CN102621240A - Quick determination method for free unsymmetrical dimethylhydrazine in daminozide pesticide - Google Patents

Abstract

The invention relates to an analytic method for remnant unsymmetrical dimethylhydrazine in daminozide. The method using formaldehyde as derivating agent includes the steps: preparing standard unsymmetrical dimethylhydrazine solution, drawing a standard curve, preparing to-be-detected sample solution, sequentially infiltrating the prepared to-be-detected sample solution into a chromatograph, recording a peak area, substituting the peak area into the standard curve to obtain a UDMH (unsymmetrical dimethylhydrazine) remnant value, and the like. The method solves the technical problem that using conventional analytic methods is difficult to detect trace remnant unsymmetrical dimethylhydrazine in daminozide, and is significant to production and quality control of daminozide products.

Description

The rapid assay methods of free uns-dimethylhydrazine in the alar-85 agricultural chemicals

Technical field

The present invention relates to the remaining analytical approach of uns-dimethylhydrazine in a kind of alar-85, belong to analysis of agricultural drugs technical field.

Background technology

China is after later 1960s begins production alar-85 product; After getting into 21st century, production technology has had very large progress, in recent years; In order to adapt to the demand of international market; Produced the alar-85 product of uns-dimethylhydrazine remnants less than 30ppm, conventional analytical approach is difficult to detect uns-dimethylhydrazine micro residue in the alar-85, therefore; Seek a kind of scientific and effective analytical approach that detects uns-dimethylhydrazine residual volume in the alar-85, the production and the quality control of alar-85 product had great importance.

Summary of the invention

The object of the invention provides the free uns-dimethylhydrazine check and analysis method that uns-dimethylhydrazine remnants in a kind of alar-85 are lower than 30ppm.

Technical solution of the present invention:

The rapid assay methods of free uns-dimethylhydrazine in the alar-85 agricultural chemicals, its special character is: may further comprise the steps:

1] configuration uns-dimethylhydrazine standard solution: accurately pipette 500 μ L standard uns-dimethylhydrazines and annotate in the 250mL volumetric flask, the water constant volume faces the time spent dilution and derives; The uns-dimethylhydrazine standard solution of at least three concentration of configuration is with 0.5mg/mL-1mg/mL formaldehyde-derived 2min-30min;

2] standard solution for preparing is squeezed into chromatograph successively, be the UDMH peak, the note peak area with the peak that goes out about C-18 post 9min; Get three peak area values under three concentration, in order to the drawing standard curve, the sample size that is used for the drawing standard curve is 1 μ L;

3] take by weighing alar-85 sample 1.00g in the 10ml volumetric flask, add 5.0% NaOH solution 5.0ml dissolving, add 0.5mg/mL-1mg/mL formalin again to scale, shake up, reaction 2min-30min tests immediately;

4] testing sample solution for preparing is squeezed into chromatograph successively, be the UDMH peak with the peak that goes out about C-18 post 9min, the note peak area, UDMH peak area value that must this sample promptly draws the UDMH residual value with this peak area value substitution typical curve.

The advantage that the present invention had:

Formaldehyde has following advantage as derivating agent: formaldehyde does not almost have absorption in the ultraviolet region, and the mensuration of sample is not disturbed, and has simplified the selection of chromatographic separation condition.

Description of drawings

Fig. 1 is uns-dimethylhydrazine content-absorbance typical curve of drawing according to the measurement data of embodiment 1.

Fig. 2 is the chromatogram of embodiment 1 testing sample solution.

Fig. 3 is uns-dimethylhydrazine content-absorbance typical curve of drawing according to the measurement data of embodiment 2.

Fig. 4 is the chromatogram of embodiment 2 testing sample solutions.

Embodiment

Embodiment 1

1] formalin that in three 250mL volumetric flasks, adds 0.5mg/mL accurately adds 5.0ul, 10.0ul, 15.0ul standard uns-dimethylhydrazine respectively near scale in three volumetric flasks, add formalin to scale, shake up, and reaction 15min, room temperature is placed.Can obtain the uns-dimethylhydrazine standard solution of 20.0ppm (v/v), 40.0ppm (v/v), 60.0ppm (v/v).

2] standard solution for preparing is squeezed into chromatograph successively, and carry out writing task, be the UDMH peak, the note peak area with the peak that goes out about C-18 post 9min.Can get three peak area values under three concentration, draw the typical curve of uns-dimethylhydrazine content and peak area, like Fig. 1.

Uns-dimethylhydrazine (ppm)	20	40	60
				Peak area	140022	273981	399487

3] take by weighing alar-85 sample 1.00g in the 10ml volumetric flask, add 5.0% NaOH solution 5.0ml dissolving, add 0.8mg/mL formalin again, shake up reaction 15min to scale.

4] testing sample solution for preparing is squeezed into chromatograph successively, be the UDMH peak with the peak that goes out about C-18 post 9min, the note peak area is seen Fig. 2.UDMH peak area value that can this sample is 141309, and it is 26.47ppm that this peak area substitution typical curve is promptly drawn the UDMH residual value.

Embodiment 2

1] formalin that in three 250mL volumetric flasks, adds 1.0mg/mL accurately adds 2.5ul, 7.5ul, 12.5ul standard uns-dimethylhydrazine respectively near scale in three volumetric flasks, add formalin to scale, shake up, and reaction 25min, room temperature is placed.Can obtain the uns-dimethylhydrazine standard solution of 10.0ppm (v/v), 30.0ppm (v/v), 50.0ppm (v/v).

2] standard solution for preparing is squeezed into chromatograph successively, and carry out writing task, be the UDMH peak, the note peak area with the peak that goes out about C-18 post 9min.Can get three peak area values under three concentration, draw the typical curve of uns-dimethylhydrazine content and peak area, like Fig. 3.

Uns-dimethylhydrazine (ppm)	10	30	50
				Peak area	68685	200206	323578

3] take by weighing alar-85 sample 1.00g in the 10ml volumetric flask, add 5.0% NaOH solution 5.0ml dissolving, add 1.0mg/mL formalin again, shake up reaction 25min to scale.

4] testing sample solution for preparing is squeezed into chromatograph successively, be the UDMH peak with the peak that goes out about C-18 post 9min, the note peak area is seen Fig. 4.UDMH peak area value that can this sample is 73256, and it is 13.67ppm that this peak area substitution typical curve is promptly drawn the UDMH residual value.

Uns-dimethylhydrazine belongs to III level toxicant, can cause injury in various degree to the central nervous system of human body, liver, kidney etc., is the carcinogenic substance of generally acknowledging, the amount of the residual uns-dimethylhydrazine of alar-85 of the outlet U.S. requires to be lower than 30 * 10 ^-4%.The uns-dimethylhydrazine assay method mainly contains AAS and vapor-phase chromatography etc.

The present invention is a derivating agent with formaldehyde, has set up the high performance liquid chromatography of free uns-dimethylhydrazine in a kind of simple, fast measuring alar-85 product.This method particular content is following successively: (1) instrument and reagent: Tianjin, island ClassVP-10A high performance liquid chromatograph; Dispose two yuan of gradient pump LC-10ATvp, online degasser DGU-14A, column oven CTO-10ASvp, detecting device SPD-10Avp, main frame SCL-10Avp (day island proper Tianjin company).Uns-dimethylhydrazine; Methyl alcohol is chromatographically pure (Fisherchemicals, the U.S.); Formalin, NaH ₂PO ₄, NaOH to be pure for analyzing; Water is the secondary redistilled water.(2) chromatographic condition Venusil C-18 post (150mm * 416mm i.d., 5 μ m).Moving phase is V (20mmol/L PBS, pH 7.0): V (methyl alcohol)=94: 6, uses preceding with 0.45 μ m membrane filtration.Flow velocity 1.0mL/min, 25 ℃ of column temperatures detect wavelength 237nm.

Claims (1)

1. the rapid assay methods of free uns-dimethylhydrazine in the alar-85 agricultural chemicals is characterized in that: may further comprise the steps:

1] configuration uns-dimethylhydrazine standard solution: accurately pipette 500 μ L standard uns-dimethylhydrazines and annotate in the 250mL volumetric flask, the water constant volume faces the time spent dilution and derives; The uns-dimethylhydrazine standard solution of at least three concentration of configuration is with 0.5mg/mL-1mg/mL formaldehyde-derived 2min-30min;

2] standard solution for preparing is squeezed into chromatograph successively, be the UDMH peak, the note peak area with the peak that goes out about C-18 post 9min; Get three peak area values under three concentration, in order to the drawing standard curve, the sample size that is used for the drawing standard curve is 1 μ L;

3] take by weighing alar-85 sample 1.00g in the 10ml volumetric flask, add 5.0% NaOH solution 5.0ml dissolving, add 0.5mg/mL-1mg/mL formalin again to scale, shake up, reaction 2min-30min tests immediately;

4] testing sample solution for preparing is squeezed into chromatograph successively, be the UDMH peak with the peak that goes out about C-18 post 9min, the note peak area, UDMH peak area value that must this sample promptly draws the UDMH residual value with this peak area value substitution typical curve.

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