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百草枯

百草枯用途

【用途1】
属速效灭生性触杀型除草剂,广泛用于橡胶、香蕉、甘蔗、果园、农田等地除草
【用途2】
速效、广谱、触杀型、灭生性除草剂。联吡啶阳离子迅速被植物叶子吸收后,在绿色组织中通过光合作用和呼吸作用被还原成联吡啶游离基,又经自氧化作用使叶组织中的水和氧形成过氧化氢和过氧游离基,破坏叶绿体层膜,使光合作用和叶绿素合成中止,促使干枯。该药剂在苗前使用,与土接触失去活性,对喷药后出土的农作物幼苗没有影响。对褐色树皮没有作用,木本植物树干安全。光照会增加药效发挥。阴天延缓药剂显效。在小麦、油菜收割后,不经翻耕,对前茬禾秆和田间杂草,直接用20%水剂30~45mL/100m2,对水3~4.5kg进行叶面处理。水稻收割后也可用此法。还可用于果园、桑园、橡胶园、茶园、水稻田、麦田杂草(牛毛毡、莎草科、看麦娘、猪殃殃、繁缕、狗尾草、蟋蟀草、竹叶草等),一般用20%水剂30~45mL/100m2,对水3.75kg喷雾。
【用途3】
百草枯是一个大品种非选择性除草剂,在作物出苗前使用,能触杀地面杂草,使之干枯,用于果园、桑园、橡胶园、稻田、旱地以及免耕种植地的除草。
【用途4】
N,N′-二甲基-4,4-偶联吡啶是除草剂百草枯的中间体。
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百草枯名称

[ CAS 号 ]:
4685-14-7

[ 中文名 ]:
百草枯

[ 英文名 ]:
paraquat

[中文别名 ]:

[英文别名 ]:

百草枯物理化学性质

[ 密度 ]:
0.9748 (rough estimate)

[ 沸点 ]:
310.75°C (rough estimate)

[ 分子式 ]:
C12H14N2++

[ 分子量 ]:
186.25300

[ 精确质量 ]:
186.11600

[ PSA ]:
7.76000

[ LogP ]:
1.00260

[ 外观性状 ]:
灰白色粉末

[ 折射率 ]:
1.5600 (estimate)

[ 储存条件 ]:
库房通风低温干燥,与食品原料分开储运

百草枯毒性和生态

CHEMICAL IDENTIFICATION

RTECS NUMBER :
DW1960000
CHEMICAL NAME :
4,4'-Bipyridinium, 1,1'-dimethyl-
CAS REGISTRY NUMBER :
4685-14-7
LAST UPDATED :
199806
DATA ITEMS CITED :
45
MOLECULAR FORMULA :
C12-H14-N2
MOLECULAR WEIGHT :
186.28
WISWESSER LINE NOTATION :
T6KTJ A1 D- DT6KTJ A1

HEALTH HAZARD DATA

ACUTE TOXICITY DATA

TYPE OF TEST :
LDLo - Lowest published lethal dose
ROUTE OF EXPOSURE :
Oral
SPECIES OBSERVED :
Human - man
DOSE/DURATION :
171 mg/kg
TOXIC EFFECTS :
Lungs, Thorax, or Respiration - fibrosis, focal (pneumoconiosis) Gastrointestinal - changes in structure or function of esophagus Gastrointestinal - ulceration or bleeding from stomach
TYPE OF TEST :
LDLo - Lowest published lethal dose
ROUTE OF EXPOSURE :
Oral
SPECIES OBSERVED :
Human - man
DOSE/DURATION :
1690 mg/kg
TOXIC EFFECTS :
Lungs, Thorax, or Respiration - respiratory depression Gastrointestinal - ulceration or bleeding from stomach Kidney, Ureter, Bladder - renal function tests depressed
TYPE OF TEST :
LDLo - Lowest published lethal dose
ROUTE OF EXPOSURE :
Oral
SPECIES OBSERVED :
Human - man
DOSE/DURATION :
343 mg/kg
TOXIC EFFECTS :
Gastrointestinal - changes in structure or function of esophagus Gastrointestinal - ulceration or bleeding from stomach Kidney, Ureter, Bladder - renal function tests depressed
TYPE OF TEST :
LD50 - Lethal dose, 50 percent kill
ROUTE OF EXPOSURE :
Oral
SPECIES OBSERVED :
Rodent - rat
DOSE/DURATION :
100 mg/kg
TOXIC EFFECTS :
Details of toxic effects not reported other than lethal dose value
TYPE OF TEST :
LD50 - Lethal dose, 50 percent kill
ROUTE OF EXPOSURE :
Intraperitoneal
SPECIES OBSERVED :
Rodent - rat
DOSE/DURATION :
14800 ug/kg
TOXIC EFFECTS :
Lungs, Thorax, or Respiration - acute pulmonary edema Gastrointestinal - other changes Liver - other changes
TYPE OF TEST :
LD50 - Lethal dose, 50 percent kill
ROUTE OF EXPOSURE :
Unreported
SPECIES OBSERVED :
Rodent - rat
DOSE/DURATION :
250 mg/kg
TOXIC EFFECTS :
Behavioral - somnolence (general depressed activity) Behavioral - convulsions or effect on seizure threshold Behavioral - changes in motor activity (specific assay)
TYPE OF TEST :
LD50 - Lethal dose, 50 percent kill
ROUTE OF EXPOSURE :
Oral
SPECIES OBSERVED :
Rodent - mouse
DOSE/DURATION :
120 mg/kg
TOXIC EFFECTS :
Details of toxic effects not reported other than lethal dose value
TYPE OF TEST :
LD50 - Lethal dose, 50 percent kill
ROUTE OF EXPOSURE :
Unreported
SPECIES OBSERVED :
Rodent - mouse
DOSE/DURATION :
198 mg/kg
TOXIC EFFECTS :
Behavioral - somnolence (general depressed activity) Behavioral - convulsions or effect on seizure threshold Behavioral - changes in motor activity (specific assay)
TYPE OF TEST :
LD50 - Lethal dose, 50 percent kill
ROUTE OF EXPOSURE :
Oral
SPECIES OBSERVED :
Mammal - dog
DOSE/DURATION :
25 mg/kg
TOXIC EFFECTS :
Details of toxic effects not reported other than lethal dose value
TYPE OF TEST :
LD50 - Lethal dose, 50 percent kill
ROUTE OF EXPOSURE :
Oral
SPECIES OBSERVED :
Mammal - cat
DOSE/DURATION :
35 mg/kg
TOXIC EFFECTS :
Details of toxic effects not reported other than lethal dose value
TYPE OF TEST :
LD50 - Lethal dose, 50 percent kill
ROUTE OF EXPOSURE :
Administration onto the skin
SPECIES OBSERVED :
Rodent - rabbit
DOSE/DURATION :
236 mg/kg
TOXIC EFFECTS :
Details of toxic effects not reported other than lethal dose value
TYPE OF TEST :
LD50 - Lethal dose, 50 percent kill
ROUTE OF EXPOSURE :
Oral
SPECIES OBSERVED :
Rodent - guinea pig
DOSE/DURATION :
30 mg/kg
TOXIC EFFECTS :
Details of toxic effects not reported other than lethal dose value
TYPE OF TEST :
LD50 - Lethal dose, 50 percent kill
ROUTE OF EXPOSURE :
Oral
SPECIES OBSERVED :
Bird - chicken
DOSE/DURATION :
262 mg/kg
TOXIC EFFECTS :
Details of toxic effects not reported other than lethal dose value
TYPE OF TEST :
LD50 - Lethal dose, 50 percent kill
ROUTE OF EXPOSURE :
Oral
SPECIES OBSERVED :
Mammal - species unspecified
DOSE/DURATION :
70 mg/kg
TOXIC EFFECTS :
Details of toxic effects not reported other than lethal dose value
TYPE OF TEST :
TDLo - Lowest published toxic dose
ROUTE OF EXPOSURE :
Intraperitoneal
SPECIES OBSERVED :
Rodent - rat
DOSE/DURATION :
45 mg/kg/6D-I
TOXIC EFFECTS :
Cardiac - changes in heart weight Liver - other changes Endocrine - changes in spleen weight
TYPE OF TEST :
Mutation test systems - not otherwise specified
TYPE OF TEST :
Cytogenetic analysis
TYPE OF TEST :
Sperm Morphology

MUTATION DATA

TYPE OF TEST :
Cytogenetic analysis
TEST SYSTEM :
Rodent - hamster Lung
REFERENCE :
MUREAV Mutation Research. (Elsevier Science Pub. B.V., POB 211, 1000 AE Amsterdam, Netherlands) V.1- 1964- Volume(issue)/page/year: 412,187,1998 *** REVIEWS *** ACGIH TLV-TWA 0.5 mg/m3, total dust DTLVS* The Threshold Limit Values (TLVs) and Biological Exposure Indices (BEIs) booklet issues by American Conference of Governmental Industrial Hygienists (ACGIH), Cincinnati, OH, 1996 Volume(issue)/page/year: TLV/BEI,1997 ACGIH TLV-TWA 0.1 mg/m3, respirable dust DTLVS* The Threshold Limit Values (TLVs) and Biological Exposure Indices (BEIs) booklet issues by American Conference of Governmental Industrial Hygienists (ACGIH), Cincinnati, OH, 1996 Volume(issue)/page/year: TLV/BEI,1997 *** U.S. STANDARDS AND REGULATIONS *** MSHA STANDARD-air:TWA 0.5 mg/m3 (skin) DTLVS* The Threshold Limit Values (TLVs) and Biological Exposure Indices (BEIs) booklet issues by American Conference of Governmental Industrial Hygienists (ACGIH), Cincinnati, OH, 1996 Volume(issue)/page/year: 3,195,1971 OSHA PEL (Gen Indu):8H TWA 0.5 mg/m3 (skin), respirable dust CFRGBR Code of Federal Regulations. (U.S. Government Printing Office, Supt. of Documents, Washington, DC 20402) Volume(issue)/page/year: 29,1910.1000,1994 OSHA PEL (Construc):8H TWA 0.5 mg/m3 (skin), respirable dust CFRGBR Code of Federal Regulations. (U.S. Government Printing Office, Supt. of Documents, Washington, DC 20402) Volume(issue)/page/year: 29,1926.55,1994 OSHA PEL (Shipyard):8H TWA 0.5 mg/m3 (skin), respirable dust CFRGBR Code of Federal Regulations. (U.S. Government Printing Office, Supt. of Documents, Washington, DC 20402) Volume(issue)/page/year: 29,1915.1000,1993 OSHA PEL (Fed Cont):8H TWA 0.5 mg/m3 (skin) CFRGBR Code of Federal Regulations. (U.S. Government Printing Office, Supt. of Documents, Washington, DC 20402) Volume(issue)/page/year: 41,50-204.50,1994 *** OCCUPATIONAL EXPOSURE LIMITS *** OEL-AUSTRALIA:TWA 0.1 mg/m3 JAN 1993 OEL-BELGIUM:TWA 0.1 mg/m3 JAN 1993 OEL-DENMARK:TWA 0.1 mg/m3;Skin JAN 1993 OEL-FINLAND:TWA 0.1 mg/m3;STEL 0.3 mg/m3;Skin JAN 1993 OEL-FRANCE:TWA 0.1 mg/m3 JAN 1993 OEL-HUNGARY:STEL 0.05 mg/m3;Skin JAN 1993 OEL-THE NETHERLANDS:TWA 0.1 mg/m3 JAN 1993 OEL-THE PHILIPPINES:TWA 0.5 mg/m3;Skin JAN 1993 OEL-THAILAND:TWA 0.5 mg/m3 JAN 1993 OEL IN BULGARIA, COLOMBIA, JORDAN, KOREA check ACGIH TLV OEL IN NEW ZEALAND, SINGAPORE, VIETNAM check ACGIH TLV *** NIOSH STANDARDS DEVELOPMENT AND SURVEILLANCE DATA *** NIOSH RECOMMENDED EXPOSURE LEVEL (REL) : NIOSH REL TO PARAQUAT, respirable dust-air:10H TWA 0.1 mg/m3 (Sk) REFERENCE : NIOSH* National Institute for Occupational Safety and Health, U.S. Dept. of Health, Education, and Welfare, Reports and Memoranda. Volume(issue)/page/year: DHHS #92-100,1992
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百草枯安全信息

[ 危害码 (欧洲) ]:
T:Toxic

[ 风险声明 (欧洲) ]:
R26/27/28

[ 安全声明 (欧洲) ]:
S1-S13-S45

[ 危险品运输编码 ]:
UN 2781

[ 包装等级 ]:
II

[ 危险类别 ]:
6.1(a)

[ 海关编码 ]:
3808931100

百草枯上下游产品

百草枯制备

制备方法一
以吡啶与镁粉为原料,在钠沙引发下生成二聚物,然后用硝基甲烷氧化,经分离、结晶得4,4'-联二吡啶,收率53%。
4,4'-联二吡啶与氯乙酸作用,在NaH2PO4与EDTA二钠盐的催化作用下合成百草枯,收率97.7%。
或采用低温钠工艺:将金属钠溶于液氨中,得到带有自由电子的钠离子氨溶液。再在溶剂存在下与吡啶反应,于-30~-20℃二聚得4,4'-四氢联吡啶的二钠(离子态)。将其于-20~-0℃用空气氧化得4,4'-联吡啶,最后用水稀释,在压力下与氯甲烷反应合成百草枯。
制备方法二
吡啶先季碱化为N-甲基吡啶盐酸盐,再在催化剂存在下二聚得1,1'-二甲基-4,4'-二氢联吡啶,继而氧化得百草枯。该法收率高,工艺简单。技术关键是二聚反应及产品的后处理。
二聚反应使用的催化剂是氰化钠,溶剂为二甲基亚砜或醇-水(醇中水含量为10%~25%,不大于40%)。反应温度40~90℃,介擀为碱性;氧化过程常用氧化剂是二氧化硫、氯气等。反应条件不同,收率差别较大。实例1:将N-甲基吡啶氯化物3.1g溶于10mL水中,于室温氮气下,迅速加入搅拌着的2.5g氰化钠、1g氢氧化钠、40mL乙醇的混合液中,加毕加热回流1.5h,冷却,在紫色反应混合物中加入10mL液体二氧化硫,反应混合物变橙色,以N-甲基吡啶盐计收率94%。实例2:将N-甲基吡啶氯化物溶于10mL水中,于室温氮气下加2.5g氰化钠、1g氢氧化钠及40mL乙醇,室温下搅拌30min,再加热回流30min,冷却,鼓泡通氯气,直到反应混合物蓝色消失,再将反应液用碳酸钠中和至pH值9.2。以N-甲基吡啶氯化物计收率95%。
产品后处理方法有萃取法、络合法等。如萃取法:百草枯阳离子400份和N-甲基吡啶阳离子166份溶于10000份水中,真空浓缩,其残渣用20000份氯仿萃取3次,留下的残渣含百草枯阳离子398份,N-甲基吡啶氯化物1份。氯仿萃取液重复用水萃取之。

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百草枯海关

[ 海关编码 ]: 3808931100

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