CN103175933A - Method for quantitatively detecting alkylphenol polyoxyethylene in daily chemical products - Google Patents

Abstract

The invention discloses a method for quantitatively detecting alkylphenol polyoxyethylene in daily chemical products, belonging to the technical field of analysis of daily chemical products. The method comprises the following steps of: preparing test samples, detecting the test samples via a high performance liquid chromatography, separating substances to be detected through a method for hybridizing a reversed-phase C18 column with an HILIC (Hydrophilic Interaction Liquid Chromatography) silica gel chromatography column, and quantitatively detecting the content of the alkylphenol polyoxyethylene in a daily chemical product through a fluorescence molar absorption coefficient method. Due to the method disclosed by the invention, the technical problem of great quantification errors of the alkylphenol polyoxyethylene can be effectively solved, and thus the method is very suitable for precise quantification and batch detection on the alkylphenol polyoxyethylene in the daily chemical products, provides important technical support for the mass control and the safety monitoring of the daily chemical products, and has good economic and social benefits.

Description

The method of APES in the quantitative measurement daily chemical product

Technical field

The present invention relates to the daily chemical product analysis field, particularly relate to the method for APES in a kind of quantitative measurement daily chemical product.

Background technology

APES (APEO _S) be a class non-ionics that is made by alkyl phenol and reacting ethylene oxide, because it has good wetting, infiltration, emulsification, dispersion, solubilising and cleaning function, be widely used in the industries such as daily-use chemical industry.According to statistics, APEO _SUse is with NPE (NP _nEO) or OPEO (OP _nEO) be main, both account for more than 95% of total amount altogether, and often add wherein a kind of material in use.Yet, due to APEO _SHave eco-toxicity, relatively poor biodegradability and may cause the environment incretion interference problem.European Union's 2003/53/EC instruction limits it and uses content lower than the 0.1%(weight percent in chemicals and prepared product thereof).China standard GB/T13171.1-2009 " washing powder " (phosphorous type), GB/T1317.2-2009 " washing powder " (without phosphorus type) and QB/T1224-2007 " dress material washes agent by liquid " all require to ban use of APEO _S

At present, bibliographical information is for APEO _SThe detection method of content mainly contains infra-red sepectrometry, GC-MS(gas chromatography-mass spectrography), liquid chromatography-uv detection method, liquid chromatography-fluorescence detection and Liquid Chromatography-Tandem Mass Spectrometry.Research object is mainly surrounding medium (water body and mud etc.), food, leather and textile, washing agent etc., and covers APEO in various daily chemical products _SDetection rarely have report.in addition, the relevant criterion of China's present is (as GB/T23322-2009 " the mensuration APES of textile surface activating agent ", GB/T23972-2009 " the mensuration high performance liquid chromatography/mass spectroscopy of alkylphenol and polyoxyethylene alkylphenol ether in dyeing and finishing auxiliaries for textile ", SN/T1850.1-2006 " the mensuration high performance liquid chromatography of alkyl benzene phenols and polyoxyethylene alkylphenol ether in textile " etc.) adopt reversed-phase liquid chromatography or reversed-phase liquid chromatography-mass spectrometric hyphenated technique, utilize appearance time and mass spectrum ion pair APES to measure.Yet, exist the compound form of different polymerization degree in different products due to APES, the appearance time of different polymerization degree is different, and the span scope of appearance time is larger, thereby causes adopting appearance time quantitatively to judge APES.And, because the APES molecular size range of different polymerization degree differs greatly, if in the situation that various degree of polymerization morphologization compounds are effectively separated, only adopt ultraviolet or fluorescence to carry out quantitatively can causing serious quantitative error.And adopt mass spectrometry quantitatively also may cause the relative abundance of fragmention inconsistent because of the existence of isomers, various mass spectrum ions add and thing (M+NH4 in addition, M+Na, M+K) abundance be subjected to the impact of system larger, also may cause deviation qualitatively.

In sum, develop a kind of novel chromatographic resolution and quantitative technique APES in daily chemical product is carried out accurate quantitative analysis mensuration, can promote the product quality of daily chemical product is carried out supervision and management effectively, to guaranteeing that the healthy and safe of consumer has very important significance.

Summary of the invention

Based on this, the object of the invention is to overcome the defective of prior art, the method for APES in a kind of quantitative measurement daily chemical product is provided, the method has advantages of that accuracy is high.

For achieving the above object, the present invention takes following technical scheme:

A kind of method of APES in quantitative measurement daily chemical product adopts high performance liquid chromatography to measure, and comprises the following steps:

(1) preparation test sample

Take sample in the constant volume container, add acetonitrile solution, with the abundant homogeneous of sample, ultrasonic extraction; Use the acetonitrile solution constant volume, centrifugal, get supernatant, filtering membrane obtains test sample;

(2) high-performance liquid chromatogram determination

Test sample is carried out high-performance liquid chromatogram determination, and condition is as follows:

Chromatographic column: anti-phase C ₁₈Cascaded H ILIC silica gel chromatographic column after post;

Column temperature: 30 ± 5 ℃;

Mobile phase: 10 ± 5mMol/L ammonium acetate aqueous solution and acetonitrile, gradient elution;

Flow velocity: constant current speed 1 ± 0.2mL/min;

Detecting device: fluorescence detector, excitation wavelength are 230 ± 10mn, and emission wavelength is 296 ± 10nm;

(3) quantitative calculation method

A. standard substance is measured by above-mentioned steps (2), is obtained the standard substance spectrogram, then calculate as follows fluorescence molar absorption coefficient (ε):

$\mathrm{\ϵ}=\frac{A\×M}{C\×V}\×{10}^9$

Wherein, ε is the fluorescence molar absorption coefficient, and unit is AU/mol; A is peak area, and unit is AU; M is molal weight, and unit is g/mol; C is concentration, and unit is mg/L; V is sampling volume, and unit is μ L;

B. sample is measured by above-mentioned steps (1) (2), obtained the sample spectrogram, then calculate as follows mean molecular weight M _{On average}:

Wherein, ∑ A is the peak area sum of all polymerization single polymerization monomers; A _nIt is the peak area of n monomer for the degree of polymerization; M _nIt is the molecular weight of n monomer for the degree of polymerization;

C. APES content w in calculation sample by the following method:

Wherein, ∑ A is the peak area sum of all polymerization single polymerization monomers, M _{On average}Be mean molecular weight; V ₁Be constant volume, unit is mL; V ₂Be sampling volume, unit is μ L; ε is the fluorescence molar absorption coefficient, and unit is AU/mol; M is sampling quality, and unit is g.

In embodiment, in step (2), described chromatographic column is Poroshell 120EC-C therein ₁₈Series connection Atlantis Hilic Slica post after post, described Poroshell 120EC-C ₁₈The specification of post is 75 * 4.6mm, 2.7 μ m, and the specification of described Atlantis Hilic Slica post is 250 * 4.6mm, 5 μ m.

In embodiment, in step (2), described mobile phase A is: the 10mM ammonium acetate aqueous solution therein; Mobile phase B is: acetonitrile; Gradient elution program: 0～4min keeps 3%A; 4～26min, 3%A～20%A.

In embodiment, in step (2), the excitation wavelength of fluorescence detector is 230nm therein, and emission wavelength is 296nm.

In embodiment, in step (2), described column temperature is 30 ℃ therein.

In embodiment, in step (2), described flow velocity is 1mL/min therein.

In embodiment, described step (1) is: accurately take the 0.5g sample, be placed in 10mL tool plug centrifuge tube, adding volume ratio is the acetonitrile solution 9mL of 8:2 therein, and whirlpool mixes, and ultrasound wave extracts 15min, uses the acetonitrile solution constant volume; Extract is through the centrifugal 5min of 15000r/min, and supernatant obtains test sample with 0.45 μ m membrane filtration.

Compared with prior art, the present invention has following beneficial effect:

The present invention adopts the content of APES in liquid chromatography separation-fluorescence Molar absorptivity quantitative measurement daily chemical product, n nonylphenol polyoxyethylene ether (NP _nEO) and OPEO (OP _nEO) the method quantitative limit (S/N=10) of content is 40.0mg/kg, and average recovery rate is 99.5%～105.7%, and relative standard deviation is less than 12.5%.Adopt method of the present invention to detect APES content in daily chemical product, pre-treatment is simple, and accuracy is high.By the dissimilar chromatographic column of tandem compound, can be with each monomer and matrix good separation; By measuring mean molecular weight, adopt the fluorescence Molar absorptivity quantitative, can effectively solve the large technical barrier of quantitative error of APES, be fit to very much accurate quantification and the batch detection of APES in daily chemical product; Be the daily chemical product quality control, the daily chemical product safety monitoring provides the important technology support, has good economic and social profit.

Description of drawings

Fig. 1 is the chromatogram of the standard solution of NPE in embodiment 1;

Fig. 2 is the chromatogram of the standard solution of OPEO in embodiment 1;

Fig. 3 is the chromatogram of liquid detergent sample in embodiment 1;

Fig. 4 is the chromatogram of cosmetic cream sample 1 in embodiment 2;

Fig. 5 is the chromatogram of cosmetic cream sample 2 in embodiment 3.

Embodiment

Describe the present invention in detail below in conjunction with the drawings and specific embodiments.

NPE (NP in embodiment 1 liquid detergent sample _nEO) and OPEO (OP _nEO) mensuration of content

1. preparation sample

Accurately take 0.5g (being accurate to 0.001g) liquid detergent sample, be placed in 10mL tool plug centrifuge tube, add approximately 9mL acetonitrile solution (8:2, v/v), after mixing on the vortex oscillation device makes sample dispersion, be placed in ultrasonic generator and extract 15min, be settled to scale with acetonitrile solution.Extract with 0.45 μ m membrane filtration, obtains test sample through the centrifugal 5min of 15000r/min.

Pipette NPE (the pure pharmaceutical worker of Japanese woods, 100 μ g/mL) and OPEO (the pure pharmaceutical worker of Japanese woods, 100 μ g/mL), take acetonitrile solution as solvent, above-mentioned NPE and OPEO are diluted to 2.0mg/L, 4.0mg/L, 10.0mg/L, 20.0mg/L, 50.0mg/L, and solution gets standard samples.

2. high-performance liquid chromatogram determination

2.1 NPE (NP _nEO) and OPEO (OP _nEO) foundation of reference substance chromatogram.

Accurate absorption 10 μ L concentration are that the standard model solution of 10.0mg/L injects high performance liquid chromatograph, measure according to following high-efficient liquid phase chromatogram condition, obtain NPE (NP ₁₅EO) and OPEO (OP ₁₀EO) chromatogram of reference substance (respectively as Fig. 1, shown in Figure 2).

Chromatographic column: Poroshell 120EC-C ₁₈(75 * 4.6mm, 2.7 μ m) the Atlantis Hilic Slica (250 * 4.6mm, 5 μ m) that connects;

Column temperature: 30 ℃;

Mobile phase: 10mM ammonium acetate aqueous solution (A) and acetonitrile (B); Gradient elution program: 0～4min keeps 3%A; 4～26min, 3%A～20%A; Rear operation 6min;

Flow velocity: constant current speed 1mL/min;

Detecting device: Agilent fluorescence detector (FLD) is as detecting device, fluorescence exciting wavelength: 230nm; Emission wavelength: 296nm.

2.2 the foundation of test sample chromatogram.

The accurate 10 μ L test sample solution of drawing inject high performance liquid chromatographs, according to above-mentioned high effective liquid chromatography for measuring, obtain chromatogram, as shown in Figure 3, and by appearance time judge to add material be NPEO.

3. quantitatively calculate

3.1 calculate fluorescence molar absorption coefficient (ε):

$\mathrm{\ϵ}=\frac{A\×M}{C\×V}\×{10}^9$

Wherein, ε is the fluorescence molar absorption coefficient, and unit is AU/mol; A is the standard substance peak area, and unit is AU; M is the standard substance molal weight, and unit is g/mol; C is concentration, and unit is mg/L; V is sampling volume, and unit is μ L;

With NP _nThe pure pharmaceutical worker of EO(Japan woods) concentration is that the standard solution of 10 μ g/mL is example, and according to its liquid phase spectrogram, the fluorescence molar absorption coefficient is calculated as follows shown in table 1:

The NP of table 1 different polymerization degree monomer _nEO fluorescence molar absorption coefficient

Be NPE and the OPEO standard solution of 2.0mg/L, 4.0mg/L, 10.0mg/L, 20.0mg/L, 50.0mg/L, 100.0mg/L by concentration precision absorption from low to high 10 μ L concentration, carrying out high performance liquid chromatography according to above-mentioned condition successively detects, calculate according to the method described above respectively the fluorescence molar absorption coefficient value that 2.0mg/L, 4.0mg/L, 10.0mg/L, 20.0mg/L, 50.0mg/L, 100.0mg/L standard solution at different levels draw, average again, be final fluorescence molar absorption coefficient in quantitative scope, the results are shown in Table 2.

Table 2 standard operation solution records mean molecular weight and fluorescence molar absorption coefficient ε

3.2 calculate mean molecular weight (M _{On average}):

Wherein, ∑ A is the peak area sum of all polymerization single polymerization monomers in the test sample spectrogram; A _nIt is the peak area of n monomer for the degree of polymerization; M _nIt is the molecular weight of n monomer for the degree of polymerization;

In present case, under same instrument and study condition, take liquid detergent as sample, obtain liquid phase spectrogram as shown in Figure 3, its mean molecular weight is calculated as follows table 3:

NPE (NP in table 3 liquid detergent sample _nEO) mean molecular weight

Wherein, because the APES of different polymerization degree appearance time on spectrogram is different, so its polymerization degree n can be judged by appearance time, concrete NP _1-15EO and OP _1-10EO monomer appearance time sees the following form 4, and calculates accordingly the APES molecular weight of this degree of polymerization.

Table 4NP _1-15EO and OP _1-10The EO monomer appearance time table of comparisons

3.3 APES content (w) in calculation sample:

Wherein, ∑ A is the peak area sum of all polymerization single polymerization monomers, M _{On average}Be mean molecular weight; V ₁Be constant volume, unit is mL; V ₂Be sampling volume, unit is μ L; ε is a mole absorption intensity, and unit is AU/mol; M is sampling quality, and unit is g.

Calculate NPEO content in liquid detergent according to following formula:

$\→w=\frac{134794.3\×662.4\×10}{2.81\×{10}^{13}\×0.5\×10}\×{10}^6=6.4\%.$

Obtain that in this liquid detergent sample, NPEO content is 6.4%.

NPE (NP in embodiment 2 cosmetic cream samples 1 _nEO) and OPEO (OP _nEO) mensuration of content

1. preparation sample

With embodiment 1

2. high-performance liquid chromatogram determination

With embodiment 1, obtain the test sample chromatogram, as shown in Figure 4, and by appearance time judge to add material be NPEO.

3. quantitatively calculate

3.1 calculate fluorescence molar absorption coefficient (ε)

With table 2 gained fluorescence molar absorption coefficient ε in embodiment 1.

3.2 calculate mean molecular weight (M _{On average})

In present case, under same instrument and study condition, take cosmetic cream 1 as sample, obtain liquid phase spectrogram as shown in Figure 4, its mean molecular weight computing method are with embodiment 1, table 5 specific as follows:

NPE (NP in table 5 cosmetic cream sample 1 _nEO) mean molecular weight

3.3 APES content (w) in calculation sample:

$\→w=\frac{6186.7\×603.4\×10}{2.81\×{10}^{13}\×0.5\×10}\×{10}^6=0.26\%.$

Obtain that in this cosmetic cream sample 1, NPEO content is 0.26%.

NPE (NP in embodiment 3 cosmetic cream samples 2 _nEO) and OPEO (OP _nEO) mensuration of content

1. preparation sample

With embodiment 1

2. high-performance liquid chromatogram determination

With embodiment 1, obtain the test sample chromatogram, as shown in Figure 5, and by appearance time judge to add material be OPEO.

3. quantitatively calculate

3.1 calculate fluorescence molar absorption coefficient (ε)

With table 2 gained fluorescence molar absorption coefficient ε in embodiment 1.

3.2 calculate mean molecular weight (M _{On average})

In present case, under same instrument and study condition, take cosmetic cream 2 as sample, obtain liquid phase spectrogram as shown in Figure 5, its mean molecular weight computing method are with embodiment 1, table 6 specific as follows:

OPEO (OP in table 6 cosmetic cream sample 2 _nEO) mean molecular weight

3.3 APES content (w) in calculation sample:

$\→w=\frac{5852.9\×592.4\×10}{2.87\×{10}^{13}\×0.5\×10}\×{10}^6=0.24\%.$

Obtain that in this cosmetic cream sample 2, OPEO content is 0.24%.

The mensuration of test example 1 quantitative scope

take acetonitrile solution as solvent, to mix mark NPE (the pure pharmaceutical worker of Japanese woods, 100 μ g/mL) and OPEO (the pure pharmaceutical worker of Japanese woods, 100 μ g/mL) be diluted to 2.0mg/L, 4.0mg/L, 10.0mg/L, 20.0mg/L, 50.0mg/L, by concentration precision absorption from low to high 10 μ L, carrying out high performance liquid chromatography according to the condition of embodiment 1 successively detects, calculate respectively 2.0mg/L, 4.0mg/L, 10.0mg/L, 20.0mg/L, 50.0mg/L, 100.0mg/L the fluorescence molar absorption coefficient value that standard solution at different levels draw, average again, be final fluorescence molar absorption coefficient in quantitative scope, table 2 in result such as embodiment 1.

According to table 2 result as can be known, in the 2-100mg/L concentration range, record NP _nEO and OP _nThe fluorescence molar absorption coefficient ε relative standard deviation of EO is all less than 5%, and therefore in this scope, the method for APES in quantitative measurement daily chemical product of the present invention can be used for quantitative measurement.

Test example 2 recovery tests

According to the detectability of method, to toner sample, cream frost sample, samples of latex, liquid detergent sample, washing powder sample, shampoo sample, according to the addition in table 2, add standard solution in each sample, carry out 4 experiments.Obtain average recovery rate and precision, result sees table 7.

Table 7 NPE (NP _nEO) and OPEO (OP _nEO) six kinds of dailyization

The average recovery (n=3) of adding in chemical product

The demonstration of table 7 result, in the experiment of matrix mark-on, the recovery of standard addition of six kinds of daily chemical product matrix is good.

The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.Should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.

Claims (7)

1. the method for APES in a quantitative measurement daily chemical product, is characterized in that, adopts high performance liquid chromatography to measure, and comprises the following steps:

(1) preparation test sample

Take sample in the constant volume container, add acetonitrile solution, with the abundant homogeneous of sample, ultrasonic extraction; Use the acetonitrile solution constant volume, centrifugal, get supernatant, filtering membrane obtains test sample;

(2) high-performance liquid chromatogram determination

Test sample is carried out high-performance liquid chromatogram determination, and condition is as follows:

Chromatographic column: anti-phase C ₁₈Cascaded H ILIC silica gel chromatographic column after post;

Column temperature: 30 ± 5 ℃;

Mobile phase: 10 ± 5mMol/L ammonium acetate aqueous solution and acetonitrile, gradient elution;

Flow velocity: constant current speed 1 ± 0.2mL/min;

Detecting device: fluorescence detector, excitation wavelength are 230 ± 10mn, and emission wavelength is 296 ± 10nm;

(3) quantitative calculation method

A. standard substance is measured by above-mentioned steps (2), is obtained the standard substance spectrogram, then calculate as follows fluorescence molar absorption coefficient ε:

Wherein, ε is the fluorescence molar absorption coefficient, and unit is AU/mol; A is peak area, and unit is AU; M is molal weight, and unit is g/mol; C is concentration, and unit is mg/L; V is sampling volume, and unit is μ L;

B. sample is measured by above-mentioned steps (1) (2), obtained the sample spectrogram, then calculate as follows mean molecular weight M _{On average}:

Wherein, ∑ A is the peak area sum of all polymerization single polymerization monomers; A _nIt is the peak area of n monomer for the degree of polymerization; M _nIt is the molecular weight of n monomer for the degree of polymerization;

C. APES content w in calculation sample by the following method:

Wherein, ∑ A is the peak area sum of all polymerization single polymerization monomers, M _{On average}Be mean molecular weight; V ₁Be constant volume, unit is mL; V ₂Be sampling volume, unit is μ L; ε is the fluorescence molar absorption coefficient, and unit is AU/mol; M is sampling quality, and unit is g.

2. the method for APES in quantitative measurement daily chemical product according to claim 1, is characterized in that, in step (2), described chromatographic column is Poroshell 120 EC-C ₁₈Series connection Atlantis Hilic Slica post after post, described Poroshell 120 EC-C ₁₈The specification of post is 75 * 4.6mm, 2.7 μ m, and the specification of described Atlantis Hilic Slica post is 250 * 4.6mm, 5 μ m.

3. the method for APES in quantitative measurement daily chemical product according to claim 1, is characterized in that, in step (2), described mobile phase A is: the 10mM ammonium acetate aqueous solution; Mobile phase B is: acetonitrile; Gradient elution program: 0～4min keeps 3%A; 4～26min, 3%A～20%A.

4. the method for APES in quantitative measurement daily chemical product according to claim 1, is characterized in that, in step (2), the excitation wavelength of fluorescence detector is 230nm, and emission wavelength is 296nm.

5. the method for APES in quantitative measurement daily chemical product according to claim 1, is characterized in that, in step (2), described column temperature is 30 ℃.

6. the method for APES in quantitative measurement daily chemical product according to claim 1, is characterized in that, in step (2), described flow velocity is 1mL/min.

7. the method for APES according to claim 1-6 described quantitative measurement daily chemical products of any one, it is characterized in that, described step (1) is: accurately take the 0.5g sample, be placed in 10mL tool plug centrifuge tube, adding volume ratio is the acetonitrile solution 9mL of 8:2, whirlpool mixes, and ultrasound wave extracts 15 min, uses the acetonitrile solution constant volume; Extract is through the centrifugal 5min of 15000r/min, and supernatant obtains test sample with 0.45 μ m membrane filtration.

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