Morpholin Chemische Eigenschaften,Einsatz,Produktion Methoden
ERSCHEINUNGSBILD
FARBLOSE HYGROSKOPISCHE FLüSSIGKEIT MIT CHARAKTERISTISCHEM GERUCH.
CHEMISCHE GEFAHREN
Zersetzung beim Verbrennen unter Bildung giftiger Rauche (Stickstoffoxide, Kohlenmonoxid). Mittelstarke Base. Reagiert mit starken Oxidationsmitteln unter Feuergefahr. Greift Kunststoffe, Gummi und Beschichtungen an. Instabil bei Lagerung in Kupfer- oder Zinkbehältern.
ARBEITSPLATZGRENZWERTE
TLV: 20 ppm (als TWA); Hautresorption; Krebskategorie A4 (nicht klassifizierbar als krebserzeugend für den Menschen); (ACGIH 2005).
MAK: 10 ppm, 36 mg/m? Spitzenbegrenzung: überschreitungsfaktor I(2); Schwangerschaft: Gruppe D; (DFG 2006).
EG Arbeitsplatz-Richtgrenzwerte: 36 mg/m? 10 ppm (als TWA); 72 mg/m? 20 ppm (als STEL); (EG 2006)
AUFNAHMEWEGE
Aufnahme in den Körper durch Inhalation, über die Haut und durch Verschlucken.
INHALATIONSGEFAHREN
Beim Verdampfen bei 20°C kann schnell eine gesundheitsschädliche Kontamination der Luft eintreten.
WIRKUNGEN BEI KURZZEITEXPOSITION
WIRKUNGEN BEI KURZZEITEXPOSITION: Die Substanz verätzt die Augen, die Haut und die Atemwege. ätzend beim Verschlucken. Inhalation der Substanz kann zu Lungenödem führen (s.Anm.).
WIRKUNGEN NACH WIEDERHOLTER ODER LANGZEITEXPOSITION
Möglich sind Auswirkungen auf Leberund Nieren.
LECKAGE
Ausgelaufene Flüssigkeit möglichst in abdichtbaren Behältern sammeln. Reste mit Sand oder inertem Absorptionsmittel aufnehmen und an einen sicheren Ort bringen. Persönliche Schutzausrüstung: Vollschutzanzug mit umgebungsluftunabhängigem Atemschutzgerät.
R-Sätze Betriebsanweisung:
R10:Entzündlich.
R20/21/22:Gesundheitsschädlich beim Einatmen,Verschlucken und Berührung mit der Haut.
R34:Verursacht Verätzungen.
S-Sätze Betriebsanweisung:
S23:Gas/Rauch/Dampf/Aerosol nicht einatmen(geeignete Bezeichnung(en) vom Hersteller anzugeben).
S36:DE: Bei der Arbeit geeignete Schutzkleidung tragen.
S45:Bei Unfall oder Unwohlsein sofort Arzt zuziehen (wenn möglich, dieses Etikett vorzeigen).
Aussehen Eigenschaften
C4H9ON; Tetrahydrooxazin. Farblose Flüssigkeit mit aminartigem Geruch.
Gefahren für Mensch und Umwelt
Verursacht Verätzungen. Gesundheitsschädlich beim Verschlucken, Einatmen und Berührung mit der Haut.
Nicht mit Säureanhydriden, Säurechloriden und Säuren in Berührung bringen.
Entzündlich.
LD
50 (oral, Ratte): 1450 mg/kg
Schutzmaßnahmen und Verhaltensregeln
Schutzhandschuhe als kurzzeitiger Spritzschutz.
Verhalten im Gefahrfall
Persönliche Maßnahmen: Dämpfe nicht einatmen.
Mit flüssigkeitsbindendem Material aufnehmen. Der Entsorgung zuführen. Nachreinigen
Kohlendioxid, Pulver.
Brennbar. Im Brandfall werden gefährliche Gase freigesetzt. Mit Luft Bildung explosionsfähiger Gemische möglich.
Erste Hilfe
Nach Hautkontakt: Mit reichlich Wasser abwaschen.
Nach Augenkontakt: Mit reichlich Wasser bei geöffnetem Lidspalt mindestens 15 Minuten ausspülen. Sofort Augenarzt hinzuziehen.
Nach Einatmen: Frischluft. Arzt hinzuziehen.
Nach Verschlucken: Mund mit reichlich Wasser ausspülen. Sofort Arzt hinzuziehen.
Nach Kleidungskontakt: Kontaminierte Kleidung sofort entfernen.
Ersthelfer: siehe gesonderten Anschlag
Sachgerechte Entsorgung
Als halogenfreie, organische Lösemittelabfälle.
Chemische Eigenschaften
Morpholine is a colorless to yellow liquid with a weak ammonia or fish-like odor. The odor threshold is 0.01 ppm. The reactivity of morpholine is mainly due to its secondary amine group. It readily undergoes organic condensations, alkylations, and arylations, resulting in the formation of various N-substituted morpholine compounds. Ethers are relatively chemically inert, hence the oxygen is of relatively little consequence except as a member of the heterocyclic ring (Texaco Chemical Co. 1982).
Physikalische Eigenschaften
Colorless, mobile, oily, hygroscopic, flammable liquid with a weak ammonia-like odor.
Experimentally determined detection and recognition odor threshold concentrations were 40 μg/m
3
(11 ppb
v) and 25 μg/m
3 (70 ppb
v), respectively (Hellman and Small, 1974). Forms explosive
vapors at temperatures >35 °C.
Verwenden
Morpholine is made by dehydrating ethanolamines. Its main
use is as a rubber accelerator in manufacturing tires. This
process requires high temperature (300°F) and pressure,
which increase the hazards. Morpholine is also used as a
boiler water additive, brightener for detergents, and corrosion
inhibitor, in the preservation of book paper, in waxes and
polishes, and in organic synthesis.
Vorbereitung Methode
Morpholine is produced by reacting diethylene glycol, ammonia, and a small amount of hydrogen over a hydrogenation catalyst at 150-400°C and 30-400 atmospheres with the morpholine being recovered by fractional distillation. Various byproducts include 2-(2-aminoethoxy)ethanol and Af-alkylmorpholines (NRC 1981).
Allgemeine Beschreibung
An aqueous solution with a fishlike odor. Corrosive to tissue and moderately toxic by ingestion and inhalation.
Air & Water Reaktionen
Highly flammable. Water soluble.
Reaktivität anzeigen
MORPHOLINE dissolved in water neutralizes acids in exothermic reactions to form salts plus water. May be incompatible with isocyanates, halogenated organics, peroxides, phenols (acidic), epoxides, anhydrides, and acid halides. Flammable gaseous hydrogen may be generated in combination with strong reducing agents, such as hydrides.
Hazard
Flammable, moderate fire risk. Toxic byingestion and inhalation, irritant to skin, absorbedby skin. Eye damage and upper respiratory tractirritant. Questionable carcinogen.
Health Hazard
May cause toxic effects if inhaled or ingested/swallowed. Contact with substance may cause severe burns to skin and eyes. Fire will produce irritating, corrosive and/or toxic gases. Vapors may cause dizziness or suffocation. Runoff from fire control or dilution water may cause pollution. Morpholine is readily absorbed through the skin; it causes nasal irritation when inhaled, with coughing, bronchial irritation, and pulmonary edema at increasingly higher concentrations. Upon ingestion, it causes hemorrhage in the gastrointestinal tract, with possible diarrhea; liver and kidney damage may occur if sufficient amounts are ingested or inhaled. Morpholine itself is not a carcinogen on the basis of available data.
Brandgefahr
Flammable/combustible material. May be ignited by heat, sparks or flames. Vapors may form explosive mixtures with air. Vapors may travel to source of ignition and flash back. Most vapors are heavier than air. They will spread along ground and collect in low or confined areas (sewers, basements, tanks). Vapor explosion hazard indoors, outdoors or in sewers. Runoff to sewer may create fire or explosion hazard. Containers may explode when heated. Many liquids are lighter than water.
Industrielle Verwendung
The total industrial consumption of morpholine is 11,000 metric tons/year. The largest usage for morpholine (33%) is in the rubber industry as an intermediate in the production of delayed-action accelerators for the polymerization of rubber, as stabilizers against heat-aging effects, and as bloom inhibitors in butyl rubber vulcanization. A second large proportion (25%) of morpholine production is used as an inhibitor to combat carbonic acid corrosion in condensate return lines of steam boiler systems. Morpholine is an intermediate in the manufacture of optical brighteners utilized by the soap and detergent industry. Morpholine reacts readily with fatty acids, forming soaps used in the formulation of self-polishing waxes and polishes and in coatings for the food industry. N-methyl morpholine and TV-ethyl morpholine are used as catalysts in the manufacture of polyurethane foams. Morpholine derivatives are utilized in pharmaceutical applications, as bactericides, fungicides, and herbicides, and as separating agents for oils. Other derivatives are utilized in the textile and printing industry as adjuvants, whitening agents, stabilizers, ink eradicators, and paper conditioners (Mjos 1978; NRC 1981; Texaco Chemical Co. 1982).
Sicherheitsprofil
Moderately toxic by
ingestion, inhalation, skin contact, and
intraperitoneal routes. Mutation data
reported. A corrosive irritant to skin, eyes,
and mucous membranes. Can cause kidney damage. Questionable carcinogen with
experimental neoplastigenic data.
Flammable liquid. A very dangerous fire
hazard when exposed to flame, heat, or
oxidizers; can react with oxidizing materials.
To fight fire, use alcohol foam, CO2, dry
chemical. Mixtures with nitromethane are
explosive. May ignite spontaneously in
contact with cellulose nitrate of high surface
area. When heated to decomposition it emits
highly toxic fumes of NOx.
Toxikologie
Common signs of toxicity following repeated dosing are local irritation and inflammations of the stomach, respiratory tract, and eyes, as well as systemic effects primarily on the liver and kidneys. In rats, exposure to 250 mL/m3 (890 mg kg-1 d-1, 6 h/d, 5 d/week, 90 d) and to up to 150 mL/m3 (543 mg/m3, 6 h/d, 5 d/week, 104 weeks) produced focal erosions and squamous-cell metaplasia of the nasal cavities and turbinates and ocular irritation, but no hematological or organ effects; at 90 mg/m3 (25 mL/m3, subchronic) and 36 mg/m3 (10 mL/m3, chronic), no treatment-related effects at all were identified. These data may be taken as NOAELs, although one earlier Russian publication claimed that some adverse effects were conspicuous on the spleen and in the red and white blood counts in rats and guinea pigs after four-month inhalation of 70 mg/m3 and less.
mögliche Exposition
Morpholine is used as a separating
agent for volatile amines; an intermediate for textile
lubricants; in the synthesis of rubber accelerators and pharmaceuticals.
It is also used as a solvent; as a boiler water
additive; and in the formulation of waxes, polishers and
cleaners.
Carcinogenicity
Morpholine did not produce an
increase in tumors in rats that inhaled from 10 to 150 ppm for
2 years. No tumors were seen in rats fed 5000 ppm
morpholine for 8 weeks and observed for their lifetime.
Morpholine fed concurrently with sodium nitrate increased
the numbers of hepatocellular carcinomas and sarcomas
of the liver and lungs of rats and mice, probably mediated
through the formation of N-nitrosomorpholine.
The authors concluded that morpholine itself was either
weakly carcinogenic or that a nitrate from an unknown source
was present. No cancers were produced when 6330 ppm
morpholine was added to the drinking water of mice for
their lifetimes. Concurrent exposure of morpholine
plus nitrite or nitrogen dioxide increased the tumor incidence
in a variety of species. In a feeding
study where morpholine (0.5% in diet) and sodium
nitrate were given concurrently for 23 weeks, rats showed no
evidence of cancer.
Environmental Fate
Biological. Heukelekian and Rand (1955) reported a 5-d BOD value of 0.0 g/g which is 0.0% of
the ThOD value of 1.84 g/g.
Poupin et al. (1998) isolated a Mycobacterium strain RP1 from a contaminated activated sludge
that utilized morpholine as the sole source of carbon, nitrogen, and energy. The investigators
proposed the following degradation pathway: 2-hydroxymorpholine → (2-(2-aminoethoxy)acetaldehyde
→ 2-(2-aminoethoxy)acetate → glycolate and ethanolamine.
Chemical/Physical. In an aqueous solution, chloramine reacted with morpholine to form Nchloromorpholine
(Isaac and Morris, 1983). The aqueous reaction of nitrogen dioxide (1–99 ppm)
and morpholine yielded N-nitromorpholine (Cooney et al., 1987).
Slowly decomposes in the absence of oxygen.
Stoffwechsel
Early reports indicated that morpholine was excreted unchanged after administration to rats (Tanaka et al 1978), dogs (Rhodes and Case 1977), and rabbits (Van Stee et al 1981). Sohn et al (1982b, 1982c) reported that approximately 80% of a radioactive dose was excreted in the urine within 24 h when administered intraperitoneally to rats, hamsters, and guinea pigs. Although 99% of the excreted dose was unmetabolized in the rat and hamster, 20% of the dose appeared in the urine of guinea pigs as N-methylmorpholine-N-oxide. N-Hydroxymorpholine and N-methylmorpholine were also detected in extracts of guinea pig tissues. Studies of the metabolism of morpholine-containing pharmaceutical agents in humans and animals indicate that the morpholine moiety may be hydroxylated or oxidized at C2 and C3, with subsequent ring cleavage (Oelschlager and Al Shaik 1985).
Versand/Shipping
UN2054 Morpholine, Hazard class: 8; Labels:
8-Corrosive material, 3-Flammable liquid.
läuterung methode
Dry morpholine with KOH, fractionally distil it, then reflux it with Na, and again fractionally distil it. Dermer & Dermer [J Am Chem Soc 59 1148 1937] precipitated it as the oxalate by adding slowly to slightly more than 1 molar equivalent of oxalic acid in EtOH. The precipitate is filtered off and recrystallised twice from 60% EtOH [1:1 salt has m 190-195o(dec)]. Addition of the oxalate to concentrated aqueous NaOH regenerated the base, which is separated and dried with solid KOH, then sodium, before being fractionally distilled. The hydrochloride has m 178-179o (from MeOH/Et2O), and the picrate has m 151.6o (from aqueous EtOH). [Beilstein 27 II 3, 27 III/IV 15.]
Inkompatibilitäten
Strong acids, strong oxidizers; metals,
nitro compounds. Corrosive to metals; attacks copper and
its compounds.
Waste disposal
Controlled incineration
(incinerator equipped with a scrubber or thermal unit to
reduce nitrogen oxides emissions).
Morpholin Upstream-Materialien And Downstream Produkte
Upstream-Materialien
Downstream Produkte
