CN103728398B - A kind of Ion-pair Liquid Chromatography measures the method for dyeing and finishing auxiliaries for textile neutral line alkyl benzene sulfonate - Google Patents
A kind of Ion-pair Liquid Chromatography measures the method for dyeing and finishing auxiliaries for textile neutral line alkyl benzene sulfonate Download PDFInfo
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Abstract
The present invention discloses a kind of method that Ion-pair Liquid Chromatography measures dyeing and finishing auxiliaries for textile neutral line alkyl benzene sulfonate, belongs to LAS residue analysis detection field in dyeing and finishing auxiliaries for textile.Step is: 1) sample solution preparation: under ultrasonic assistant, use intensive polar solvent sample dissolution; 2) Solid phase extraction; 3) after Ion-pair Liquid Chromatography is separated, detect with fluorescence detector; Take neopelex as benchmark, carry out qualitative analysis by the chromatographic retention of LAS in duplicate solution and standard solution, special finger-print, carry out quantified by external standard method with the peak area sum of 4 of LAS key components.Ion-pair Liquid Chromatography of the present invention measures the method for LAS in dyeing and finishing auxiliaries for textile, and detection sensitivity is high, antijamming capability is strong, qualitative, quantitative is accurate.
Description
Technical field
The present invention relates to linear alkyl benzene sulfonate detection technique field, is a kind ofly adopt that ultrasound on extracting, Solid phase extraction, Ion-pair Liquid Chromatography are separated, fluorescence detector measures the method for various dyeing and finishing auxiliaries for textile neutral line alkyl benzene sulfonate in particular.
Background technology
Dyeing and finishing auxiliaries for textile can be divided into anionic, cationic, nonionic and amphoteric, wherein the application of anionic surfactant-linear alkyl benzene sulfonate (LAS) class surfactant widely, and LAS has become the designate of daily anionic surfactant.LAS, the LINER ALKYL BENZENE SULPHONIC ACID SOFT 96 sodium being 10 ~ 13 by carbon chain lengths usually forms (chemical structural formula is see Fig. 1), and hydrophobic group is alkyl phenyl, and hydrophilic group is sulfonic group.80% is had for surfactant in textile auxiliary, LAS is commonly used for high temperature levelling agent, various types of dyeing and finishing auxiliaries for textile such as look levelling agent, high-effective penetrating refining agent, spun silk softening agent, detergent repaiied by scouring and dyeing degreaser, salt tolerant high temperature levelling agent, the smooth silicone oil emulsion of negative ion, the special bright glue of water-based, terylene, is widely used in the textile process processes such as spinning, starching, dyeing, stamp, arrangement.
The LAS used in caused by spinning industrial production, a part to be adsorbed on textile fiber and may with consumer's dress afterwards and use procedure in and transfer on human body skin, most LAS can be discharged in the water environment of China along with dyeing and finishing wastewater.Research shows: LAS has certain toxicity to aquatic animal and plant, and C10-LAS is 5.9mg/L to the EC50 of fish, and along with the lengthening of alkyl hydrophobic chain, the toxicity of LAS can improve.For this reason, on September 16th, 1996, Denmark's energy and Ministry of environment have formally issued a regulation and have been called 823 regulations, LAS are listed in the list of substances of " imperfect ".In May, 2002, the L133/29 official gazette that EU Committee issues " COMMISSIONDECISIONonestablishingtheecologicalcriteriafor theawardoftheCommunityeco-labeltotextileproductsandamend ingDecision1999/178/EC(is about the resolution of setting up ecological spinning Product labelling and supplement 1999/178/EC) ", namely European Union of European Union textile eco-label Eco-label(2002/371/EC resolves).Require in the 13 section that resolves this European Union official: must not use containing chemical assistants such as LAS, APEO, EDTA, DTPA, DSDMAC in textile dyeing and finishing.Issued, have in the whole world Oeko-Tex Standard Oeko-texstandard1000(AssessmentoftheEnvironmentallyFrien dlyTextile of material impact power by international ecological textile test and research association) also explicitly call for and must not use containing chemical assistants such as LAS, DSDMAC in the production run of the textile hanging with Oeko-Tex label.Therefore; in order to Protection of consumer is healthy and ecologic environment; and ensure inapplicable harmful auxiliary agent in order to the source processed from textile dyeing and finishing, carry out the cleaner production of textile industry, be badly in need of the assay method formulating dyeing and finishing auxiliaries for textile neutral line alkyl benzene sulfonate (LAS).
Ion-pair chromalography refers to by adding suitable gegenion, and the sample of homo-ionization forms ion pair, and this ion pair compound molecule, with neutral or non-polar molecule is the same, obtain good liquid chromatography and is separated.
China has comparatively early promulgated the bioassay standard GB/T7494-87 " the mensuration MBAS spectrophotometry of water quality anionic surfactant " of LAS in water quality, this standard specifies the blue compound generated in LAS reaction with chloroform recovery methylene blue, then detects with spectrophotometer.The method detection is sensitive, cost is low, but qualitative inaccurate, is difficult to the anionic surfactant distinguishing other type.Standard GB/T 13199-91 " the mensuration potentiometric titration of water quality anionic detergent " defines and uses potentiometric determination LAS, and the method is only applicable to the mensuration of constant LAS, can not be used for the lower residual quantity rank of LAS content and detect.Standard GB/T/T23325-2009 " the mensuration linear alkyl benzene sulfonate of textile surface activating agent " defines LAS residual in LC-MS/MS textile, method accurately, fast, but LC-MS/MS is expensive, testing cost is high, and the matrix detected is the fiber textile of solid-state form instead of the dyeing and finishing auxiliaries of liquid form.Seen publicity patent of invention " a kind of anion surface active soil extract and assay method " (application number: 201110053749.9) and " a kind of method measuring anionic surfactant in surface water " (application number: 201110150474.0), be all adopt sub-methyl blue spectrum analysis detect.In the existing report of the research about LAS residue detection, overwhelming majority research is all the detection of LAS residual in water environment, and all adopt high performance liquid chromatography (HPLC) separation, diode array detector (or UV-detector) detection, liquid-phase condition is not optimized when HPLC detects, the chromatogram of LAS retain and degree of separation all poor, and larger with the disturbing effect be subject to during ultraviolet light detection LAS.At present, research report and method standard that in dyeing and finishing auxiliaries for textile, LAS residue analysis detects is had no.
Summary of the invention
1, the technical matters that will solve is invented
For in dyeing and finishing auxiliaries for textile matrix, dopant species is more, content is higher, interference is larger, and target analytes LAS more, the complex structure that is the potpourri of a series of homolog and isomers, chemical composition, chemical polarity is comparatively strong, on the anti-phase C18 post of routine, be difficult to the feature that chromatogram retains, the invention provides a kind of method that Ion-pair Liquid Chromatography method measures dyeing and finishing auxiliaries for textile neutral line alkyl benzene sulfonate, effectively can purify sample, remove impurity; Increasing its chromatogram on anti-phase C18 post to retain by adding the anion binding of kation to reagent and LAS to generate the lower compound of polarity in mobile phase, producing the LAS finger-print that specificity is stronger; For phenyl ring in LAS chemical constitution uv absorption and can the special nature of emitting fluorescence, select fluorescence detector to detect, effectively can reduce the spectra1 interfer-of other material.
2, technical scheme
Solution principle: the sulfonate radical containing strong polarity in the chemical constitution of linear alkyl benzene sulfonate of the present invention, need by adding kation to reagent in mobile phase, alkyl sulfonate ion and kation association reaction is made to generate the more weak compound of polarity, thus increase the chromatogram reservation of compound on conventional C18 post, improve the degree of separation analyzing thing.In liquid chromatography, conventional ammonium acetate is as ion-pairing agent, is reacted generate the more weak compound of polarity by the acetate ion of its ionization and ammonium radical ion and strong polar analytes.The negative ion of benzene sulfonamide acid group is gone out because LAS is ionizable, this ionic molecule amount is larger, and ammonium radical ion molecular weight, be difficult to reagent the polarity fundamentally changing LAS using ammonium acetate as kation, the chromatogram of the LAS after being combined with ammonium radical ion on anti-phase C18 post retains still poor.The present invention selects biphosphate TBuA to be ion-pairing agent, the molecular weight of the kation dihydro TBuA ionized out is larger, after the benzene sulfonamide acid group anion binding ionized with LAS, the compound that polarity is more weak can be generated, reduce the polarity of target analytes, increase the liquid chromatography reservation analyzing thing.
Ion-pair Liquid Chromatography measures a method for dyeing and finishing auxiliaries for textile neutral line alkyl benzene sulfonate, and step is:
1) sample solution preparation: take dyeing and finishing auxiliaries for textile sample and be about 1g(and be accurate to 0.0001g), be placed in 50mL volumetric flask, with strong polar solvent constant volume.Be placed in ultrasonic generator, the ultrasonic process of normal temperature about 30min.
2) Solid-Phase Extraction (SPE) purification: select specification to be that strong anion exchange (SAX) post of 500mg/5mL is as solid-phase extraction column; First with 5mL methyl alcohol activation SAX post, then use 10mL water balance; Pipette 5mL sample solution on the SAX post activated, let alone to adsorb 10min; Use leacheate drip washing SAX post again, remove impurity, give up the solution after drip washing; Finally use the LAS on elution SAX post, collect elute soln; Draw ammonia spirit with dropper, regulate the pH value of elute soln, make it in 6.5 ~ 8.0 scopes.Be concentrated into Rotary Evaporators micro-dry, then be settled to 5mL with intensive polar solvent.
3) Ion-pair Liquid Chromatography analysis detects: liquid-phase chromatographic column is anti-phase C18 post, and specification is 5 μm × 2.1mm × 100mm, and column temperature is 30 DEG C, and sample size is 10 μ L; Mobile phase A be kation to reagent solution, Mobile phase B is acetonitrile, carries out gradient elution, detects with fluorescence detector (FLD); Take neopelex as reference material, qualitative and quantitative analysis is carried out to sample solution.
Above-mentioned dyeing and finishing auxiliaries for textile is be applied to the auxiliary agent of textile in the technological processs such as spinning, starching, dyeing, stamp, arrangement, as various types of dyeing and finishing auxiliaries for textile such as look levelling agent, high-effective penetrating refining agent, spun silk softening agent, detergent repaiied by high temperature levelling agent, scouring and dyeing degreaser, salt tolerant high temperature levelling agent, the smooth silicone oil emulsion of negative ion, the special bright glue of water-based, terylene.Above-mentioned linear alkyl benzene sulfonate (LAS) refers to that structure is R-C
6h
4-SO
3a series of alkyl benzene sulfonates of-(wherein R is straight chained alkyl).(referred to as C10-LAS, molecule is C to conventional linear alkyl benzene sulfonate ten sodium alkyl benzene sulfonate
16h
25sO
3na), (referred to as C11-LAS, molecule is C to undecyl benzene sulfonic acid sodium salt
17h
27sO
3na), (referred to as C12-LAS, molecule is C to neopelex
18h
29sO
3na) and tridecyl benzene sulfonate (referred to as C13-LAS, molecule is C
19h
31sO
34 kinds of compounds such as Na).As the neopelex of reference material, containing 4 kinds of main compound (neopelexes such as C10-LAS, C11-LAS, C12-LAS and C13-LAS, a series of homologs, wherein the content of different carbon chain compound is by analysis: 18%(C10), 23%(C11), 32%(C12), 23%(C13), 3%(C14), 1%(other), low content compound is difficult to detect, so just detect this four kinds of main compound.) potpourri, the average carbon number of alkyl chain is 12, and mean molecular weight is 344.4.
Above-mentioned intensive polar solvent is the mixed solution of first alcohol and water, and preferred reagent is methyl alcohol+water (50+50, v/v).
ELUTION METHOD in above-mentioned Solid phase extraction is: methanol solution and the 5mL methyl alcohol drip washing SAX post of using 5mL2% acetic acid successively, gives up leacheate.
Elution process in above-mentioned Solid phase extraction is: divide three wash-out SAX posts with 15mL eluent, and eluent is the mixed solution that isopyknic methyl alcohol and 2mol/L hydrochloric acid solution are configured to, and collects eluent.
The described kation as liquid chromatogram mobile phase A is quarternary ammonium salt compound to reagent, and kation is the biphosphate TBuA solution of 2.5mmol/L to reagent solution.
The flow velocity that described liquid chromatography is separated is 0.8ml/L, and gradient elution program is in table 1.
Table 1 gradient elution program
| Time/min | Mobile phase A/% | Mobile phase B/% |
| 0 | 50 | 50 |
| 2 | 50 | 50 |
| 9 | 30 | 70 |
| 11 | 30 | 70 |
| 13 | 50 | 50 |
| 15 | 50 | 50 |
The excitation wavelength of described fluorescence detector is 230nm, emission wavelength is 310nm.
3, beneficial effect:
The invention discloses a kind of method that Ion-pair Liquid Chromatography measures dyeing and finishing auxiliaries for textile neutral line alkyl benzene sulfonate, retain by adding the anion binding of kation to reagent and LAS generate the lower compound of polarity in mobile phase and increasing its chromatogram on anti-phase C18 post, produce unique, that specificity is stronger LAS finger-print; Select fluorescence detector to detect, effectively reduce the spectra1 interfer-of other material.Relative standard deviation (RSD) value is between 0.81% ~ 4.25%; Under 25mg/kg Pitch-based sphere, average recovery rate is 91.3%, RSD value is 6.71%; Under 100mg/kg and 1000mg/kg Pitch-based sphere, the recovery is higher, and RSD value is lower.Within the scope of the Pitch-based sphere of (25 ~ 1000) mg/kg, the recovery is in 90% ~ 100% scope, and RSD value is all less than 7%, and the recovery of this method and precision data all meet the analytical technology index of residue, and method is accurate.
Accompanying drawing explanation
Fig. 1 is the chemical structural drawing of LINER ALKYL BENZENE SULPHONIC ACID SOFT 96 sodium;
Fig. 2 is the Ion-pair Liquid Chromatography figure of neopelex standard solution;
Fig. 3 is the liquid chromatogram of neopelex standard solution when not using ion-pairing agent;
Fig. 4 is that spun silk softening agent sample is without Solid phase extraction (a) and the liquid chromatogram after Solid phase extraction (b).
Embodiment
Method of testing
(1) main agents, material and instrument and equipment:
2.5mmol/L biphosphate TBuA solution: take 0.849g biphosphate TBuA, is settled to 1000mL by water-soluble solution.
The methanol solution of 2% acetic acid: pipette 2mL acetic acid in 10mL volumetric flask, by methanol constant volume, shake up.
2mol/L hydrochloric acid solution: pipette 1.7mL concentrated hydrochloric acid in 10mL volumetric flask, use water constant volume, shake up.
2mol/L hydrochloric acid solution: methyl alcohol (1:1): pipette isopyknic methyl alcohol and 2mol/L hydrochloric acid solution in beaker, mixing
Neopelex reference material (CASNo:25155-30-0): purity >=80%, containing 4 kinds of main compound such as C10-LAS, C11-LAS, C12-LAS and C13-LAS, the average carbon number of alkyl chain is 12, and mean molecular weight is 344.4.
Standard Stock solutions (500mg/L): accurately take a certain amount of neopelex reference material, is dissolved in methyl alcohol+water (50+50, v/v), and constant volume also mixes, and is kept in the environment of 0 DEG C ~ 4 DEG C.
Standard working solution: accurately draw standard reserving solution, with methyl alcohol+water (50+50, v/v) stepwise dilution, is accurately mixed with the series standard working solution that concentration is 0.5mg/L, 1.0mg/L, 5.0mg/L, 10.0mg/L, 20.0mg/L, 50.0mg/L.
High performance liquid chromatograph (HPLC), is furnished with fluorescence detector (FLD).
Ultrasonic generator, with water-bath.
Solid-phase extraction column: strong anion exchange column (SAX), 500mg/5mL.
Solid-phase extraction device, is furnished with vacuum pumping pump.
(2) detecting step:
1) sample solution preparation: take dyeing and finishing auxiliaries for textile sample and be about 1g(and be accurate to 0.0001g), be placed in 50mL volumetric flask, with methyl alcohol+water (50+50, v/v) constant volume.Be placed in ultrasonic generator, the ultrasonic process of normal temperature about 30min.
2) Solid-Phase Extraction (SPE) purification: first with 5mL methyl alcohol activation SAX post, then use 10mL water balance; Pipette 5mL sample solution on the SAX post activated, let alone to adsorb 10min; Use the methanol solution drip washing SAX post of 2% acetic acid again, remove impurity, give up the solution after drip washing; Finally use 2mol/L hydrochloric acid solution: the LAS on methyl alcohol (1:1) eluant solution SAX post, collect elute soln; Draw ammonia spirit with dropper, regulate the pH value of elute soln, make it in 6.5 ~ 8.0 scopes, be concentrated into Rotary Evaporators micro-dry, then use methyl alcohol+water (50+50, v/v) to be settled to 5mL.
3) Ion-pair Liquid Chromatography analysis detects:
A) chromatographic column: C18 post, 5 μm, 4.6mm × 150mm or quite person;
B) flow velocity: 0.8mL/min;
C) column temperature: 30 DEG C;
D) sample size: 10 μ L;
E) detecting device: fluorescence detector (FLD);
F) excitation wavelength: 230nm, emission wavelength: 310nm;
G) mobile phase A: 2.5mmol/L biphosphate TBuA solution, Mobile phase B: acetonitrile;
H) gradient elution program: in table 1.
(3) qualitative and quantitative analysis
Concentration is series standard working solution and sample solution difference sample introduction under the HPLC condition of above setting of 0.5mg/L, 1.0mg/L, 5.0mg/L, 10.0mg/L, 20.0mg/L, 50.0mg/L, detects with fluorescence detector (FLD).In the range of linearity that standard working solution and sample solution response all should detect at instrument.Qualitative analysis is carried out, qualitative confirmation R-C by the retention time of component chromatographic peak tested in duplicate solution and standard working solution, finger-print and spectrum
6h
4-SO
3na(R=C10 ~ C13).
With the concentration of series standard working solution for horizontal ordinate, with R-C
6h
4-SO
3na(R=C10 ~ C13) peak area sum be ordinate, drawing standard working curve.According to the peak area sum of component tested in sample solution, standard working curve is tried to achieve R-C total in sample solution
6h
4-SO
3na(R=C10 ~ C13) concentration.
When adopting above-mentioned analysis condition, the HPLC-FLD of 5.0mg/L neopelex standard solution analyzes chromatogram and sees Fig. 2.
(4) method measures lower bound
The signal to noise ratio (S/N ratio) (S/N=10) of matrix blank solution and standard working curve calculate and measure lower bound per sample, and it is 25mg/kg that method of the present invention measures lower bound.
Comparative example 1: do not add kation and the high performance liquid chromatography of reagent is separated
(1) sample solution: 5.0mg/L neopelex standard solution, directly analyzes with HPLC-FLD.
(2) HPLC-FLD analysis condition:
A) chromatographic column: C18 post, 5 μm, 4.6mm × 150mm or quite person;
B) flow velocity: 0.8mL/min;
C) column temperature: 30C;
D) sample size: 10 μ L;
E) detecting device: fluorescence detector (FLD);
F) excitation wavelength: 230nm, emission wavelength: 310nm;
G) mobile phase A: 30mmol/L ammonium acetate solution, Mobile phase B: acetonitrile;
H) elution program: 60%A+40%B, isocratic elution.
(3) test findings
Not being both of instrumental conditions in the present embodiment 1 and defined terms of the present invention, does not add kation to reagent in mobile phase A, but ammonium acetate solution conventional in using current Research Literature to report is as buffer solution, and all the other are identical.Concentration is the instrumental conditions direct injection analysis of more than the LAS standard solution of 5.0mg/L, and the chromatogram that HPLC-FLD analyzes is shown in Fig. 3.As can be seen from Figure 3, when not using Ion-pair Liquid Chromatography, LAS is difficult to chromatogram and retains on the anti-phase C18 post of routine, and degree of separation is poor, cannot tell the component information of LAS.
The chromatogram that HPLC-FLD under the instrumental conditions that the LAS standard solution of Fig. 2 to be concentration be 5.0mg/L specifies in the present invention analyzes.Because the present invention is when high performance liquid chromatography is separated, kation is added to phosphorylating reagent dihydro TBuA (i.e. Ion-pair Liquid Chromatography) at mobile phase, generate the more weak compound of polarity by the kation of LAS and the cationoid reaction of biphosphate TBuA to retain to increase its chromatogram on anti-phase C18 post, obtain good chromatogram to retain and higher degree of separation, obtain unique, the finger-print that specificity is stronger shown in Fig. 2, be conducive to the accurate qualitative and quantitative analysis of LAS.
Comparative example 2: the sample analysis not adopting Solid phase extraction
(1) actual sample
The commodity that sample is provided by certain famous dyeing and finishing auxiliaries production company domestic, name is called: spun silk softening agent, and sample is the slight milkiness shape of white.
(2) detecting step
1) sample solution preparation: take sample and be about 1g(and be accurate to 0.0001g), be placed in 50mL volumetric flask, with methyl alcohol+water (50+50, v/v) constant volume.Be placed in ultrasonic generator, the ultrasonic process of normal temperature about 30min.Draw settled solution, directly carry out Ion-pair Liquid Chromatography analysis detection.
2) Ion-pair Liquid Chromatography analysis detects:
A) chromatographic column: C18 post, 5 μm, 4.6mm × 150mm or quite person;
B) flow velocity: 0.8mL/min;
C) column temperature: 30 DEG C;
D) sample size: 10 μ L;
E) detecting device: fluorescence detector (FLD);
F) excitation wavelength: 230nm, emission wavelength: 310nm;
G) mobile phase A: 2.5mmol/L biphosphate TBuA solution, Mobile phase B: acetonitrile;
H) gradient elution program: in table 1.
(3) test findings
Compared with the detecting step that detecting step in the present embodiment 2 and the present invention specify, lack Solid-Phase Extraction (SPE) purifying step, all the other are identical.Fig. 4 (a) is the chromatogram of the chromatogram of the detecting step test in spun silk softening agent sample the present embodiment 2, the detecting step test that Fig. 4 (b) specifies for the present invention of spun silk softening agent sample.By comparing discovery, comparatively serious without impurity interference in the sample chromatogram figure that SPE purification is analyzed, cannot accurate calculation sample chromatographic peak area, also just cannot carry out accurate quantitative analysis to sample; Sample chromatogram figure after SPE purification, clearly can find out the special finger-print of LAS, impurity does not have obvious interference to the component of LAS, and clean-up effect is obvious.
Embodiment 1: actual woven dyeing and finishing auxiliaries sample detection
(1), actual sample
Sample is produced by domestic certain famous dyeing and finishing auxiliaries production company and for the dyeing and finishing auxiliaries for textile of market sale, and provides the theoretical value of the LAS amount added in these dyeing and finishing auxiliaries processes of configuration.Have 9 kinds of dyeing and finishing auxiliaries for textile, can be applicable in the multiple textile dyeing and finishing treatment process processes such as spinning, starching, dyeing, stamp, arrangement.
(2), detecting step
1) sample solution preparation: take dyeing and finishing auxiliaries for textile sample and be about 1g(and be accurate to 0.0001g), be placed in 50mL volumetric flask, with methyl alcohol+water (50+50, v/v) constant volume.Be placed in ultrasonic generator, the ultrasonic process of normal temperature about 30min.
2) Solid-Phase Extraction (SPE) purification: first with 5mL methyl alcohol activation SAX post, then use 10mL water balance; Pipette 5mL sample solution on the SAX post activated, let alone to adsorb 10min; Use the methanol solution drip washing SAX post of 2% acetic acid again, remove impurity, give up the solution after drip washing; Finally use 2mol/L hydrochloric acid solution: the LAS on methyl alcohol (1:1) eluant solution SAX post, collect elute soln; Draw ammonia spirit with dropper, regulate the pH value of elute soln, make it in 6.5 ~ 8.0 scopes, be concentrated into Rotary Evaporators micro-dry, then use methyl alcohol+water (50+50, v/v) to be settled to 5mL.
3) Ion-pair Liquid Chromatography analysis detects:
A) chromatographic column: C18 post, 5 μm, 4.6mm × 150mm or quite person;
B) flow velocity: 0.8mL/min;
C) column temperature: 30 DEG C;
D) sample size: 10 μ L;
E) detecting device: fluorescence detector (FLD);
F) excitation wavelength: 230nm, emission wavelength: 310nm;
G) mobile phase A: 2.5mmol/L biphosphate TBuA solution, Mobile phase B: acetonitrile;
H) gradient elution program: in table 1.
(3), test findings
The theoretical value of LAS and actual detected value in table 4 dyeing and finishing auxiliaries for textile sample
Note: detection error=(actual detected value-theoretical value)/theoretical value × 100%
Table 4 lists the theoretical quantity adding LAS in the content of LAS in the 9 kinds of auxiliary agents detected through the present invention and sample actual disposition.As can be seen from the table, all there is not false positive and false negative phenomenon in 9 kinds of auxiliary agent sample detection, actual detected value and theoretical values, and the absolute value of the numerical value of deviation is therebetween not more than 5%, shows the qualitative and quantitative analysis of the inventive method all accurately and reliably.Carry out five parallel experiments to each dyeing and finishing auxiliaries for textile, relative standard deviation (RSD) value of five testing results, between 0.81% ~ 4.25%, shows that the inventive method is reliable and stable.
Embodiment 2: recovery of standard addition is tested
(1), test specimen
Produced by domestic certain famous dyeing and finishing auxiliaries production company and for the scouring and dyeing degreaser of market sale, in sample, do not detect LAS.In this negative sample, add the LAS standard solution of three concentration levels such as 25mg/kg, 100mg/kg and 1000mg/kg, the sample after mark-on measures by the inventive method.Each mark-on horizontal sample does five parallel samples.
(2), detecting step
1) sample solution preparation: take dyeing and finishing auxiliaries for textile sample and be about 1g(and be accurate to 0.0001g), be placed in 50mL volumetric flask, with methyl alcohol+water (50+50, v/v) constant volume.Be placed in ultrasonic generator, the ultrasonic process of normal temperature about 30min.
2) Solid-Phase Extraction (SPE) purification: first with 5mL methyl alcohol activation SAX post, then use 10mL water balance; Pipette 5mL sample solution on the SAX post activated, let alone to adsorb 10min; Use the methanol solution drip washing SAX post of 2% acetic acid again, remove impurity, give up the solution after drip washing; Finally use 2mol/L hydrochloric acid solution: the LAS on methyl alcohol (1:1) eluant solution SAX post, collect elute soln; Draw ammonia spirit with dropper, regulate the pH value of elute soln, make it in 6.5 ~ 8.0 scopes, be concentrated into Rotary Evaporators micro-dry, then use methyl alcohol+water (50+50, v/v) to be settled to 5mL.
3) Ion-pair Liquid Chromatography analysis detects:
A) chromatographic column: C18 post, 5 μm, 4.6mm × 150mm or quite person;
B) flow velocity: 0.8mL/min;
C) column temperature: 30 DEG C;
D) sample size: 10 μ L;
E) detecting device: fluorescence detector (FLD);
F) excitation wavelength: 230nm, emission wavelength: 310nm;
G) mobile phase A: 2.5mmol/L biphosphate TBuA solution, Mobile phase B: acetonitrile;
H) gradient elution program: in table 1.
(3), test findings
Three spiked levels graded levels samples through the inventive method is actual detect after numerical value in table 5, calculate average recovery rate and relative standard deviation (RSD) value of lower five parallel experiments of each mark-on level.
Table 5 adds the recovery of standard addition test figure of LAS to negative scouring and dyeing degreaser
As can be seen from Table 5: under 25mg/kg Pitch-based sphere, average recovery rate is 91.3%, RSD value is 6.71%; Under 100mg/kg and 1000mg/kg Pitch-based sphere, the recovery is higher, and RSD value is lower.Within the scope of the Pitch-based sphere of (25 ~ 1000) mg/kg, the recovery is in 90% ~ 100% scope, and RSD value is all less than 7%, and show that the recovery of this method and precision data all meet the analytical technology index of residue, method is accurate.
Claims (3)
1. Ion-pair Liquid Chromatography measures a method for dyeing and finishing auxiliaries for textile neutral line alkyl benzene sulfonate, the steps include:
1) sample solution preparation: take dyeing and finishing auxiliaries for textile sample 1g, be placed in 50mL volumetric flask, with strong polar solvent constant volume, be placed in ultrasonic generator, normal temperature ultrasonic process 30min; Wherein dyeing and finishing auxiliaries for textile is be applied to the auxiliary agent of textile in the technological processs such as spinning, starching, dyeing, stamp or arrangement: the special bright glue of high temperature levelling agent, scouring and dyeing degreaser, the smooth silicone oil emulsion of negative ion, water-based, terylene repair look levelling agent, high-effective penetrating refining agent, spun silk softening agent or detergent; Intensive polar solvent is the mixed solution of first alcohol and water, the methyl alcohol+water of common solvent to be v/v be 50+50;
2) Solid phase extraction: strong anion exchange column is as solid-phase extraction column; First with methyl alcohol activation, then watering balance; Pipette 5mL sample solution on the strong anion exchange column activated, let alone to adsorb 10min; Use leacheate drip washing strong anion exchange column again, remove impurity, give up the solution after drip washing; Finally use the linear alkyl benzene sulfonate on elution strong anion exchange column, collect elute soln; Draw ammonia spirit with dropper, regulate the pH value of elute soln, make it in 6.5 ~ 8.0 scopes, be concentrated into Rotary Evaporators micro-dry, then be settled to 5mL with intensive polar solvent; Wherein linear alkyl benzene sulfonate refers to that structure is R-C
6h
4-SO
3-alkyl benzene sulfonate, wherein R is straight chained alkyl; ELUTION METHOD is successively with methanol solution and 5mL methyl alcohol drip washing strong anion exchange column that 5mL acetic acid concentration of volume percent is 2%, divide three wash-out strong anion exchange columns with 15mL eluent, eluent is the mixed solution that isopyknic methyl alcohol and 2mol/L hydrochloric acid solution are configured to;
3) Ion-pair Liquid Chromatography analysis detects: liquid-phase chromatographic column is anti-phase C18 post, and specification is 5 μm × 2.1mm × 100mm, and column temperature is 30 DEG C, and sample size is 10 μ L; Mobile phase A be kation to reagent solution, Mobile phase B is acetonitrile, carries out gradient elution, detects with fluorescence detector (FLD); Take neopelex as reference material, qualitative and quantitative analysis is carried out to sample solution; Wherein as the neopelex of reference material, containing C10-LAS, C11-LAS, C12-LAS and C13-LAS4 kind main compound, the average carbon number of alkyl chain is 12, and mean molecular weight is 344.4; Be quarternary ammonium salt compound as the kation of liquid chromatogram mobile phase A to reagent, kation is the biphosphate TBuA solution of 2.5mmol/L to reagent solution.
2. method according to claim 1, is characterized in that step 3) in liquid chromatography be separated flow velocity be 0.8ml/L, gradient elution program is in table 1:
Table 1 gradient elution program
。
3. method according to claim 1, is characterized in that step 3) in fluorescence detector work time excitation wavelength be 230nm, emission wavelength is 310nm.
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