Some standard content:
ICS65.100
Registration No.: 10927-2002
Chemical Industry Standard of the People's Republic of China
HG3699-2002
Dicofol Technical
Issued on September 28, 2002
Implemented on June 1, 2003
Issued by the State Economic and Trade Commission of the People's Republic of China
Chapter 3 and Chapter 5 of this standard are mandatory, and the rest are recommended. HG3699-2002
This standard is formulated based on the quality level of domestic dicofol technical, with reference to the FAO standards of the Food and Agriculture Organization of the United Nations and the analytical methods of the International Pesticide Analysis Coordination Committee (CIPAC). This standard was proposed by the Policy and Regulations Department of the former State Administration of Petroleum and Chemical Industry. This standard is under the jurisdiction of the National Pesticide Standardization Technical Committee (CSBTS/TC133). The responsible drafting unit of this standard is the Pesticide Testing Institute of the Ministry of Agriculture. The participating drafting unit of this standard is Jiangsu Yangnong Chemical Group Co., Ltd. The main drafters of this standard are Li Guoping, Zhao Yonghui, Fan Wenzhong, Liu Ping, and Ji E. The Secretariat of the National Pesticide Standardization Technical Committee is responsible for interpreting this standard. Dicofol technical
Other names, structural formulas and basic physical and chemical parameters of the active ingredient dicofol of this product are as follows:ISO common name: dicofol
CAS registration number: 115-32-2
CIPAC digital code: 123
Chemical name: 2,2,2-trichloro-1,1-bis(4-cyanophenyl)ethanolStructural formula:
Empirical formula: CuH,Cl,
Relative molecular mass: 370.5 (according to the 1997 international relative atomic mass)Biological activity: Mite killing
Melting point: 78.5℃~79.5℃
Relative density: 1.4 5 (25℃)
Vapor pressure: 0.053mPa
HG3699--2002
Solubility: slightly soluble in water, soluble in most organic solvents, such as ether, acetone, benzene, toluene, chloroform, difluoromethane Stability: stable in acid, unstable in alkali and hydrolyzed, stable below 80℃ The isomers of trichlorodicofol, ortho-trichlorodicofol also have biological activity, and its structural formula is as follows: C
1 Scope
This standard specifies the requirements, test methods, and marking, labeling, packaging and storage of trichlorodicofol technical. This standard applies to trichlorodicofol technical composed of trifluorodicofol technical and impurities generated in its production. 2 Normative references
The clauses in the following documents become the clauses of this standard through reference in this standard. For any dated referenced document, all subsequent amendments (excluding errata) or revisions are not applicable to this standard. However, parties that reach an agreement based on this standard are encouraged to study whether the latest versions of these documents can be used. For any undated referenced document, the latest version is applicable to this standard. GB/T601
GB/T 603
GB/T1250
GB/T1600
GB/T1604
GB/T1605
Preparation of standard solutions for titration analysis (volume analysis) of chemical reagents Preparation of preparations and products used in chemical reagent test methods Methods for expressing and determining limit values Methods for determining moisture content in pesticides
Acceptance rules for commercial pesticides
Sampling methods for commercial pesticides
GB3796 General rules for pesticide packaging
3 Requirements
3.1 Appearance: brown viscous paste or waxy mass, free of foreign impurities. (79)
HG3699--2002
3.2 The control indicators of dicofol technical shall meet the requirements of Table 1. Table 1 Control items of dicofol technical material Index item
Superior grade
Total active ingredient content (dicofol + o-, p-dicofol) Dicofol content/total active ingredient content Full boiling impurities (DDT) content
Acidity (in H2SO4)
Xylene insoluble matter
aP-, p-dicofol.
Unit is mass fraction (%)
Qualified products
b In this standard, DDT impurities include o,p-DDT, p,p-DDT, p,p'-DDE and p,p-CIDDT. 4 Test methods
4.1 Sampling
According to the "commodity original drug sampling" method in GB/T1605, the sampling packages are determined by random sampling (when melting the sample, the temperature shall not exceed 75℃), and the final sampling volume shall not be less than 100g. 4.2 Identification test
High performance liquid chromatography: This identification test can be carried out simultaneously with the determination of the content of the active ingredient. Under the same chromatographic operating conditions, the relative difference between the retention time of two chromatographic peaks in the sample solution and the retention time of the chromatographic peaks of dicofol, o-, and p-dicofol in the standard solution is within 1.5%.
4.3 Determination of the content of dicofol and o-, and p-dicofol 4.3.1 Summary of the method
The sample uses methanol decahydrate decaglacial acetic acid as the mobile phase, and uses a C column and an ultraviolet detector. The effective components in the sample are separated and determined by high performance liquid chromatography using the external standard method.
4.3.2 Instruments
High performance liquid chromatograph: with ultraviolet variable wavelength detector. Chromatographic data processor.
Chromatographic column 250mm×4.6mm (id) stainless steel column, filled with SUPELCOSILLC-8 (or other similar), 5μm filler. Micro-injector: 50μL.
4.3.3 Reagents and solutions
Methanol, high purity.
Water: freshly distilled water.
Glacial acetic acid.
Standard sample of dicofol, known content.
Ortho, para-dicofol standard sample: known content. 4.3.4 HPLC operating conditions
Mobile phase: methanol + water + glacial acetic acid = 75 + 25 + 0.2. Mobile phase flow rate 1.3mL/min.
Column temperature: 30℃.
Detection wavelength: 235nm.
Injection volume: 10μL.
Retention time: about 9min for ortho, para-dicofol and about 13min for dicofol. HG3699—2002
The above operating parameters are typical. According to the different instrument requirements, the given operating parameters can be appropriately adjusted to obtain the best results. A typical HPLC chromatogram of dicofol technical is shown in Figure 1. 2
1-o,p-dicofol, 2-dicofol Figure 1 HPLC chromatogram of dicofol technical 4.3.5 Determination steps
4.3.5.1 Preparation of standard solution
Weigh 0.05g (accurate to 0.0002g) of dicofol standard sample and 0.01g (accurate to 0.0002g) of o,p-dicofol standard sample in a 100mL volumetric flask, dissolve and dilute to volume with methanol, and mix well. 4.3.5.2 Preparation of sample solution
Weigh 0.06g of sample (accurate to 0.0002g) into a 100mL volumetric flask, dissolve and make up to volume with methanol, mix well, and filter if necessary (dicofol technical drug is viscous or waxy, so it needs to be dissolved in a 70℃ constant temperature box before weighing and fully stirred). 4.3.5.3 Determination
Under the above operating conditions, after the instrument is stable, continuously inject several needles of standard solution, calculate the relative response value of each needle, and when the relative response value of two adjacent needles changes by less than 1.5%, inject the needle in the order of standard solution, sample solution, sample solution, and standard solution. 4.3.6 Calculation
Average the peak areas of dicofol or (o-, p-dicofol peak isomers) in the two needles of sample solution and the two needles of standard solution before and after the sample solution.
4.3.6.1 The content of dicofol expressed as mass fraction l (%) and the content of o-,p-dicofol expressed as mass fraction wz (%) are calculated according to formula (1) and formula (2) respectively: wi=
Wherein:
A2mgP2
Ai--the average value of the peak area of dicofol in the sample solution mal
the mass of the dicofol standard sample, in grams (g); P.The mass fraction of trichlorodicofol in the standard sample, expressed in %; A The average value of the peak area of trichlorodicofol in the standard sample solution; m The mass of the sample, in grams (g);
A-———The average value of the peak area of o-, p-dicofol in the sample solution; P2~The mass fraction of o-, p-dicofol in the standard sample, expressed in %; A
-The average value of the peak area of o-, p-dicofol in the standard sample solution; (81)
（2）
HG3699—2002
mz—-The mass of o-, p-dicofol standard, in grams (g). 4.3.6.2 The total active ingredient content expressed as mass fraction: calculated according to formula (3): -w+w
Wherein:
e——mass fraction of trifluorodicofol, expressed in %; Wg——mass fraction of o-, p-dicofol, expressed in %. 4.3.6.3 The percentage of trichlorodicofol content/total active ingredient content X is calculated according to formula (4): Xw×100.
——mass fraction of trichlorodicofol, expressed in %; a
——mass fraction of total active ingredients, expressed in %. 4.3.7 Allowable difference
For two parallel determinations, the difference in trifluorodicofol content should not be greater than 1.5%, and the difference in o-, p-dicofol content should not be greater than 0.5%. 4.4 Determination of the content of drop boiling impurities (DDT?) 4.4.1 Summary of the method
The sample is dissolved in methanol, methanol decahydrate + glacial acetic acid is used as the mobile phase, a Cs column and a UV detector are used, and the DDT impurity in the sample is separated and determined by high performance liquid chromatography using P, p-DDE standard. 4.4.2 Instruments
Same as 4.3.2.
4.4.3 Reagents and solutions
P, p-DDE standard: known mass fraction greater than or equal to 98.0%. 0, P-DDT standard: no interference peak.
P, p'-DDT standard: no interference peak.
P, p-CIDDT standard: no interference peak
Qualitative solution: 0.004 mg/mL DDT methanol solution. Methanol: chromatographic grade.
Water: freshly distilled or twice distilled filling water.
Glacial acetic acid: analytical grade.
4.4.4 HPLC operating conditions
Same as 4.3.4.
Retention time: 0, p-DDT 20minp, p-DDT 22minp, p-DDE 23minp, p-CIDDT 36min. 4.4.5 Determination steps
4.4.5.1 Preparation of standard solution
Weigh about 0.02g (accurate to 0.0001.g) of P, p-DDE standard sample in a 50mL volumetric flask, dissolve and dilute with methanol, mix well, and use it as solution A. Accurately transfer 0.5mL of solution A to a 50mL volumetric flask, dilute with methanol, mix well, and use it as standard solution. 4.4.5.2 Preparation of sample solution
Weigh 0.5g of the original drug (accurate to 0.0001g) into a 50mL volumetric flask, dissolve it with methanol, make up to volume, and mix well. (The original drug of dicofol is viscous or waxy. Before weighing, it needs to be placed in a 70℃ oven to melt and stir thoroughly. Too high temperature and too long heating time may cause dicofol to decompose).
4.4.5.3 Determination
4.4.5.3.1 Solvent blank: Under the above operating conditions, after the instrument is stable, inject 10μL of methanol used to dissolve the sample. There should be no chromatographic peaks that interfere with the determination of impurities.
4.4.5.3.2 Qualitative analysis of impurity peaks: Inject 10μL of qualitative solution and determine the retention time of the four DDTy peaks. HG3699-2002
4.4.5.3.3 Continuously inject several needles of standard solution, calculate the relative response value of each needle, and when the relative response value of two adjacent needles changes less than 1.5%, inject the needle in the order of standard solution, sample solution, sample solution, and standard solution. The separation effect is shown in Figure 2. If the peak of dicofol is tailing, the peak processing parameters of the integrator should be correctly set so that the peak of the droplet ladder-related impurities located on its tail can be integrated as tail peak or peak-to-valley. 1-o, p-triclorac; 2-triclorac: 3-o, p-DDT: 4-p, p-DDT: 5-o, p-DDT; 6-p, p-DDT; 7-p, p-DDT Hysteresis diagram 2 DDTY sample separation chromatogram
4.4.5.4 Calculation
The mass fraction of DDT W4 (%) is calculated according to formula (5): AamP
AmzX100
Where:||t t||A1—the average value of the peak area of p-DDE in the standard solution; (5)
Az—the average value of the sum of the areas of all the peaks of o,P-DDT, P,p-DDT, P,P-DDE, P,p'-CIDDT in the sample solutionmi—the mass of the standard sample of P,p-DDE, in milligrams (mg);mzthe mass of the sample, in milligrams (mg)P—the mass fraction of p,p-DDE in the standard sample, expressed in %. 4.4.6 Allowable difference
The relative deviation of DDT content in two parallel determinations shall not exceed 20%. 4.5 Determination of acidity
4.5.1 Reagents and solutions
Sodium hydroxide standard titration solution: c(NaOH)=0.02mol/L, prepared according to the provisions of GB/T601. Bromocresol green indicator solution: 1g/L, prepared according to the provisions of GB/T603. Acetone.
4.5.2 Operation steps
Accurately weigh 0.7g of sample (accurate to 0.0002g), place in a 250mL conical flask, add 20mL acetone to dissolve it, add 50mL water and 6 drops of bromocresol green indicator solution, and titrate with sodium hydroxide standard titration solution until the blue color is the end point. At the same time, make a blank determination. 4.5.3 Calculation
The acidity of the sample expressed as the mass fraction of sulfuric acid, ws (%), is calculated according to formula (6): es
Wherein:
c(Vi-V2)X0.049
-the concentration of the standard sodium hydroxide solution, in moles per liter (mol/L); (83)
HG3699—2002
V,-the volume of the standard sodium hydroxide solution consumed when titrating the sample, in milliliters (mL); V,-the volume of the standard sodium hydroxide solution consumed when titrating the blank, in milliliters (mL): m—the mass of the sample, in grams (g); 0.049 is the mass of sulfur in grams equivalent to 1.00mL of the standard sodium hydroxide solution Lc(NaOH)=0.02mol/L.
4.5.4 Allowable differencebzxz.net
The relative deviation of the results of two parallel determinations shall not exceed 15%. 4.6 Determination of moisture
Carry out according to the Karl Fischer method in GB/T1600, and it is allowed to use a micro-moisture meter with equivalent accuracy. 4.7 Determination of xylene insoluble matter
4.7.1 Reagents
Xylene.
4.7.2 Instruments
Erlenmeyer flask 250mL.
Glass sand pot: G3.
Oven: (110±2)℃.
4.7.3 Determination steps
Weigh 10g of sample (accurate to 0.01g), put it into a conical flask, add 60mL of xylene, and shake until all soluble matter is dissolved. Use the filtered solution that has been constant weight and then use 60mL of xylene to wash the conical flask three times and filter it by suction. Place the crucible in an oven at 110℃ and dry for 30min, take it out and cool it to room temperature, and weigh it.
The content of xylene insoluble matter in the sample expressed as mass fraction W (%) is calculated according to formula (7): 2g m = mo×100
Wherein:
m1—the mass of the crucible and insoluble matter after constant weight, in grams (g); mo—the mass of the crucible, in grams (g); m——the mass of the sample, in grams (g). 4.8 Inspection and acceptance of products
The relevant provisions of GB/T1604 shall be followed, and the rounded value comparison method of GB/T1250 shall be used for the processing of limit values. 5 Marking, labeling, packaging, storage and transportation
5.1 The marking, labeling and packaging of dicofol technical shall comply with the relevant provisions of GB3796. 5.2 The dicofol technical shall be packaged in clean and dry iron drums, with a net content of 200kg per drum. 5.3 Other forms of packaging may be used according to user requirements or order agreements, but they must comply with the relevant provisions of GB3796. 5.4 Packages should be stored in ventilated and dry warehouses. (7)
5.5 During storage and transportation, prevent moisture and sunlight, do not mix with food, seeds, and feed, avoid contact with skin and eyes, and prevent inhalation through the mouth and nose. 5.6 Safety: Dicofol is a low-toxic pesticide. Wear protective gloves and clean protective clothing when using this product. Wash with soap and water immediately after application. If it gets into eyes, wash with water. There is no special antidote. Induce vomiting if ingested orally. Do not mix with alkaline pesticides to avoid decomposition and loss of efficacy.
5.7 Warranty period: Under the specified storage and transportation conditions, the quality guarantee period of Dicofol is two years from the date of production. 6
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