Toluene diisocyanate production

Toluene is a primary feedstock used to produce various organic compounds. It is used to produce diisocyanates. Isocyanates contain the functional group —N = C = O, and diisocyanates contain two of these. The two main diisocyanates are toluene 2,4-diisocyanate and toluene 2,6-diisocyanate. The production of diisocyanates in North America is close to a billion pounds annually. More than 90% of toluene diisocyanate production is used for making polyurethanes foams. The latter are used as flexible fill in furniture, bedding, and cushions. In rigid form it is used for insulation, hard shell coatings, building materials, auto parts, and roller skate wheels. 

Centrifuge and distillation residues froc toluene diisocyanate production (R T)... 

Yield for the process at low catalyst loading is 95%. AJ-Methyl-toluenediamiae, one of the reaction by-products, represents not only a reduction ia yield, but also a highly objectionable impurity ia the manufacture of toluene diisocyanate. Low concentrations of CO (0.3—6% volume) control this side reaction. 

Toluene Diisocyanate. Toluene diisocyanate is the basic raw material for production of flexible polyurethane foams. It is produced by the reaction sequence shown below, in which toluene is dinitrated, the dinitrotoluene is hydrogenated to yield 2,4-diaminotoluene, and this diamine in turn is treated with phosgene to yield toluene 2,4-diisocyanate. 

No by-product is formed from this reaction. Toluene diisocyanate (Chapter 10) is a widely used monomer. Diols and triols produced from the reaction of glycerol and ethylene oxide or propylene oxide are suitable for producing polyurethanes. 

Chemoenzymatic synthesis of alkyds (oil-based polyester resins) was demonstrated. PPL-catalyzed transesterification of triglycerides with an excess of 1,4-cyclohexanedimethanol mainly produced 2-monoglycerides, followed by thermal polymerization with phthalic anhydride to give the alkyd resins with molecular weight of several thousands. The reaction of the enzymatically obtained alcoholysis product with toluene diisocyanate produced the alkyd-urethane. 

Biodegradable poly(phosphoester-urethanes) containing bisglycophosphite as the chain extender were synthesized. Methylene bis-4-phenyl isocyanate (MDI) and toluene diisocyanate (TDI) were initially used as diisocyanates. Since there was a concern that the degradation products could be toxic, the ethyl 2,6-diisocyanatohexanoate (LDI) was synthesized and replaced the MDI (or TDI). The hydrolytic stability and solubility of these polymers were tested. Preliminary release studies of 5-fluorouracil from MDI based poly(phosphoester-urethane) and methotrexate from LDI based poly(phosphoester-urethane) are also reported. 

Depending on starting diamines these are three toluene diisocyanates, i.e > 80,20 65,35 or 100 per cent 2, 4 toluene diisocyanate. All these are commercially available. They are respiratory irritants and should be handled carefully 80,20 toluene diisocyanate is used widely for production of flexible foams. 

Uses Preparation of 3,4-dichloroaniline solvent for a wide variety of organic compounds and for oxides of nonferrous metals solvent carrier in products of toluene diisocyanate intermediate for dyes fumigant insecticide for termites degreasing hides and wool metal polishes degreasing agent for metals, wood, and leather industrial air control disinfectant heat transfer medium. 

Uses. Intermediate in the production of toluene diisocyanate, which is used to produce polyurethane in the production of dyes... 

By analogy to toluene diisocyanate, exposure of humans to sufficient concentrations is expected to cause irritation of the eyes, nose, and throat a choking sensation and a productive cough of paroxysmal type with retrosternal soreness and chest pain. ... 

Uses/Sources. Intermediate in organic synthesis, especially production of toluene diisocyanate and polymethylene poly-phenylisocyanate in metallurgy to separate ores by chlorination of the oxides and volatilization occurs as a product of combustion whenever a volatile chlorine compound comes in contact with a flame or very hot metal originally manufactured as an agent for chemical warfare during World War I... 

The two key isocyanates that are used in the greatest volumes for polyurethane polymers are toluene diisocyanate (TDl) and methylene diphenyl diisocyanate (MDl). Both isocyanates are produced first by nitration of aromatics (toluene and benzene, respectively), followed by hydrogenation of the nitro aromatics to provide aromatic amines. In the case of MDl, the aniline intermediate is then condensed with formaldehyde to produce methylene dianiline (MDA), which is a mixture of monomeric MDA and an oligomeric form that is typical of aniline/formaldehyde condensation products [2]. The subsequent reaction of phosgene with the aromatic amines provides the isocyanate products. Isocyanates can also be prepared by the reaction of aromatic amines with dimethylcarbonate [3, 4]. This technology has been tested at the industrial pilot scale, but is not believed to be practiced commercially at this time. 

We will return to these reactions later in connection with polyurethanes because one monomer in polyurethanes is toluene diisocyanate, and the first step in its synthesis is the production of dinitrotoluene. 

To a flask containing a solution of 8.7 gm (0.05 mole) of 2,4-toluene diisocyanate in 200 ml of anhydrous ether is slowly added a mixture of 0.432 gm (0.024 mole) of water, 50 ml of anhydrous ether, and 0.5 ml of pyridine at room temperature. The urea derivative precipitates as a fine powder, and then 10 ml water is added and the mixture stirred for an additional hr. The product is filtered, washed several times with 1 1 anhydrous petroleum ether-diethyl ether, dried to yield the product, m.p. 172°-175°C (% yield not reported). 

In a 250-ml three-necked flask, polypropylene glycol (0.02 mol) and 2,4-toluene diisocyanate (0.042 mol) were added and reacted under conditions provided in Table 1. When the reaction was completed, all products were isolated as transparent colorless liquids. 

Important commercial isocyanates include the diisocyanate monomers toluene diisocyanate (TDI), methylene diphenyl diisocyanate (MDI), hexamethylene diisocyanate (HDI), and MDI-, TDI-, and HDI-based isocyanates (e.g., prepolymers and polyisocyanates). World-wide production volume is estimated at over 12 billion lb. Isocyanates (diisocyanates, polyisocyanates, and prepolymers) all cause similar health effects, most commonly asthma [32]. Isocyanates are reported to be the leading attributable cause of work-related asthma [16]. Isocyanates are potent sensitizers that can trigger a severe and potentially fatal asthma attack in sensitized persons at very low isocyanate exposure levels [16]. Toluene diisocyanate is reasonably anticipated to be a human carcinogen by National Toxicology Program. 

Worldwide production capacities for toluene diisocyanates in 1987 were reported as (thousand tonnes) western hemisphere, 356 eastern Europe, 46 western Europe, 380 and Japan and the Far East, 88 (Ulrich, 1989). Worldwide production capacities in 1993 were reported as (thousand tonnes) North America, 485 Europe, 530 Pacific region, 308 and Latin America, 102.5 (Anon., 1995). 

According to the 1981-83 National Occupational Exposure Survey (NOES, 1997), approximately 40 000 workers in the United States were potentially exposed to toluene diisocyanates (see General Remarks). Occupational exposures to toluene diisocyanates may occur during their production and in the production of polyurethane foams, elastomers, coatings, adhesives and finishes. Exposure may also occur in the use of some polyurethane products. Data on occupational exposure levels have been presented in a previous monograph (lARC, 1986). More recent exposure levels have been reported in connection with epidemiological (Section 2) and toxicological (Section 4) studies. 

The major metabolites of toluene diisocyanates in both animals and humans are toluene diamines and their acetylated products (Rosenberg Savolainen, 1985 Bartels et al., 1993 Lind et al., 1996). 

The toxicokinetics of 2,4- and 2,6-toluenediisocyanates in 11 chronically exposed workers at two flexible foam polyurethane production plants have been reported. The toluene diisocyanate concentrations in air varied between 0.4 and 4 pg/m in one plant and in the other between 10 and 120 p-g/m. In one of the plants, the plasma 2,4-toluene diamine levels were 0.4-1 ng/mL before a 4-5-week holiday and 0.2-0.5 ng/mL afterwards. The corresponding plasma levels of 2,6-toluene diamine were 2-6 and 0.5-2 ng/mL, respectively. In the other plant, the plasma 2,4-toluene diamine concentrations were 2-23 ng/mL before the holiday and 0.5-6 ng/mL afterwards and those of 2,6-toluene diamine were 7-24 ng/mL before and 3-6 ng/mL afterwards. The plasma concentrations of 2,4-toluene diamine were 2-24 ng/mL before a 12-day holiday, and 1-14 ng/mL afterwards. The corresponding values for plasma 2,6-toluene diamine were 12-29 and 8-17 ng/mL, respectively. The urinary elimination rates for 2,4-toluene diamine before the holiday were 0.04-0.54 and 0.02-0.18 pg/li afterwards. The corresponding values for 2,6-toluene diamine were 0.18-0.76 pg/li before and 0.09-0.27 pg/h after the holiday. The half-life in urine ranged from 5.8 to 11 days for 2,4- and... 

Amberlite XAD-2 and XAD-4 resins, for example, contain significant quantities of alkyl derivatives of benzene, styrene, naphthalene, and biphenyl as received from the supplier. PUF products, on the other hand, generally contain numerous contaminants peculiar to one of the several patented commercial manufacturing processes. These include, but are not limited to, the following classes of chemical contaminants isocyanate derivatives (e.g., toluene diisocyanates), alkyl amines, aliphatic acids, and brominated aromatics (e.g., fire retardants). 

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