毒理学数据:
1、急性毒性：LD50：5800mg/kg(大鼠经口)；LC50：14PPm,4小时(大鼠吸入）
2、对皮肤、眼睛和黏膜有强烈的刺激作用，长期接触可引起支气管炎，少数病例呈哮喘状态，支气管扩张甚至肺心病等。工作场所空气中有毒物质时间加权平均容许浓度为0.1mg/m3；有毒物质短时间接触容许浓度为0.2mg/m3。
CHEMICAL IDENTIFICATION
-
RTECS NUMBER :
-
CZ6300000
-
CHEMICAL NAME :
-
Benzene, 2,4-diisocyanato-1-methyl-
-
CAS REGISTRY NUMBER :
-
584-84-9
-
BEILSTEIN REFERENCE NO. :
-
0744602
-
LAST UPDATED :
-
199712
-
DATA ITEMS CITED :
-
68
-
MOLECULAR FORMULA :
-
C9-H6-N2-O2
-
MOLECULAR WEIGHT :
-
174.17
-
WISWESSER LINE NOTATION :
-
OCNR B1 ENCO
HEALTH HAZARD DATA
ACUTE TOXICITY DATA
-
TYPE OF TEST :
-
Open irritation test
-
ROUTE OF EXPOSURE :
-
Administration onto the skin
-
SPECIES OBSERVED :
-
Rodent - rabbit
-
TYPE OF TEST :
-
Standard Draize test
-
ROUTE OF EXPOSURE :
-
Administration onto the skin
-
SPECIES OBSERVED :
-
Rodent - rabbit
-
TYPE OF TEST :
-
Standard Draize test
-
ROUTE OF EXPOSURE :
-
Administration into the eye
-
SPECIES OBSERVED :
-
Rodent - rabbit
-
TYPE OF TEST :
-
TCLo - Lowest published toxic concentration
-
ROUTE OF EXPOSURE :
-
Inhalation
-
SPECIES OBSERVED :
-
Human - woman
-
DOSE/DURATION :
-
300 ppt/8H/5D
-
TOXIC EFFECTS :
-
Lungs, Thorax, or Respiration - respiratory obstruction
-
TYPE OF TEST :
-
TCLo - Lowest published toxic concentration
-
ROUTE OF EXPOSURE :
-
Inhalation
-
SPECIES OBSERVED :
-
Human
-
DOSE/DURATION :
-
20 ppb/2Y
-
TOXIC EFFECTS :
-
Lungs, Thorax, or Respiration - cough Lungs, Thorax, or Respiration - sputum
-
TYPE OF TEST :
-
TCLo - Lowest published toxic concentration
-
ROUTE OF EXPOSURE :
-
Inhalation
-
SPECIES OBSERVED :
-
Human
-
DOSE/DURATION :
-
500 ppb
-
TOXIC EFFECTS :
-
Sense Organs and Special Senses (Olfaction) - effect, not otherwise specified Lungs, Thorax, or Respiration - other changes
-
TYPE OF TEST :
-
TCLo - Lowest published toxic concentration
-
ROUTE OF EXPOSURE :
-
Inhalation
-
SPECIES OBSERVED :
-
Human
-
DOSE/DURATION :
-
80 ppb
-
TOXIC EFFECTS :
-
Sense Organs and Special Senses (Olfaction) - effect, not otherwise specified Sense Organs and Special Senses (Eye) - effect, not otherwise specified Lungs, Thorax, or Respiration - other changes
-
TYPE OF TEST :
-
LD50 - Lethal dose, 50 percent kill
-
ROUTE OF EXPOSURE :
-
Oral
-
SPECIES OBSERVED :
-
Rodent - rat
-
DOSE/DURATION :
-
5800 mg/kg
-
TOXIC EFFECTS :
-
Gastrointestinal - other changes
-
TYPE OF TEST :
-
LC50 - Lethal concentration, 50 percent kill
-
ROUTE OF EXPOSURE :
-
Inhalation
-
SPECIES OBSERVED :
-
Rodent - rat
-
DOSE/DURATION :
-
14 ppm/4H
-
TOXIC EFFECTS :
-
Sense Organs and Special Senses (Eye) - lacrimation Behavioral - excitement Lungs, Thorax, or Respiration - dyspnea
-
TYPE OF TEST :
-
LC50 - Lethal concentration, 50 percent kill
-
ROUTE OF EXPOSURE :
-
Inhalation
-
SPECIES OBSERVED :
-
Rodent - mouse
-
DOSE/DURATION :
-
10 ppm/4H
-
TOXIC EFFECTS :
-
Lungs, Thorax, or Respiration - structural or functional change in trachea or bronchi Lungs, Thorax, or Respiration - changes in pulmonary vascular resistance
-
TYPE OF TEST :
-
LD50 - Lethal dose, 50 percent kill
-
ROUTE OF EXPOSURE :
-
Intravenous
-
SPECIES OBSERVED :
-
Rodent - mouse
-
DOSE/DURATION :
-
56 mg/kg
-
TOXIC EFFECTS :
-
Details of toxic effects not reported other than lethal dose value
-
TYPE OF TEST :
-
LC50 - Lethal concentration, 50 percent kill
-
ROUTE OF EXPOSURE :
-
Inhalation
-
SPECIES OBSERVED :
-
Rodent - rabbit
-
DOSE/DURATION :
-
11 ppm/4H
-
TOXIC EFFECTS :
-
Behavioral - excitement Lungs, Thorax, or Respiration - dyspnea Gastrointestinal - changes in structure or function of salivary glands
-
TYPE OF TEST :
-
LD50 - Lethal dose, 50 percent kill
-
ROUTE OF EXPOSURE :
-
Administration onto the skin
-
SPECIES OBSERVED :
-
Rodent - rabbit
-
DOSE/DURATION :
-
>16 mL/kg
-
TOXIC EFFECTS :
-
Details of toxic effects not reported other than lethal dose value
-
TYPE OF TEST :
-
LC50 - Lethal concentration, 50 percent kill
-
ROUTE OF EXPOSURE :
-
Inhalation
-
SPECIES OBSERVED :
-
Rodent - guinea pig
-
DOSE/DURATION :
-
13 ppm/4H
-
TOXIC EFFECTS :
-
Lungs, Thorax, or Respiration - structural or functional change in trachea or bronchi Lungs, Thorax, or Respiration - changes in pulmonary vascular resistance Lungs, Thorax, or Respiration - pleural effusion
-
TYPE OF TEST :
-
LD50 - Lethal dose, 50 percent kill
-
ROUTE OF EXPOSURE :
-
Oral
-
SPECIES OBSERVED :
-
Bird - wild bird species
-
DOSE/DURATION :
-
100 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 :
-
Oral
-
SPECIES OBSERVED :
-
Rodent - rat
-
DOSE/DURATION :
-
15 gm/kg/10D-I
-
TOXIC EFFECTS :
-
Gastrointestinal - other changes Liver - other changes Related to Chronic Data - death
-
TYPE OF TEST :
-
TCLo - Lowest published toxic concentration
-
ROUTE OF EXPOSURE :
-
Inhalation
-
SPECIES OBSERVED :
-
Rodent - rat
-
DOSE/DURATION :
-
204 ug/m3/24H/84D-C
-
TOXIC EFFECTS :
-
Behavioral - muscle contraction or spasticity Biochemical - Enzyme inhibition, induction, or change in blood or tissue levels - true cholinesterase Biochemical - Metabolism (Intermediary) - lipids including transport
-
TYPE OF TEST :
-
TCLo - Lowest published toxic concentration
-
ROUTE OF EXPOSURE :
-
Inhalation
-
SPECIES OBSERVED :
-
Rodent - rat
-
DOSE/DURATION :
-
102 ppb/24H/7D-C
-
TOXIC EFFECTS :
-
Lungs, Thorax, or Respiration - structural or functional change in trachea or bronchi
-
TYPE OF TEST :
-
TCLo - Lowest published toxic concentration
-
ROUTE OF EXPOSURE :
-
Inhalation
-
SPECIES OBSERVED :
-
Rodent - rat
-
DOSE/DURATION :
-
26 ppm/6H/5W-I
-
TOXIC EFFECTS :
-
Lungs, Thorax, or Respiration - structural or functional change in trachea or bronchi Lungs, Thorax, or Respiration - chronic pulmonary edema Related to Chronic Data - death
-
TYPE OF TEST :
-
TCLo - Lowest published toxic concentration
-
ROUTE OF EXPOSURE :
-
Inhalation
-
SPECIES OBSERVED :
-
Rodent - mouse
-
DOSE/DURATION :
-
990 ppb/6H/14D-I
-
TOXIC EFFECTS :
-
Sense Organs and Special Senses (Olfaction) - effect, not otherwise specified
-
TYPE OF TEST :
-
TDLo - Lowest published toxic dose
-
ROUTE OF EXPOSURE :
-
Inhalation
-
SPECIES OBSERVED :
-
Rodent - rabbit
-
DOSE/DURATION :
-
1500 ppb/71D-I
-
TOXIC EFFECTS :
-
Lungs, Thorax, or Respiration - structural or functional change in trachea or bronchi Related to Chronic Data - death
-
TYPE OF TEST :
-
TCLo - Lowest published toxic concentration
-
ROUTE OF EXPOSURE :
-
Inhalation
-
SPECIES OBSERVED :
-
Rodent - guinea pig
-
DOSE/DURATION :
-
3100 ppb/4H/5D-I
-
TOXIC EFFECTS :
-
Lungs, Thorax, or Respiration - structural or functional change in trachea or bronchi Blood - changes in leukocyte (WBC) count
-
TYPE OF TEST :
-
TCLo - Lowest published toxic concentration
-
ROUTE OF EXPOSURE :
-
Inhalation
-
SPECIES OBSERVED :
-
Rodent - rabbit
-
DOSE/DURATION :
-
1500 ppb/6H/79D-I
-
TOXIC EFFECTS :
-
Lungs, Thorax, or Respiration - structural or functional change in trachea or bronchi
MUTATION DATA
-
TYPE OF TEST :
-
Sister chromatid exchange
-
TEST SYSTEM :
-
Rodent - hamster Ovary
-
REFERENCE :
-
EMMUEG Environmental and Molecular Mutagenesis. (Alan R. Liss, Inc., 41 E. 11th St., New York, NY 10003) V.10- 1987- Volume(issue)/page/year: 13,133,1989 *** REVIEWS *** ACGIH TLV-Not classifiable as a human carcinogen 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-STEL 0.14 mg/m3 (0.02 ppm) 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 0.036 mg/m3 (0.005 ppm) 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 IARC Cancer Review:Animal Sufficient Evidence IMEMDT IARC Monographs on the Evaluation of Carcinogenic Risk of Chemicals to Man. (WHO Publications Centre USA, 49 Sheridan Ave., Albany, NY 12210) V.1- 1972- Volume(issue)/page/year: 39,287,1986 IARC Cancer Review:Human No Adequate Data IMEMDT IARC Monographs on the Evaluation of Carcinogenic Risk of Chemicals to Man. (WHO Publications Centre USA, 49 Sheridan Ave., Albany, NY 12210) V.1- 1972- Volume(issue)/page/year: 39,287,1986 IARC Cancer Review:Group 2B IMSUDL IARC Monographs, Supplement. (WHO Publications Centre USA, 49 Sheridan Ave., Albany, NY 12210) No.1- 1979- Volume(issue)/page/year: 7,56,1987 TOXICOLOGY REVIEW ANAEA3 Annals of Allergy. (American College of Allergists, POB 20671, Bloomington, MN 55420) V.1- 1943- Volume(issue)/page/year: 35,165,1975 TOXICOLOGY REVIEW AOHYA3 Annals of Occupational Hygiene. (Pergamon Press Inc., Maxwell House, Fairview Park, Elmsford, NY 10523) V.1- 1958- Volume(issue)/page/year: 17,143,1974 TOXICOLOGY REVIEW JJOMDZ JOM, Journal of Occupational Medicine. (American Occupational Medicine Assoc., 150 N. Wacker Dr., Chicago, IL 60606) V.10- 1968- Volume(issue)/page/year: 15,808,1973 TOXICOLOGY REVIEW CMTVAS Cahiers de Medecine du Travail. (Association Professionnelle Belge des Medecine du Travail, rue du Bultia, 6280 Gerpinnes, Belgium) V.1- 1963- Volume(issue)/page/year: 10(3),49,1973 *** U.S. STANDARDS AND REGULATIONS *** MSHA STANDARD:air-CL 0.02 ppm (0.14 mg/m3) 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: 3,260,1971 OSHA PEL (Gen Indu):CL 0.02 ppm (0.14 mg/m3) 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):CL 0.02 ppm (0.14 mg/m3) 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):CL 0.02 ppm (0.14 mg/m3) 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):CL 0.02 ppm (0.14 mg/m3) 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-ARAB Republic of Egypt:TWA 0.02 ppm (0.14 mg/m3) JAN 1993 OEL-BELGIUM:TWA 0.005 ppm (0.036 mg/m3);STEL 0.02 ppm JAN 1993 OEL-DENMARK:TWA 0.005 ppm (0.035 mg/m3);Carcinogen JAN 1993 OEL-FRANCE:TWA 0.01 ppm (0.08 mg/m3);STEL 0.02 ppm (0.16 mg/m3) JAN 1993 OEL-GERMANY:TWA 0.01 ppm (0.07 mg/m3) JAN 1993 OEL-HUNGARY:STEL 0.04 mg/m3 JAN 1993 OEL-JAPAN:TWA 0.02 ppm (0.14 mg/m3) JAN 1993 OEL-THE NETHERLANDS:TWA 0.02 ppm (0.14 mg/m3);Skin JAN 1993 OEL-THE PHILIPPINES:TWA 0.02 ppm (0.14 mg/m3) JAN 1993 OEL-RUSSIA:STEL 0.05 mg/m3 JAN 1993 OEL-SWEDEN:TWA 0.005 ppm (0.04 mg/m3);STEL 0.01 ppm (0.07 mg/m3) JAN 1993 OEL-SWITZERLAND:TWA 0.005 ppm (0.04 mg/m3);STEL 0.01 ppm JAN 1993 OEL-THAILAND:TWA 0.02 ppm (0.14 mg/m3) JAN 1993 OEL-TURKEY:TWA 0.02 ppm (0.14 mg/m3) JAN 1993 OEL-UNITED KINGDOM:TWA 0.02 mg/m3;STEL 0.07 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 TOLUENE DIISOCYANATE-air:CA lowest feasible conc 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 NIOSH OCCUPATIONAL EXPOSURE SURVEY DATA : NOHS - National Occupational Hazard Survey (1974) NOHS Hazard Code - 73390 No. of Facilities: 2310 (estimated) No. of Industries: 47 No. of Occupations: 54 No. of Employees: 26654 (estimated) NOES - National Occupational Exposure Survey (1983) NOES Hazard Code - 73390 No. of Facilities: 838 (estimated) No. of Industries: 19 No. of Occupations: 30 No. of Employees: 10921 (estimated) No. of Female Employees: 545 (estimated)
|
![butyl N-[5-(butoxycarbonylamino)-2-methyl-phenyl]carbamate结构式](https://www.chemsrc.com/caspic/173/7469-49-0.png)
![ethyl N-[5-(ethoxycarbonylamino)-2-methyl-phenyl]carbamate结构式](https://www.chemsrc.com/caspic/290/7450-62-6.png)
![1-(2-hydroxyethyl)-3-[3-(2-hydroxyethylcarbamoylamino)-4-methylphenyl]urea结构式](https://www.chemsrc.com/caspic/485/30042-54-7.png)
①常压法 将熔融的二氨基甲苯（105-110℃）溶解于邻二氯苯，配成10%-20%的溶液；将光气溶于邻二氯苯，含量为25%-50%。两种溶液在混合器中混合、加热至80-200℃，使之反应，产物是甲苯二异氰酸酯、氯化氢及其他副产物。末反应的光气、邻二氯苯与反应产物一并送入蒸发塔以分离出部分溶剂，蒸出的邻二氯苯再作为回收光气的吸收剂。蒸发塔釜液送入预蒸发器进行闪蒸，蒸出的甲苯二异氰酸酯与邻二氯苯进入蒸馏塔，此塔顶回收得纯溶剂，釜液精馏得甲苯二异氰酸酯。 ②加压法 该法所用溶剂一般为氯苯。液态光气与10%-20%的二氨基甲苯的氯苯溶液80-120℃MPa压力下，在循环管路中进行反应，管路中的循环比为10-40。反应粗产物通过缓冲器进入反应器，反应器用加热器加热。反应器顶部逸出的氯化氢回收得副产盐酸，其中含有的少量光气经冷凝器冷凝后进入光气贮槽。反应粗产物进入蒸发塔于0.1-0.5MPa压力下蒸出光气。塔釜是甲苯二异氰酸酯、氯苯及其他副产物，进一步蒸馏精制，回收氯苯，得到甲苯二异氰酸酯。 原料配比：光气/二氨基甲苯（物质的量比）3：6（非循环过程）。消耗定额（kg/t）：常压法二氨基甲苯1280（常压法）、905（加压法）；光气1250（常压法）、2260（加压法）；邻二氯苯3-10（常压法）；氯苯218（加压法）。 （二）硝基化合物羰基化法 该法从芳烃硝基化合物出发，采用铬、铑、钯等羰基化催化剂，在60-150℃、686-981MPa压力下，与CO直接反应生成甲苯二异氯酸酯。 （三）碳酸二甲酯法该法是自20世纪80年代以来甲醇氧化羰基化法碳酸二甲酯工业化后面新开发的用碳酸二甲酯取代光气生产甲苯二异氰酸酯的一种方法。具有设备简单、无公害、不用光气等诸多弊病。随着碳酸二甲酯的不断开发，生产规模不断扩大，其价格将逐渐降低。相信在环境问题日益被重视的今天，该法将更具有生命力。