DIMETHYL FORMAMIDE –A PROFITABLE INVESTMENT Dimethylformamide is an organic compound with the formula (CH3)2NC (O) H. Commonly abbreviated as DMF (although this acronym is sometimes used for dimethylfuran), this colourless liquid is miscible with water and the majority of organic liquids. DMF is a common solvent for chemical reactions. Pure dimethylformamide is odourless whereas technical grade or degraded samples often have a fishy smell due to impurity of dimethylamine. Its name is derived from the fact that it is a derivative of formamide, the amide of formic acid. Dimethylformamide is a polar (hydrophilic) aprotic solvent with a high boiling point. It facilitates reactions that follow polar mechanisms, such as SN2 reactions. Dimethylformamide can be synthesized from methyl formate and dimethylamine or by reaction of dimethylamine with carbon monoxide. PROPERTIES: Alternate name CAS number Molecular formula Purity Appearance Odour Density (at 20 deg.C) Solubility Melting point Boiling point DMF 68-12-2 (CH3)2 CHON >99% Colorless, hygroscopic liquid Characteristic amine like odour 0.95 g per cm3 Freely miscible with water -60o c 152oc-154oc PRODUCT APPLICATIONS Dimethyl formamide is an important chemical raw material and also a solvent. It is mainly used in polyurethane, acrylic fiber/spandex fiber, pharmaceutical, pesticide, dyestuff and electronic sectors. CHEMICAL PROPERTIES: Critical Temperature: 374°C (705.2°F) Specific Gravity: 0.949 (Water = 1) Vapor Pressure: 0.3 kPa (@ 20°C) Vapor Density: 2.51 (Air = 1) Dispersion Properties: Soluble in water, diethyl ether, and acetone. Corrosivity: Non-corrosive in presence of glass. REACTIVITY Can react vigorously with oxidizing agents, halogenated hydrocarbons, and inorganic nitrates. Incompatible with carbon tetrachloride, alkyl aluminums, sodium tetrahydroborate, nitrates, chromic acid. Diisocyanatomethane, triethylaluminum, sodium hydride, lithium azide, metallic sodium, bromine, magnesium. Nitrate, potassium permanganate, nitric acid, chromium trioxide, borohydrides, phosphorus trioxide, diborane, octafluoroisobutyrate, sodium nitrite, perchloryl fluoride, potassium methyl 4,4'-dinitrobutyrate. Reaction with inorganic acid chlorides, such as phosphorous oxychloride and thionyl chloride, may form dimethylcarbamoyl, a suspect carcinogen. NATURE OF APPLICATION 1. DMF is widely used in the production and processing of polymers, Spinning solvent for polyacrylonitrile fibre and polyurethane fibre (spandex) and processing solvent for production of polyurethane artificial and synthetic leather. 2. DMF is used for the separation and refining of acetylene from crude olefin gas. 3. DMF is used in extracting butadiene from the C4 distillate obtained by naphtha cracking, etc. and in separating isoprene from C5 distillate. 4. Used as a solvent for recovery of H2S or SO2 or elimination of HCl, Cl, HBr etc. in hydrocarbons. 5. DMF is also used in extracting solvent of aromatic hydrocarbons in petroleum refining. 6. Gases like acetylene that are difficult to liquefy and handle safely can be stored and transported easily by dissolving them in DMF with a porous carrier solid (Ex. Calcium Silicate). 7. DMF is widely used as a solvent for reaction. Generally acetylation, chlorination, sulfonation and various condensation and polymerization reactions are among those where DMF is used as a solvent. 8. It is an excellent solvent for sulphonamide, vitamins, nitro furan, quinoline, adrenaline, amine chlorides, etc. It is widely used in the production of pharmaceuticals as a reaction solvent, extracting solvent and crystallizing bath. 9. DMF easily dissolves basic dye pigments nitroso pigments, phthalocyanine pigments, azo pigments and acid dye metal salts. It is also used as a solvent of colouring agent or an infiltrating ink for various films, wood, leather, resins etc. 10. DMF alone or as mixed with methylene chloride, is used as a remover of varnish or lacquers. INDUSTRIES SERVED Pharmaceuticals, Dyestuff and Pigment, Polymers SAFETY Reactions including the use of sodium hydride in DMF as a solvent are somewhat hazardous; exothermic decompositions have been reported at temperatures as low as 26 °C. On a laboratory scale any thermal runaway is (usually) quickly noticed and brought under control with an ice bath and this remains a popular combination of reagents. On a pilot plant scale, on the other hand, several accidents have been reported. TOXICITY DMF has been linked to cancer in humans, and it is thought to cause birth defects. In some sectors of industry, women are banned from working with DMF. For many reactions, it can be replaced with dimethyl sulfoxide. Most manufacturers of DMF list 'Life' or 'Chronic' as a health hazard in their MSDS since DMF is not readily disposed of by the body. According to IARC, DMF is a possible carcinogen, although EPA does not consider it a cancer risk. PACKAGING • 418.87 (190 kg) steel drums • Full Truck Load, 80 drums/shipment • Bulk Tank Truck • Rail Car INDIAN PRODUCERS Presently, only RCF Ltd. has the capacity to produce DMF in India. Their 2,500 TPA plant at Thai, based on technology from Acid Amirie Technologies Inc., USA is likely to go into commercial production shortly. They are likely to double their capacity to 5,000 TPA by 1996. The decision to expand will be taken after the 2,500 TPA DMF plant is fully operational through the CO route. Vam Organic Chemicals initiated work on a 3,000 TPA DMF project at Gajraula with technology from UCB, Belgium. They are planning only one step in this process. They will procure methyl formate from outside and react it with DMA to obtain DMF. The plant engineering is complete and is likely to go on stream shortly. There is no scope for additional capacity (in case RCF doubles their capacity to 5,000 TPA) till 1999-2000, considering a demand projection of around 7,400 tonnes by 1999-2000. PRODUCTION Total installed capacity is estimated around 3 lakh tonnes world wide compared to a total demand of about 1.8 lakh tonnes (including captive use). There are 16 existing plants worldwide. USA, Brazil and Canada share 24% of the total capacity, Europe (Germany, Spain, U.K., Belgium) share 38% of the total installed capacity, where as balance is shared by other countries. Globally, demand is shrinking or at least stagnant especially in Europe and America due to environmental reasons. DMF DEMAND SCENARIO DMF finds its domestic end use in the following applications: i) As a solvent in acrylic fiber production ii) In the manufacture of drugs and Pharmaceuticals iii) In polyurethane (PU) processing iv) Other miscellaneous application such as dyestuffs, paints, pigments etc Estimated percentage consumption by each end-use sector is given below. Acrylic Fiber 44% Drugs and Pharmaceuticals 38% Polyurethane Processing 8% Miscellaneous 10% TOTAL 100% DEMAND DRIVERS IN GLOBAL MARKET DMF markets exhibiting significant growth in the immediate future will include synthetic/artificial leather, electronics and acrylic fibers. Driven by the global fashion market, elastic fibers (elastane) have experienced the biggest expansion. These fibers are based on elastomeric polyurethanes. Consumption of DMF in synthetic/artificial leather, particularly in China, is expected to result in significant increases in world consumption, in terms of volume and annual growth rates. ASSESSMENT OF GLOBAL DEMANDS China is the largest consumer of DMF in the world market because of large Synthetic/artificial leather (polyurethane based) markets—an application that is comparatively miniscule in most other regions. Consumption in electronics, mainly in the manufacture of printed circuit boards, is a large market in Asia, especially Taiwan, the Republic of Korea and Japan. Global demand is 0.9 million metric tonnes per annum Most DMF is consumed as a solvent in chemical production. Global capacity utilization declined to nearly 55% in 2009 from 58% in 2007 as a result of a much faster pace of capacity expansions. Between 2007 and 2009, world capacity for DMF grew at an average annual rate of just over 6%, surpassing world consumption, which grew at an average annual rate of 1.7% during the same period. Increased Asian consumption, mainly in China, was balanced by declining demand in most other world regions because of the global recession. The technology licensors are: 1)AcidAmineTechnologiesInc. Plants available worldwide are mainly based on the technology supplied by AAT, USA. 2) U.C.B. S.A. SCENARIO IN CHINA China is the largest producer and consumer of DMF. The four largest importers of DMF were Japan, India, Taiwan and the Republic of Korea, together accounting for 63% of world imports in 2009. China and the Republic of Korea are the largest exporters, accounting for 53% and 27%, respectively, of world exports in 2009. China is the largest consumer of DMF because of large synthetic/artificial leather (polyurethane based) markets—an application that is comparatively miniscule in most other regions. Consumption in electronics, mainly in the manufacture of printed circuit boards, is a large market in Asia, especially Taiwan, the Republic of Korea and Japan. Consumption of DMF in synthetic/artificial leather, particularly in China, is expected to result in significant increases in world consumption, in terms of volume and annual growth rates. Unlike most other markets, demand for DMF in Asia, mainly China, is forecast to exhibit moderate to significant growth in most applications. Production facilities in the Americas, Europe and Asia are at risk for shutdowns. PROCESS FOR PRODUCTION There are two process routes for the manufacture of DMF namely direct synthesis and two-step process. 1) Direct synthesis 2) Two step process DIRECT SYNTHESIS The direct or one-step synthesis of DMF begins with either pure carbon monoxide or a gas stream containing carbon monoxide. This is reacted in a continuous process with N, N-dimethylamine (DMA), by using a solution of alkali alkoxide (usually sodium methoxide) in methanol as catalyst. Methyl formate is presumably formed as an intermediate. The reaction mixture passes over an external heat exchanger to remove the excess heat generated and to ensure thorough mixing of the components. The reaction is conducted between 0.5 and 11 MPa at 50~200°C. The reaction mixture exits the reactor through a decompression cham¬ber. In addition to N,N-dimethylformamide, the crude product contains methanol. A certain amount of acid or water deactivates any catalyst present resulting in the formation of sodium formate. Dissolved carbon monoxide, together with inert gases, escapes from the mixture during decompression and the off-gases are removed by combustion. Preliminary distillation is followed by second distilla¬tion in a separate column, here; dimethyl formamide is separated from methanol which contains traces of N, N-dimethylamine. Further distillation results in a product of 99.9% purity. TWO STEP PROCESS The two step process for the synthesis of N,N-dimethylformamide differs from direct synthesis because methyl formate is prepared separately and introduced in the form of 96% pure (commercial -grade) material. Equimolar amounts of methyl formate and N, N-dimethylamine are subjected to a continuous reaction at 60-100°C and 0.1 - 0.3 MPa. The resulting product is a mixture of N, N-dimethylformamide and methanol. The purification process involves distillation and is analogous to that described for direct synthesis. However, no separation of salts is required because no catalysts are involved in the process. Due to the corrosive properties of both starting materials and products, stainless steel has to be used as material of construction for production facilities. HANDLING PROCEDURE AND EQUIPMENTS Workers handling this material must be thoroughly trained in its hazards and its safe use, and must wear appropriate protective equipment and clothing. Keep away from all ignition sources. Ground and bond equipment and containers to prevent a static charge buildup, use spark-resistant tools, and avoid splash filling of containers. Avoid generating mists or vapors. Use the smallest amount possible for the purpose, in well-ventilated areas. Keep work area free of incompatible substances and extraneous materials, particularly those which can burn. Do not return contaminated material to the original containers. Keep containers closed when not in use. Empty containers may contain hazardous PROGNOSIS DMF demand in India is expected to nearly double from the level of 2150 tonnes in 1991-92 to 4100 tonnes by 1995-96. The increase in demand is mainly due to upward trend in acrylic fiber production capacity.