection z=
Absor(:,240:300);As principal component spectroscopic data, b=Absor (:, [1:239 301:1500]) is chosen;As other
The spectroscopic data of component (background).
Wherein selected liquid phase chromatogram condition are as follows:
Chromatographic column: C18 chromatographic column (4.6mm*150mm)；
Mobile phase: the aqueous solution prepared using 1g four butyl bromation amine and 3g sodium dihydrogen phosphate as buffer solution, wash by gradient
It is de-；
0-30min；Acetonitrile: water=40:60(V/V)；
30-55min；Acetonitrile: water=5:95(V/V)；
55-80min；Acetonitrile: water=95:5 (V/V)；
Flow velocity: 1.0mL/min；
Sample volume: 20 μ L；
Column temperature: 20 DEG C；
Detection wavelength: 270nm；
The content of para-ester diazonium salt in S113, measurement reference para-ester diazo liquid:
Respectively to absorbance matrix M1With active principle spectroscopic data Z1Summation integral is carried out, the ratio integrated by the two
Calculate the content x of active principle para-ester diazonium salt in reference para-ester diazo liquid1It is 87.65%；
The Signal separator of S114, the active principle of reference para-ester diazo liquid and other components:
With singular value decomposition to active principle spectroscopic data Z1With other component spectra data B1Dimensionality reduction is carried out, using judgement
System independent variable method method determines active principle spectroscopic data Z1Number of principal components m1For 4 and other component spectra data B1's
Number of principal components n1It is 6, from other component spectra data B after dimensionality reduction16 column are used as background spectrum data H before middle selection, from dimensionality reduction
Active principle spectroscopic data Z afterwards14 column are used as effective spectroscopic data S before middle selection；
The reference para-ester diazo liquid in various concentration is calculated separately out from spectrum data matrix A using oblique projection algorithm
The signal of middle active principle and other components, is denoted as ZF respectivelyaAnd BJb, while the basis of active principle when obtaining zero-dose is rung
Induction signal zjWith the base response signal b of other componentsj, zj=-46.788, bj=48.501, it the results are shown in Table 1, Fig. 3, Fig. 4；
S12, series para-ester diazo liquid sample to be measured is prepared in real time:
During para-ester diazo-reaction, liquid relief was successively used every 2-5 minutes since being added dropwise sodium nitrite solution
Pipe takes a certain amount of (about 0.1-0.2mL) reaction solution in 100mL beaker, and distilled water is diluted to beaker 100mL scale and obtains F1-F9
Number para-ester diazo liquid sample to be measured；
S13, it is adopted respectively using ultraviolet-visible fiber spectrometer immediately after obtaining each para-ester diazo liquid sample to be measured
Collect the spectroscopic data G1-G9 of para-ester diazo liquid sample to be measured；
The content of para-ester diazonium salt in S14, measurement para-ester diazo liquid to be measured:
Using Matlab computing platform, spectroscopic data G1 is imported, in conjunction with oblique projection algorithm, calculates No. F1 para-ester weight to be measured
The active principle para-ester diazonium salt signal value D of nitrogen liquid sampleaWith the signal value D of other componentsb, by formula I measure No. F1 to
Survey the content y of the para-ester diazonium salt in para-ester diazo liquid sample1,
In formula I；
DaAnd DbThe active principle of para-ester diazo liquid respectively to be measured and the signal of other components；
ZFaAnd BJbThe respectively signal of the active principle of reference para-ester diazo liquid and other components；
zj And bjFor the base response signal of active principle under zero-dose and other components；
x1For the content of reference para-ester diazonium salt；
S15, step S14 is repeated, successively imports spectroscopic data G2-G9, in conjunction with oblique projection algorithm, sequentially determining F2-F9
The content of para-ester diazonium salt in para-ester diazo liquid sample to be measured, when obtaining the differential responses of para-ester diazo-reaction process
Between under para-ester diazonium salt changes of contents situation, realize process control, as a result see Fig. 5.
, azo dyes synthesis coupled processes analysis detection
Firstly, steps are as follows for diazonium salt coupling reaction:
Diazo-reaction liquid pH value is adjusted with solid sodium bicarbonate to stablize after 7.2, keeps ice bath at the reaction temperatures, point
0.01mol H acid dry powder 3.85g H acid is added in diazotizing solution by two batches, and electric stirring reacts 10-15min.
Step S2, the coupled processes analysis detection of azo dyes synthesis comprises the following steps:
S21, coupled processes reaction product analysis model is established:
S211, pipetted respectively from coupling reaction liquid 50 μ L, 100 μ L, 150 μ L, 200 μ L, 250 μ L, 300 μ L solution to
In 100mL volumetric flask, constant volume is shaken up, and obtains reference coupling reaction liquid O1-O5；It should using the acquisition of ultraviolet-visible fiber spectrometer
Reference coupling reaction liquid O1-O5Spectroscopic data, obtain spectrum data matrix O；
S212, from reference coupling reaction liquid O1-O5In take reference coupling reaction liquid O4, under selected liquid phase chromatogram condition
Liquid-phase chromatographic analysis is carried out, the content x of its active principle (Reactive dye red M-3BE) is calculated with peak area normalization method2, determine the activity
The content x of black KN-B dyestuff2It is 85.43%；Its multi-wavelength ultraviolet-visible luminous intensity is acquired simultaneously in efficient liquid phase chromatographic analysis
Formatted data M2, and luminous intensity formatted data is converted to the absorbance matrix M under different time multi-wavelength3, such as Fig. 6；Selected
Liquid phase chromatogram condition is as follows:
Chromatographic column: C18 chromatographic column (4.6mm*150mm)；
Mobile phase: using the aqueous solution that 1g four butyl bromation amine and 3g sodium dihydrogen phosphate are prepared as buffer solution；Gradient is washed
It is de-；
0-30min；Acetonitrile: water=40:60(V/V)；
30-55min；Acetonitrile: water=5:95(V/V)
55-80min；Acetonitrile: water=95:5 (V/V)
Flow velocity: 1.0mL/min；
Sample volume: 20 μ L；
Column temperature: 20 DEG C；
Detection wavelength: 270nm；
S213, to select wavelength be 315nm to absorbance matrix M3Mapping, judge active principle Reactive dye red M-3BE goes out peak position
It sets, and then from absorbance matrix M3In isolate active principle active black -4KN spectroscopic data Z2With other component spectra data B2,
As shown in Figure 7；Selection Z=Absor (:, 931:1113);As principal component spectroscopic data, choose B=Absor (:, [1:930
1114:3500]);Spectroscopic data as other backgrounds.
S214, using judging that system independent variable counting method determines azo dyes spectroscopic data Z2With other component spectra numbers
According to B2Number of principal components m2It is 5；Using singular value decomposition [u, s, v]=SVD [B2] to other component spectra data B2Carry out dimensionality reduction；
5 column selection preceding in data u is gone out and is used as background spectrum data BJ；Same azo dyes spectroscopic data Z2Dimensionality reduction chooses azo dye
Expect spectroscopic data Z2Intermediate 5 column datas are as active principle (Reactive dye red M-3BE) spectroscopic data ZF；
S215, using Matlab computing platform, import effective component spectra data ZF, background spectrum data BJ and reference be even
Reaction solution series of concentrations spectrum data matrix O is closed, in conjunction with oblique projection algorithm, calculates in coupling reaction liquid active principle and other groups
The signal divided, is denoted as ZaAnd Bb, it is fitted to obtain linear equation y21And y22, record the intercept z of equationj1And bj1, the zj1And bj1Table respectively
Show the base response signal of active principle and other components under zero-dose, zj1And bj2Respectively -8.5014, -3.9408, such as table 2
With shown in Fig. 8, Fig. 9.
S22, series coupling reaction liquid sample to be measured is prepared in real time:
During diazonium salt coupling reaction, a certain amount of (about 0.1- was taken with pipette every 1~2 minute from being added after H acid
Coupling reaction liquid 0.2mL) is diluted to beaker 100mL scale in beaker, with distilled water, obtains P1-P9Number coupling reaction to be measured
Liquid sample；
S23, spectrometer collection multi-wavelength ultraviolet-visible spectrum is used immediately after obtaining each coupling reaction liquid sample to be measured
Data Q1-Q9；
The content of azo dyes in S24, measurement coupling reaction liquid to be measured:
Using Matlab computing platform, multi-wavelength ultraviolet-visible light modal data Q is imported1, in conjunction with oblique projection algorithm, calculate
P out1Active principle (Reactive dye red M-3BE) the signal value O of number coupling reaction liquid sample to be measuredaWith the signal value O of background componentb, lead to
It crosses the calculating of formula II and acquires P1The content y of Reactive dye red M-3BE in number coupling reaction liquid sample to be measured2；
In formula II；
OaAnd ObThe active principle of coupling reaction liquid respectively to be measured and other constituent signals；
ZaAnd BbThe respectively active principle of reference coupling reaction liquid and other constituent signals；
zj1And bj1For the base response signal of active principle under zero-dose and other components；
x2For the content of the azo dyes of reference coupling reaction liquid；
S25, step S24 is repeated, successively imports multi-wavelength ultraviolet-visible light modal data Q2-Q9, in conjunction with oblique projection algorithm, according to
Secondary measurement P2-P9The content of active principle Reactive dye red M-3BE in number coupling reaction liquid sample to be measured, obtains coupling reaction process
The changes of contents situation of Reactive dye red M-3BE under the differential responses time realizes process control, shown in the result is shown in Figure 10.
In order to verify the accurate of established para-ester diazonium salt analysis model and coupled processes reaction product analysis model
Property, following test now is made to para-ester diazonium salt analysis model and coupled processes reaction product analysis model respectively:
(1) para-ester diazonium salt analysis model is verified
Pipette the para-ester of 80 μ L, 120 μ L, 140 μ L respectively with pipette from same para-ester diazo-reaction product
Into 100mL volumetric flask, distilled water constant volume shakes up diazo liquid, obtains sample to be tested para-ester diazotising reaction mixture S1-S3；It adopts
Solution S is acquired respectively with ultraviolet-visible fiber spectrometer1-S3Multi-wavelength ultraviolet-visible light modal data, while to solution S1-
S3Carry out efficient liquid phase chromatographic analysis；
Using Matlab computing platform, sample to be tested para-ester diazotising reaction mixture S is successively imported1-S3Multi-wavelength it is purple
Outside-visible spectrum data successively calculate sample to be tested para-ester diazotising reaction mixture S in conjunction with oblique projection algorithm1-S3Have
Imitate component para-ester diazonium salt signal value DaWith the signal value D of other componentsb, tested para-ester is acquired by the calculating of above-mentioned formula I
The content y of diazonium salt1.And by the content results and high performance liquid chromatography of para-ester diazonium salt in the para-ester diazo liquid measured
The result measured is made comparisons, and comparison result is referring to table 3.
(2) coupled processes product analysis model is verified
From 200 μ L solution are pipetted in coupling reaction liquid respectively into 3 100mL volumetric flasks, distilled water constant volume shakes up, obtains
To sample to be tested coupling product solution O1-O3；Solution O is acquired using UV, visible light fiber spectrometer respectively1-O3Multi-wavelength it is purple
Outside-visible spectrum data, while to solution O1-O3Carry out efficient liquid phase chromatographic analysis；
Using Matlab computing platform, sample to be tested coupling product solution O is successively imported1-O3Multi-wavelength ultraviolet-visible
Spectroscopic data successively calculates sample to be tested coupling product solution O in conjunction with oblique projection algorithm1-O3Active principle (active black
KN-B) signal value OaWith the signal value O of background componentb, Reactive dye red M-3BE in coupling reaction liquid to be measured is acquired by the calculating of formula II
Content y2.And measure dyestuff (Reactive dye red M-3BE) content results in the coupling reaction liquid measured and high performance liquid chromatography
As a result it makes comparisons, compares referring to table 4.
Claims (4)
1. a kind of azo dyes synthesis process rapid analysis method, it is characterised in that: the method comprising the steps of S1, azo dyes close
At diazo process analysis detection and step S2, azo dyes synthesis coupled processes analysis detection；The step S1 is
During para-ester diazo-reaction, comprise the following steps:
S11, para-ester diazonium salt analysis model is established,
S12, series para-ester diazo liquid sample to be measured is prepared in real time,
S13, spectrometer collection multi-wavelength ultraviolet-visible spectrum number is used immediately after obtaining each para-ester diazo liquid sample to be measured
According to,
The content of para-ester diazonium salt in S14, measurement para-ester diazo liquid to be measured；
S15, step S14 is repeated, measures the para-ester diazonium salt under the differential responses time of para-ester diazo-reaction process
Content realizes process control；
The step S2 is comprised the following steps during diazonium salt coupling reaction:
S21, coupled processes reaction product analysis model is established,
S22, series coupling reaction liquid sample to be measured is prepared in real time,
S23, spectrometer collection multi-wavelength ultraviolet-visible spectrum number is used immediately after obtaining each coupling reaction liquid sample to be measured
According to,
The content of azo dyes in S24, measurement coupling reaction liquid to be measured,
S25, step S24 is repeated, measures the content of the azo dyes under the differential responses time of coupling reaction process, realize process
Control；
In step s 11, the para-ester diazonium salt analysis model of establishing includes following process:
The acquisition of S111, reference para-ester diazonium salt ultraviolet-visible light modal data:
The solution of different volumes is pipetted respectively from the para-ester diazo liquid of para-ester diazo-reaction process to 100mL volumetric flask
In, constant volume shakes up, and obtains the reference para-ester diazo liquid of series of concentrations；It is dense using ultraviolet-visible fiber spectrometer acquisition series
The spectroscopic data of the reference para-ester diazo liquid of degree, obtains spectrum data matrix A；
Active principle and other components in S112, liquid chromatogram-spectrum combination separation reference para-ester diazo liquid:
A kind of reference para-ester diazo liquid is arbitrarily chosen from the reference para-ester diazo liquid of series of concentrations, in selected liquid phase color
Liquid-phase chromatographic analysis is carried out under spectral condition, while acquiring multi-wavelength ultraviolet-visible luminous intensity formatted data M；By luminous intensity format
Data are converted to the absorbance matrix M under different time under multi-wavelength1；Some wavelength therein is chosen to absorbance matrix M1
Mapping, judges the peak position of active principle, by absorbance matrix M1Middle active principle spectroscopic data Z1With other component spectra data
B1It separates；
The content of para-ester diazonium salt in S113, measurement reference para-ester diazo liquid:
Respectively to absorbance matrix M1With active principle spectroscopic data Z1Summation integral is carried out, the ratio calculation integrated by the two
Out in reference para-ester diazo liquid active principle para-ester diazonium salt content x1；
The Signal separator of S114, the active principle of reference para-ester diazo liquid and other components:
With singular value decomposition to active principle spectroscopic data Z1With other component spectra data B1Dimensionality reduction is carried out, using judging system
Independent variable method method determines active principle spectroscopic data Z1Number of principal components m1With other component spectra data B1Number of principal components
n1, from other component spectra data B after dimensionality reduction1N before middle selection1Column are used as background spectrum data H, from effective group after dimensionality reduction
It is divided modal data Z1M before middle selection1Column are used as effective spectroscopic data S；
Have in the reference para-ester diazo liquid of various concentration using oblique projection algorithm from being calculated separately out in spectrum data matrix A
The signal for imitating component and other components, is denoted as ZF respectivelyaAnd BJb, while the base response letter of active principle when obtaining zero-dose
Number zjWith the base response signal b of other componentsj；
In step S14, the content of para-ester diazonium salt includes following content in the measurement para-ester diazo liquid to be measured:
Using Matlab computing platform, the multi-wavelength ultraviolet-visible light modal data of para-ester diazo liquid sample to be measured is imported, in conjunction with
Oblique projection algorithm calculates the active principle para-ester diazonium salt signal value D of para-ester diazo liquid to be measuredaWith the letter of other components
Number value Db, the content y for acquiring tested para-ester diazonium salt is calculated by formula I1:
In formula I；
DaAnd DbThe active principle of para-ester diazo liquid respectively to be measured and the signal of other components；
ZFaAnd BJbThe respectively signal of the active principle of reference para-ester diazo liquid and other components；
zjAnd bjFor the base response signal of active principle under zero-dose and other components；
x1For the content of reference para-ester diazonium salt；
In the step s 21, the coupled processes reaction product analysis model of establishing comprises the following steps:
S211, from the solution of different volumes is pipetted in coupling reaction liquid respectively into 100mL volumetric flask, constant volume shakes up, and is
The reference coupling reaction liquid of column concentration；The reference coupling reaction liquid of the series of concentrations is acquired using ultraviolet-visible fiber spectrometer
Spectroscopic data, obtain spectrum data matrix O；
S212, appoint from the reference coupling reaction liquid of series of concentrations and take portion, carry out liquid phase under selected liquid phase chromatogram condition
Chromatography calculates the content x of its azo dyes with peak area normalization method2；It is more that it is acquired simultaneously in efficient liquid phase chromatographic analysis
Length ultraviolet-visual intensity formatted data M2, and luminous intensity formatted data is converted to the extinction under different time multi-wavelength
Spend matrix M3；
S213, a certain wavelength of selection are to absorbance matrix M3It maps, behind the peak position for judging azo dyes, from absorbance matrix M3
In isolated azo dyes spectroscopic data Z2With other component spectra data B2；
S214, using judging that system independent variable counting method determines azo dyes spectroscopic data Z2With other component spectra data B2
Number of principal components m2；Using singular value decomposition [u, s, v]=SVD [B2] to other component spectra data B2Carry out dimensionality reduction；By data u
In preceding m2Column selection, which goes out, is used as background spectrum data BJ；Same azo dyes spectroscopic data Z2Dimensionality reduction chooses azo dyes spectrum number
According to Z2Intermediate m2Column data is as active principle spectroscopic data ZF；
S215, computation platform import effective component spectra data ZF, background spectrum data BJ and reference coupling reaction liquid system
Column concentration optical spectrum data matrix O calculates the signal of active principle and other components in coupling reaction liquid in conjunction with oblique projection algorithm,
It is denoted as ZaAnd Bb, it is fitted to obtain linear equation y21And y22, record the intercept z of equationj1And bj1, the zj1And bj1Respectively indicate zero-dose
The base response signal of lower active principle and other components；
In step s 24, the content of azo dyes includes following content in the measurement coupling reaction liquid to be measured:
Using Matlab computing platform, the multi-wavelength ultraviolet-visible light modal data of coupling reaction liquid sample to be measured is imported, in conjunction with oblique
Projection algorithm calculates the active principle azo dyes signal value O of coupling reaction liquid to be measuredaWith the signal value O of background componentb, lead to
It crosses formula II and calculates the content y for acquiring azo dyes in coupling reaction liquid to be measured2:
In formula II,
OaAnd ObThe active principle of coupling reaction liquid respectively to be measured and other constituent signals；
ZaAnd BbThe respectively active principle of reference coupling reaction liquid and other constituent signals；
zj1And bj1For the base response signal of active principle under zero-dose and other components；
x2For the content of the azo dyes of reference coupling reaction liquid.
2. azo dyes synthesis process rapid analysis method according to claim 1, it is characterised in that: in step S112
In, the selected liquid phase chromatogram condition are as follows:
Chromatographic column: C18 chromatographic column (4.6mm*150mm)；
Mobile phase: using the aqueous solution that 1g four butyl bromation amine and 3g sodium dihydrogen phosphate are prepared as buffer solution, gradient elution；
0-30min；Acetonitrile: water=40:60(V/V)；
30-55min；Acetonitrile: water=5:95(V/V)；
55-80min；Acetonitrile: water=95:5 (V/V)；
Flow velocity: 1.0mL/min；
Sample volume: 20 μ L；
Column temperature: 20 DEG C；
Detection wavelength: 270nm.
3. azo dyes synthesis process rapid analysis method according to claim 1, it is characterised in that: in step s 12,
The real-time preparation series para-ester diazo liquid sample to be measured includes following content:
During diazo-reaction, para-ester diazonium was taken with pipette every 2~5 minutes since being added dropwise sodium nitrite solution
Liquid is diluted to beaker 100mL scale in beaker, with distilled water, obtains series para-ester diazo liquid sample to be measured.
4. azo dyes synthesis process rapid analysis method according to claim 1, it is characterised in that: in step S22,
The real-time preparation series coupling reaction liquid sample to be measured includes following content:
During diazonium salt coupling reaction, a certain amount of coupling reaction was taken with pipette every 1~2 minute from being added after H acid
Liquid is diluted to beaker 100mL scale in beaker, with distilled water, obtains series coupling reaction liquid sample to be measured.
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