CN102692463A - Method for detecting aromatic acyl chloride product by adopting high performance liquid chromatography method - Google Patents

Abstract

The invention relates to a method for detecting an aromatic acyl chloride product by adopting a high performance liquid chromatography method, and belongs to the field of chemical detection methods. The method is characterized by detecting the aromatic acyl chloride product by adopting the high performance liquid chromatography and mainly comprising the following steps of: sampling the aromatic acyl chloride product and preparing a sample in the presence of dry inert gas; weighing 0.1-2g of the aromatic acyl chloride sample to be detected in the presence of the dry inert gas, and esterifying for 10-60 minutes; and under selected chromatographic conditions, after an instrument baseline is stabilized, measuring 0.45Mul of sample solution to be filtered with an organic filter membrane, carrying out determination, quantifying by adopting an area normalization method, and calculating the content of each component. The method disclosed by the invention is a simple, rapid and accurate aromatic acyl chloride product detection method and has important industrial value and academic significance on production guidance.

Description

High performance liquid chromatography detects the method for aromatic series acyl chloride product

Technical field

The present invention relates to the method that a kind of high performance liquid chromatography detects aromatic series acyl chloride product, belong to chemical detection method field.

Background technology

Aromatic series acyl chloride product (especially paraphthaloyl chloride and m-phthaloyl chloride) is one type of important fine chemicals intermedium, and for example paraphthaloyl chloride and m-phthaloyl chloride product just are used as the reaction monomers use in the synthetic production of aramid fiber 1414 and 1313.Along with the fast development of domestic high-performance fiber, bring rare opportunity to develop for the application and the market of paraphthaloyl chloride and m-phthaloyl chloride.In " high-technology field that state key is supported " of Department of Science and Technology's issue in 2008, clearly classify the high-technology field that state key is supported to " crucial polymer monomer manufacturing technology " in the high performance polymer structured material of field of new as.2010 new and high technology fiber industry " 12 " list Fanglun l414 " pilot scale is tackled key problems the industrialization production phase ", aramid fiber 1313 " industrialization is to the industrialized production stage " in; Strengthen " equipment, raw material, fiber " tackling key problem synchronously; Improve the competitiveness the expanding application field.Similarly application also occurs in the production of other high-performance polymer resin, aromatic polyester for example, polyaryletherketone etc.Yet; Can promptly be high-purity as the prerequisite condition of aromatic series acyl chlorides product that polymerization reaction monomer uses; Content is more than 99.9%; Otherwise will molecular weight, color and luster, mechanical property and the thermal stability of high-performance polymer naval stores be produced serious influence, it is very crucial therefore accurately to detect aromatic series acyl chloride product gas purity.Less to the research report of aromatic series acyl chloride product inspection method both at home and abroad, " gas chromatographic analysis of the synthetic and product of paraphthaloyl chloride ": adopt the sodium methoxide esterification, adopt gas chromatographic analysis then, this method recovery is undesirable, and about 97%." gas chromatographic analysis of phthalyl chloride and impurity thereof ": in the presence of pyridine, be solvent with the chloroform, 1g sample+1ml methyl alcohol carries out esterification reaction of organic acid; Adopt packed column; Flame ionization ditector, this method esterification is fierce, and proportioning is unreasonable; It is incomplete to be prone to esterification, the incomplete baseline separation of component peaks." purity analysis of paraphthaloyl chloride ": adopt chloride ion-selective electrode to measure the chlorine method of living, all convert active chlorine to chlorion, the impurity that contains nonactive chlorine so just detects not come out with other impurity.Fusing point in other reports detects, titration detects, the GC chromatogram detects the detection method complex operation, and accuracy and sensitivity can't be satisfied the demand of real work.In addition, because the self-characteristic of aromatic series acyl chloride product, in producing processes such as preparation, sampling detection, packing, transportation,, can cause partially aromatic acyl chloride product to go bad, influence product purity if can not accomplish fully and water, the isolated operation of oxygen.Therefore; Pass through method improvement; Develop a kind of simply, the detection method of aromatic series acyl chloride product fast and accurately, have important commercial value and academic significance to instructing to produce, content of the present invention is exactly the exploitation of the high effective liquid chromatography for detecting of relevant aromatic series acyl chloride product.

Summary of the invention

According to the deficiency of prior art, the technical matters that the present invention will solve is: the method that provides a kind of high performance liquid chromatography to detect aromatic series acyl chloride product, the present invention be a kind of simply, the detection method of aromatic series acyl chloride product fast and accurately.

The technical solution adopted for the present invention to solve the technical problems is: provide a kind of high performance liquid chromatography to detect the method for aromatic series acyl chloride product, it is characterized in that with high performance liquid chromatography aromatic series acyl chloride product being detected, key step is following:

(1) under the dry inert gas protection, aromatic series acyl chloride product is carried out the sample circuit sample preparation;

(2) the fragrant same clan to be measured sample is got 0.1～2g under the dry inert gas protection, carried out esterification 10-60 minute;

(3) under selected chromatographic condition, after the instrument baseline stability, the solution sample introduction behind the organic membrane filtration of 0.45 μ l of materialsing is measured, and the area normalization standard measure calculates each component concentration.

Contain following group in the described aromatic series acyl chlorides structure:

Wherein X represents halogen atom, R ₁, R ₂, R ₃, R ₄, R ₅For alkyl, aryl, halogen atom or hydrogen atom and In one or more,

In X be halogen atom, wherein the aromatic series acyl chlorides is preferably:

Described inert gas is nitrogen, argon gas or helium,

Described inert gas nitrogen.

Preferred 30 minutes of described esterification time.

Described alcohols esterified solvent is absolute methanol or absolute ethyl alcohol,

The preferred absolute methanol of described alcohols esterified solvent.

Described alcohols esterified solvent purity>=99.9%, moisture≤0.01%;

Described liquid phase chromatogram condition is following:

Moving phase: methyl alcohol+water+glacial acetic acid;

Detecting device: the ultraviolet absorption detector of variable wavelength, wavelength 220～350nm;

Column temperature: 20～40 ℃;

Flow velocity: 1.0～1.5ml/min;

Sample size: 10～20 μ l;

Chromatographic column: anti-phase C18 post.

The invention has the beneficial effects as follows: be a kind of simply, the detection method of aromatic series acyl chloride product fast and accurately, have important commercial value and academic significance to instructing to produce.

Embodiment

Below in conjunction with embodiment the present invention is done and to further describe:

Embodiment 1

(1) preparation of sample solution: sample tap is taken a sample from the production scene under nitrogen protection, and puts into the nitrogen protection case.In the nitrogen protection case, get the 0.5g paraphthaloyl chloride, be added in the triangular flask that is placed with the 100mL absolute methanol, on stirrer, be stirred to fully dissolving, and esterification 30 minutes, sample solution.

(2) liquid phase chromatogram condition: moving phase: methyl alcohol+water+glacial acetic acid=63+37+1, detecting device: the ultraviolet absorption detector of variable wavelength, wavelength 242nm; Column temperature: 30 ℃; Flow velocity: 1.5mL/min, sample size: 10 μ L, chromatographic column: 150mm * 4.6mm * 5 μ mC18 posts.

(3) sample determination: under selected chromatographic condition, after the instrument baseline stability, the solution sample introduction behind the organic membrane filtration of 0.45 μ L of materialsing is measured, and the area normalization standard measure calculates each component concentration.

$\mathrm{wi}=\frac{\mathrm{Ai}}{\mathrm{\ΣA}}\×100...\left(1\right)$

In the formula:

The content of wi---component i;

The peak area of Ai---component i;

The peak area of Σ A---all components.

Twice sample introduction paraphthaloyl chloride result: the first time 99.98%, the second time 99.96%, average 99.97%.

Embodiment 2

Repeatability, detectability test:

According to the preparation method of the sample solution among the embodiment 1, according to step and the liquid phase chromatogram condition of embodiment 1, respectively 5 groups of paraphthaloyl chloride samples to be measured, table 1 is paraphthaloyl chloride replica test data

Table 1 paraphthaloyl chloride replica test data

According to the preparation method of the sample solution among the embodiment 1, according to step and the liquid phase chromatogram condition of embodiment 1, the detection of paraphthaloyl chloride is limited to 0.5 ~ 8ng.

Embodiment 3

Recovery test:

Preparation method according to the sample solution among the embodiment 1; According to step and the liquid phase chromatogram condition of embodiment 1,, add the known standard amount of high, medium and low 5 concentration at the sample of concentration known; Do recovery test, table 2 is paraphthaloyl chloride recovery test data.

Table 2 paraphthaloyl chloride recovery test data

Sample	Concentration known	Add concentration	Measured value	The recovery, %
					1	0.1021	0.0983	0.2001	99.7
2	0.1021	0.1232	0.2256	100.2
					3	0.1021	0.1842	0.2845	99.0
4	0.1021	0.2254	0.3269	99.7
					5	0.1021	0.3042	0.4070	100.2

Claims (9)

1. the method for a high performance liquid chromatography detection aromatic series acyl chloride product is characterized in that with high performance liquid chromatography aromatic series acyl chloride product being detected, and key step is following:

(1) under the dry inert gas protection, aromatic series acyl chloride product is carried out the sample circuit sample preparation;

(2) the fragrant same clan to be measured sample is got 0.1～2g under the dry inert gas protection, carried out esterification 10-60 minute;

(3) under selected chromatographic condition, after the instrument baseline stability, the solution sample introduction behind the organic membrane filtration of 0.45 μ l of materialsing is measured, and the area normalization standard measure calculates each component concentration.

2. detect the method for aromatic series acyl chloride product according to claims 1 described high performance liquid chromatography, it is characterized in that containing in the described aromatic series acyl chlorides structure following group:

Wherein X represents halogen atom, R ₁, R ₂, R ₃, R ₄, R ₅For alkyl, aryl, halogen atom or hydrogen atom and

In one or more, In X be halogen atom, wherein the aromatic series acyl chlorides is preferably:

3. detect the method for aromatic series acyl chloride product according to claims 1 described high performance liquid chromatography, it is characterized in that described inert gas is nitrogen, argon gas or helium.

4. detect the method for aromatic series acyl chloride product according to claims 3 described high performance liquid chromatographies, it is characterized in that described inert gas nitrogen.

5. detect the method for aromatic series acyl chloride product according to claims 1 described high performance liquid chromatography, it is characterized in that described esterification time preferred 30 minutes.

6. detect the method for aromatic series acyl chloride product according to claims 1 described high performance liquid chromatography, it is characterized in that described alcohols esterified solvent is absolute methanol or absolute ethyl alcohol.

7. detect the method for aromatic series acyl chloride product according to claims 6 described high performance liquid chromatographies, it is characterized in that the preferred absolute methanol of described alcohols esterified solvent.

8. detect the method for aromatic series acyl chloride product according to claims 7 described high performance liquid chromatographies, it is characterized in that described alcohols esterified solvent purity>=99.9%, moisture≤0.01%.

9. detect the method for aromatic series acyl chloride product according to claims 5 described high performance liquid chromatographies, it is characterized in that described liquid phase chromatogram condition is following:

Moving phase: methyl alcohol+water+glacial acetic acid;

Detecting device: the ultraviolet absorption detector of variable wavelength, wavelength 220～350nm;

Column temperature: 20～40 ℃;

Flow velocity: 1.0～1.5ml/min;

Sample size: 10～20 μ l;

Chromatographic column: anti-phase C18 post.