Винилацетат

Описание

Vinyl acetate monomer (VAM) is a colourless liquid, immiscible or slightly soluble in water. VAM is a flammable liquid. VAM has a sweet, fruity smell (in small quantities), with sharp, irritating odour at higher levels. VAM is an essential chemical building block used in a wide variety of industrial and consumer products. VAM is a key ingredient in emulsion polymers, resins, and intermediates used in paints, adhesives, coatings, textiles, wire and cable polyethylene compounds, laminated safety glass, packaging, automotive plastic fuel tanks, and acrylic fibres. Vinyl acetate is used to produce polyvinyl acetate emulsions and resins. Very small residual levels of vinyl acetate have been found present in products manufactured using VAM, such as moulded plastic items, adhesives, paints, food packaging containers, and hairspray.

Химические свойства

Vinyl acetate is a colorless, flammable liquid with a pungent odor. The odor threshold is 0.12 ppm 0.3 ppm (NY, NJ).it is the precursor to polyvinyl acetate, an important polymer in industry.

Физические свойства

Colorless, watery liquid with a pleasant, fruity odor. Experimentally determined detection and recognition odor threshold concentrations were 400 μg/m³ (120 ppb_v) and 1.4 mg/m³ (400 ppb_v), respectively (Hellman and Small, 1974).

Использование

Vinyl acetate is primarily used to produce polyvinyl acetate emulsions and polyvinyl alcohol. The principal use of these emulsions has been in adhesives, paints, textiles, and paper products.

Подготовка

The major industrial route involves the reaction of ethylene and acetic acid with oxygen in the presence of a palladium catalyst.
Ethylene + acetic acid + 1/2 O₂ → Vinyl acetate +H₂O
But by products are also generated:
Ethylene + 3 O₂ → 2CO₂ + 2H₂O
Vinyl acetate is also prepared by the gas-phase addition of acetic acid to acetylene.

Методы производства

Vinyl acetate is an industrial chemical that is produced in large amounts in the United States. The worldwide production capacity of vinyl acetate monomer (VAM) was estimated at 6,154,000 tonnes/annum in 2007, with most capacity concentrated in the United States (1,585,000 all in Texas), China (1,261,000), Japan (725,000) and Taiwan (650,000) . The average list price for 2008 was $1600/tonne. Celanese is the largest producer (ca 25% of the worldwide capacity), while other significant producers include China Petrochemical Corporation (7 %), Chang Chun Group (6%) and LyondellBasell (5%).
It is a key ingredient in furniture-glue.

Реакции

Vinyl acetate undergoes many of the reactions anticipated for an alkene and an ester. Bromine adds to give the dibromide. Hydrogen halides add to give 1-haloethyl acetates, which cannot be generated by other methods because of the non - availability of the corresponding halo-alcohols. Acetic acid adds in the presence of palladium catalysts to give ethylidene diacetate, CH₃CH(OAc)₂. It undergoes transesterification with a variety of carboxylic acids.The alkene also undergoes Diels - Alder and 2 + 2 cycloadditions.

Общее описание

Vinyl acetate appears as a clear colorless liquid. Flash point 18 °F. Density 7.8 lb / gal. Slightly soluble in water. Vapors are heavier than air. Vapors irritate the eyes and respiratory system. May polymerize if heated or contaminated. If polymerization occurs inside a container, the container may violently rupture. Used to make adhesives, paints, and plastics.

Реакции воздуха и воды

Highly flammable. Slightly soluble in water.

Профиль реактивности

Vinyl acetate may undergo spontaneous exothermic polymerization on exposure to light. Reacts with air or water to produces peroxides that initiate explosively violent polymerization. Reacts with hydrogen peroxide to form explosive peracetic acid. Reacts with oxygen to form explosive peroxides. Forms explosive Vinyl acetate ozonide on contact with ozone. Undergoes violent or explosive reactions with 2-aminoethanol, chlorosulfonic acid, ethylenediamine, mineral acids (hydrochloric acid, hydrofluoric acid, nitric acid, sulfuric acid, oleum), and peroxides [Lewis, 3rd ed., 1993, p. 1311]. Polymerization initiated by dibenzoyl peroxide in ethyl acetate accelerated out of control, ignited and exploded [Vervalin, 1973, p. 81]. Polymerization in toluene solution has caused several large industrial explosions [MCA Case History No. 2087].

Угроза здоровью

Vinyl acetate has been related to reproductive abnormalities. It is a skin and upper respiratory tract irritantand a central nervous system depressant. Exposure caused gradual deterioration of heart muscles.

Пожароопасность

When heated to decomposition, Vinyl acetate burns and emits acrid fumes. Highly dangerous when exposed to heat, flames or oxidizers; explosion hazard with strong acids and strong oxidizers. Incompatible with alumina, oxidizing materials, 2-aminoethanol, chlorosulfonic acid; ethyleneimine; 36% hydrochloric acid; 48.7% hydrofluoric acid; 70% nitric acid; oleum; 96% sulfuric acid; ethylene diamine; peroxides and silica gel. Avoid light or any polymerizing initiator. Hazardous polymerization can be initiated by organic and inorganic peroxides; azo compounds; redox systems (including organometallic components); light; and high energy radiation.

Профиль безопасности

Confirmed carcinogen with experimental carcinogenic and tumorigenic data. Moderately toxic by ingestion, inhalation, and intraperitoneal routes. A skin and eye irritant. Experimental reproductive effects. Human mutation data reported. Highly dangerous fire hazard when exposed to heat, flame, or oxidzers. A storage hazard, it may undergo spontaneous exothermic polymerization. Reaction with air or water to form peroxides that catalyze an exothermic polymerization reaction has caused several large industrial explosions. Reaction with hydrogen peroxide forms the explosive peracetic acid. Reacts with oxygen above 50℃ to form an unstable explosive peroxide. Reacts with ozone to form the explosive vinyl acetate ozonide. Solution polymerization of the acetate dmolved in toluene has resulted in large industrial explosions. Polymerization reaction with dibenzoyl peroxide + ethyl acetate may release ignitable and explosive vapors. The vapor may react vigorously with desiccants (e.g., sihca gel or alumina). Incompatible (explosive) with 2-amino ethanol, chlorosulfonic acid, ethylenediamine, ethyleneimine, HCl, HF, HNO3, oleum, peroxides, H2SO4. See also ESTERS.

Возможный контакт

Vinyl acetate is used primarily in polymerization processes to produce polyvinyl acetate; polyvinyl alcohol, and vinyl acetate copolymer. The polymers, usually made as emulsions, suspensions, solutions, or resins, are used to prepare adhesives, paints, paper coatings, and textile finishes. Low molecular weight vinyl acetate is used as a chewing gum base.

Канцерогенность

There is inadequate evidence in humans for the carcinogenicity of vinyl acetate. There is limited evidence in experimental animals for the carcinogenicity of vinyl acetate. Therefore, IARC has classified vinyl acetate as possibly carcinogenic to humans (Group 2B). This conclusion was based on the following evidence: vinyl acetate is rapidly transformed into acetaldehyde in human blood and animal tissues, there is sufficient evidence in experimental animals for the carcinogenicity of acetaldehyde, both vinyl acetate and acetaldehyde induce nasal cancer in rats after administration by inhalation, and vinyl acetate and acetaldehyde are genotoxic in human cells in vitro and in animals in vivo .

Перевозки

UN1301 Vinyl acetate, stabilized, Hazard Class: 3; Labels: 3-Flammable liquid.

Методы очистки

Inhibitors such as hydroquinone and other impurities are removed by drying with CaCl2 and fractionally distilling under nitrogen, then refluxing briefly with a small amount of benzoyl peroxide and redistilling it under nitrogen. Store it in the dark at 0o. Add inhibitor (~0.004%) for storage. [Beilstein 2 IV 176.]

Несовместимости

Vinyl acetate may undergo spontaneous exothermic polymerization on exposure to light. Vapors may form explosive mixture with air. Incompatible with oxidizers (chlorates, nitrates, peroxides, permanganates, perchlorates, chlorine, bromine, fluorine, etc.); contact may cause fires or explosions. Keep away from alkaline materials, strong bases, strong acids, oxoacids, epoxides, strong light and UV. The vapor may react vigorously with silica gel or aluminum, acids, bases, silica gel; alumina, oxidizers, azo compounds. Ozone readily polymerizes in elevated temperatures, under the influence of light, or peroxides. Usually contains a stabilizer to prevent polymerization.

Утилизация отходов

Dissolve or mix the material with a combustible solvent and burn in a chemical incinerator equipped with an afterburner and scrubber. All federal, state, and local environmental regulations must be observed.