1,3-БУТАДИЕН химические свойства, назначение, производство
Описание
1,3-Butadiene is a simple conjugated diene. It is a colourless gas with a mild aromatic or gasoline-like odour and incompatible with phenol, chlorine dioxide, copper, and crotonaldehyde. The gas is heavier than air and may travel along the ground; distant ignition is possible. It is an important industrial chemical used as a monomer in the production of synthetic rubber. Most butadiene is polymerised to produce synthetic rubber. While polybutadiene itself is a very soft, almost liquid, material, polymers prepared from mixtures of butadiene with styrene or acrylonitrile, such as ABS, are both tough and elastic. Styrene–butadiene rubber is the material most commonly used for the production of automobile tyres. Smaller amounts of butadiene are used to make nylon via the intermediate adiponitrile, other synthetic rubber materials such as chloroprene, and the solvent sulpholane. Butadiene is used in the industrial production of cyclododecatriene via a trimerisation reaction.
1,3-Butadiene structure
Химические свойства
Butadiene is a gas, b.p. -4°C.
Физические свойства
Colorless gas with a mild, aromatic or gasoline-like odor. Experimentally determined detection
and recognition odor threshold concentrations were 1.0 mg/m3 (0.45 ppmv) and 2.4 mg/m3 (1.1
ppmv), respectively (Hellman and Small, 1974).
Использование
Synthetic elastomers (styrene-butadiene, polybutadiene, neoprene, nitriles), ABS resins, chemical intermediate.
1,3-Butadiene can undergo a four-component coupling reaction with aryl Grignard reagents, and alkyl fluorides in the presence of nickel catalyst to form 1,6-octadiene carbon compound substituted with alkyl and aryl groups at the 3- and 8-positions.
1,3-Butadiene is a useful diene for Diels Alder reaction.
It may be used in the synthesis of the following:
- 1-Silyl-substituted 1,3-butadienes, by [RuHCl(CO)(PCy3)2]-catalyzed silylative coupling of terminal (E)-1,3-dienes with vinylsilanes.
- Synthetic rubber and thermoplastic resins.
- Disilylated dimers by reacting with chlorosilanes.
- Octa-2,7-dien-1-ol via palladium catalyzed-hydrodimerization.
Определение
ChEBI: 1,3-Butadiene is a butadiene with unsaturation at positions 1 and 3. It is a chemical made from the processing of petroleum. About 75% of the manufactured 1,3-butadiene is used to make synthetic rubber. Synthetic rubber is widely used for tires on cars and trucks.
Подготовка
Butadiene is obtained when n-butenes are dehydrogenated:
n-Butenes are mostly obtained from the catalytic cracking operations carried
out on various petroleum fractions; thermal cracking processes usually give
low yields of butenes. The dehydrogenation of n-butenes is carried out by
mixing the feed with steam (which lowers the partial pressures of the
reactants) and passing over a catalyst such as mixed calcium/nickel phosphate stabilized with chromium oxide at about 650??C.
Методы производства
Except for a small amount of butadiene produced by the
oxydehydrogenation of n-butane, most of butadiene is produced
commercially as a by-product of ethylene production
during the steam cracking of hydrocarbon streams. It is
separated and purificated from other components by extractive
distillation, using acetonitrile and dimethylformamide as
solvents.
Общее описание
1,3-Butadiene is a colorless gas with a mild, aromatic, gasoline-like odor. It is shipped as a liquefied gas under its vapor pressure. Contact with the liquid can cause frostbite. It is easily ignited. Its vapors are heavier than air and a flame can flash back to the source of leak very easily. It can asphyxiate by the displacement of air. It must be shipped inhibited as butadiene is liable to polymerization. If polymerization occurs in the container, It may violently rupture. Under prolonged exposure to fire or intense heat the containers may rupture violently and rocket. It is used to make synthetic rubber and plastics, and to make other chemicals.
Реакции воздуха и воды
Highly flammable. In contact with air, butadiene may form violently explosive peroxides, which can be exploded by mild heat or shock. Solid butadiene absorbs enough oxygen at sub atmospheric pressures to make 1,3-BUTADIENE explode violently when heated just above its melting point [Ind. Eng. Chem. 51:733 1959].
Профиль реактивности
A colorless gas, 1,3-BUTADIENE can react with oxidizing reagents. Upon long exposure to air 1,3-BUTADIENE forms explosive peroxides. They are sensitive to heat or shock; sudden polymerization may occur [Scott, D. A., Chem. Eng. News, 1940, 18, p.404]. Butadiene polyperoxides are insoluble in liquefied butadiene (m. p. -113° C, b. p. -2.6° C) and progressively separate leading to local concentration build up. Self-heating from a spontaneous decomposition will lead to explosion [Hendry, D. G. et al., Ind. Eng. Chem., 1968, 7, p. 136, 1145]. Explodes on contact with aluminum tetrahydroborate, potentially explosive reaction with chlorine dioxide (peroxide) and crotonaldehyde (above 180° C). Reaction with sodium nitrite forms a spontaneously flammable product [Sax, 9th ed., 1996, p. 539].
Опасность
A confirmed carcinogen. Irritant in high
concentration. Highly flammable gas or liquid,
explosive limits in air 2–11%. May form explosive
peroxides on exposure to air. Must be kept inhibited
during storage and shipment. Inhibitors often used
are di-n-butylamine or phenyl-β-naphthylamine.
Storage is usually under pressure or in insulated
tanks <35F (<1.67C).
Угроза здоровью
The toxicity of 1,3-butadiene has been foundto be very low in humans and animals. It isan asphyxiant. In humans, low toxic effectsmay be observed at exposure to 2000 ppmfor 7 hours. The symptoms may be hallucinations,distorted perception, and irritation ofeyes, nose, and throat. Higher concentrationsmay result in drowsiness, lightheadedness,and narcosis. High dosages of 1,3-butadienewas toxic to animals by inhalation and skincontact. General anesthetic effects and respiratorydepression were noted. Concentrationsof 25–30% may be lethal to rats and rabbits.Contact with the liquefied gas can cause burnand frostbite.
Exposure to 1,3-butadiene caused cancersin the stomach, lungs, and blood in ratsand mice. It is suspected to be a humancarcinogen. It is a mutagen and a teratogen.
Пожароопасность
Behavior in Fire: Vapors heavier than air and may travel a considerable distance to a source of ignition and flashback. Containers may explode in a fire due to polymerization.
Использование в материалах
1,3-Butadiene is noncorrosive and may be used
with any common metals. Steel is recommended
for tanks and piping in butadiene service by
some authorities. If used with plastics, compatibility
must be confirmed. Welded rather than
threaded connections are similarly recommended
because 1,3-butadiene tends to leak
through even extremely small openings. If
threaded connections are used, Schedule 80
pipe should be used. Before being exposed to
1,3-butadiene that is not inhibited, iron surfaces
should be treated with an appropriate reducing
agent such as sodium nitrite because polymerization
is accelerated by oxygen (even if present
as in ferrous oxide), as well as by heat.
Профиль безопасности
Confirmed carcinogen
with experimental carcinogenic and
neoplastigenic data. An experimental
teratogen. Mutation data reported.
Inhalation of high concentrations can cause
unconsciousness and death. Human
systemic effects by inhalation: cough,
hallucinations, dstorted perceptions,
changes in the visual field and other
Канцерогенность
1,3-Butadiene is known to be a human carcinogen based on sufficient evidence of carcinogenicity from studies in humans, including epidemiological and mechanistic studies. 1,3-Butadiene was first listed in the Fifth Annual Report on Carcinogens in 1989 as reasonably anticipated to be a human carcinogen based on sufficient evidence of carcinogenicity from studies in experimental animals. The listing was revised to known to be a human carcinogen in the Ninth Report on Carcinogens in 2000.
Экологическая судьба
Surface Water. The estimated volatilization half-life of 1,3-butadiene in a model river 1 m deep,
flowing 1 m/sec and a wind speed of 3 m/sec is 3.8 h (Lyman et al., 1982).
Photolytic. The following rate constants were reported for the reaction of 1,3-butadiene and OH
radicals in the atmosphere: 6.9 x 10-11 cm3/molecule·sec (Atkinson et al., 1979) and 6.7 x 10-11
cm3/molecule·sec (Sablji? and Güsten, 1990). Atkinson and Carter (1984) reported a rate constant
of 6.7–8.4 x 10-11 cm3/molecule·sec for the reaction of 1,3-butadiene and ozone in the atmosphere.
Photooxidation reaction rate constants of 2.13 x 10-13 and 7.50 x 10-18 cm3/molecule·sec were
reported for the reaction of 1,3-butadiene and NO3 (Benter and Schindler, 1988; Sablji? and
Güsten, 1990). The half-life in air for the reaction of 1,3-butadiene and NO3 radicals is 15 h
(Atkinson et al., 1984a).
Chemical/Physical. Will polymerize in the presence of oxygen if no inhibitor is present
(Hawley, 1981).
хранилище
1,3-Butadiene is stored in a cool and wellventilatedlocation separated from combustibleand oxidizing substances. Smallamounts of stabilizers, such as o-dihydroxybenzene,p-tert-butylcatechol, or aliphaticmercaptans, are added to prevent its polymerizationor peroxides formation. The cylindersare stored vertically and protected againstphysical damage.
Утилизация отходов
Disposal of l,3-butadiene by venting, incineration,
using a suitable flare system, or by other
means may be subject to permitting by federal,
state, provincial, or local regulations. Persons
involved with disposal of 1,3-butadiene should
check with the environmental authorities having
jurisdiction to determine the applicability of
permitting regulations to disposal activities.
1,3-БУТАДИЕН препаратная продукция и сырье
сырьё
препарат
Cross-linking agent
Carboxy styrene-butadiene latex
МЕТАКРИЛОНИТРИЛ
1-бутен
1,2,3,6-Tetrahydrophthalic anhydride
modified filling agent SBR
5-ETHYLIDENE-2-NORBORNENE
Muscone
N,N,N',N'-Тетраметил-2-бутен-1,4-диамин
2-(2-CHLOROETHOXY)-BENZENESULFONAMIDE
CYCLODODECANE
VITAMIN K4
СУЛЬФОЛАН
butadiene-styrene latex
Поливинилпирролидон
ВИНИЛЦИКЛОГЕКСЕНДИОКСИД
3-Sulfolene
КАПТАН
Менадион
Nitrile rubber NBR
цис-1,2,3,6-тетрагидрофталевый ангидрид
Малеинового гидразида
Адипонитрил
1,2,3,4-Tetrabromobutane
ПОЛИБУТАДИЕНОВЫЙ ДИАКРИЛАТ
ГЕКСАМЕТИЛЕНДИАМИН
1,2,5,6,9,10-Hexabromocyclododecane
ПОЛИСТИРОЛ-В-полибутадиена-В-ПОЛИСТИРОЛ
DOWEX(R) 1X8
КИСЛОТА додекандионовая
2,4,4-Триметил-1-пентен
ABS смолы
2-БУТАНОЛ
FUSEL OIL
Циклододека-1,5,9-триен
IRONE
butadiene resin emulsion LHYJ-DS50
Ti(Co)Ziegler catalyst
1,4-гексадиен
N-Hydroxymethyl-3,4,5,6-tetrahydrophthalimide