JP2017096865A - Assaying method for trace chlorine content - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method to make possible accurate assaying of any trace chlorine content in a high-matrix containing sample with a combined 1 mass% content or more of halogen atoms and/or sulfur atoms selected from fluorine, bromine and iodine.SOLUTION: An assaying method for trace chlorine content comprises a pretreating step of decomposing a 1 mass% content or more of halogen selected from fluorine, bromine and iodine and a step of assaying the concentration of chlorine contained in the sample by analyzing the decomposed sample with an induction-combined plasma-triple quadrupole type analyzing device.SELECTED DRAWING: None

Description

  The present invention relates to a method for quantifying trace chlorine components. Specifically, the present invention relates to a method for highly sensitive determination of trace chlorine components in a sample containing 1% by mass or more of halogen atoms and / or sulfur atoms selected from fluorine, bromine and iodine.

  Conventionally, compounds containing halogen such as chlorine and bromine have been used as flame retardants in electrical and electronic equipment. Such flame retardants sometimes cause dioxins when incinerated and discarded, causing environmental pollution. In production, chlorine and bromine in the raw material can cause deterioration of production equipment, corrosion, and the like. Therefore, the transition to halogen-free alternatives is in progress. Thus, interest in halogen-free is increasing in the field of electronic materials, and the demand for halogen-free is increasing not only for flame retardants but also for materials and raw materials of electronic devices.

  The quantitative determination of the trace chlorine component in the sample is generally performed by a combustion apparatus-ion chromatograph method. In quantitative determination of trace chlorine components in low matrix samples containing less than 1% by mass of halogen atoms and / or sulfur atoms selected from fluorine, bromine and iodine, highly sensitive quantitative analysis can be achieved by increasing the amount of decomposition. Is possible. On the other hand, in the case of a high matrix sample containing 1% by mass or more of the halogen atoms and / or sulfur atoms, if the amount of decomposition is increased, the ion exchange capacity in the separation column of the ion chromatograph introduction system may be exceeded. Element recovery is significantly reduced. Therefore, it is necessary to suppress the amount of decomposition and increase the dilution rate, and it is difficult to quantify with high sensitivity and high accuracy.

  This invention is made | formed in view of the said situation, and it aims at providing the method which can quantify a trace amount chlorine component accurately also in a high matrix sample.

  As a result of intensive studies to achieve the above-mentioned object, the present inventor uses a inductively coupled plasma-triple quadrupole mass spectrometer as a detector to detect a small amount of chlorine components in a high matrix sample with high sensitivity. -The present invention has been completed by finding that it can be quantitatively determined with high accuracy.

Accordingly, the present invention provides the following method for quantifying trace chlorine components.
1. A pretreatment step for decomposing a sample containing 1% by mass or more of halogen and / or sulfur atoms selected from fluorine, bromine and iodine, and analyzing the decomposed sample by an inductively coupled plasma-triple quadrupole mass spectrometer By doing so, the trace amount chlorine component quantification method including the process of quantifying the chlorine concentration contained in the sample.
2. The quantitative determination method of 1 trace chlorine component whose said sample is an organic material.

  According to the method of the present invention, since the influence of the high matrix contained is eliminated by measuring by inductively coupled plasma-triple quadrupole mass spectrometry, the amount of decomposition during pretreatment is equivalent to that of the low matrix sample. Can be disassembled. Therefore, it is possible to analyze a small amount of chlorine in the sample with high sensitivity and high accuracy.

  The method for quantifying a trace chlorine component of the present invention includes a pretreatment step for decomposing a sample containing 1% by mass or more of halogen and / or sulfur atoms selected from fluorine, bromine and iodine, and inductively coupled plasma of the decomposed sample. A step of quantifying the chlorine concentration contained in the sample by analyzing with a triple quadrupole mass spectrometer;

  The method of the present invention is particularly suitable for the determination of trace chlorine components contained in a sample containing 1% by mass or more of fluorine.

  The sample to be measured by the method of the present invention may be an organic material or an inorganic material. Although it does not specifically limit as said organic material, The organic compound used as an organic EL material, a semiconductor material, a functional material, etc. is mentioned. The inorganic material is not particularly limited, and examples thereof include fluorine-containing glass, inorganic fluoride products used in semiconductor manufacturing and optical materials, and the like. Of these, the method of the present invention is suitable for the determination of trace chlorine components in organic materials.

  The first step in the method of the present invention is a pretreatment step for decomposing a sample. The method for decomposing the sample may be a conventionally known method, and examples thereof include heat decomposition, acid decomposition, and alkali decomposition. The pretreatment method may be appropriately selected according to the sample to be measured. However, thermal decomposition is preferable from the viewpoint of high accuracy and high sensitivity.

  When heat decomposition is performed as pretreatment, the pretreatment is performed by heating the sample in a combustion furnace at about 900 to 1,100 ° C. for vaporization, and collecting the vaporized sample with an absorbing solution. The time required for the thermal decomposition is not particularly limited as long as it is sufficient to vaporize the sample, but it is usually about 5 to 20 minutes. Examples of the absorbing liquid include a mixed aqueous solution of sodium carbonate and sodium hydrogen carbonate, an alkaline absorbing liquid such as an aqueous ammonia solution and an aqueous tetramethylammonium hydroxide solution, and water.

  Next, chlorine in the pretreated sample is quantified using an inductively coupled plasma-triple quadrupole mass spectrometer. Inductively coupled plasma-triple quadrupole mass spectrometry is a triple quadrupole in which a sample is ionized by inductively coupled plasma (ICP) and connected in series with a collision reaction cell between two quadrupole mass spectrometers. This is mass spectrometry performed by a mass spectrometer.

  As a method for calculating the chlorine concentration, any of an internal standard method, an external standard method, and a standard addition method may be used. In the case of the internal standard method, examples of the internal standard substance include phosphate ions, tartrate ions, halogen elements other than the target element, and sulfur.

  According to the method of the present invention, it is possible to quantify a trace amount of chlorine of about 100 ng as a lower limit in 1 g of a sample. The upper limit of quantifiable chlorine is not particularly limited, but about 1 mg per 1 g of sample is preferable.

  EXAMPLES Hereinafter, although a synthesis example, an Example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited to the following Example. In addition, the measurement apparatuses and measurement samples used in the examples are as follows.

[Automatic combustion equipment]
Mitsubishi Chemical Analytic AQF-2100H
[Inductively coupled plasma-triple quadrupole mass spectrometer]
Agilent 8800 Series Triple Quadrupole ICP-MS from Agilent Technologies
Internal standard: Phosphate ion [ion chromatograph]
Thermo Fisher Scientific ICS-1600
Separation column: IonPac AS23 (4 mm inner diameter) manufactured by Thermo Fisher Scientific
Guard column: Thermo Fisher Scientific IonPac AG23 (inner diameter 4 mm)
Eluent: 4.5 mmol / L sodium carbonate and 0.8 mmol / L sodium bicarbonate mixed aqueous solution Eluent flow rate: 1.0 mL / min
Detector: Electrical conductivity (use suppressor)
[Measurement sample]
An organic compound represented by the following formula. The organic compound was synthesized according to International Publication No. 2006/025342.

[Example 1]
A 25 mg sample was precisely weighed on a ceramic boat. After that, it is set in an automatic combustion device, put into a 1000 ° C. tubular furnace and thermally decomposed, and the generated halogen is absorbed in 3 mL of an absorbing solution (4.0 mmol / L sodium carbonate and 0.8 mmol / L sodium bicarbonate mixed aqueous solution). It was. The solution was recovered, and the chlorine component was measured by inductively coupled plasma-triple quadrupole mass spectrometry (ICP-MS / MS).

[Comparative Example 1]
A 25 mg sample was precisely weighed on a ceramic boat. After that, it is set in an automatic combustion device, put into a 1000 ° C. tube furnace and thermally decomposed, and the generated halogen is absorbed in 5 mL of an absorbing solution (4.5 mmol / L sodium carbonate and 0.8 mmol / L sodium bicarbonate mixed aqueous solution). It was. The chlorine component in the solution was measured by an ion chromatograph (IC).

  In Example 1 and Comparative Example 1, the measurement was performed twice and the average value was calculated. The results are shown in Table 1.

  The quantitative values were different between the two analytical methods. In the ion chromatography method, since the ion exchange capacity of the separation column was exceeded, chlorine could not be recovered and could not be accurately quantified. On the other hand, in the inductively coupled plasma-triple quadrupole mass spectrometry, chlorine was recovered and could be quantified with high accuracy.

Claims (2)

A pretreatment step for decomposing a sample containing 1% by mass or more of halogen and / or sulfur atoms selected from fluorine, bromine and iodine, and analyzing the decomposed sample by an inductively coupled plasma-triple quadrupole mass spectrometer By doing so, the trace amount chlorine component quantification method including the process of quantifying the chlorine concentration contained in the sample.   The method for quantifying a trace chlorine component according to claim 1, wherein the sample is an organic material.