1,4-丁二醇(BDO)

1,4-丁二醇(BDO)用途

【用途一】
用作溶剂和增湿剂，也用于制增塑剂、药物、聚酯树脂、聚氨基甲酸酯树脂等
【用途二】
用作色谱分析试剂，也用于有机合成
【用途三】
1,4-丁二醇用途广泛。在美国和西欧一半以上用于生产四氢呋喃，其次用于生产γ-丁内酯和聚对苯二甲酸丁二醇酯，后者是迅速发展中的工程塑料；1,4-丁二醇作为增链剂和聚酯原料用于生产聚氨酯弹性体和软质聚氨酯泡沫塑料；1,4-丁二醇制得的酯类是纤维素、聚氯乙烯、聚丙烯酸酯类和聚酯类的良好增塑剂。1,4-丁二醇具有良好的吸湿性的增柔性，可作明胶软化剂和吸水剂，玻璃纸和其他未用纸的处理剂。还可制备N-甲基吡咯烷酮、N-乙烯基吡咯烷酮及其他吡咯烷酮衍生物，也用于制备维生素B6、农药、除草剂以及作用多种工艺过程的溶剂、增塑剂、润滑剂、增湿剂、柔软性、胶粘剂和电镀工业的光亮剂。
【用途四】
溶剂。湿润剂。增塑剂的中间体。制造聚氨基甲酸酯高弹体的交联剂。有机合成。制造四氢呋喃。

1,4-丁二醇(BDO)名称

[ CAS 号 ]:
110-63-4

[ 中文名 ]:
1,4-丁二醇

[ 英文名 ]:
1,4-Butanediol

[中文别名 ]:

[英文别名 ]:

1,4-Butandiol
1,4-Butanediol
Dabco BDO
MFCD00002968
EINECS 203-786-5
Diol 14B
BDO
butane-1,4-diol
agrisynthb1d
1,4-Dihydroxybutane

1,4-丁二醇(BDO)物理化学性质

[ 密度 ]:
1.0±0.1 g/cm3

[ 沸点 ]:
228.0±0.0 °C at 760 mmHg

[ 熔点 ]:
20 °C

[ 分子式 ]:
C₄H₁₀O₂

[ 分子量 ]:
90.121

[ 闪点 ]:
105.9±13.0 °C

[ 精确质量 ]:
90.068077

[ PSA ]:
40.46000

[ LogP ]:
-1.02

[ 外观性状 ]:
黏的无色液体

[ 蒸汽密度 ]:
3.1 (vs air)

[ 蒸汽压 ]:
0.0±1.0 mmHg at 25°C

[ 折射率 ]:
1.441

[ 储存条件 ]:
库房通风低温干燥,与氧化剂分开存放

[ 稳定性 ]:
Stable. Combustible. Incompatible with strong oxidizing agents, mineral acids, acid chlorides, acid anhydrides.

[ 水溶解性 ]:
Miscible

1,4-丁二醇(BDO)MSDS

详细MSDS(安全技术说明书)

1,4-丁二醇(BDO)毒性和生态

CHEMICAL IDENTIFICATION

RTECS NUMBER :: EK0525000

CHEMICAL NAME :: 1,4-Butanediol

CAS REGISTRY NUMBER :: 110-63-4

BEILSTEIN REFERENCE NO. :: 1633445

LAST UPDATED :: 199712

DATA ITEMS CITED :: 19

MOLECULAR FORMULA :: C4-H10-O2

MOLECULAR WEIGHT :: 90.14

WISWESSER LINE NOTATION :: Q4Q

HEALTH HAZARD DATA

ACUTE TOXICITY DATA

TYPE OF TEST :: LDLo - Lowest published lethal dose

ROUTE OF EXPOSURE :: Unreported

SPECIES OBSERVED :: Human - woman

DOSE/DURATION :: 300 mg/kg

TOXIC EFFECTS :: Behavioral - altered sleep time (including change in righting reflex)

REFERENCE :: PHARAT Pharmazie. (VEB Verlag Volk und Gesundheit, Neue Gruenstr. 18, Berlin DDR-1020, Ger. Dem. Rep.) V.1- 1946- Volume(issue)/page/year: 3,110,1948

TYPE OF TEST :: LDLo - Lowest published lethal dose

ROUTE OF EXPOSURE :: Rectal

SPECIES OBSERVED :: Human - man

DOSE/DURATION :: 429 mg/kg

TOXIC EFFECTS :: Details of toxic effects not reported other than lethal dose value

REFERENCE :: PHARAT Pharmazie. (VEB Verlag Volk und Gesundheit, Neue Gruenstr. 18, Berlin DDR-1020, Ger. Dem. Rep.) V.1- 1946- Volume(issue)/page/year: 3,110,1948

TYPE OF TEST :: LD50 - Lethal dose, 50 percent kill

ROUTE OF EXPOSURE :: Oral

SPECIES OBSERVED :: Rodent - rat

DOSE/DURATION :: 1525 mg/kg

TOXIC EFFECTS :: Behavioral - altered sleep time (including change in righting reflex) Behavioral - somnolence (general depressed activity) Blood - other changes

REFERENCE :: HYSAAV Hygiene and Sanitation (USSR). English translation of GISAAA. (Springfield, VA) 1964-71. Discontinued. Volume(issue)/page/year: 33(1-3),41,1968

TYPE OF TEST :: LCLo - Lowest published lethal concentration

ROUTE OF EXPOSURE :: Inhalation

SPECIES OBSERVED :: Rodent - rat

DOSE/DURATION :: 15 gm/m3/4H

TOXIC EFFECTS :: Sense Organs and Special Senses (Olfaction) - effect, not otherwise specified Lungs, Thorax, or Respiration - other changes Nutritional and Gross Metabolic - weight loss or decreased weight gain

REFERENCE :: INHTE5 Inhalation Toxicology. (Hemisphere Publishing Corp., c/o Taylor & Francis Inc., 1900 Frost Rd., Suite 101, Bristol, PA 19007) V.1- 1989- Volume(issue)/page/year: 3,379,1991

TYPE OF TEST :: LD50 - Lethal dose, 50 percent kill

ROUTE OF EXPOSURE :: Intraperitoneal

SPECIES OBSERVED :: Rodent - rat

DOSE/DURATION :: 1070 mg/kg

TOXIC EFFECTS :: Details of toxic effects not reported other than lethal dose value

REFERENCE :: JPPMAB Journal of Pharmacy and Pharmacology. (Pharmaceutical Soc. of Great Britain, 1 Lambeth High St., London SEI 7JN, UK) V.1- 1949- Volume(issue)/page/year: 26,597,1974

TYPE OF TEST :: LD50 - Lethal dose, 50 percent kill

ROUTE OF EXPOSURE :: Oral

SPECIES OBSERVED :: Rodent - mouse

DOSE/DURATION :: 2062 mg/kg

TOXIC EFFECTS :: Behavioral - altered sleep time (including change in righting reflex) Behavioral - somnolence (general depressed activity) Blood - other changes

REFERENCE :: HYSAAV Hygiene and Sanitation (USSR). English translation of GISAAA. (Springfield, VA) 1964-71. Discontinued. Volume(issue)/page/year: 33(1-3),41,1968

TYPE OF TEST :: LD50 - Lethal dose, 50 percent kill

ROUTE OF EXPOSURE :: Intraperitoneal

SPECIES OBSERVED :: Rodent - mouse

DOSE/DURATION :: 1650 mg/kg

TOXIC EFFECTS :: Details of toxic effects not reported other than lethal dose value

REFERENCE :: TXAPA9 Toxicology and Applied Pharmacology. (Academic Press, Inc., 1 E. First St., Duluth, MN 55802) V.1- 1959- Volume(issue)/page/year: 49,385,1979

TYPE OF TEST :: LD50 - Lethal dose, 50 percent kill

ROUTE OF EXPOSURE :: Oral

SPECIES OBSERVED :: Rodent - rabbit

DOSE/DURATION :: 2531 mg/kg

TOXIC EFFECTS :: Behavioral - altered sleep time (including change in righting reflex) Behavioral - somnolence (general depressed activity) Blood - other changes

REFERENCE :: HYSAAV Hygiene and Sanitation (USSR). English translation of GISAAA. (Springfield, VA) 1964-71. Discontinued. Volume(issue)/page/year: 33(1-3),41,1968

TYPE OF TEST :: LD50 - Lethal dose, 50 percent kill

ROUTE OF EXPOSURE :: Oral

SPECIES OBSERVED :: Rodent - guinea pig

DOSE/DURATION :: 1200 mg/kg

TOXIC EFFECTS :: Behavioral - altered sleep time (including change in righting reflex) Behavioral - somnolence (general depressed activity) Blood - other changes

REFERENCE :: HYSAAV Hygiene and Sanitation (USSR). English translation of GISAAA. (Springfield, VA) 1964-71. Discontinued. Volume(issue)/page/year: 33(1-3),41,1968 ** OTHER MULTIPLE DOSE TOXICITY DATA **

TYPE OF TEST :: TDLo - Lowest published toxic dose

ROUTE OF EXPOSURE :: Oral

SPECIES OBSERVED :: Rodent - rat

DOSE/DURATION :: 5460 mg/kg/26W-I

TOXIC EFFECTS :: Blood - changes in serum composition (e.g. TP, bilirubin, cholesterol) Biochemical - Enzyme inhibition, induction, or change in blood or tissue levels - true cholinesterase Biochemical - Metabolism (Intermediary) - other carbohydrates

REFERENCE :: GISAAA Gigiena i Sanitariya. For English translation, see HYSAAV. (V/O Mezhdunarodnaya Kniga, 113095 Moscow, USSR) V.1- 1936- Volume(issue)/page/year: 33(1),37,1968

TYPE OF TEST :: TDLo - Lowest published toxic dose

ROUTE OF EXPOSURE :: Oral

SPECIES OBSERVED :: Rodent - rat

DOSE/DURATION :: 14 gm/kg/28D-I

TOXIC EFFECTS :: Blood - other changes Biochemical - Enzyme inhibition, induction, or change in blood or tissue levels - dehydrogenases Biochemical - Enzyme inhibition, induction, or change in blood or tissue levels - other transferases

REFERENCE :: PJOMEY Polish Journal of Occupational Medicine. (Polish Journal of Occupational Medicine, P.O. Box 199, 90-950 Lodz, Poland) V.1-3; 1988-90. Discontinued. Volume(issue)/page/year: 3,421,1990

TYPE OF TEST :: TCLo - Lowest published toxic concentration

ROUTE OF EXPOSURE :: Inhalation

SPECIES OBSERVED :: Rodent - rat

DOSE/DURATION :: 5200 mg/m3/6H/2W-I

TOXIC EFFECTS :: Blood - changes in serum composition (e.g. TP, bilirubin, cholesterol) Blood - changes in erythrocyte (RBC) count Nutritional and Gross Metabolic - weight loss or decreased weight gain

REFERENCE :: INHTE5 Inhalation Toxicology. (Hemisphere Publishing Corp., c/o Taylor & Francis Inc., 1900 Frost Rd., Suite 101, Bristol, PA 19007) V.1- 1989- Volume(issue)/page/year: 3,379,1991 *** NIOSH STANDARDS DEVELOPMENT AND SURVEILLANCE DATA *** NIOSH OCCUPATIONAL EXPOSURE SURVEY DATA : NOHS - National Occupational Hazard Survey (1974) NOHS Hazard Code - M0752 No. of Facilities: 226 (estimated) No. of Industries: 7 No. of Occupations: 22 No. of Employees: 16785 (estimated) NOES - National Occupational Exposure Survey (1983) NOES Hazard Code - M0752 No. of Facilities: 759 (estimated) No. of Industries: 21 No. of Occupations: 25 No. of Employees: 16811 (estimated) No. of Female Employees: 3870 (estimated)

1,4-丁二醇(BDO)安全信息

[ 危害码 (欧洲) ]:
Xn:Harmful

[ 风险声明 (欧洲) ]:
R22

[ 安全声明 (欧洲) ]:
S36

[ WGK德国 ]:
1

[ RTECS号 ]:
EK0525000

[ 包装等级 ]:
I; II; III

[ 危险类别 ]:
6.1

[ 海关编码 ]:
2905399090

1,4-丁二醇(BDO)合成路线

详细合成路线

1,4-丁二醇(BDO)上下游产品

1,4-丁二醇(BDO)上游产品

1,4-丁二醇(BDO)下游产品

1,4-丁二醇(BDO)制备

1、①乙炔法　先以乙炔和甲醛在Cu-Bi催化剂存在下，于98kPa、80 -95℃ 反应制成1,4-丁炔二醇。后者再经骨架镍催化，于1.372-2.06MPa、50 -60℃ 加氢成1,4-丁烯二酸盐，继之以Ni-Cu-Mn/Al2O3进一步催化加氢（13.7-20.6MPa、120 -140℃ ）成1,4-丁二醇，经离子交换树脂除去金属离子后，再经蒸馏提纯得纯品。

②改进的乙炔法上述工艺已经经过改良，开发了硅酸镁为载体的催化剂，并加入了铋，从而抑制了铜聚反应，并使丁炔二醇合成系统在低而安全的乙炔分压下进行操作，免除了燃爆危险。在丁炔二醇低压合成系统，使用一连续搅拌釜，通入37%的甲醇，以12%Cu-2%Bi/硅酸镁（数字为催化剂中金属的质量分数）为催化剂，反应温度95℃，乙炔分压0.1MPa，PH值5-6。惰性气体用作稀释剂以减小乙炔分压从而使爆炸危险最小化。丁炔干杯醇以甲醛计转化率为95%，炔丙醇回收。丁炔二醇的理论产率为95%。氢化工序改良为两段加氢：35%丁炔二醇水溶液与乙酸铜一起流入连续搅拌釜式反应器，以Ranny Ni为催化剂，在温度50-60℃、氢气压力1.4-2.0MPa下操作，产生含有部分氢化和羰基化合物的粗BDO蒸气。粗BDO蒸气在一填充Ni-Cu-Mn/硅胶催化剂的固定床反应器再一次加氢，反应温度120-140℃、氢气压力13.8-20.7MPa。ISP公司研究发现：硅胶载体在第二段高压氢化反应条件下自身降解，导致反应器压力脉动。为此，开发了由15%Ni-7%Cu-05%Mn/AI组成的一种新催化剂，该催化剂在反应条件下活性高，自身稳定，寿命长。1,4-丁二醇产率以乙炔计为93.1%。

2 、顺酐加氢法以丁烷为原料生产的工艺有：Huntsman/Kvaerner法、BPAmcoc/Lurgi Geminox法和Sisas 法。其中，Kvaerner法工艺过程为：在固定床上以钒基催化剂，将正丁烷气相氧化成顺酐(MA)，再将顺酐转化成相应的顺酐二甲酯(DMM)，进一步气相加氢/水解得到BDO。 MA和过量的甲醇发生酯化反应生成DMM，以酸性离子交换树脂为催化剂，在70-80℃，MA转化率为100%，DMM产率为99%。DMM气相加氢工艺以铜为引发剂，在170-190℃、4-7MPa 下，反应系统氢气/酯进料摩尔比通常为（250-350）：1。加氢得到的粗BDO和GHF产率以DMM进料计大于99%。粗产品经多塔连续蒸馏，精制成BDO、γ-丁内酯、四氢呋喃产品，甲醇回收并循环至配化工序。BDO总产率以MA计为98%-99%，主要副产品为丁醇（0.1%-0.2%）。

3、丁二烯法　由1,3-丁二烯与乙酸与氧气进行乙酰氧化反应，生成1,4-二乙酰氧基-2-丁烯，再经加氢、水解制成。副产THF，乙酸则循环使用。

4、1,4-二氯丁烯法 1,4-二氯丁烯是丁二烯生产氯丁二烯过程的中间产物，以其为原料，经水解、加氢而得1,4-丁二醇。

5.制法：

于装有搅拌器、两个回流冷凝器、滴液漏斗的3L反应瓶中，加入新鲜的金属钠60g(2.6mol)，迅速加入由丁二酸二乙酯(2)35g(0.2mol)与700mL无水乙醇配成的溶液，反应剧烈进行，必要时可用冰水浴冷却。待反应平稳后，加热反应(浴温可达130℃)以使金属钠全部反应完(约0.5～1h)。冰水浴冷却，滤出析出的氯化钠。滤液中加入300g无水碳酸钾以除去水和酸。过滤，滤饼用热乙醇提取两次。合并滤液和提取液，蒸出乙醇，有固体盐析出。加入干燥的丙酮，过滤，蒸出丙酮。剩余物减压蒸馏，收集133～135℃/2.4kPa的馏分，得1,4-丁二醇(1)13g,收率72%。

1,4-丁二醇(BDO)海关

[ 海关编码 ]: 2905399002

[ 中文概述 ]:
2905399002 1,4-丁二醇。监管条件:AB(入境货物通关单,出境货物通关单)。增值税率:17.0%。退税率:9.0%。最低关税:5.5%。普通关税:30.0%

[ 申报要素 ]: 品名, 成分含量, 用途, 包装, 原产地证据文件及编号(例附原产地证书, 原产于沙特阿拉伯或台湾地区的

[ 监管条件 ]: A.入境货物通关单 B.出境货物通关单

[ 检验检疫 ]: R.进口食品卫生监督检验 S.出口食品卫生监督检验

[ Summary ]:
2905399002 butane-1,4-diol。supervision conditions:AB(certificate of inspection for goods inward,certificate of inspection for goods outward)。VAT:17.0%。tax rebate rate:9.0%。MFN tarrif:5.5%。general tariff:30.0%