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Chemical Industry Standard of the People's Republic of China
HG2319—92
Butyl ester technical
Published on June 1, 1992
Ministry of Chemical Industry of the People's Republic of China
Implemented on January 1, 1993
Chemical Industry Standard of the People's Republic of China
2,4-D
Butyl ester technical
Subject content and scope of application
HG2319—92
This standard specifies the technical conditions, test methods, inspection rules, and marking, packaging, transportation and storage requirements for 2,4-D butyl ester technical. This standard applies to 2,4-D butyl ester technical synthesized by chlorination, condensation, esterification (or esterification followed by condensation) process with phenol, chlorine, monochloroacetic acid, n-butanol, sodium hydroxide and other main raw materials. Active ingredient: 2,4-D-butyl ester
Chemical name: 2,4-dichlorophenoxyacetic acid n-butyl ester Structural formula:
Molecular formula: C12H1/C120s
-CHCOO-CHg
Relative molecular mass: 277.15 (according to the international relative atomic mass in 1989). 2 Reference standards
GB1604
GB1605
Pesticide acceptance rules
Commercial pesticide sampling method
General rules for pesticide packaging
GB3796
3 Technical requirements
3.1 Appearance: Brown oily single-phase liquid, without visible suspended matter and sediment. 3.224-D butyl ester technical shall also meet the following index requirements: %(m/m)
2,4-D butyl ester content
Total ester content
Free phenol (calculated as 2,4-dichlorophenol)
Free acid (calculated as 2,4-D acid)
Note: 21 is the measured value of the mass percentage of 2,4-D butyl ester. 4 Test method
4.1 Determination of 2,4-D butyl ester content
4.1.1 Summary of method
Approved by the Ministry of Chemical Industry of the People's Republic of China on June 1, 1992. Superior product
First-class product
Qualified product
Implemented on January 1, 1993
HG2319-92
The sample was dissolved in chloroform and separated and determined on a mixed column of tetrachlorophthalic acid glycol polyester and Apizolide L/Chromosorb W-AWDMCS 180-250um with diisobutyl phthalate as the internal standard. 4.1.2 Reagents and solutions
Chloroform (GB682);
2,4-D butyl ester standard: known content; Diisobutyl phthalate: internal standard, identified by this method as having no interfering impurities; Tetrachlorophthalic acid glycol polyester: gas chromatography stationary phase; Apizone L: gas chromatography stationary phase;
Chromosorb W-AWDMCS: 180~250μm (60~80 mesh) carrier for gas chromatography; Internal standard solution: weigh 3.5g of diisobutyl phthalate, place it in a 100mL volumetric flask, add chloroform to dissolve, dilute to the scale, and shake well.
4.1.3 Instruments
Gas chromatograph: with hydrogen flame ionization detector; chromatographic column: 2m long, 3mm inner diameter stainless steel column, filled with 1.7% tetrachlorophthalic acid ethylene glycol polyester and 0.3% Apizolide L/Chromosorb W-AWDMCS180~250um filler; recorder or gas chromatography data processor; micro-injector: 10uL.
4.1.4 Operation steps
4.1.4.1 Coating of stationary liquid
Accurately weigh 0.100g of tetrachlorophthalic acid glycol polyester and 0.020g of Apizoline L stationary liquid into a 250mL beaker, add an appropriate amount (about 25mL) of chloroform to completely dissolve it, add a certain amount of carrier (about 6g) according to the pre-prepared ratio, gently shake to mix evenly and evaporate the solvent to near dryness, then place the beaker in an oven at 110℃ for 1h, take it out and place it in a desiccator. 4.1.4.2 Filling of chromatographic column
Connect a funnel to the inlet end of the column, plug the outlet end with gauze, and connect it to the vacuum pump with a rubber tube. Turn on the vacuum pump, add the dried column filler in batches from the funnel, tap the tube wall continuously to make the filler fill the chromatographic column evenly and tightly, and plug the two ends of the column with silanized glass wool.
4.1.4.3 Aging of the chromatographic column
Connect the inlet of the chromatographic column to the vaporizer, and do not connect the outlet to the detector for the time being. Aging at least 48 hours at a column temperature of 210℃ with a carrier flow rate of 20mL/min.
4.1.5 Chromatographic operating conditions
Temperature:
Column chamber 170℃;
Vaporizer chamber 260℃;
Detection chamber 260℃;
Gas flow rate:
Carrier (N2) 20mL/min;
Air 320mL/min;
Hydrogen 32mL/min;
Injection volume: 0.6uL;
Retention time:
2,4-D butyl ester about 11min;
Internal standard about 6.7min.
HG2319—92
Gas chromatogram of 2,4-D butyl ester
1—Solvent; 2,3,4,5—Unknown impurities; 6—Chlorophenoxyacetic acid n-butyl ester; 7—Internal standard; 8—2,4-dichlorophenoxyacetic acid isobutyl ester; 9—2,4-D butyl ester; 10—Trichlorophenoxyacetic acid n-butyl ester The above gas chromatography conditions are typical operating parameters. Analysts can make appropriate adjustments to the operating conditions according to the characteristics of the instrument to obtain the best results.
4.1.6 Determination steps
4.1.6.1 Preparation of standard solution
Weigh 0.1g (accurate to 0.0002g) of 2,4-D butyl ester standard sample and place it in a 5mL ground-mouth glass bottle. Use a pipette to accurately add 2mL of internal standard solution and shake it.
4.1.6.2 Preparation of sample solution
Weigh about 0.1g of the original drug sample containing 2,4-D butyl ester (accurate to 0.0002g), place it in a 5mL glass bottle with a ground stopper, accurately add 2mL of internal standard solution with a pipette, and shake well. 4.1.6.3 Sample determination
Under the selected conditions, after the instrument is stable, use a micro-injector to inject and analyze in the following order: standard solution, sample solution, sample solution, standard solution. The relative deviation of the peak area ratio of 2,4-D butyl ester to the internal standard in the two sample solutions and the two standard solutions before and after the sample should not be greater than 1.5%, otherwise the injection needs to be repeated. 4.1.6.4 Calculation
Calculate the average value of the peak area ratio of 2,4-D butyl ester to the internal standard in the two sample solutions and the two standard solutions before and after the sample. The mass percentage of 2,4-D butyl ester is calculated according to formula (1): Timaw
Wu Zhong:-
the average value of the peak area ratio of 2,4-D butyl ester to the internal standard in the sample solution;*2—the average value of the peak area ratio of 2,4-D butyl ester to the internal standard in the standard solution; m1—the mass of the sample, g;Www.bzxZ.net
m2—the mass of the standard, g;
the mass percentage of the standard, %.
4.1.6.5 Allowable difference
HG2319-92
The difference between the results of two parallel determinations should not be greater than 1.5%. 4.2 Determination of total esters
4.2.1 Method summary
Use the normalized result of the corrected 2,4-D butyl ester peak area to calculate the ratio of total esters to 2,4-D butyl ester, and then multiply it by the content of 2,4-D butyl ester to obtain the total ester content.
4.2.2 Operation steps
Same as in 4.1.
4.2.3 Calculation
According to the chromatogram obtained for each injection in 4.1.6.3, calculate the peak areas of corrected monochlorophenoxyacetic acid n-butyl ester, 2,4-D butyl ester, 2,4-dichlorophenoxyacetic acid isobutyl ester, and trichlorophenoxyacetic acid n-butyl ester. The mass percentage of total esters2 is calculated according to formula (2): (fiA+A2+A+f2A)
Where: 1——2,4-D butyl ester content;
f1 ——Relative correction factor of monochlorophenoxyacetic acid n-butyl ester to 2,4-D butyl ester, (1.143); relative correction factor of monotrichlorophenoxyacetic acid n-butyl ester to 2,4-D butyl ester, (0.890); f2
Peak area of monochlorophenoxyacetic acid n-butyl ester; A2——Peak area of 2,4-D butyl ester;
As——Peak area of 2,4-dichlorophenoxyacetic acid isobutyl ester; A. Peak area of monotrichlorophenoxyacetic acid n-butyl ester. Note: The total ester result is the average of the two calculation results. 4.3 Determination of free acid and free phenol
4.3.1 Method summary
The sample is dissolved in ethanol, first with methyl red as the indicator, and 0.0.1mol/L sodium hydroxide standard titration solution is titrated until yellow, at which time all the free acid in the solution is neutralized. Then phenol is added as an indicator, and 0.1mol/L sodium hydroxide standard titration solution is continued to be titrated until all the free phenol is neutralized.
4.3.2 Reagents and solutions
Absolute ethanol (GB678);
Sodium hydroxide standard titration solution: ci(NaOH)=0.01mol/L, c2(NaOH)=0.1mol/L, prepared and calibrated according to GB601; methyl red indicator: 1g methyl red ethanol solution; phenolphthalein indicator: 10g/L phenolyl ethanol solution. 4.3.3 Analysis steps
Weigh 1g (accurate to 0.0002g) of 2,4-D butyl ester technical sample and place it in a 250mL conical flask, add 50mL of absolute ethanol to dissolve, and shake well. Add 3 drops of methyl red solution and titrate with 0.01mol/L sodium hydroxide standard titration solution until the solution turns yellow. Note the volume of sodium hydroxide standard titration solution consumed (V1). Add 3 drops of phenolphthalein solution and titrate with 0.1mol/L sodium hydroxide standard titration solution until the solution turns red. The end point is when it does not fade in half a minute. Note the volume of sodium hydroxide standard titration solution consumed (V1). Perform a blank experiment with the same steps. 4.3.4 Calculate the acidity mass percentage as according to formula (3): C1(V1-V)X0.221
wherein: C1 is the actual concentration of the sodium hydroxide standard titration solution, mol/L; Vi is the volume of the sodium hydroxide standard titration solution consumed in the titration of the free acid, mL; m is the mass of the sample, g; (3) HG2319-92 0.221 is the mass of 2,4-dihydrochloric acid equivalent to 1.00 mL of the sodium hydroxide standard titration solution (c(Na0H)=1.000 mol/L) expressed in grams.
The mass percentage of free phenol is 4, calculated according to formula (4): 2(VV)×0.163×100
Wherein: C2——actual concentration of standard sodium hydroxide titration solution, mol/L; V2——volume of standard sodium hydroxide titration solution consumed for titrating free phenol, mL; V'2——volume of standard sodium hydroxide titration solution consumed for titrating blank, mL; m
mass of sample, g;
0.163——mass of 2,4-dichlorophenol equivalent to 1.00mL standard sodium hydroxide titration solution [c(Na0H）=1.000mol/L], expressed in grams.
5 Inspection rules
5.12,4-D butyl ester technical products shall be inspected by the quality supervision and inspection department of the manufacturer. The manufacturer shall ensure that all 2,4-D butyl ester technical products shipped out of the factory meet the requirements of this standard. Each batch of 2,4-D butyl ester technical products shipped out of the factory shall be accompanied by a quality certificate. 5.2 The batch size of each batch of 2,4-D butyl ester technical products shall not exceed the capacity of the packaging storage tank. 5.3 The sampling method shall be carried out in accordance with GB1605.
5.4 The user unit has the right to verify whether the received 2,4-D butyl ester technical meets the requirements of this standard in accordance with the various provisions in the product standard. 5.5 In the inspection results, if any index does not meet the standard, re-sampling shall be carried out from twice the number of packages for verification. If the re-verification result shows that only one index does not meet the requirements, the entire batch of products shall be unqualified. 5.6 When the supply and demand parties have disputes over product quality, they can be resolved through negotiation or the statutory inspection agency shall conduct arbitration analysis in accordance with the inspection methods specified in this standard.
6 Marking, packaging, transportation and purchase and storage
6.1 The marking and packaging of 2,4-D butyl ester technical shall comply with the relevant provisions of GB3796, and shall be marked with the trademark and production license number. 6.2 2,4-D butyl ester technical shall be packaged in 200kg iron drums, and other forms of packaging may also be used according to user requirements. All containers for packaging 2,4-D butyl ester technical must be dedicated and shall not contain other pesticides. 6.3 During storage and transportation, strictly prevent moisture and sunlight, maintain good ventilation, and shall not be mixed with food, seeds, and feed, avoid contact with the skin, and prevent inhalation through the mouth.
6.4 The validity period is 2 years from the date of manufacture, and it is guaranteed that all indicators meet the standard requirements within 2 years. Additional remarks:
This standard was proposed by the Science and Technology Department of the Ministry of Chemical Industry of the People's Republic of China. This standard was drafted and technically coordinated by the Shenyang Chemical Industry Research Institute of the Ministry of Chemical Industry, and the 9719 Factory of the Chinese People's Liberation Army participated in the drafting. The main drafters of this standard are Jiang Minyi, Yuan Chunfeng, Li Xiujie, Wang Xuecheng, Mei Baogui, Zhang Zhenhua and Zhang Daidi.4 The validity period is 2 years from the date of leaving the factory, and it is guaranteed that all indicators meet the standard requirements within 2 years. Additional remarks:
This standard is proposed by the Science and Technology Department of the Ministry of Chemical Industry of the People's Republic of China. This standard is drafted and technically coordinated by the Shenyang Chemical Research Institute of the Ministry of Chemical Industry, and the 9719 Factory of the Chinese People's Liberation Army participated in the drafting. The main drafters of this standard are Jiang Minyi, Yuan Chunfeng, Li Xiujie, Wang Xuecheng, Mei Baogui, Zhang Zhenhua, and Zhang Daidi. 54 The validity period is 2 years from the date of leaving the factory, and it is guaranteed that all indicators meet the standard requirements within 2 years. Additional remarks:
This standard is proposed by the Science and Technology Department of the Ministry of Chemical Industry of the People's Republic of China. This standard is drafted and technically coordinated by the Shenyang Chemical Research Institute of the Ministry of Chemical Industry, and the 9719 Factory of the Chinese People's Liberation Army participated in the drafting. The main drafters of this standard are Jiang Minyi, Yuan Chunfeng, Li Xiujie, Wang Xuecheng, Mei Baogui, Zhang Zhenhua, and Zhang Daidi. 5
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