CN105259281A - Method for determination of karanal content of plastic toy material - Google Patents

Abstract

The invention discloses a method for determination of karanal content of a plastic toy material, belongs to the technical field of analysis and especially relates to a method for determination of karanal content of a plastic toy material by a gas chromatography-mass spectrometer combined process. The method comprises crushing a sample, carrying out mixing to obtain a uniform mixture, weighing the uniform sample to be detected, dissolving the sample by N, N-dimethylformamide, carrying out balance at a temperature of 80 DEG C for 30min, carrying out determination by a headspace-gas chromatography-mass spectrometer combined method and carrying out quantification by an external standard method. The method is suitable for determination of karanal content of a plastic toy material, is simple and convenient and has a high precision.

Description

The assay method of karanal content in a kind of plastic toy material

Technical field

The invention belongs to analysis technical field, relate to the assay method of karanal content in a kind of plastic toy material, especially relate to a kind of method that gas chromatograph-mass spectrometer (GCMS) coupling measures karanal content in plastic toy material.

Background technology

Karanal, have another name called 2-(2,4-dimethyl-3-cyclohexyl)-5-methyl-5-(1-methyl-propyl)-1,3-dioxy oxane, 2-(4,6-dimethyl-3-cyclohexyl)-5-methyl-5-(1-methyl-propyl)-1,3-dioxy oxane, these two kinds of structures are the comparatively common isomers of karanal, see following formula.

Karanal has the isomers of multiple chirality, under seeing:

1，3-Dioxane，2-(2，4-dimethyl-3-cyclohexen-1-yl)-5-methyl-5-(1-methylpropyl)-

1，3-Dioxane，2-[(1R，2R)-2，4-dimethyl-3-cyclohexen-1-yl]-5-methyl-5-(1-methylpropyl)-，cis-rel-

1，3-Dioxane，2-[(1R，2R)-2，4-dimethyl-3-cyclohexen-1-yl]-5-methyl-5-(1-methylpropyl)-，trans-rel-

1，3-Dioxane，2-[(1S，2S)-2，4-dimethyl-3-cyclohexen-1-yl]-5-methyl-5-(1-methylpropyl)-，cis-

1，3-Dioxane，2-[(1S，2R)-2，4-dimethyl-3-cyclohexen-1-yl]-5-methyl-5-(1-methylpropyl)-，cis-

1，3-Dioxane，2-[(1R，2S)-2，4-dimethyl-3-cyclohexen-1-yl]-5-methyl-5-(1-methylpropyl)-，cis-

1，3-Dioxane，2-[(1R，2R)-2，4-dimethyl-3-cyclohexen-1-yl]-5-methyl-5-(1-methylpropyl)-，cis-

1，3-Dioxane，2-[(1S，2S)-2，4-dimethyl-3-cyclohexen-1-yl]-5-methyl-5-(1-methylpropyl)-，trans-

1，3-Dioxane，2-[(1S，2R)-2，4-dimethyl-3-cyclohexen-1-yl]-5-methyl-5-(1-methylpropyl)-，trans-

1，3-Dioxane，2-[(1R，2S)-2，4-dimethyl-3-cyclohexen-1-yl]-5-methyl-5-(1-methylpropyl)-，trans-

1，3-Dioxane，2-[(1R，2R)-2，4-dimethyl-3-cyclohexen-1-yl]-5-methyl-5-(1-methylpropyl)-，trans-

Karanal is colourless liquid, and tool is strong dry, have the wooden amber aroma sending out property, lasting ability by force, molecular formula C ₁₇h ₃₀o ₂, molecular weight 266.43, boiling point is higher than 250 DEG C, and water-soluble 0.61 ± 0.06mg/L is (at 19.7-20.2 DEG C; PH7.7-8.1), be the fragrance raw material with the dry imperial saliva banksia rose, be widely used in the daily chemical products such as perfume, soap, washing powder.Meanwhile, it also has outstanding fabric lasting ability, is widely used in shampoo and fabric softening agent.In European Union, karanal has been listed in the high attention rate material (SVHC) of European chemical balance motion office ECHA the 13rd crowd.

At present, toy manufacturer, for exploiting market, expands sales volume, and research and development diversification toy product, fragrance of wherein having expects that toy arises at the historic moment.At tool fragrance expect in the processing and making process of toy, often add lasting ability strong, the spices and essence of thick taste, and karanal because of lasting ability strong and there is strong ambergris enjoy toy manufacturer to favor.But, karanal is because having high persistence and high bioaccumulation, may cause certain harm to human body and environment, be put in REACH the 13 batch of high concern list of substances, in the toy trade imported and exported for Europe, the interpolation of karanal is by by the restriction of high degree.But, Chinese toy industry exports towards European Union area in a large number, in order to tackle REACH regulation, in the fragrant plastic toy of tool, the detection of the content of karanal necessitates index, so that can strictly the content of karanal in control finished toy in manufacturing process.

At present, the researchist of association area stresses in the synthesis of karanal and application, pertinent literature research and national standard not yet find to adopt HS GC MS test card garland aldehyde method for plastic toy material, and therefore the present invention sets up karanal content method in a kind of plastic toy of detection easily and efficiently material and has the meaning of Chinese medicine.

Summary of the invention

Technical matters to be solved by this invention is, provides the assay method of karanal content in a kind of plastic toy material.For achieving the above object, the present invention takes following design proposal:

The method that HS GC MS detects karanal content in plastic toy material comprises the steps:

By sample comminution, mixing.Take even testing sample 0.1-0.5 gram, add organic solvent DMF 10ml, temperature 80 DEG C, balance 30 minutes, measure by HS GC GC-MS, concrete instrument condition is:

Carrier gas: helium;

Flow rate of carrier gas: 1.00ml/min;

Chromatographic column: DB-5,15m × 0.25mm × 0.1 μm;

Sampling system: head space

Sample size: 1ml;

Injector temperature: 270 DEG C;

Transmission line temperature: 280 DEG C,

Column temperature: 70 DEG C keep 2min, and 20 DEG C/min is warming up to 290 DEG C, keep 10min;

MS condition: EI;

Ion source temperature 230 DEG C;

SIM mode scans;

Characteristic ion is m/z=120.0,157.0,107.0,266.0,69.0, and wherein m/z120 is quota ion.

Take karanal standard items, dissolve with methyl alcohol and as standard reserving solution after constant volume, be then the standard solution with finite concentration gradient with methanol dilution further, according to standard substance quality and response fit standard working curve;

Result of calculation, in sample, the computing formula of karanal content is

X＝c/m

In formula:

The content of karanal in X-sample, unit is milligrams per kilogram (mg/kg);

C-sample introduction sample concentration (μ g);

M-sample mass, unit is gram (g).

Preferably, testing sample 0.2 gram is taken

Preferably, the concentration of described standard solution is the gradient use liquid of 0.5,1.0,2.0,5,10 μ g.

Preferably, the described gas chromatograph-mass spectrometer that utilizes to the condition that sample treatment solution detects is: carrier gas: helium; Flow rate of carrier gas: 1.00ml/min; Chromatographic column: DB-5,15m × 0.25mm × 0.1 μm; Sample size: 1ml; Injector temperature: 270 DEG C; Transmission line temperature: 280 DEG C, column temperature: 70 DEG C keep 2min, and 20 DEG C/min is warming up to 290 DEG C, keep 10min;

MS condition: EI; Ion source temperature 230 DEG C; SIM mode scans; And qualitative according to mass spectra peak, external standard peak area method is quantitative.Characteristic ion: m/z=120.0,157.0,107.0,266.0,69.0;

Preferably, described external standard peak area method is quantitative, take m/z=120.0 as quota ion.

Karanal standard substance (isomers) total ion current figure is shown in Fig. 1, and four kinds of isomers retention times are at 7.3-8.0min.

Effective effect: advantage of the present invention is: adopt method of the present invention to detect the content of karanal in plastic toy material, fast effectively, RSD% is not more than 5%, detects and is limited to 0.02mg/kg.As can be seen here, method of the present invention, for detecting the detection of karanal in toy material, providing a kind of method being convenient to implement reliably, having higher precision and lower detection limit, can meet detection needs.

Accompanying drawing explanation

Fig. 1 karanal standard substance total ion current figure

Fig. 2 karanal standard substance mass spectrogram

Embodiment

Embodiment 1, the detection of karanal content in tygon plastic toy:

Precision takes karanal standard items (purity 95.5%) 13.09mg, methyl alcohol dissolve and constant volume be 25.0mL, concentration 500mg/L as storing solution, with methanol dilution 50 times, concentration 10mg/L, then dilution is the standard solution of 0.5,1.0,2.0,5,10 μ g.

Pulverized by solid sample, mix, get even testing sample 0.2002g, accurate weighing to 0.0001 gram, is placed in ml headspace bottle, adds 10mLN, N-dimethylformamide, analyzes after 80 DEG C of balance 30min with head space-GC-MS.

Detecting instrument is Shimadzu GC/MS-QP2010Ultra, joins HS-20 headspace sampling system;

Testing conditions is:

Carrier gas: helium;

Flow rate of carrier gas: 1.00ml/min;

Chromatographic column: DB-5,15m × 0.25mm × 0.1 μm;

Sampling system: HS-20 headspace sampling system

Sample size: 1ml;

Injector temperature: 270 DEG C;

Transmission line temperature: 280 DEG C,

Column temperature: 70 DEG C keep 2min, and 20 DEG C/min is warming up to 290 DEG C, keep 10min;

MS condition: EI;

Ion source temperature 230 DEG C;

SIM mode scans;

And qualitative according to mass spectra peak, external standard peak area method is quantitative.Characteristic ion: m/z=120.0,157.0,107.0,266.0,69.0;

In sample, the computing formula of karanal content is

X＝c/m---------------------------(1)

In formula:

The content of karanal in X-sample, unit is milligrams per kilogram (mg/kg);

C-sample introduction sample concentration (μ g);

M-sample mass, unit is gram (g).

Through calculating, result is:

In sample, the content of karanal calculates by formula (1), and result is as follows:

Apply specific case herein to set forth principle of the present invention and embodiment, the explanation of above embodiment just understands method of the present invention and core concept thereof for helping; Meanwhile, for one of ordinary skill in the art, according to thought of the present invention, all will change in specific embodiments and applications, in sum, this description should not be construed as limitation of the present invention.

Claims (3)

1. the assay method of karanal content in plastic toy material, is characterized in that described assay method comprises the steps:

A. sample preparation: by sample comminution, mixing, takes even testing sample 0.1-0.5 gram, adds 10mL organic solvent dissolution, and 80 DEG C balance 30 minutes, and HS GC GC-MS measures;

B. working curve: take karanal standard items, methyl alcohol dissolves and is diluted to series standard working fluid, and HS GC GC-MS measures, linear fit;

C. HS GC GC-MS detects;

D. calculate

In sample, the computing formula of karanal content is

X＝c/m

In formula:

The content of karanal in X-sample, unit is milligrams per kilogram (mg/kg);

C-sample introduction sample concentration (μ g);

M-sample mass, unit is gram (g).

2. sample preparation steps according to claim 1, is characterized in that described organic solvent is DMF.

3. HS GC GC-MS detecting step according to claim 1, is characterized in that described instrument condition is:

Carrier gas: helium;

Flow rate of carrier gas: 1.00ml/min;

Chromatographic column: DB-5,15m × 0.25mm × 0.1 μm;

Sampling system: head space

Sample size: 1ml;

Injector temperature: 270 DEG C;

Transmission line temperature: 280 DEG C,

Column temperature: 70 DEG C keep 2min, and 20 DEG C/min is warming up to 290 DEG C, keep 10min;

MS condition: EI;

Ion source temperature 230 DEG C;

SIM mode scans;

And qualitative according to mass spectra peak, external standard peak area method is quantitative, and characteristic ion is m/z=120.0, and 157.0,107.0,266.0,69.0, wherein m/z120 is quota ion.